2024 |
Hasler, R; Mor, D C; Aktug, G; Fossati, S; Vu, V T; Tamayo, A; Giordani, E; Ricciardi, E; Giacomini, P; Perutka, J; Onder, K; Kleber, C; Samorì, P; Huang, C -J; Dostalek, J Surface plasmon resonance biosensor with anti-crossing modulation readout Journal Article In: Sens. Actuators B Chem., 417 (136163), 2024. @article{Hasler2024b, title = {Surface plasmon resonance biosensor with anti-crossing modulation readout}, author = {R. Hasler and D. C. Mor and G. Aktug and S. Fossati and V. T. Vu and A. Tamayo and E. Giordani and E. Ricciardi and P. Giacomini and J. Perutka and K. Onder and C. Kleber and P. Samorì and C.-J. Huang and J. Dostalek}, editor = {ELSEVIER}, url = {https://doi.org/10.1016/j.snb.2024.136163}, year = {2024}, date = {2024-10-15}, journal = {Sens. Actuators B Chem.}, volume = {417}, number = {136163}, abstract = {A novel approach to surface plasmon resonance (SPR) biosensors providing simplified label-free monitoring of biomolecular affinity binding events is reported. It is based on the interrogation of anti-crossing surface plasmon modes traveling along opposite interfaces of a thin metal film on the top of a tailored multi-periodic grating structure. It allows for diffraction-based backside excitation of surface plasmons without the need of optical matching of the sensor chip to a prism and it allows avoiding of optical probing through the analyzed liquid sample. In conjunction with low angular dispersion of resonantly excited surface plasmon modes, it provides sensitive and versatile optical interrogation of SPR changes associated with biomolecular binding-induced refractive index variations. Direct readout with a fiber optic probe, as well as multi-channel configuration compatible with regular SPR readers, is implemented with the use of sensor chips prepared by mass production-compatible UV-nanoimprint lithography. The potential of the reported SPR sensor chips is illustrated by its ability to characterize affinity interaction of antibodies specific to cancer biomarker CSPG4 on antifouling mixed thiolated self-assembled monolayer with zwitterionic carboxybetaine and sulfobetaine headgroups.}, keywords = {}, pubstate = {published}, tppubtype = {article} } A novel approach to surface plasmon resonance (SPR) biosensors providing simplified label-free monitoring of biomolecular affinity binding events is reported. It is based on the interrogation of anti-crossing surface plasmon modes traveling along opposite interfaces of a thin metal film on the top of a tailored multi-periodic grating structure. It allows for diffraction-based backside excitation of surface plasmons without the need of optical matching of the sensor chip to a prism and it allows avoiding of optical probing through the analyzed liquid sample. In conjunction with low angular dispersion of resonantly excited surface plasmon modes, it provides sensitive and versatile optical interrogation of SPR changes associated with biomolecular binding-induced refractive index variations. Direct readout with a fiber optic probe, as well as multi-channel configuration compatible with regular SPR readers, is implemented with the use of sensor chips prepared by mass production-compatible UV-nanoimprint lithography. The potential of the reported SPR sensor chips is illustrated by its ability to characterize affinity interaction of antibodies specific to cancer biomarker CSPG4 on antifouling mixed thiolated self-assembled monolayer with zwitterionic carboxybetaine and sulfobetaine headgroups. |
Fu, G; Yang, H; Zhao, W; Samorì, P; Zhang, T 2D Conjugated Polymer Thin Films for Organic Electronics: Opportunities and Challenges Journal Article In: Adv. Mater, 36 (2311541), 2024. @article{Fu2024, title = {2D Conjugated Polymer Thin Films for Organic Electronics: Opportunities and Challenges}, author = {G. Fu and H. Yang and W. Zhao and P. Samorì and T. Zhang}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202311541}, year = {2024}, date = {2024-09-12}, journal = {Adv. Mater}, volume = {36}, number = {2311541}, abstract = {2D conjugated polymers (2DCPs) possess extended in-plane π-conjugated lattice and out-of-plane π–π stacking, which results in enhanced electronic performance and potentially unique band structures. These properties, along with predesignability, well-defined channels, easy postmodification, and order structure attract extensive attention from material science to organic electronics. In this review, the recent advance in the interfacial synthesis and conductivity tuning strategies of 2DCP thin films, as well as their application in organic electronics is summarized. Furthermore, it is shown that, by combining topology structure design and targeted conductivity adjustment, researchers have fabricated 2DCP thin films with predesigned active groups, highly ordered structures, and enhanced conductivity. These films exhibit great potential for various thin-film organic electronics, such as organic transistors, memristors, electrochromism, chemiresistors, and photodetectors. Finally, the future research directions and perspectives of 2DCPs are discussed in terms of the interfacial synthetic design and structure engineering for the fabrication of fully conjugated 2DCP thin films, as well as the functional manipulation of conductivity to advance their applications in future organic electronics.}, keywords = {}, pubstate = {published}, tppubtype = {article} } 2D conjugated polymers (2DCPs) possess extended in-plane π-conjugated lattice and out-of-plane π–π stacking, which results in enhanced electronic performance and potentially unique band structures. These properties, along with predesignability, well-defined channels, easy postmodification, and order structure attract extensive attention from material science to organic electronics. In this review, the recent advance in the interfacial synthesis and conductivity tuning strategies of 2DCP thin films, as well as their application in organic electronics is summarized. Furthermore, it is shown that, by combining topology structure design and targeted conductivity adjustment, researchers have fabricated 2DCP thin films with predesigned active groups, highly ordered structures, and enhanced conductivity. These films exhibit great potential for various thin-film organic electronics, such as organic transistors, memristors, electrochromism, chemiresistors, and photodetectors. Finally, the future research directions and perspectives of 2DCPs are discussed in terms of the interfacial synthetic design and structure engineering for the fabrication of fully conjugated 2DCP thin films, as well as the functional manipulation of conductivity to advance their applications in future organic electronics. |
X. Han S. Wan, He Zou Mavric Wang Piotrowski Bandela Samorì Wang Leydecker Thumu L J A Y M A K P Z T U In: Adv. Sci., 11 (2401973), 2024. @article{Han2024, title = {Tunable Emissive CsPbBr3/Cs4PbBr6 Quantum Dots Engineered by Discrete Phase Transformation for Enhanced Photogating in Field-Effect Phototransistors}, author = {X. Han, S. Wan, L. He, J. Zou, A. Mavric, Y. Wang, M. Piotrowski, A. K. Bandela, P. Samorì, Z. Wang, T. Leydecker, U. Thumu}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/advs.202401973}, year = {2024}, date = {2024-08-27}, journal = {Adv. Sci.}, volume = {11}, number = {2401973}, abstract = {Precise control of quantum structures in hybrid nanocrystals requires advancements in scientific methodologies. Here, on the design of tunable CsPbBr3/Cs4PbBr6 quantum dots are reported by developing a unique discrete phase transformation approach in Cs4PbBr6 nanocrystals. Unlike conventional hybrid systems that emit solely in the green region, this current strategy produces adjustable luminescence in the blue (450 nm), cyan (480 nm), and green (510 nm) regions with high photoluminescence quantum yields up to 45%, 60%, and 85%, respectively. Concentration-dependent studies reveal that phase transformation mechanisms and the factors that drive CsBr removal occur at lower dilutions while the dissolution–recrystallization process dominates at higher dilutions. When the polymer-CsPbBr3/Cs4PbBr6 integrated into a field-effected transistor the resulting phototransistors featured enhanced photosensitivity exceeding 105, being the highest reported for an n-type phototransistor, while maintaining good transistor performances as compared to devices consisting of polymer-CsPbBr3 NCs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Precise control of quantum structures in hybrid nanocrystals requires advancements in scientific methodologies. Here, on the design of tunable CsPbBr3/Cs4PbBr6 quantum dots are reported by developing a unique discrete phase transformation approach in Cs4PbBr6 nanocrystals. Unlike conventional hybrid systems that emit solely in the green region, this current strategy produces adjustable luminescence in the blue (450 nm), cyan (480 nm), and green (510 nm) regions with high photoluminescence quantum yields up to 45%, 60%, and 85%, respectively. Concentration-dependent studies reveal that phase transformation mechanisms and the factors that drive CsBr removal occur at lower dilutions while the dissolution–recrystallization process dominates at higher dilutions. When the polymer-CsPbBr3/Cs4PbBr6 integrated into a field-effected transistor the resulting phototransistors featured enhanced photosensitivity exceeding 105, being the highest reported for an n-type phototransistor, while maintaining good transistor performances as compared to devices consisting of polymer-CsPbBr3 NCs. |
Han, B; Samorì, P Engineering the Interfacing of Molecules with 2D Transition Metal Dichalcogenides: Enhanced Multifunctional Electronics Journal Article In: Acc. Chem. Res., 57 , pp. 2532–2545, 2024. @article{Han2024b, title = {Engineering the Interfacing of Molecules with 2D Transition Metal Dichalcogenides: Enhanced Multifunctional Electronics}, author = {B. Han and P. Samorì}, editor = {ACS Publcation}, url = {https://doi.org/10.1021/acs.accounts.4c00338}, year = {2024}, date = {2024-08-19}, journal = {Acc. Chem. Res.}, volume = {57}, pages = {2532–2545}, abstract = {Conspectus Engineering all interfaces between different components in electronic devices is the key to control and optimize fundamental physical processes such as charge injection at metal–semiconductor interfaces, gate modulation at the dielectric–semiconductor interface, and carrier modulation at semiconductor–environment interfaces. The use of two-dimensional (2D) crystals as semiconductors, by virtue of their atomically flat dangling bond-free structures, can facilitate the tailoring of such interfaces effectively. In this context, 2D transition metal dichalcogenides (TMDs) have garnered tremendous attention over the past two decades owing to their exclusive and outstanding physical and chemical characteristics such as their strong light–matter interactions and high charge mobility. These properties position them as promising building blocks for next-generation semiconductor materials. The combination of their large specific surface area, unique electronic structure, and properties highly sensitive to environmental changes makes 2D TMDs appealing platforms for applications in optoelectronics and sensing. While a broad arsenal of TMDs has been made available that exhibit a variety of electronic properties, the latter are unfortunately hardly tunable. To overcome this problem, the controlled functionalization of TMDs with molecules and assemblies thereof represents a most powerful strategy to finely tune their surface characteristics for electronics. Such functionalization can be used not only to encapsulate the electronic material, therefore enhancing its stability in air, but also to impart dynamic, stimuli-responsive characteristics to TMDs and to selectively recognize the presence of a given analyte in the environment, demonstrating unprecedented application potential. In this Account, we highlight the most enlightening recent progress made on the interface engineering in 2D TMD-based electronic devices via covalent and noncovalent functionalization with suitably designed molecules, underlining the remarkable synergies achieved. While electrode functionalization allows modulating charge injection and extraction, the functionalization of the dielectric substrate enables tuning of the carrier concentration in the device channel, and the functionalization of the upper surface of 2D TMDs allows screening the interaction with the environment and imparts molecular functionality to the devices, making them versatile for various applications. The tailored interfaces enable enhanced device performance and open up avenues for practical applications. This Account specifically focuses on our recent endeavor in the unusual properties conferred to 2D TMDs through the functionalization of their interfaces with stimuli-responsive molecules or molecular assemblies. This includes electrode-functionalized devices with modulable performance and charge carriers, molecular-bridged TMD network devices with overall enhanced electrical properties, sensor devices that are highly responsive to changes in the external environment, in particular, electrochemically switchable transistors that react to external electrochemical signals, optically switchable transistors that are sensitive to external light inputs, and multiresponsive transistors that simultaneously respond to multiple external stimuli including optical, electrical, redox, thermal, and magnetic inputs and their application in the development of unprecedented memories, artificial synapses, and logic inverters. By presenting the current challenges, opportunities, and prospects in this blooming research field, we will discuss the powerful integration of such strategies for next-generation electronic digital devices and logic circuitries, outlining future directions and potential breakthroughs in interface engineering. Copyright © 2024 The Authors. Published by American Chemical Society}, keywords = {}, pubstate = {published}, tppubtype = {article} } Conspectus Engineering all interfaces between different components in electronic devices is the key to control and optimize fundamental physical processes such as charge injection at metal–semiconductor interfaces, gate modulation at the dielectric–semiconductor interface, and carrier modulation at semiconductor–environment interfaces. The use of two-dimensional (2D) crystals as semiconductors, by virtue of their atomically flat dangling bond-free structures, can facilitate the tailoring of such interfaces effectively. In this context, 2D transition metal dichalcogenides (TMDs) have garnered tremendous attention over the past two decades owing to their exclusive and outstanding physical and chemical characteristics such as their strong light–matter interactions and high charge mobility. These properties position them as promising building blocks for next-generation semiconductor materials. The combination of their large specific surface area, unique electronic structure, and properties highly sensitive to environmental changes makes 2D TMDs appealing platforms for applications in optoelectronics and sensing. While a broad arsenal of TMDs has been made available that exhibit a variety of electronic properties, the latter are unfortunately hardly tunable. To overcome this problem, the controlled functionalization of TMDs with molecules and assemblies thereof represents a most powerful strategy to finely tune their surface characteristics for electronics. Such functionalization can be used not only to encapsulate the electronic material, therefore enhancing its stability in air, but also to impart dynamic, stimuli-responsive characteristics to TMDs and to selectively recognize the presence of a given analyte in the environment, demonstrating unprecedented application potential. In this Account, we highlight the most enlightening recent progress made on the interface engineering in 2D TMD-based electronic devices via covalent and noncovalent functionalization with suitably designed molecules, underlining the remarkable synergies achieved. While electrode functionalization allows modulating charge injection and extraction, the functionalization of the dielectric substrate enables tuning of the carrier concentration in the device channel, and the functionalization of the upper surface of 2D TMDs allows screening the interaction with the environment and imparts molecular functionality to the devices, making them versatile for various applications. The tailored interfaces enable enhanced device performance and open up avenues for practical applications. This Account specifically focuses on our recent endeavor in the unusual properties conferred to 2D TMDs through the functionalization of their interfaces with stimuli-responsive molecules or molecular assemblies. This includes electrode-functionalized devices with modulable performance and charge carriers, molecular-bridged TMD network devices with overall enhanced electrical properties, sensor devices that are highly responsive to changes in the external environment, in particular, electrochemically switchable transistors that react to external electrochemical signals, optically switchable transistors that are sensitive to external light inputs, and multiresponsive transistors that simultaneously respond to multiple external stimuli including optical, electrical, redox, thermal, and magnetic inputs and their application in the development of unprecedented memories, artificial synapses, and logic inverters. By presenting the current challenges, opportunities, and prospects in this blooming research field, we will discuss the powerful integration of such strategies for next-generation electronic digital devices and logic circuitries, outlining future directions and potential breakthroughs in interface engineering. Copyright © 2024 The Authors. Published by American Chemical Society |
Gullace, S; Abruzzese, M; Cusin, L; Saleh, G; Thorat, S B; Gamberini, A; Bellani, S; Ciesielski, A; Bonaccorso, F; P. Samorì, Covalent organic framework-based Li–S batteries: functional separators promoting Li+ transport and polysulfide trapping Journal Article In: J. Mater. Chem. A, 12 , pp. 25359–25370, 2024. @article{Gullace2024, title = {Covalent organic framework-based Li–S batteries: functional separators promoting Li+ transport and polysulfide trapping}, author = {S. Gullace and M. Abruzzese and L. Cusin and G. Saleh and S. B. Thorat and A. Gamberini and S. Bellani and A. Ciesielski and F. Bonaccorso and , P. Samorì, }, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d4ta03930k}, year = {2024}, date = {2024-08-17}, journal = {J. Mater. Chem. A}, volume = {12}, pages = {25359–25370}, abstract = {Lithium–sulphur batteries (LSBs) prevail as a viable alternative to Li-ion batteries due to their high theoretical specific capacity (1672 mA h gS−1). However, the formation of soluble polysulfides and their shuttle from the cathode to the anode cause irreversible capacity loss and uncontrolled self-discharge, limiting the performance of commercially available prototypes. In this work, we present a comparative analysis of two Kagome-shaped imine-based covalent organic frameworks (COFs) as functional modifiers for polypropylene (Celgard) separators in LSBs. We demonstrate, by using the KS60@Celgard separator modified with an optimized content of COF with the thienothiophene linker, the realization of LSBs reaching a specific discharge capacity of 850 mA h gS−1 at C5. The proposed separator has an extraordinarily high Li+ diffusion coefficient (DLi+) of 1.6 × 10−7 cm2 s−1 at the first cathodic peak, as well as the lowest S8 : Li2Sx content ratio in the ex situ post mortem XPS analysis. These findings demonstrate that the use of separators modified with COFs allows the mitigation of shuttle effect, and is further accompanied by an efficient oxidation of Li2Sx to S8 (electrocatalytic effect). The equivalent K60@Celgard, based on a COF carrying a phenyl linker, results in LSBs with a specific discharge capacity of 599 mA h gS−1. This work highlights the synergistic effect of polysulfide retention, selective Li+ sieving and electrocatalytic activity of COF-modified Celgard separators in the development of high-performance LSBs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Lithium–sulphur batteries (LSBs) prevail as a viable alternative to Li-ion batteries due to their high theoretical specific capacity (1672 mA h gS−1). However, the formation of soluble polysulfides and their shuttle from the cathode to the anode cause irreversible capacity loss and uncontrolled self-discharge, limiting the performance of commercially available prototypes. In this work, we present a comparative analysis of two Kagome-shaped imine-based covalent organic frameworks (COFs) as functional modifiers for polypropylene (Celgard) separators in LSBs. We demonstrate, by using the KS60@Celgard separator modified with an optimized content of COF with the thienothiophene linker, the realization of LSBs reaching a specific discharge capacity of 850 mA h gS−1 at C5. The proposed separator has an extraordinarily high Li+ diffusion coefficient (DLi+) of 1.6 × 10−7 cm2 s−1 at the first cathodic peak, as well as the lowest S8 : Li2Sx content ratio in the ex situ post mortem XPS analysis. These findings demonstrate that the use of separators modified with COFs allows the mitigation of shuttle effect, and is further accompanied by an efficient oxidation of Li2Sx to S8 (electrocatalytic effect). The equivalent K60@Celgard, based on a COF carrying a phenyl linker, results in LSBs with a specific discharge capacity of 599 mA h gS−1. This work highlights the synergistic effect of polysulfide retention, selective Li+ sieving and electrocatalytic activity of COF-modified Celgard separators in the development of high-performance LSBs. |
Dai, S; Xie, M; Wang, C; Wang, Y; Han, B; Xu, S; Wang, K; Zhuravlova, A; Xu, B; Chi, L; Tian, W; Samorì, P; Liu, Z Highly efficient organic–graphene hybrid photodetectors via molecular peripheral editing Journal Article In: J. Mater. Chem. C, 12 (14667–14674), 2024. @article{Dai2024, title = {Highly efficient organic–graphene hybrid photodetectors via molecular peripheral editing}, author = {S. Dai and M. Xie and C. Wang and Y. Wang and B. Han and S. Xu and K. Wang and A. Zhuravlova and B. Xu and L. Chi and W. Tian and P. Samorì and Z. Liu}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d4tc02010c}, year = {2024}, date = {2024-08-12}, journal = {J. Mater. Chem. C}, volume = {12}, number = {14667–14674}, abstract = {Hybrid systems based on graphene and organic molecules are highly appealing for “correcting” the limited optoelectronic properties of 2D materials. However, an in-depth understanding of the correlation between the structure of the molecular sensitizer and the physical properties of the hybrid toward high-performance organic–graphene hybrid photodetectors remains elusive. Herein, an ad hoc molecular design via a peripheral editing approach on the organic molecules is employed to elucidate the structure–property relationship when interfaced with graphene forming hybrid systems. Efficient doping of graphene can be attained by physisorption of tetrathiafulvalene molecules exposing electron-donating peripheral groups, benefiting from a strong coupling yielding efficient charge transfer, ultimately leading to photodetectors with an ultra-high responsivity of 1.1 × 107 A W−1 and a specific detectivity of 6.5 × 1014 Jones, thereby outperforming state-of-the-art graphene-based photodetectors. These results offer valuable insights for future optimization of graphene-based photodetectors through molecular functionalization.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Hybrid systems based on graphene and organic molecules are highly appealing for “correcting” the limited optoelectronic properties of 2D materials. However, an in-depth understanding of the correlation between the structure of the molecular sensitizer and the physical properties of the hybrid toward high-performance organic–graphene hybrid photodetectors remains elusive. Herein, an ad hoc molecular design via a peripheral editing approach on the organic molecules is employed to elucidate the structure–property relationship when interfaced with graphene forming hybrid systems. Efficient doping of graphene can be attained by physisorption of tetrathiafulvalene molecules exposing electron-donating peripheral groups, benefiting from a strong coupling yielding efficient charge transfer, ultimately leading to photodetectors with an ultra-high responsivity of 1.1 × 107 A W−1 and a specific detectivity of 6.5 × 1014 Jones, thereby outperforming state-of-the-art graphene-based photodetectors. These results offer valuable insights for future optimization of graphene-based photodetectors through molecular functionalization. |
Safuta, M; Valentini, C; Ciesielski, A; Samorì, Paolo In: Nanoscale, 16 , pp. 15824–15833, 2024. @article{Safuta2024, title = {Tailoring electrochemically exfoliated graphene electroactive pathways in cementitious composites for structural health monitoring of constructions}, author = {M. Safuta and C. Valentini and A. Ciesielski and Paolo Samorì}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d4nr01764a}, year = {2024}, date = {2024-08-06}, journal = {Nanoscale}, volume = {16}, pages = {15824–15833}, abstract = {Manipulating and exerting a nanoscale control over the structure of multicomponent materials represents a powerful strategy for tailoring multifunctional composites for structural health monitoring applications. The use of self-sensing, electroactive cementitious composites in large-scale applications is severely hindered by the absence of clear directives and a thorough understanding of the electrical conduction mechanisms taking place within the cement matrix. Here we report on a nanoscale approach towards this goal which is accomplished via the development of a novel, multifunctional cementitious composite incorporating electrochemically exfoliated graphene (EEG). The use of commercially available poly(carboxylate ether)-based superplasticizer allowed us to embed in the cement mortar up to 0.8 wt% of EEG which is fully dispersed in the matrix. The multiscale investigation made it possible to assess the effect of such high dosages of EEG on the mechanical performance and hydration degree of cementitious composites. We used electrochemical impedance spectroscopy to monitor the formation of electroactive EEG-based percolation paths for charge transfer within cement mortar, the latter displaying resistivities of 2.67 kΩ cm as well as EEG-cement-EEG capacitive paths with capacitance of 2.20 × 10−10 F cm−1 for composites incorporating 0.6 wt% of EEG. Noteworthy, we have proposed here for the first time an electrical equivalent circuit for the impedance spectroscopy analysis of cementitious composites with high loadings of graphene, exceeding the percolation threshold. These findings underscore the potential of nanoscale structures for civil engineering applications and more specifically may open new avenues for the technological application of graphene-based cementitious composites in self-sensing structures.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Manipulating and exerting a nanoscale control over the structure of multicomponent materials represents a powerful strategy for tailoring multifunctional composites for structural health monitoring applications. The use of self-sensing, electroactive cementitious composites in large-scale applications is severely hindered by the absence of clear directives and a thorough understanding of the electrical conduction mechanisms taking place within the cement matrix. Here we report on a nanoscale approach towards this goal which is accomplished via the development of a novel, multifunctional cementitious composite incorporating electrochemically exfoliated graphene (EEG). The use of commercially available poly(carboxylate ether)-based superplasticizer allowed us to embed in the cement mortar up to 0.8 wt% of EEG which is fully dispersed in the matrix. The multiscale investigation made it possible to assess the effect of such high dosages of EEG on the mechanical performance and hydration degree of cementitious composites. We used electrochemical impedance spectroscopy to monitor the formation of electroactive EEG-based percolation paths for charge transfer within cement mortar, the latter displaying resistivities of 2.67 kΩ cm as well as EEG-cement-EEG capacitive paths with capacitance of 2.20 × 10−10 F cm−1 for composites incorporating 0.6 wt% of EEG. Noteworthy, we have proposed here for the first time an electrical equivalent circuit for the impedance spectroscopy analysis of cementitious composites with high loadings of graphene, exceeding the percolation threshold. These findings underscore the potential of nanoscale structures for civil engineering applications and more specifically may open new avenues for the technological application of graphene-based cementitious composites in self-sensing structures. |
Montes-García, V; Valentini, C; Klymovych, D; Kukułka, W; Shi, L; Patroniak, V; Samorì, P; Ciesielski, Artur Template-assisted synthesis of hollow anthraquinone-based covalent organic frameworks for aqueous zinc-ion hybrid supercapacitors Journal Article In: Chem. Commun., 60 , pp. 9408–9411, 2024. @article{Montes-García2024b, title = {Template-assisted synthesis of hollow anthraquinone-based covalent organic frameworks for aqueous zinc-ion hybrid supercapacitors}, author = {V. Montes-García and C. Valentini and D. Klymovych and W. Kukułka and L. Shi and V. Patroniak and P. Samorì and Artur Ciesielski}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d4cc03216k}, year = {2024}, date = {2024-08-06}, journal = {Chem. Commun.}, volume = {60}, pages = {9408–9411}, abstract = {Anthraquinone-based hollow COFs were synthesized via a template-assisted method involving polystyrene nanospheres as the hard template, which enabled doubling the specific capacitance and energy density compared to non-templated COFs. Our approach can be extended to other COFs, offering a promising strategy for enhancing the performance of COF-based electrodes in energy storage applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Anthraquinone-based hollow COFs were synthesized via a template-assisted method involving polystyrene nanospheres as the hard template, which enabled doubling the specific capacitance and energy density compared to non-templated COFs. Our approach can be extended to other COFs, offering a promising strategy for enhancing the performance of COF-based electrodes in energy storage applications. |
Guo, H; Montes-García, V; Peng, H; Samorì, P; Ciesielski, A Molecular Connectors Boosting the Performance of MoS2 Cathodes in Zinc-Ion Batteries Journal Article In: Small, 20 (2310338), 2024. @article{Guo2024, title = {Molecular Connectors Boosting the Performance of MoS2 Cathodes in Zinc-Ion Batteries }, author = {H. Guo and V. Montes-García and H. Peng and P. Samorì and A. Ciesielski}, editor = {Wiley Online Library}, url = {https://onlinelibrary.wiley.com/doi/10.1002/smll.202310338}, year = {2024}, date = {2024-07-18}, journal = {Small}, volume = {20}, number = {2310338}, abstract = {Zinc-ion batteries (ZIBs) are promising energy storage systems due to high energy density, low-cost, and abundant availability of zinc as a raw material. However, the greatest challenge in ZIBs research is lack of suitable cathode materials that can reversibly intercalate Zn2+ ions. 2D layered materials, especially MoS2-based, attract tremendous interest due to large surface area and ability to intercalate/deintercalate ions. Unfortunately, pristine MoS2 obtained by traditional protocols such as chemical exfoliation or hydrothermal/solvothermal methods exhibits limited electronic conductivity and poor chemical stability upon charge/discharge cycling. Here, a novel molecular strategy to boost the electrochemical performance of MoS2 cathode materials for aqueous ZIBs is reported. The use of dithiolated conjugated molecular pillars, that is, 4,4′-biphenyldithiols, enables to heal defects and crosslink the MoS2 nanosheets, yielding covalently bridged networks (MoS2-SH2) with improved ionic and electronic conductivity and electrochemical performance. In particular, MoS2-SH2 electrodes display high specific capacity of 271.3 mAh g−1 at 0.1 A g−1, high energy density of 279 Wh kg−1, and high power density of 12.3 kW kg−1. With its outstanding rate capability (capacity of 148.1 mAh g−1 at 10 A g−1) and stability (capacity of 179 mAh g−1 after 1000 cycles), MoS2-SH2 electrodes outperform other MoS2-based electrodes in ZIBs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Zinc-ion batteries (ZIBs) are promising energy storage systems due to high energy density, low-cost, and abundant availability of zinc as a raw material. However, the greatest challenge in ZIBs research is lack of suitable cathode materials that can reversibly intercalate Zn2+ ions. 2D layered materials, especially MoS2-based, attract tremendous interest due to large surface area and ability to intercalate/deintercalate ions. Unfortunately, pristine MoS2 obtained by traditional protocols such as chemical exfoliation or hydrothermal/solvothermal methods exhibits limited electronic conductivity and poor chemical stability upon charge/discharge cycling. Here, a novel molecular strategy to boost the electrochemical performance of MoS2 cathode materials for aqueous ZIBs is reported. The use of dithiolated conjugated molecular pillars, that is, 4,4′-biphenyldithiols, enables to heal defects and crosslink the MoS2 nanosheets, yielding covalently bridged networks (MoS2-SH2) with improved ionic and electronic conductivity and electrochemical performance. In particular, MoS2-SH2 electrodes display high specific capacity of 271.3 mAh g−1 at 0.1 A g−1, high energy density of 279 Wh kg−1, and high power density of 12.3 kW kg−1. With its outstanding rate capability (capacity of 148.1 mAh g−1 at 10 A g−1) and stability (capacity of 179 mAh g−1 after 1000 cycles), MoS2-SH2 electrodes outperform other MoS2-based electrodes in ZIBs. |
Valentini, C; Montes-García, V; Cusin, L; Pakulski, D; Wlazło, M; Samorì, P; Ciesielski, A Peri-Xanthenoxanthene-Based Covalent Organic Frameworks for High-Performance Aqueous Zn-Ion Hybrid Supercapacitors Journal Article In: Small Sci., 4 (2400031), 2024. @article{Valentini2024b, title = {Peri-Xanthenoxanthene-Based Covalent Organic Frameworks for High-Performance Aqueous Zn-Ion Hybrid Supercapacitors}, author = {C. Valentini and V. Montes-García and L. Cusin and D. Pakulski and M. Wlazło and P. Samorì and A. Ciesielski}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/smsc.202400031}, year = {2024}, date = {2024-07-11}, journal = {Small Sci.}, volume = {4}, number = {2400031}, abstract = {Aqueous zinc-ion hybrid supercapacitors (Zn-HSCs) are promising devices for sustainable and efficient energy storage. However, they suffer from a limited energy density compared to lithium-ion batteries. This limitation can be overcome by developing novel electrode materials, with covalent organic frameworks (COFs) standing out as a particularly intriguing option. Herein, peri-xanthenoxanthene (PXX) has been integrated for the first time into a COF scaffold to take advantage of its straightforward synthesis, chemical stability, π-conjugated backbone, and heteroatom content endowing reversible redox reactions at low potentials. Two novel hexagonal COFs have been designed and synthesized by tethering of a PXX-diamine unit having a C2 symmetry with two distinct tris-aldehydes acting as C3-symmetric cornerstones, i.e., triformyl benzene (TFB) and triformylphloroglucinol (Tp), ultimately yielding COF PXX(PhNH2)2-TFB and COF PXX(PhNH2)2-Tp, respectively. As cathodes in Zn-HSCs, COF PXX(PhNH2)2-Tp exhibits a remarkable specific capacitance, energy, and power densities (237 F g−1, 106.6 Wh kg−1, and 3.0 kW kg−1, respectively), surpassing those of COF PXX(PhNH2)2-TFB (109 F g−1, 49.1 Wh kg−1, and 0.67 kW kg−1). Importantly, both COFs display outstanding long-term stability, over 5000 charge/discharge cycles, with capacitance retention >92%. These findings underscore the potential of PXX-based COFs as high-performance cathode materials for HSCs, thereby offering a promising new avenue for energy storage technologies.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Aqueous zinc-ion hybrid supercapacitors (Zn-HSCs) are promising devices for sustainable and efficient energy storage. However, they suffer from a limited energy density compared to lithium-ion batteries. This limitation can be overcome by developing novel electrode materials, with covalent organic frameworks (COFs) standing out as a particularly intriguing option. Herein, peri-xanthenoxanthene (PXX) has been integrated for the first time into a COF scaffold to take advantage of its straightforward synthesis, chemical stability, π-conjugated backbone, and heteroatom content endowing reversible redox reactions at low potentials. Two novel hexagonal COFs have been designed and synthesized by tethering of a PXX-diamine unit having a C2 symmetry with two distinct tris-aldehydes acting as C3-symmetric cornerstones, i.e., triformyl benzene (TFB) and triformylphloroglucinol (Tp), ultimately yielding COF PXX(PhNH2)2-TFB and COF PXX(PhNH2)2-Tp, respectively. As cathodes in Zn-HSCs, COF PXX(PhNH2)2-Tp exhibits a remarkable specific capacitance, energy, and power densities (237 F g−1, 106.6 Wh kg−1, and 3.0 kW kg−1, respectively), surpassing those of COF PXX(PhNH2)2-TFB (109 F g−1, 49.1 Wh kg−1, and 0.67 kW kg−1). Importantly, both COFs display outstanding long-term stability, over 5000 charge/discharge cycles, with capacitance retention >92%. These findings underscore the potential of PXX-based COFs as high-performance cathode materials for HSCs, thereby offering a promising new avenue for energy storage technologies. |
Chen, Y; Wang, H; Chen, H; Zhang, W; Pätzel, M; Han, B; Wang, K; Xu, S; Montes-García, V; McCulloch, I; Hecht, S; Samorì, P Li Promoting Long Afterglow Organic Light-Emitting Transistor for Memory Optocoupler Module Journal Article In: Adv. Mater., 36 (2402515), 2024. @article{Chen2024, title = {Li Promoting Long Afterglow Organic Light-Emitting Transistor for Memory Optocoupler Module}, author = {Y. Chen and H. Wang and H. Chen and W. Zhang and M. Pätzel and B. Han and K. Wang and S. Xu and V. Montes-García and I. McCulloch and S. Hecht and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202402515}, year = {2024}, date = {2024-07-04}, journal = {Adv. Mater.}, volume = {36}, number = {2402515}, abstract = {The artificial brain is conceived as advanced intelligence technology, capable to emulate in-memory processes occurring in the human brain by integrating synaptic devices. Within this context, improving the functionality of synaptic transistors to increase information processing density in neuromorphic chips is a major challenge in this field. In this article, Li-ion migration promoting long afterglow organic light-emitting transistors, which display exceptional postsynaptic brightness of 7000 cd m−2 under low operational voltages of 10 V is presented. The postsynaptic current of 0.1 mA operating as a built-in threshold switch is implemented as a firing point in these devices. The setting-condition-triggered long afterglow is employed to drive the photoisomerization process of photochromic molecules that mimic neurotransmitter transfer in the human brain for realizing a key memory rule, that is, the transition from long-term memory to permanent memory. The combination of setting-condition-triggered long afterglow with photodiode amplifiers is also processed to emulate the human responding action after the setting-training process. Overall, the successful integration in neuromorphic computing comprising stimulus judgment, photon emission, transition, and encoding, to emulate the complicated decision tree of the human brain is demonstrated.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The artificial brain is conceived as advanced intelligence technology, capable to emulate in-memory processes occurring in the human brain by integrating synaptic devices. Within this context, improving the functionality of synaptic transistors to increase information processing density in neuromorphic chips is a major challenge in this field. In this article, Li-ion migration promoting long afterglow organic light-emitting transistors, which display exceptional postsynaptic brightness of 7000 cd m−2 under low operational voltages of 10 V is presented. The postsynaptic current of 0.1 mA operating as a built-in threshold switch is implemented as a firing point in these devices. The setting-condition-triggered long afterglow is employed to drive the photoisomerization process of photochromic molecules that mimic neurotransmitter transfer in the human brain for realizing a key memory rule, that is, the transition from long-term memory to permanent memory. The combination of setting-condition-triggered long afterglow with photodiode amplifiers is also processed to emulate the human responding action after the setting-training process. Overall, the successful integration in neuromorphic computing comprising stimulus judgment, photon emission, transition, and encoding, to emulate the complicated decision tree of the human brain is demonstrated. |
Valentini, C; Montes-García, V; Ciesielski, A; Samorì, P Boosting Zinc Hybrid Supercapacitor Performance via Thiol Functionalization of Graphene-Based Cathodes Journal Article In: Adv. Sci., 11 (2309041), 2024. @article{Valentini2024, title = {Boosting Zinc Hybrid Supercapacitor Performance via Thiol Functionalization of Graphene-Based Cathodes}, author = {C. Valentini and V. Montes-García and A. Ciesielski and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/advs.202309041}, year = {2024}, date = {2024-06-12}, journal = {Adv. Sci.}, volume = {11}, number = {2309041}, abstract = {Zinc hybrid supercapacitors (Zn-HSCs) hold immense potential toward the next-generation energy storage systems, effectively spanning the divide between conventional lithium-ion batteries (LIBs) and supercapacitors. Unfortunately, the energy density of most of Zn-HSCs has not yet rivalled the levels observed in LIBs. The electrochemical performance of aqueous Zn-HSCs can be enhanced through the chemical functionalization of graphene-based cathode materials with thiol moieties as they will be highly suitable for favoring Zn2+ adsorption/desorption. Here, a single-step reaction is employed to synthesize thiol-functionalized reduced graphene oxide (rGOSH), incorporating both oxygen functional groups (OFGs) and thiol functionalities, as demonstrated by X-ray photoelectron spectroscopy (XPS) studies. Electrochemical analysis reveals that rGOSH cathodes exhibit a specific capacitance (540 F g−1) and specific capacity (139 mAh g−1) at 0.1 A g−1 as well as long-term stability, with over 92% capacitance retention after 10 000 cycles, outperforming chemically reduced graphene oxide (CrGO). Notably, rGOSH electrodes displayed an exceptional maximum energy density of 187.6 Wh kg−1 and power density of 48.6 kW kg−1. Overall, this study offers an unprecedented powerful strategy for the design and optimization of cathode materials, paving the way for efficient and sustainable energy storage solutions to meet the increasing demands of modern energy applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Zinc hybrid supercapacitors (Zn-HSCs) hold immense potential toward the next-generation energy storage systems, effectively spanning the divide between conventional lithium-ion batteries (LIBs) and supercapacitors. Unfortunately, the energy density of most of Zn-HSCs has not yet rivalled the levels observed in LIBs. The electrochemical performance of aqueous Zn-HSCs can be enhanced through the chemical functionalization of graphene-based cathode materials with thiol moieties as they will be highly suitable for favoring Zn2+ adsorption/desorption. Here, a single-step reaction is employed to synthesize thiol-functionalized reduced graphene oxide (rGOSH), incorporating both oxygen functional groups (OFGs) and thiol functionalities, as demonstrated by X-ray photoelectron spectroscopy (XPS) studies. Electrochemical analysis reveals that rGOSH cathodes exhibit a specific capacitance (540 F g−1) and specific capacity (139 mAh g−1) at 0.1 A g−1 as well as long-term stability, with over 92% capacitance retention after 10 000 cycles, outperforming chemically reduced graphene oxide (CrGO). Notably, rGOSH electrodes displayed an exceptional maximum energy density of 187.6 Wh kg−1 and power density of 48.6 kW kg−1. Overall, this study offers an unprecedented powerful strategy for the design and optimization of cathode materials, paving the way for efficient and sustainable energy storage solutions to meet the increasing demands of modern energy applications. |
Sensi, M; de Oliveira, Furlan R; Berto, M; Paradisi, A; Greco, P; Bortolotti, C A; Samorì, P; Biscarini, F How Biorecognition Affects the Electronic Properties of Reduced Graphene Oxide in Electrolyte-Gated Transistor Immunosensors Journal Article In: Adv. Funct. Mater., 34 (2313871), 2024. @article{Sensi2024, title = {How Biorecognition Affects the Electronic Properties of Reduced Graphene Oxide in Electrolyte-Gated Transistor Immunosensors}, author = {M. Sensi and R. Furlan de Oliveira and M. Berto and A. Paradisi and P. Greco and C. A. Bortolotti and P. Samorì and F. Biscarini}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adfm.202313871}, year = {2024}, date = {2024-05-10}, journal = {Adv. Funct. Mater.}, volume = {34}, number = {2313871}, abstract = {Ambipolar electrolyte-gated transistors (EGTs) based on reduced graphene oxide (rGO) have been demonstrated as ultra-sensitive and highly specific immunosensors. However, the physics and chemistry ruling the device operation are still not fully unraveled. In this work, the aim is to elucidate the nature of the observed sensitivity of the device. Toward this aim, a physical–chemical model that, coupled with the experimental characterization of the rGO-EGT, allows one to quantitatively correlate the biorecognition events at the gate electrode and the electronic properties of rGO-EGT is proposed. The equilibrium of biorecognition occurring at the gate electrode is shown to determine the apparent charge neutrality point (CNP) of the rGO channel. The multiparametric analysis of the experimental transfer characteristics of rGO-EGT reveals that the recognition events modulate the CNP voltage, the excess carrier density Δn, and the quantum capacitance of rGO. This analysis also explains why hole and electron carrier mobilities, interfacial capacitance, the curvature of the transfer curve, and the transconductances are insensitive to the target concentration. The understanding of the mechanisms underlying the transistor transduction of the biorecognition events is key for the interpretation of the response of the rGO-EGT immunosensors and to guide the design of novel and more sensitive devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Ambipolar electrolyte-gated transistors (EGTs) based on reduced graphene oxide (rGO) have been demonstrated as ultra-sensitive and highly specific immunosensors. However, the physics and chemistry ruling the device operation are still not fully unraveled. In this work, the aim is to elucidate the nature of the observed sensitivity of the device. Toward this aim, a physical–chemical model that, coupled with the experimental characterization of the rGO-EGT, allows one to quantitatively correlate the biorecognition events at the gate electrode and the electronic properties of rGO-EGT is proposed. The equilibrium of biorecognition occurring at the gate electrode is shown to determine the apparent charge neutrality point (CNP) of the rGO channel. The multiparametric analysis of the experimental transfer characteristics of rGO-EGT reveals that the recognition events modulate the CNP voltage, the excess carrier density Δn, and the quantum capacitance of rGO. This analysis also explains why hole and electron carrier mobilities, interfacial capacitance, the curvature of the transfer curve, and the transconductances are insensitive to the target concentration. The understanding of the mechanisms underlying the transistor transduction of the biorecognition events is key for the interpretation of the response of the rGO-EGT immunosensors and to guide the design of novel and more sensitive devices. |
Liang, R -R; Xu, S; Han, Z; Yang, Y; Wang, K -Y; Huang, Z; Rushlow, J; Cai, P; Samorì, P; Zhou, H -C In: J. Am. Chem. Soc., 146 , pp. 9811–9818, 2024. @article{Liang2024, title = {Exceptionally High Perfluorooctanoic Acid Uptake in Water by a Zirconium-Based Metal–Organic Framework through Synergistic Chemical and Physical Adsorption}, author = {R.-R. Liang and S. Xu and Z. Han and Y. Yang and K.-Y. Wang and Z. Huang and J. Rushlow and P. Cai and P. Samorì and H.-C. Zhou}, editor = {ACS Publcation}, url = {https://doi.org/10.1021/jacs.3c14487}, year = {2024}, date = {2024-04-10}, journal = {J. Am. Chem. Soc.}, volume = {146}, pages = {9811–9818}, abstract = {Perfluorooctanoic acid (PFOA) is an environmental contaminant ubiquitous in water resources, which as a xenobiotic and carcinogenic agent, severely endangers human health. The development of techniques for its efficient removal is therefore highly sought after. Herein, we demonstrate an unprecedented zirconium-based MOF (PCN-999) possessing Zr6 and biformate-bridged (Zr6)2 clusters simultaneously, which exhibits an exceptional PFOA uptake of 1089 mg/g (2.63 mmol/g), representing a ca. 50% increase over the previous record for MOFs. Single-crystal X-ray diffraction studies and computational analysis revealed that the (Zr6)2 clusters offer additional open coordination sites for hosting PFOA. The coordinated PFOAs further enhance the interaction between coordinated and free PFOAs for physical adsorption, boosting the adsorption capacity to an unparalleled high standard. Our findings represent a major step forward in the fundamental understanding of the MOF-based PFOA removal mechanism, paving the way toward the rational design of next-generation adsorbents for per- and polyfluoroalkyl substance (PFAS) removal.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Perfluorooctanoic acid (PFOA) is an environmental contaminant ubiquitous in water resources, which as a xenobiotic and carcinogenic agent, severely endangers human health. The development of techniques for its efficient removal is therefore highly sought after. Herein, we demonstrate an unprecedented zirconium-based MOF (PCN-999) possessing Zr6 and biformate-bridged (Zr6)2 clusters simultaneously, which exhibits an exceptional PFOA uptake of 1089 mg/g (2.63 mmol/g), representing a ca. 50% increase over the previous record for MOFs. Single-crystal X-ray diffraction studies and computational analysis revealed that the (Zr6)2 clusters offer additional open coordination sites for hosting PFOA. The coordinated PFOAs further enhance the interaction between coordinated and free PFOAs for physical adsorption, boosting the adsorption capacity to an unparalleled high standard. Our findings represent a major step forward in the fundamental understanding of the MOF-based PFOA removal mechanism, paving the way toward the rational design of next-generation adsorbents for per- and polyfluoroalkyl substance (PFAS) removal. |
Hensel, R C; Vizio, Di B; Montes-García, V; Yang, J; Ilie, G G; Sedona, F; Sambi, M; Samorì, P; Cester, A; Agnoli, S; Casalini, S Graphene Acetic Acid-Based Hybrid Supercapacitor and Liquid-Gated Transistor Journal Article In: Adv. Electron. Mater., 10 (2300685), 2024. @article{Hensel2024, title = {Graphene Acetic Acid-Based Hybrid Supercapacitor and Liquid-Gated Transistor}, author = {R. C. Hensel and B. Di Vizio and V. Montes-García and J. Yang and G. G. Ilie and F. Sedona and M. Sambi and P. Samorì and A. Cester and S. Agnoli and S. Casalini}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/aelm.202300685}, year = {2024}, date = {2024-04-01}, journal = {Adv. Electron. Mater.}, volume = {10}, number = {2300685}, abstract = {Supercapacitors and transistors are two key devices for future electronics that must combine portability, high performance, easy scalability, etc. Graphene-related materials (GRMs) are frequently chosen as active materials for these applications given their unique physical properties that are tunable via chemical functionalization. Up to date, among GRMs, only reduced graphene oxide (rGO) showed sufficient versatility and processability in mild media, rendering it suitable for integration in these two types of devices. Here, a sound alternative to rGO is provided, namely graphene acetic acid (GAA), whose physico-chemical features offer specific advantages. In particular, the use of a GAA-based cathode in a zinc hybrid supercapacitor (Zn-HSC) delivers state-of-the-art gravimetric capacitance of ≈400 F g−1 at a current density of 0.05 A g−1. Conversely, GAA-based LGT, supported onto Si/SiO2, shows an ambipolar behavior in 0.1 m NaCl, featuring a clear p-doping quantified by Dirac voltage higher than 100 mV. Such a device is successfully implemented in paper fluidics, thereby demonstrating the feasibility of real-time monitoring.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Supercapacitors and transistors are two key devices for future electronics that must combine portability, high performance, easy scalability, etc. Graphene-related materials (GRMs) are frequently chosen as active materials for these applications given their unique physical properties that are tunable via chemical functionalization. Up to date, among GRMs, only reduced graphene oxide (rGO) showed sufficient versatility and processability in mild media, rendering it suitable for integration in these two types of devices. Here, a sound alternative to rGO is provided, namely graphene acetic acid (GAA), whose physico-chemical features offer specific advantages. In particular, the use of a GAA-based cathode in a zinc hybrid supercapacitor (Zn-HSC) delivers state-of-the-art gravimetric capacitance of ≈400 F g−1 at a current density of 0.05 A g−1. Conversely, GAA-based LGT, supported onto Si/SiO2, shows an ambipolar behavior in 0.1 m NaCl, featuring a clear p-doping quantified by Dirac voltage higher than 100 mV. Such a device is successfully implemented in paper fluidics, thereby demonstrating the feasibility of real-time monitoring. |
Montes-García, V; Samorì, P Humidity Sensing with Supramolecular Nanostructures Journal Article In: Adv. Mater., 36 (2208766), 2024. @article{Montes-García2024, title = {Humidity Sensing with Supramolecular Nanostructures}, author = {V. Montes-García and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202208766}, year = {2024}, date = {2024-03-21}, journal = {Adv. Mater.}, volume = {36}, number = {2208766}, abstract = {Precise monitoring of the humidity level is important for the living comfort and for many applications in various industrial sectors. Humidity sensors have thus become one among the most extensively studied and used chemical sensors by targeting a maximal device performance through the optimization of the components and working mechanism. Among different moisture-sensitive systems, supramolecular nanostructures are ideal active materials for the next generation of highly efficient humidity sensors. Their noncovalent nature guarantees fast response, high reversibility, and fast recovery time in the sensing event. Herein, the most enlightening recent strategies on the use of supramolecular nanostructures for humidity sensing are showcased. The key performance indicators in humidity sensing, including operation range, sensitivity, selectivity, response, and recovery speed are discussed as milestones for true practical applications. Some of the most remarkable examples of supramolecular-based humidity sensors are presented, by describing the finest sensing materials, the operating principles, and sensing mechanisms, the latter being based on the structural or charge-transport changes triggered by the interaction of the supramolecular nanostructures with the ambient humidity. Finally, the future directions, challenges, and opportunities for the development of humidity sensors with performance beyond the state of the art are discussed.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Precise monitoring of the humidity level is important for the living comfort and for many applications in various industrial sectors. Humidity sensors have thus become one among the most extensively studied and used chemical sensors by targeting a maximal device performance through the optimization of the components and working mechanism. Among different moisture-sensitive systems, supramolecular nanostructures are ideal active materials for the next generation of highly efficient humidity sensors. Their noncovalent nature guarantees fast response, high reversibility, and fast recovery time in the sensing event. Herein, the most enlightening recent strategies on the use of supramolecular nanostructures for humidity sensing are showcased. The key performance indicators in humidity sensing, including operation range, sensitivity, selectivity, response, and recovery speed are discussed as milestones for true practical applications. Some of the most remarkable examples of supramolecular-based humidity sensors are presented, by describing the finest sensing materials, the operating principles, and sensing mechanisms, the latter being based on the structural or charge-transport changes triggered by the interaction of the supramolecular nanostructures with the ambient humidity. Finally, the future directions, challenges, and opportunities for the development of humidity sensors with performance beyond the state of the art are discussed. |
Sinnott, A D; Kelly, A; Gabbett, C; Munuera, J; Doolan, L; Möbius, M; Ippolito, S; Samorì, P; Coleman, J N; Cross, G L W Mechanical Properties of Conducting Printed Nanosheet Network Thin Films Under Uniaxial Compression Journal Article In: Adv. Mater., 36 (2306954), 2024. @article{Sinnott2024, title = {Mechanical Properties of Conducting Printed Nanosheet Network Thin Films Under Uniaxial Compression}, author = {A. D. Sinnott and A. Kelly and C. Gabbett and J. Munuera and L. Doolan and M. Möbius and S. Ippolito and P. Samorì and J. N. Coleman and G. L. W. Cross}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202306954}, year = {2024}, date = {2024-03-01}, journal = {Adv. Mater.}, volume = {36}, number = {2306954}, abstract = {Thin film networks of solution processed nanosheets show remarkable promise for use in a broad range of applications including strain sensors, energy storage, printed devices, textile electronics, and more. While it is known that their electronic properties rely heavily on their morphology, little is known of their mechanical nature, a glaring omission given the effect mechanical deformation has on the morphology of porous systems and the promise of mechanical post processing for tailored properties. Here, this work employs a recent advance in thin film mechanical testing called the Layer Compression Test to perform the first in situ analysis of printed nanosheet network compression. Due to the well-defined deformation geometry of this unique test, this work is able to explore the out-of-plane elastic, plastic, and creep deformation in these systems, extracting properties of elastic modulus, plastic yield, viscoelasticity, tensile failure and sheet bending vs. slippage under both out of plane uniaxial compression and tension. This work characterizes these for a range of networks of differing porosities and sheet sizes, for low and high compression, as well as the effect of chemical cross linking. This work explores graphene and MoS2 networks, from which the results can be extended to printed nanosheet networks as a whole.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Thin film networks of solution processed nanosheets show remarkable promise for use in a broad range of applications including strain sensors, energy storage, printed devices, textile electronics, and more. While it is known that their electronic properties rely heavily on their morphology, little is known of their mechanical nature, a glaring omission given the effect mechanical deformation has on the morphology of porous systems and the promise of mechanical post processing for tailored properties. Here, this work employs a recent advance in thin film mechanical testing called the Layer Compression Test to perform the first in situ analysis of printed nanosheet network compression. Due to the well-defined deformation geometry of this unique test, this work is able to explore the out-of-plane elastic, plastic, and creep deformation in these systems, extracting properties of elastic modulus, plastic yield, viscoelasticity, tensile failure and sheet bending vs. slippage under both out of plane uniaxial compression and tension. This work characterizes these for a range of networks of differing porosities and sheet sizes, for low and high compression, as well as the effect of chemical cross linking. This work explores graphene and MoS2 networks, from which the results can be extended to printed nanosheet networks as a whole. |
Jeong, Y; Samorì, P Functionalized 2D transition metal dichalcogenide inks via liquid-phase exfoliation for practical applications Journal Article In: Bull. Korean Chem. Soc., 45 , pp. 110–124, 2024. @article{Jeong2024, title = {Functionalized 2D transition metal dichalcogenide inks via liquid-phase exfoliation for practical applications}, author = {Y. Jeong and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/bkcs.12807}, year = {2024}, date = {2024-02-23}, journal = {Bull. Korean Chem. Soc.}, volume = {45}, pages = {110–124}, abstract = {Transition metal dichalcogenides (TMDs) are promising 2D materials which are attracting significant interest because of their distinctive physicochemical properties. The possibility of being exfoliated and dispersed in liquid solutions offers a viable pathway to scalable production. This personal account focuses on recent advancements in 2D TMD inks produced by liquid-phase exfoliation (LPE) methods and intercalation-based electrochemical exfoliation. In particular, different LPE production strategies, like ultrasonication LPE, high-shear mixing exfoliation, and microfluidization, are introduced alongside a broad range of liquid media employed to provide functionalized TMD inks. The main advantage of TMD inks is its scalability, for practical applications in printed optoelectronics, energy storage, and conversion. Furthermore, the chemical functionalization of TMD inks can solve the poor electrical conductivity attributed to edge defects inherent in TMD inks. Finally, the ultimate orientations for future applications of chemically functionalized TMD devices are forecasted, with a specific focus on wearable and flexible printed electronics.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Transition metal dichalcogenides (TMDs) are promising 2D materials which are attracting significant interest because of their distinctive physicochemical properties. The possibility of being exfoliated and dispersed in liquid solutions offers a viable pathway to scalable production. This personal account focuses on recent advancements in 2D TMD inks produced by liquid-phase exfoliation (LPE) methods and intercalation-based electrochemical exfoliation. In particular, different LPE production strategies, like ultrasonication LPE, high-shear mixing exfoliation, and microfluidization, are introduced alongside a broad range of liquid media employed to provide functionalized TMD inks. The main advantage of TMD inks is its scalability, for practical applications in printed optoelectronics, energy storage, and conversion. Furthermore, the chemical functionalization of TMD inks can solve the poor electrical conductivity attributed to edge defects inherent in TMD inks. Finally, the ultimate orientations for future applications of chemically functionalized TMD devices are forecasted, with a specific focus on wearable and flexible printed electronics. |
Wang, Y; Han, B; Mayor, M; Samorì, P Opto-Electrochemical Synaptic Memory in Supramolecularly Engineered Janus 2D MoS2 Journal Article In: Adv. Mater., 36 (2307359), 2024. @article{Wang2024, title = {Opto-Electrochemical Synaptic Memory in Supramolecularly Engineered Janus 2D MoS2}, author = {Y. Wang and B. Han and M. Mayor and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202307359}, year = {2024}, date = {2024-02-22}, journal = {Adv. Mater.}, volume = {36}, number = {2307359}, abstract = {Artificial synapses combining multiple yet independent signal processing strategies in a single device are key enabler to achieve high-density of integration, energy efficiency, and fast data manipulation in brain-like computing. By taming functional complexity, the use of hybrids comprising multiple materials as active components in synaptic devices represents a powerful route to encode both short-term potentiation (STP) and long-term potentiation (LTP) in synaptic circuitries. To meet such a grand challenge, herein a novel Janus 2D material is developed by dressing asymmetrically the two surfaces of 2D molybdenum disulfide (MoS2) with an electrochemically-switchable ferrocene (Fc)/ ferrocenium (Fc+) redox couple and an optically-responsive photochromic azobenzene (Azo). Upon varying the magnitude of the electrochemical stimulus, it is possible to steer the transition between STP and LTP, thereby either triggering electrochemical doping of Fc/Fc+ pair on MoS2 or controlling an adsorption/desorption process of such redox species on MoS2. In addition, a lower magnitude LTP is recorded by activating the photoisomerization of azobenzene chemisorbed molecules and therefore modulating the dipole-induced doping of the 2D semiconductor. Significantly, the interplay of electrochemical and optical stimuli makes it possible to construct artificial synapses where LTP can be boosted to 4-bit (16 memory states) while simultaneously functioning as STP.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Artificial synapses combining multiple yet independent signal processing strategies in a single device are key enabler to achieve high-density of integration, energy efficiency, and fast data manipulation in brain-like computing. By taming functional complexity, the use of hybrids comprising multiple materials as active components in synaptic devices represents a powerful route to encode both short-term potentiation (STP) and long-term potentiation (LTP) in synaptic circuitries. To meet such a grand challenge, herein a novel Janus 2D material is developed by dressing asymmetrically the two surfaces of 2D molybdenum disulfide (MoS2) with an electrochemically-switchable ferrocene (Fc)/ ferrocenium (Fc+) redox couple and an optically-responsive photochromic azobenzene (Azo). Upon varying the magnitude of the electrochemical stimulus, it is possible to steer the transition between STP and LTP, thereby either triggering electrochemical doping of Fc/Fc+ pair on MoS2 or controlling an adsorption/desorption process of such redox species on MoS2. In addition, a lower magnitude LTP is recorded by activating the photoisomerization of azobenzene chemisorbed molecules and therefore modulating the dipole-induced doping of the 2D semiconductor. Significantly, the interplay of electrochemical and optical stimuli makes it possible to construct artificial synapses where LTP can be boosted to 4-bit (16 memory states) while simultaneously functioning as STP. |
Hasler, R; Fenoy, G E; Götz, A; Montes-García, V; Valentini, C; Qiu, Z; Kleber, C; Samorì, P; Müllen, K; Knoll, W "Clickable” graphene nanoribbons for biosensor interfaces Journal Article In: Nanoscale Horiz., 9 , pp. 598–608, 2024. @article{Hasler2024, title = {"Clickable” graphene nanoribbons for biosensor interfaces}, author = {R. Hasler and G. E. Fenoy and A. Götz and V. Montes-García and C. Valentini and Z. Qiu and C. Kleber and P. Samorì and K. Müllen and W. Knoll}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d3nh00590a}, year = {2024}, date = {2024-02-22}, journal = {Nanoscale Horiz.}, volume = {9}, pages = { 598–608}, abstract = {We report on the synthesis of “clickable” graphene nanoribbons (GNRs) and their application as a versatile interface for electrochemical biosensors. GNRs are successfully deposited on gold-coated working electrodes and serve as a platform for the covalent anchoring of a bioreceptor (i.e., a DNA aptamer), enabling selective and sensitive detection of Interleukin 6 (IL6). Moreover, when applied as the intermediate linker on reduced graphene oxide (rGO)-based field-effect transistors (FETs), the GNRs provide improved robustness compared to conventional aromatic bi-functional linker molecules. GNRs enable an orthogonal and covalent attachment of a recognition unit with a considerably higher probe density than previously established methods. Interestingly, we demonstrate that GNRs introduce photoluminescence (PL) when applied to rGO-based FETs, paving the way toward the simultaneous optical and electronic probing of the attached biointerface.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report on the synthesis of “clickable” graphene nanoribbons (GNRs) and their application as a versatile interface for electrochemical biosensors. GNRs are successfully deposited on gold-coated working electrodes and serve as a platform for the covalent anchoring of a bioreceptor (i.e., a DNA aptamer), enabling selective and sensitive detection of Interleukin 6 (IL6). Moreover, when applied as the intermediate linker on reduced graphene oxide (rGO)-based field-effect transistors (FETs), the GNRs provide improved robustness compared to conventional aromatic bi-functional linker molecules. GNRs enable an orthogonal and covalent attachment of a recognition unit with a considerably higher probe density than previously established methods. Interestingly, we demonstrate that GNRs introduce photoluminescence (PL) when applied to rGO-based FETs, paving the way toward the simultaneous optical and electronic probing of the attached biointerface. |
Lu, Y; Hu, Z; Petkov, P; Fu, S; Qi, H; Huang, C; Liu, Y; Huang, X; Wang, M; Zhang, P; Kaiser, U; Bonn, M; Wang, H I; Samorì, P; Coronado, E; Dong, R; Feng, X Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal–Organic Frameworks Journal Article In: J. Am. Chem. Soc., 146 , pp. 2574–2582, 2024. @article{Lu2024, title = {Tunable Charge Transport and Spin Dynamics in Two-Dimensional Conjugated Metal–Organic Frameworks}, author = {Y. Lu and Z. Hu and P. Petkov and S. Fu and H. Qi and C. Huang and Y. Liu and X. Huang and M. Wang and P. Zhang and U. Kaiser and M. Bonn and H. I. Wang and P. Samorì and E. Coronado and R. Dong and X. Feng}, editor = {ACS Publcation}, url = {https://doi.org/10.1021/jacs.3c11172}, year = {2024}, date = {2024-01-17}, journal = {J. Am. Chem. Soc.}, volume = {146}, pages = { 2574–2582}, abstract = {wo-dimensional conjugated metal–organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin–lattice relaxation time (T1) is increased up to ∼60 μs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics.}, keywords = {}, pubstate = {published}, tppubtype = {article} } wo-dimensional conjugated metal–organic frameworks (2D c-MOFs) have attracted increasing interest in electronics due to their (semi)conducting properties. Charge-neutral 2D c-MOFs also possess persistent organic radicals that can be viewed as spin-concentrated arrays, affording new opportunities for spintronics. However, the strong π-interaction between neighboring layers of layer-stacked 2D c-MOFs annihilates active spin centers and significantly accelerates spin relaxation, severely limiting their potential as spin qubits. Herein, we report the precise tuning of the charge transport and spin dynamics in 2D c-MOFs via the control of interlayer stacking. The introduction of bulky side groups on the conjugated ligands enables a significant dislocation of the 2D c-MOFs layers from serrated stacking to staggered stacking, thereby spatially weakening the interlayer interactions. As a consequence, the electrical conductivity of 2D c-MOFs decreases by 6 orders of magnitude, while the spin density achieves more than a 30-fold increase and the spin–lattice relaxation time (T1) is increased up to ∼60 μs, hence being superior to the reference 2D c-MOFs with compact stackings whose spin relaxation is too fast to be detected. Spin dynamics results also reveal that spinless polaron pairs or bipolarons play critical roles in the charge transport of these 2D c-MOFs. Our strategy provides a bottom-up approach for enlarging spin dynamics in 2D c-MOFs, opening up pathways for developing MOF-based spintronics. |
Pakulski, D; Montes-García, V; Gorczyński, A; Czepa, W; Chudziak, T; Bielejewski, M; Musiał, A; Pérez-Juste, I; Samorì, P; Ciesielski, A Two-dimensional metal–organic polymers as cathode hybrid materials for high-performance Al-batteries Journal Article In: J. Mater. Chem. A., 12 , pp. 440–450, 2024. @article{Pakulski2024, title = {Two-dimensional metal–organic polymers as cathode hybrid materials for high-performance Al-batteries}, author = {D. Pakulski and V. Montes-García and A. Gorczyński and W. Czepa and T. Chudziak and M. Bielejewski and A. Musiał and I. Pérez-Juste and P. Samorì and A. Ciesielski}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d3ta05730e}, year = {2024}, date = {2024-01-01}, journal = {J. Mater. Chem. A.}, volume = {12}, pages = { 440–450}, abstract = {Organic materials represent a promising alternative to critical raw materials for energy storage applications due to their sustainable production combined with tunable structures and functionalities. Unfortunately, the biggest limitation of organic materials is their high solubility in aqueous electrolytes, which results in a poor cycling stability. Metal–organic polymers (MOPs) have emerged as versatile organic materials, which exhibit enhanced chemical stability as well as redox activity depending on the employed building units. Here, by mastering a coordination chemistry approach, two novel MOPs were synthesized via a coordination process between tetraminobenzoquinone (TABQ) and a metal ion (i.e., zinc or copper) and were explored as cathode materials for aluminum-ion batteries. The resulting Zn-TABQ MOP exhibited superior electrochemical performance compared to other common cathode materials in Al-batteries. Specifically, Zn-TABQ revealed a specific capacity of 198 mA h g−1 at 0.05 A g−1, combined with high-capacity retention (92%) after 5000 cycles at a scan rate of 1 A g−1 and an outstanding energy density of 247 W h kg−1. We demonstrated via ex situ characterization that the electrochemically active carbonyl (C[double bond, length as m-dash]O) units of Zn-TABQ coordinate with AlCl2+ and EMIM+ ions, thereby governing the mechanism of ion storage and release by taking advantage of the nature of the reversible interaction}, keywords = {}, pubstate = {published}, tppubtype = {article} } Organic materials represent a promising alternative to critical raw materials for energy storage applications due to their sustainable production combined with tunable structures and functionalities. Unfortunately, the biggest limitation of organic materials is their high solubility in aqueous electrolytes, which results in a poor cycling stability. Metal–organic polymers (MOPs) have emerged as versatile organic materials, which exhibit enhanced chemical stability as well as redox activity depending on the employed building units. Here, by mastering a coordination chemistry approach, two novel MOPs were synthesized via a coordination process between tetraminobenzoquinone (TABQ) and a metal ion (i.e., zinc or copper) and were explored as cathode materials for aluminum-ion batteries. The resulting Zn-TABQ MOP exhibited superior electrochemical performance compared to other common cathode materials in Al-batteries. Specifically, Zn-TABQ revealed a specific capacity of 198 mA h g−1 at 0.05 A g−1, combined with high-capacity retention (92%) after 5000 cycles at a scan rate of 1 A g−1 and an outstanding energy density of 247 W h kg−1. We demonstrated via ex situ characterization that the electrochemically active carbonyl (C[double bond, length as m-dash]O) units of Zn-TABQ coordinate with AlCl2+ and EMIM+ ions, thereby governing the mechanism of ion storage and release by taking advantage of the nature of the reversible interaction |
2023 |
Zhuravlova, A; Ricciardulli, A G; Pakulski, D; Gorczyński, A; Kelly, A; Coleman, J N; Ciesielski, A; Samorì, P In: Small, 19 (2208100), 2023. @article{Zhuravlova2023, title = {High Selectivity and Sensitivity in Chemiresistive Sensing of Co(II) Ions with Liquid-Phase Exfoliated Functionalized MoS2: A Supramolecular Approach}, author = {A. Zhuravlova and A. G. Ricciardulli and D. Pakulski and A. Gorczyński and A. Kelly and J. N. Coleman and A. Ciesielski and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/smll.202208100}, year = {2023}, date = {2023-12-20}, journal = {Small}, volume = {19}, number = {2208100}, abstract = {Chemical sensing of water contamination by heavy metal ions is key as it represents a most severe environmental problem. Liquid-phase exfoliated two-dimensional (2D) transition metal dichalcogenides (TMDs) are suitable candidates for chemical sensing thanks to their high surface-to-volume ratio, sensitivity, unique electrical characteristics, and scalability. However, TMDs lack selectivity due to nonspecific analyte-nanosheet interactions. To overcome this drawback, defect engineering enables controlled functionalization of 2D TMDs. Here, ultrasensitive and selective sensors of cobalt(II) ions via the covalent functionalization of defect-rich MoS2 flakes with a specific receptor, 2,2′:6′,2″-terpyridine-4′-thiol is developed. A continuous network is assembled by healing of MoS2 sulfur vacancies in a tailored microfluidic approach, enabling high control over the assembly of thin and large hybrid films. The Co2+ cations complexation represents a powerful gauge for low concentrations of cationic species which can be best monitored in a chemiresisitive ion sensor, featuring a 1 pm limit of detection, sensing in a broad concentration range (1 pm - 1 µm) and sensitivity as high as 0.308 ± 0.010 lg([Co2+])−1 combined with a high selectivity towards Co2+ over K+, Ca2+, Mn2+, Cu2+, Cr3+, and Fe3+ cations. This supramolecular approach based on highly specific recognition can be adapted for sensing other analytes through specific ad-hoc receptors.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Chemical sensing of water contamination by heavy metal ions is key as it represents a most severe environmental problem. Liquid-phase exfoliated two-dimensional (2D) transition metal dichalcogenides (TMDs) are suitable candidates for chemical sensing thanks to their high surface-to-volume ratio, sensitivity, unique electrical characteristics, and scalability. However, TMDs lack selectivity due to nonspecific analyte-nanosheet interactions. To overcome this drawback, defect engineering enables controlled functionalization of 2D TMDs. Here, ultrasensitive and selective sensors of cobalt(II) ions via the covalent functionalization of defect-rich MoS2 flakes with a specific receptor, 2,2′:6′,2″-terpyridine-4′-thiol is developed. A continuous network is assembled by healing of MoS2 sulfur vacancies in a tailored microfluidic approach, enabling high control over the assembly of thin and large hybrid films. The Co2+ cations complexation represents a powerful gauge for low concentrations of cationic species which can be best monitored in a chemiresisitive ion sensor, featuring a 1 pm limit of detection, sensing in a broad concentration range (1 pm - 1 µm) and sensitivity as high as 0.308 ± 0.010 lg([Co2+])−1 combined with a high selectivity towards Co2+ over K+, Ca2+, Mn2+, Cu2+, Cr3+, and Fe3+ cations. This supramolecular approach based on highly specific recognition can be adapted for sensing other analytes through specific ad-hoc receptors. |
Safuta, M; Ciesielski, A; Samorì, P Controlling the Formation of Electroactive Graphene-Based Cementitious Composites: Towards Structural Health Monitoring of Civil Structures Journal Article In: Chem. Eur. J., 29 (e202301816), 2023. @article{Safuta2023, title = {Controlling the Formation of Electroactive Graphene-Based Cementitious Composites: Towards Structural Health Monitoring of Civil Structures}, author = {M. Safuta and A. Ciesielski and P. Samorì}, editor = {Chemistry Europe}, url = {https://doi.org/10.1002/chem.202301816}, year = {2023}, date = {2023-12-19}, journal = {Chem. Eur. J.}, volume = {29}, number = {e202301816}, abstract = {The development of composites combining multiple components each one imparting a specific function to the ensemble is highly sought after for disruptive applications in chemistry and materials science, with a particular importance for the realization of smart structures. Here, we report on the development of an unprecedented multifunctional cementitious composite incorporating reduced graphene oxide (rGO). By design, this material features significantly enhanced electrical properties while retaining the excellent cement's hydration and microstructure. The multiscale investigation on the chemical and physical properties of the dispersion made it possible to establish an efficient preparation protocol for rGO aqueous dispersion as well as rGO-based cementitious composites using a commercial poly(carboxylate ether)-based superplasticizer. The conduction mechanisms within the matrix of rGO containing mortars were unraveled by electrochemical impedance spectroscopy revealing conductive paths originating from bulk cement matrix and rGO nanosheets in composites with rGO loadings as low as 0.075 wt. %. For this rGO loading, we observed the reduction of the resistivity of bulk cement mortar layers from 18.3 MΩ cm to 2.8 MΩ cm. Moreover, the addition of 0.2 wt. % of rGO resulted in the formation of rGO conductive paths with the resistivity of 51.1 kΩ cm. These findings represent a major step forward towards the practical application of graphene-based materials in structural health monitoring of concrete structures.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The development of composites combining multiple components each one imparting a specific function to the ensemble is highly sought after for disruptive applications in chemistry and materials science, with a particular importance for the realization of smart structures. Here, we report on the development of an unprecedented multifunctional cementitious composite incorporating reduced graphene oxide (rGO). By design, this material features significantly enhanced electrical properties while retaining the excellent cement's hydration and microstructure. The multiscale investigation on the chemical and physical properties of the dispersion made it possible to establish an efficient preparation protocol for rGO aqueous dispersion as well as rGO-based cementitious composites using a commercial poly(carboxylate ether)-based superplasticizer. The conduction mechanisms within the matrix of rGO containing mortars were unraveled by electrochemical impedance spectroscopy revealing conductive paths originating from bulk cement matrix and rGO nanosheets in composites with rGO loadings as low as 0.075 wt. %. For this rGO loading, we observed the reduction of the resistivity of bulk cement mortar layers from 18.3 MΩ cm to 2.8 MΩ cm. Moreover, the addition of 0.2 wt. % of rGO resulted in the formation of rGO conductive paths with the resistivity of 51.1 kΩ cm. These findings represent a major step forward towards the practical application of graphene-based materials in structural health monitoring of concrete structures. |
Tassignon, B; Wang, Z; Galanti, A; Winter, De J; Samorì, P; Cornil, J; Moth-Poulsen, K; Gerbaux, P Site Selectivity of Peptoids as Azobenzene Scaffold for Molecular Solar Thermal Energy Storage Journal Article In: Chem. Eur. J., 29 (e202303168), 2023. @article{Tassignon2023, title = {Site Selectivity of Peptoids as Azobenzene Scaffold for Molecular Solar Thermal Energy Storage}, author = {B. Tassignon and Z. Wang and A. Galanti and J. De Winter and P. Samorì and J. Cornil and K. Moth-Poulsen and P. Gerbaux}, editor = {Chemistry Europe}, url = {https://doi.org/10.1002/chem.202303168}, year = {2023}, date = {2023-12-14}, journal = {Chem. Eur. J.}, volume = {29}, number = {e202303168}, abstract = {toring solar energy is a key challenge in modern science. MOlecular Solar Thermal (MOST) systems, in particular those based on azobenzene switches, have received great interest in the last decades. The energy storage properties of azobenzene (t1/2<4 days; ΔH~270 kJ/kg) must be improved for future applications. Herein, we introduce peptoids as programmable supramolecular scaffolds to improve the energy storage properties of azobenzene-based MOST systems. We demonstrate with 3-unit peptoids bearing a single azobenzene chromophore that dynamics of the MOST systems can be tuned depending on the anchoring position of the photochromic unit on the macromolecular backbone. We measured a remarkable increase of the half-life of the metastable form up to 14 days at 20 °C for a specific anchoring site, significantly higher than the isolated azobenzene moiety, thus opening new perspectives for MOST development. We also highlight that liquid chromatography coupled to mass spectrometry does not only enable to monitor the different stereoisomers during the photoisomerization process as traditionally done, but also allows to determine the thermal back-isomerization kinetics.}, keywords = {}, pubstate = {published}, tppubtype = {article} } toring solar energy is a key challenge in modern science. MOlecular Solar Thermal (MOST) systems, in particular those based on azobenzene switches, have received great interest in the last decades. The energy storage properties of azobenzene (t1/2<4 days; ΔH~270 kJ/kg) must be improved for future applications. Herein, we introduce peptoids as programmable supramolecular scaffolds to improve the energy storage properties of azobenzene-based MOST systems. We demonstrate with 3-unit peptoids bearing a single azobenzene chromophore that dynamics of the MOST systems can be tuned depending on the anchoring position of the photochromic unit on the macromolecular backbone. We measured a remarkable increase of the half-life of the metastable form up to 14 days at 20 °C for a specific anchoring site, significantly higher than the isolated azobenzene moiety, thus opening new perspectives for MOST development. We also highlight that liquid chromatography coupled to mass spectrometry does not only enable to monitor the different stereoisomers during the photoisomerization process as traditionally done, but also allows to determine the thermal back-isomerization kinetics. |
Chen, Y; Wang, H; Chen, H; Zhang, W; Xu, S; Pätzel, M; Ma, C; Wang, C; McCulloch, I; Hecht, S; Samorì, P Quasi-1D Polymer Semiconductor–Diarylethene Blends: High Performance Optically Switchable Transistors Journal Article In: Adv. Funct. Mater., 33 , pp. 2305494, 2023. @article{Chen2023, title = {Quasi-1D Polymer Semiconductor–Diarylethene Blends: High Performance Optically Switchable Transistors}, author = {Y. Chen and H. Wang and H. Chen and W. Zhang and S. Xu and M. Pätzel and C. Ma and C. Wang and I. McCulloch and S. Hecht and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adfm.202305494}, year = {2023}, date = {2023-11-09}, journal = {Adv. Funct. Mater.}, volume = {33}, pages = {2305494}, abstract = {Optically switchable field-effect transistors (OSFETs) are non-volatile photonic memory devices holding a great potential for applications in optical information storage and telecommunications. Solution processing of blends of photochromic molecules and π-conjugated polymers is a low-cost protocol to integrate simultaneously optical switching and charge transport functions in large-area devices. However, the limited reversibility of the isomerization of photochromic molecules due to steric hindrance when embedded in ordered polymeric matrices represents a severe limitation and it obliges to incorporate as much as 20% in weight of the photochromic component, thereby drastically diluting the electronic function, limiting the device performance. Herein, a comparative study of the photoresponsivity of a suitably designed diarylethene molecule is reported when embedded in the matrix of six different polymer semiconductors displaying diverse charge transport properties. In particular, this study focuses on three semi-crystalline polymers and three quasi-1D polymers. It is found that 1% w/w of 1,2-bis(5-(3,5-di-tert-butylphenyl)-2-methylthiophen-3-yl)cyclopent-1-ene in a blend with poly(indacenodithiophene-co-benzothiadiazole) is sufficient to fabricate OSFETs combining photo-modulation efficiencies of 45.5%, mobilities >1 cm2 V−1s−1, and photo-recovered efficiencies of 98.1%. These findings demonstrate that quasi-1D polymer semiconductors, because of their charge transport dominated by intra-molecular processes, epitomize the molecular design principles required for the fabrication of high-performance OSFETs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Optically switchable field-effect transistors (OSFETs) are non-volatile photonic memory devices holding a great potential for applications in optical information storage and telecommunications. Solution processing of blends of photochromic molecules and π-conjugated polymers is a low-cost protocol to integrate simultaneously optical switching and charge transport functions in large-area devices. However, the limited reversibility of the isomerization of photochromic molecules due to steric hindrance when embedded in ordered polymeric matrices represents a severe limitation and it obliges to incorporate as much as 20% in weight of the photochromic component, thereby drastically diluting the electronic function, limiting the device performance. Herein, a comparative study of the photoresponsivity of a suitably designed diarylethene molecule is reported when embedded in the matrix of six different polymer semiconductors displaying diverse charge transport properties. In particular, this study focuses on three semi-crystalline polymers and three quasi-1D polymers. It is found that 1% w/w of 1,2-bis(5-(3,5-di-tert-butylphenyl)-2-methylthiophen-3-yl)cyclopent-1-ene in a blend with poly(indacenodithiophene-co-benzothiadiazole) is sufficient to fabricate OSFETs combining photo-modulation efficiencies of 45.5%, mobilities >1 cm2 V−1s−1, and photo-recovered efficiencies of 98.1%. These findings demonstrate that quasi-1D polymer semiconductors, because of their charge transport dominated by intra-molecular processes, epitomize the molecular design principles required for the fabrication of high-performance OSFETs. |
Drożdż, W; Ciesielski, A; Stefankiewicz, A R Dynamic Cages—Towards Nanostructured Smart Materials Journal Article In: Angew. Chem. Int. Ed., 62 (e202307552), 2023. @article{Drożdż2023, title = {Dynamic Cages—Towards Nanostructured Smart Materials}, author = {W. Drożdż and A. Ciesielski and A. R. Stefankiewicz}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/anie.202307552}, year = {2023}, date = {2023-10-23}, journal = {Angew. Chem. Int. Ed.}, volume = {62}, number = {e202307552}, abstract = {The interest in capsular assemblies such as dynamic organic and coordination cages has blossomed over the last decade. Given their chemical and structural variability, these systems have found applications in diverse fields of research, including energy conversion and storage, catalysis, separation, molecular recognition, and live-cell imaging. In the exploration of the potential of these discrete architectures, they are increasingly being employed in the formation of more complex systems and smart materials. This Review highlights the most promising pathways to overcome common drawbacks of cage systems (stability, recovery) and discusses the most promising strategies for their hybridization with systems featuring various dimensionalities. Following the description of the most recent advances in the fabrication of zero to three-dimensional cage-based systems, this Review will provide the reader with the structure-dependent relationship between the employed cages and the properties of the materials.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The interest in capsular assemblies such as dynamic organic and coordination cages has blossomed over the last decade. Given their chemical and structural variability, these systems have found applications in diverse fields of research, including energy conversion and storage, catalysis, separation, molecular recognition, and live-cell imaging. In the exploration of the potential of these discrete architectures, they are increasingly being employed in the formation of more complex systems and smart materials. This Review highlights the most promising pathways to overcome common drawbacks of cage systems (stability, recovery) and discusses the most promising strategies for their hybridization with systems featuring various dimensionalities. Following the description of the most recent advances in the fabrication of zero to three-dimensional cage-based systems, this Review will provide the reader with the structure-dependent relationship between the employed cages and the properties of the materials. |
Liu, H; Yao, Y; Samorì, P Taming Multiscale Structural Complexity in Porous Skeletons: From Open Framework Materials to Micro/Nanoscaffold Architectures Journal Article In: Small Methods, 7 (2300468), 2023. @article{Liu2023, title = {Taming Multiscale Structural Complexity in Porous Skeletons: From Open Framework Materials to Micro/Nanoscaffold Architectures}, author = {H. Liu and Y. Yao and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/smtd.202300468}, year = {2023}, date = {2023-10-20}, journal = {Small Methods}, volume = {7}, number = {2300468}, abstract = {Recent developments in the design and synthesis of more and more sophisticated organic building blocks with controlled structures and physical properties, combined with the emergence of novel assembly modes and nanofabrication methods, make it possible to tailor unprecedented structurally complex porous systems with precise multiscale control over their architectures and functions. By tuning their porosity from the nanoscale to microscale, a wide range of functional materials can be assembled, including open frameworks and micro/nanoscaffold architectures. During the last two decades, significant progress is made on the generation and optimization of advanced porous systems, resulting in high-performance multifunctional scaffold materials and novel device configurations. In this perspective, a critical analysis is provided of the most effective methods for imparting controlled physical and chemical properties to multifunctional porous skeletons. The future research directions that underscore the role of skeleton structures with varying physical dimensions, from molecular-level open frameworks (<10 nm) to supramolecular scaffolds (10–100 nm) and micro/nano scaffolds (>100 nm), are discussed. The limitations, challenges, and opportunities for potential applications of these multifunctional and multidimensional material systems are also evaluated in particular by addressing the greatest challenges that the society has to face.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Recent developments in the design and synthesis of more and more sophisticated organic building blocks with controlled structures and physical properties, combined with the emergence of novel assembly modes and nanofabrication methods, make it possible to tailor unprecedented structurally complex porous systems with precise multiscale control over their architectures and functions. By tuning their porosity from the nanoscale to microscale, a wide range of functional materials can be assembled, including open frameworks and micro/nanoscaffold architectures. During the last two decades, significant progress is made on the generation and optimization of advanced porous systems, resulting in high-performance multifunctional scaffold materials and novel device configurations. In this perspective, a critical analysis is provided of the most effective methods for imparting controlled physical and chemical properties to multifunctional porous skeletons. The future research directions that underscore the role of skeleton structures with varying physical dimensions, from molecular-level open frameworks (<10 nm) to supramolecular scaffolds (10–100 nm) and micro/nano scaffolds (>100 nm), are discussed. The limitations, challenges, and opportunities for potential applications of these multifunctional and multidimensional material systems are also evaluated in particular by addressing the greatest challenges that the society has to face. |
Chudziak, T; Montes-García, V; Czepa, W; Pakulski, D; Musiał, A; Valentini, C; Bielejewski, M; Carlin, M; Tubaro, A; Pelin, M; Samorì, P; Ciesielski, A A comparative investigation of the chemical reduction of graphene oxide for electrical engineering applications Journal Article In: Nanoscale, 15 , pp. 17765–17775, 2023. @article{Chudziak2023, title = {A comparative investigation of the chemical reduction of graphene oxide for electrical engineering applications}, author = {T. Chudziak and V. Montes-García and W. Czepa and D. Pakulski and A. Musiał and C. Valentini and M. Bielejewski and M. Carlin and A. Tubaro and M. Pelin and P. Samorì and A. Ciesielski}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d3nr04521h}, year = {2023}, date = {2023-10-20}, journal = {Nanoscale}, volume = {15}, pages = {17765–17775}, abstract = {The presence of oxygen-containing functional groups on the basal plane and at the edges endows graphene oxide (GO) with an insulating nature, which makes it rather unsuitable for electronic applications. Fortunately, the reduction process makes it possible to restore the sp2 conjugation. Among various protocols, chemical reduction is appealing because of its compatibility with large-scale production. Nevertheless, despite the vast number of reported chemical protocols, their comparative assessment has not yet been the subject of an in-depth investigation, rendering the establishment of a structure–performance relationship impossible. We report a systematic study on the chemical reduction of GO by exploring different reducing agents (hydrazine hydrate, sodium borohydride, ascorbic acid (AA), and sodium dithionite) and reaction times (2 or 12 hours) in order to boost the performance of chemically reduced GO (CrGO) in electronics and in electrochemical applications. In this work, we provide evidence that the optimal reduction conditions should vary depending on the chosen application, whether it is for electrical or electrochemical purposes. CrGO exhibiting a good electrical conductivity (>1800 S m−1) can be obtained by using AA (12 hours of reaction), Na2S2O4 and N2H4 (independent of the reaction time). Conversely, CrGO displaying a superior electrochemical performance (specific capacitance of 211 F g−1, and capacitance retention >99.5% after 2000 cycles) can be obtained by using NaBH4 (12 hours of reaction). Finally, the compatibility of the different CrGOs with wearable and flexible electronics is also demonstrated using skin irritation tests. The strategy described represents a significant advancement towards the development of environmentally friendly CrGOs with ad hoc properties for advanced applications in electronics and energy storage.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The presence of oxygen-containing functional groups on the basal plane and at the edges endows graphene oxide (GO) with an insulating nature, which makes it rather unsuitable for electronic applications. Fortunately, the reduction process makes it possible to restore the sp2 conjugation. Among various protocols, chemical reduction is appealing because of its compatibility with large-scale production. Nevertheless, despite the vast number of reported chemical protocols, their comparative assessment has not yet been the subject of an in-depth investigation, rendering the establishment of a structure–performance relationship impossible. We report a systematic study on the chemical reduction of GO by exploring different reducing agents (hydrazine hydrate, sodium borohydride, ascorbic acid (AA), and sodium dithionite) and reaction times (2 or 12 hours) in order to boost the performance of chemically reduced GO (CrGO) in electronics and in electrochemical applications. In this work, we provide evidence that the optimal reduction conditions should vary depending on the chosen application, whether it is for electrical or electrochemical purposes. CrGO exhibiting a good electrical conductivity (>1800 S m−1) can be obtained by using AA (12 hours of reaction), Na2S2O4 and N2H4 (independent of the reaction time). Conversely, CrGO displaying a superior electrochemical performance (specific capacitance of 211 F g−1, and capacitance retention >99.5% after 2000 cycles) can be obtained by using NaBH4 (12 hours of reaction). Finally, the compatibility of the different CrGOs with wearable and flexible electronics is also demonstrated using skin irritation tests. The strategy described represents a significant advancement towards the development of environmentally friendly CrGOs with ad hoc properties for advanced applications in electronics and energy storage. |
Boschi, A; Kovtun, A; Liscio, F; Xia, Z; Kim, K H; Avila, Lara S; Simone, De S; Mussi, V; Barone, C; Pagano, S; Gobbi, M; Samorì, P; Affronte, M; Candini, A; Palermo, V; Liscio, A Mesoscopic 3D Charge Transport in Solution-Processed Graphene-Based Thin Films: A Multiscale Analysis Journal Article In: Small, 19 ( 2303238), 2023. @article{Boschi2023, title = {Mesoscopic 3D Charge Transport in Solution-Processed Graphene-Based Thin Films: A Multiscale Analysis}, author = {A. Boschi and A. Kovtun and F. Liscio and Z. Xia and K. H. Kim and S. Lara Avila and S. De Simone and V. Mussi and C. Barone and S. Pagano and M. Gobbi and P. Samorì and M. Affronte and A. Candini and V. Palermo and A. Liscio}, editor = {Wiley Online Library}, url = { https://doi.org/10.1002/smll.202303238}, year = {2023}, date = {2023-10-18}, journal = {Small}, volume = {19}, number = { 2303238}, abstract = {Graphene and related 2D material (GRM) thin films consist of 3D assembly of billions of 2D nanosheets randomly distributed and interacting via van der Waals forces. Their complexity and the multiscale nature yield a wide variety of electrical characteristics ranging from doped semiconductor to glassy metals depending on the crystalline quality of the nanosheets, their specific structural organization ant the operating temperature. Here, the charge transport (CT) mechanisms are studied that are occurring in GRM thin films near the metal-insulator transition (MIT) highlighting the role of defect density and local arrangement of the nanosheets. Two prototypical nanosheet types are compared, i.e., 2D reduced graphene oxide and few-layer-thick electrochemically exfoliated graphene flakes, forming thin films with comparable composition, morphology and room temperature conductivity, but different defect density and crystallinity. By investigating their structure, morphology, and the dependence of their electrical conductivity on temperature, noise and magnetic-field, a general model is developed describing the multiscale nature of CT in GRM thin films in terms of hopping among mesoscopic bricks, i.e., grains. The results suggest a general approach to describe disordered van der Waals thin films.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Graphene and related 2D material (GRM) thin films consist of 3D assembly of billions of 2D nanosheets randomly distributed and interacting via van der Waals forces. Their complexity and the multiscale nature yield a wide variety of electrical characteristics ranging from doped semiconductor to glassy metals depending on the crystalline quality of the nanosheets, their specific structural organization ant the operating temperature. Here, the charge transport (CT) mechanisms are studied that are occurring in GRM thin films near the metal-insulator transition (MIT) highlighting the role of defect density and local arrangement of the nanosheets. Two prototypical nanosheet types are compared, i.e., 2D reduced graphene oxide and few-layer-thick electrochemically exfoliated graphene flakes, forming thin films with comparable composition, morphology and room temperature conductivity, but different defect density and crystallinity. By investigating their structure, morphology, and the dependence of their electrical conductivity on temperature, noise and magnetic-field, a general model is developed describing the multiscale nature of CT in GRM thin films in terms of hopping among mesoscopic bricks, i.e., grains. The results suggest a general approach to describe disordered van der Waals thin films. |
Volpi, M; Jouclas, R; Liu, J; Liu, G; Catalano, L; McIntosh, N; Bardini, M; Gatsios, C; Modesti, F; Turetta, N; Beljonne, D; Cornil, J; Kennedy, A R; Koch, N; Erk, P; Samorì, P; Schweicher, G; Geerts, Y H Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs Journal Article In: Adv. Sci., 10 (2301914), 2023. @article{Volpi2023, title = {Enantiopure Dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophenes: Reaching High Magnetoresistance Effect in OFETs}, author = {M. Volpi and R. Jouclas and J. Liu and G. Liu and L. Catalano and N. McIntosh and M. Bardini and C. Gatsios and F. Modesti and N. Turetta and D. Beljonne and J. Cornil and A. R. Kennedy and N. Koch and P. Erk and P. Samorì and G. Schweicher and Y. H. Geerts}, editor = {Wiley Online Library}, url = { https://doi.org/10.1002/advs.202301914}, year = {2023}, date = {2023-09-15}, journal = {Adv. Sci.}, volume = {10}, number = {2301914}, abstract = {Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices. |
Han, B; Gali, S M; Dai, S; Beljonne, D; Samorì, P Isomer Discrimination via Defect Engineering in Monolayer MoS2 Journal Article In: ACS Nano, 17 , pp. 17956–17965, 2023. @article{Han2023, title = {Isomer Discrimination via Defect Engineering in Monolayer MoS2}, author = {B. Han and S. M. Gali and S. Dai and D. Beljonne and P. Samorì}, editor = {ASC Publications}, url = {https://doi.org/10.1021/acsnano.3c04194}, year = {2023}, date = {2023-09-13}, journal = {ACS Nano}, volume = {17}, pages = {17956–17965}, abstract = {The all-surface nature of two-dimensional (2D) materials renders them highly sensitive to environmental changes, enabling the on-demand tailoring of their physical properties. Transition metal dichalcogenides, such as 2H molybdenum disulfide (MoS2), can be used as a sensory material capable of discriminating molecules possessing a similar structure with a high sensitivity. Among them, the identification of isomers represents an unexplored and challenging case. Here, we demonstrate that chemical functionalization of defect-engineered monolayer MoS2 enables isomer discrimination via a field-effect transistor readout. A multiscale characterization comprising X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and electrical measurement corroborated by theoretical calculations revealed that monolayer MoS2 exhibits exceptional sensitivity to the differences in the dipolar nature of molecules arising from their chemical structure such as the one in difluorobenzenethiol isomers, allowing their precise recognition. Our findings underscore the potential of 2D materials for molecular discrimination purposes, in particular for the identification of complex isomers.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The all-surface nature of two-dimensional (2D) materials renders them highly sensitive to environmental changes, enabling the on-demand tailoring of their physical properties. Transition metal dichalcogenides, such as 2H molybdenum disulfide (MoS2), can be used as a sensory material capable of discriminating molecules possessing a similar structure with a high sensitivity. Among them, the identification of isomers represents an unexplored and challenging case. Here, we demonstrate that chemical functionalization of defect-engineered monolayer MoS2 enables isomer discrimination via a field-effect transistor readout. A multiscale characterization comprising X-ray photoelectron spectroscopy, Raman spectroscopy, photoluminescence spectroscopy, and electrical measurement corroborated by theoretical calculations revealed that monolayer MoS2 exhibits exceptional sensitivity to the differences in the dipolar nature of molecules arising from their chemical structure such as the one in difluorobenzenethiol isomers, allowing their precise recognition. Our findings underscore the potential of 2D materials for molecular discrimination purposes, in particular for the identification of complex isomers. |
Vitale, S; Puozzo, H; Saiev, S; Bonnaud, L; Ricciardulli, A G; Ciesielski, A; Beljonne, D; Samorì, P In: Chem. Mater., 35 , pp. 6909–6919, 2023. @article{Vitale2023, title = {Tuning the Piezoresistive Behavior of Graphene-Polybenzoxazine Nanocomposites: Toward High-Performance Materials for Pressure Sensing Applications}, author = {S. Vitale and H. Puozzo and S. Saiev and L. Bonnaud and A. G. Ricciardulli and A. Ciesielski and D. Beljonne and P. Samorì}, editor = {ACS Publcation}, url = {https://doi.org/10.1021/acs.chemmater.3c01191}, year = {2023}, date = {2023-09-12}, journal = {Chem. Mater.}, volume = {35}, pages = { 6909–6919}, abstract = {Flexible piezoresistive pressure sensors are key components in wearable technologies for health monitoring, digital healthcare, human–machine interfaces, and robotics. Among active materials for pressure sensing, graphene-based materials are extremely promising because of their outstanding physical characteristics. Currently, a key challenge in pressure sensing is the sensitivity enhancement through the fine tuning of the active material’s electro-mechanical properties. Here, we describe a novel versatile approach to modulating the sensitivity of graphene-based piezoresistive pressure sensors by combining chemically reduced graphene oxide (rGO) with a thermally responsive material, namely, a novel trifunctional polybenzoxazine thermoset precursor based on tris(3-aminopropyl)amine and phenol reagents (PtPA). The integration of rGO in a polybenzoxazine thermoresist matrix results in an electrically conductive nanocomposite where the thermally triggered resist’s polymerization modulates the active material rigidity and consequently the piezoresistive response to pressure. Pressure sensors comprising the rGO-PtPA blend exhibit sensitivities ranging from 10–2 to 1 kPa–1, which can be modulated by controlling the rGO:PtPA ratio or the curing temperature. Our rGO-PtPA blend represents a proof-of-concept graphene-based nanocomposite with on-demand piezoresistive behavior. Combined with solution processability and a thermal curing process compatible with large-area coatings technologies on flexible supports, this method holds great potential for applications in pressure sensing for health monitoring.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Flexible piezoresistive pressure sensors are key components in wearable technologies for health monitoring, digital healthcare, human–machine interfaces, and robotics. Among active materials for pressure sensing, graphene-based materials are extremely promising because of their outstanding physical characteristics. Currently, a key challenge in pressure sensing is the sensitivity enhancement through the fine tuning of the active material’s electro-mechanical properties. Here, we describe a novel versatile approach to modulating the sensitivity of graphene-based piezoresistive pressure sensors by combining chemically reduced graphene oxide (rGO) with a thermally responsive material, namely, a novel trifunctional polybenzoxazine thermoset precursor based on tris(3-aminopropyl)amine and phenol reagents (PtPA). The integration of rGO in a polybenzoxazine thermoresist matrix results in an electrically conductive nanocomposite where the thermally triggered resist’s polymerization modulates the active material rigidity and consequently the piezoresistive response to pressure. Pressure sensors comprising the rGO-PtPA blend exhibit sensitivities ranging from 10–2 to 1 kPa–1, which can be modulated by controlling the rGO:PtPA ratio or the curing temperature. Our rGO-PtPA blend represents a proof-of-concept graphene-based nanocomposite with on-demand piezoresistive behavior. Combined with solution processability and a thermal curing process compatible with large-area coatings technologies on flexible supports, this method holds great potential for applications in pressure sensing for health monitoring. |
Sens, M; de Oliveira, Furlan R; Berto, M; Palmieri, M; Ruini, E; Livio, P A; Conti, A; Pinti, M; Salvarani, C; Cossarizza, A; Cabot, J M; Ricart, J; Casalini, S; González-García, M B; Fanjul-Bolado, P; Bortolotti, C A; Samorì, P; Biscarini, F Reduced Graphene Oxide Electrolyte-Gated Transistor Immunosensor with Highly Selective Multiparametric Detection of Anti-Drug Antibodies Journal Article In: Adv. Mater., 35 (2211352), 2023. @article{Sens2023, title = {Reduced Graphene Oxide Electrolyte-Gated Transistor Immunosensor with Highly Selective Multiparametric Detection of Anti-Drug Antibodies}, author = {M. Sens and R. Furlan de Oliveira and M. Berto and M. Palmieri and E. Ruini and P. A. Livio and A. Conti and M. Pinti and C. Salvarani and A. Cossarizza and J. M. Cabot and J. Ricart and S. Casalini and M. B. González-García and P. Fanjul-Bolado and C. A. Bortolotti and P. Samorì and F. Biscarini}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202211352}, year = {2023}, date = {2023-09-07}, journal = {Adv. Mater.}, volume = {35}, number = {2211352}, abstract = {The advent of immunotherapies with biological drugs has revolutionized the treatment of cancers and auto-immune diseases. However, in some patients, the production of anti-drug antibodies (ADAs) hampers the drug efficacy. The concentration of ADAs is typically in the range of 1–10 pm; hence their immunodetection is challenging. ADAs toward Infliximab (IFX), a drug used to treat rheumatoid arthritis and other auto-immune diseases, are focussed. An ambipolar electrolyte-gated transistor (EGT) immunosensor is reported based on a reduced graphene oxide (rGO) channel and IFX bound to the gate electrode as the specific probe. The rGO-EGTs are easy to fabricate and exhibit low voltage operations (≤ 0.3 V), a robust response within 15 min, and ultra-high sensitivity (10 am limit of detection). A multiparametric analysis of the whole rGO-EGT transfer curves based on the type-I generalized extreme value distribution is proposed. It is demonstrated that it allows to selectively quantify ADAs also in the co-presence of its antagonist tumor necrosis factor alpha (TNF-α), the natural circulating target of IFX.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The advent of immunotherapies with biological drugs has revolutionized the treatment of cancers and auto-immune diseases. However, in some patients, the production of anti-drug antibodies (ADAs) hampers the drug efficacy. The concentration of ADAs is typically in the range of 1–10 pm; hence their immunodetection is challenging. ADAs toward Infliximab (IFX), a drug used to treat rheumatoid arthritis and other auto-immune diseases, are focussed. An ambipolar electrolyte-gated transistor (EGT) immunosensor is reported based on a reduced graphene oxide (rGO) channel and IFX bound to the gate electrode as the specific probe. The rGO-EGTs are easy to fabricate and exhibit low voltage operations (≤ 0.3 V), a robust response within 15 min, and ultra-high sensitivity (10 am limit of detection). A multiparametric analysis of the whole rGO-EGT transfer curves based on the type-I generalized extreme value distribution is proposed. It is demonstrated that it allows to selectively quantify ADAs also in the co-presence of its antagonist tumor necrosis factor alpha (TNF-α), the natural circulating target of IFX. |
Crispi, S; Nocito, G; Nastasi, F; Condorelli, G; Ricciardulli, A G; Samorì, P; Conoci, S; Neri, G Development of a novel C-dots conductometric sensor for NO sensing Journal Article In: Sens. Actuators B Chem., 390 (133957 ), 2023. @article{Crispi2023, title = {Development of a novel C-dots conductometric sensor for NO sensing}, author = {S. Crispi and G. Nocito and F. Nastasi and G. Condorelli and A. G. Ricciardulli and P. Samorì and S. Conoci and G. Neri}, editor = {Science Direct}, url = {https://doi.org/10.1016/j.snb.2023.133957}, year = {2023}, date = {2023-09-01}, journal = {Sens. Actuators B Chem.}, volume = {390}, number = {133957 }, abstract = {Carbon dots (CDs, C-dots) obtained from waste produced during the production of olive oil in Calabria (Italy) have been investigated as a gas sensing material for the sensitive and selective detection of nitric oxide (NO) in air. The obtained CDs were characterized by XPS, FT-IR and ATR-FTIR. CDs were deposited to yield a sensitive layer on a conductometric platform and tested for gas sensing, showing promising characteristics for the selective monitoring of NO in air. The response of CDs composite to NO was 1.5 @ 1250 ppm and the response and recovery times amounted to 90 and 200 s, respectively. The sensing behavior of C-dots prepared using olive waste from a different geographic location (Puglia, Italy) was also reported and compared. It has been found that the sensing behavior of the two different materials based sensors investigated towards nitrogen oxides (NO and NO2) was completely different. On the one hand, the former exhibited selectivity towards NO. On the other, the latter showed prominent selectivity towards NO2. This behavior can be ascribed to the different functional groups exposed on the C-dots surface undergoing non-covalent interactions with a marked specificity of the hydroxyl and ethers moieties for NO and NO2, respectively.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Carbon dots (CDs, C-dots) obtained from waste produced during the production of olive oil in Calabria (Italy) have been investigated as a gas sensing material for the sensitive and selective detection of nitric oxide (NO) in air. The obtained CDs were characterized by XPS, FT-IR and ATR-FTIR. CDs were deposited to yield a sensitive layer on a conductometric platform and tested for gas sensing, showing promising characteristics for the selective monitoring of NO in air. The response of CDs composite to NO was 1.5 @ 1250 ppm and the response and recovery times amounted to 90 and 200 s, respectively. The sensing behavior of C-dots prepared using olive waste from a different geographic location (Puglia, Italy) was also reported and compared. It has been found that the sensing behavior of the two different materials based sensors investigated towards nitrogen oxides (NO and NO2) was completely different. On the one hand, the former exhibited selectivity towards NO. On the other, the latter showed prominent selectivity towards NO2. This behavior can be ascribed to the different functional groups exposed on the C-dots surface undergoing non-covalent interactions with a marked specificity of the hydroxyl and ethers moieties for NO and NO2, respectively. |
Pakulski, D; Gorczyński, A; Brykczyńska, D; Montes-García, V; Czepa, W; Janica, I; Bielejewski, M; Kubicki, M; Patroniak, V; Samorì, P; Ciesielski, A New Anderson-Based Polyoxometalate Covalent Organic Frameworks as Electrodes for Energy Storage Boosted Through Keto-Enol Tautomerization Journal Article In: Angew. Chem. Int. Ed., 62 (e202305239), 2023. @article{Pakulski2023, title = {New Anderson-Based Polyoxometalate Covalent Organic Frameworks as Electrodes for Energy Storage Boosted Through Keto-Enol Tautomerization}, author = {D. Pakulski and A. Gorczyński and D. Brykczyńska and V. Montes-García and W. Czepa and I. Janica and M. Bielejewski and M. Kubicki and V. Patroniak and P. Samorì and A. Ciesielski}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/anie.202305239}, year = {2023}, date = {2023-08-07}, journal = {Angew. Chem. Int. Ed.}, volume = {62}, number = {e202305239}, abstract = {The unique electrochemical properties of polyoxometalates (POMs) render them ideal components for the fabrication of next-generation high-performance energy storage systems. However, their practical applications have been hindered by their high solubility in common electrolytes. This problem can be overcome by the effective hybridization of POMs with other materials. Here we present the design and synthesis of two novel polyoxometalate-covalent organic frameworks (POCOF) via one-pot solvothermal strategy between an amino-functionalized Anderson-type POM and a trialdehyde-based building unit. We show that structural and functional complexity can be enriched by adding hydroxyl groups in the 2,4,6 position to the benzene-1,3,5-tricarbaldehyde allowing to exploit for the first time in POCOFs the keto-enol tautomerization as additional feature to impart greater chemical stability to the COFs and enhanced properties leading to large specific surface area (347 m2/g) and superior electrochemical performance of the POCOF-1 electrodes, when compared with POCOF-2 electrodes that possess only imine-type linkage and with pristine POM electrodes. Specifically, POCOF-1 electrodes display remarkable specific, areal, and volumetric capacitance (125 F/g, 248 mF/cm2 and 41.9 mF/cm3, respectively) at a current density of 0.5 A/g, a maximum energy density (56.2 Wh/kg), a maximum power density (3.7 kW/kg) and an outstanding cyclability (90 % capacitance retention after 5000 cycles).}, keywords = {}, pubstate = {published}, tppubtype = {article} } The unique electrochemical properties of polyoxometalates (POMs) render them ideal components for the fabrication of next-generation high-performance energy storage systems. However, their practical applications have been hindered by their high solubility in common electrolytes. This problem can be overcome by the effective hybridization of POMs with other materials. Here we present the design and synthesis of two novel polyoxometalate-covalent organic frameworks (POCOF) via one-pot solvothermal strategy between an amino-functionalized Anderson-type POM and a trialdehyde-based building unit. We show that structural and functional complexity can be enriched by adding hydroxyl groups in the 2,4,6 position to the benzene-1,3,5-tricarbaldehyde allowing to exploit for the first time in POCOFs the keto-enol tautomerization as additional feature to impart greater chemical stability to the COFs and enhanced properties leading to large specific surface area (347 m2/g) and superior electrochemical performance of the POCOF-1 electrodes, when compared with POCOF-2 electrodes that possess only imine-type linkage and with pristine POM electrodes. Specifically, POCOF-1 electrodes display remarkable specific, areal, and volumetric capacitance (125 F/g, 248 mF/cm2 and 41.9 mF/cm3, respectively) at a current density of 0.5 A/g, a maximum energy density (56.2 Wh/kg), a maximum power density (3.7 kW/kg) and an outstanding cyclability (90 % capacitance retention after 5000 cycles). |
Xu, N; Shi, L; Pei, X; Zhang, W; Chen, J; Han, Z; Samorì, P; Wang, J; Wang, P; Shi, Y; Li, S Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors Journal Article In: Nat. Commun., 14 (4074), 2023. @article{Xu2023, title = {Oxidation kinetics and non-Marcusian charge transfer in dimensionally confined semiconductors}, author = {N. Xu and L. Shi and X. Pei and W. Zhang and J. Chen and Z. Han and P. Samorì and J. Wang and P. Wang and Y. Shi and S. Li}, editor = {Nature communication}, url = {https://doi.org/10.1038/s41467-023-39781-y}, year = {2023}, date = {2023-07-10}, journal = {Nat. Commun.}, volume = {14}, number = {4074}, abstract = {Electrochemical reactions represent essential processes in fundamental chemistry that foster a wide range of applications. Although most electrochemical reactions in bulk substances can be well described by the classical Marcus-Gerischer charge transfer theory, the realistic reaction character and mechanism in dimensionally confined systems remain unknown. Here, we report the multiparametric survey on the kinetics of lateral photooxidation in structurally identical WS2 and MoS2 monolayers, where electrochemical oxidation occurs at the atomically thin monolayer edges. The oxidation rate is correlated quantitatively with various crystallographic and environmental parameters, including the density of reactive sites, humidity, temperature, and illumination fluence. In particular, we observe distinctive reaction barriers of 1.4 and 0.9 eV for the two structurally identical semiconductors and uncover an unusual non-Marcusian charge transfer mechanism in these dimensionally confined monolayers due to the limit in reactant supplies. A scenario of band bending is proposed to explain the discrepancy in reaction barriers. These results add important knowledge into the fundamental electrochemical reaction theory in low-dimensional systems.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Electrochemical reactions represent essential processes in fundamental chemistry that foster a wide range of applications. Although most electrochemical reactions in bulk substances can be well described by the classical Marcus-Gerischer charge transfer theory, the realistic reaction character and mechanism in dimensionally confined systems remain unknown. Here, we report the multiparametric survey on the kinetics of lateral photooxidation in structurally identical WS2 and MoS2 monolayers, where electrochemical oxidation occurs at the atomically thin monolayer edges. The oxidation rate is correlated quantitatively with various crystallographic and environmental parameters, including the density of reactive sites, humidity, temperature, and illumination fluence. In particular, we observe distinctive reaction barriers of 1.4 and 0.9 eV for the two structurally identical semiconductors and uncover an unusual non-Marcusian charge transfer mechanism in these dimensionally confined monolayers due to the limit in reactant supplies. A scenario of band bending is proposed to explain the discrepancy in reaction barriers. These results add important knowledge into the fundamental electrochemical reaction theory in low-dimensional systems. |
Gullace, S; Cusin, L; Richard, F; Israfilov, N; Ciesielski, A; Samorì, P In: Adv. Mater. Interfaces,, 10 (2300124), 2023. @article{Gullace2023, title = {The Role of Superadsorbent Polymers on Covalent Organic Frameworks-Based Solid Electrolytes: Investigation of the Ionic Conductivity and Relaxation}, author = {S. Gullace and L. Cusin and F. Richard and N. Israfilov and A. Ciesielski and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/admi.202300124}, year = {2023}, date = {2023-06-06}, journal = {Adv. Mater. Interfaces,}, volume = {10}, number = {2300124}, abstract = {The scarcity of fossil fuels calls for immediate action toward the development of clean and renewable energy resources. In this context, proton exchange membrane fuel cells (PEMFCs) are gaining ever-increasing attention as clean technology. Although covalent organic frameworks (COFs) do not usually exhibit high intrinsic proton conductivity (σ), they have been recently proposed as solid polymer electrolytes in PEMFCs, thanks to their high crystallinity and stability to acids and bases. Here, a simple strategy is presented to improve the performance of poor COF-based proton conductors through addition of sodium polyacrylate (PANa) superadsorbent polymer. Electrochemical impedance spectroscopy investigations after activation at high temperature and relative humidity (RH) provide insights into the role of PANa, whose presence is key to preserve high σ at low RH. The humidity-dependent X-ray diffraction study reveals a strengthening of the stacking interaction along the COF (100) plane direction with increasing humidity, through the formation of H-bonding, thus promoting proton hopping. The study of the dielectric properties as a function of PANa content enables to determine a Debye relaxation regime for the COF/PANa blend with a maximum relaxation frequency of 1513 and 6606 Hz for the pristine COF and the COF/PANa blend, respectively, at their maximum operating temperatures.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The scarcity of fossil fuels calls for immediate action toward the development of clean and renewable energy resources. In this context, proton exchange membrane fuel cells (PEMFCs) are gaining ever-increasing attention as clean technology. Although covalent organic frameworks (COFs) do not usually exhibit high intrinsic proton conductivity (σ), they have been recently proposed as solid polymer electrolytes in PEMFCs, thanks to their high crystallinity and stability to acids and bases. Here, a simple strategy is presented to improve the performance of poor COF-based proton conductors through addition of sodium polyacrylate (PANa) superadsorbent polymer. Electrochemical impedance spectroscopy investigations after activation at high temperature and relative humidity (RH) provide insights into the role of PANa, whose presence is key to preserve high σ at low RH. The humidity-dependent X-ray diffraction study reveals a strengthening of the stacking interaction along the COF (100) plane direction with increasing humidity, through the formation of H-bonding, thus promoting proton hopping. The study of the dielectric properties as a function of PANa content enables to determine a Debye relaxation regime for the COF/PANa blend with a maximum relaxation frequency of 1513 and 6606 Hz for the pristine COF and the COF/PANa blend, respectively, at their maximum operating temperatures. |
Malaki, M; Jiang, X; Wang, H; Podila, R; Zhang, H; Samorì, P; Varma, R S MXenes: from past to future perspectives Journal Article In: Chem. Eng. J., 463 (142351), 2023. @article{Malaki2023, title = {MXenes: from past to future perspectives}, author = {M. Malaki and X. Jiang and H. Wang and R. Podila and H. Zhang and P. Samorì and R. S. Varma}, editor = {Science Direct}, url = {https://doi.org/10.1016/j.cej.2023.142351}, year = {2023}, date = {2023-05-01}, journal = {Chem. Eng. J.}, volume = {463}, number = {142351}, abstract = {MXenes have recently emerged as a revolutionary class of material displaying exceptional tailored-made properties. The onward journey and remarkable rise are establishing MXene-based materials as multifaceted playgrounds for the technology-oriented explorations and are offering a tool-box for the ad hoc tailoring of advanced materials capable to effectively address current and future societal challenges. Unexpected applications have witnessed a tremendous growth owing to the material’s unique chemical and physical properties including, among others, optical, electrical, mechanical and thermal characteristics. Attaining an in-depth and critical understanding on the broadest arsenal of such unique and new properties as well as the synergistic effects of the assorted characteristics will play a pivotal role for new discoveries in both, research and industrial sectors. Herein, the current challenges, bottlenecks, controversies, as well as emerging opportunities are critically discussed by providing, in a single package, comprehensive insight into chemical and physical properties with a particular focus on their disruptive potential for technological applications. The key fundamental properties ranging from electrical, magnetic, thermal, mechanical, tribological to sensing features are elucidated to stimulate emerging opportunities and lucrative potentials with the ultimate goal being the technological exploitation of newfound materials and structures with targeted attributes.}, keywords = {}, pubstate = {published}, tppubtype = {article} } MXenes have recently emerged as a revolutionary class of material displaying exceptional tailored-made properties. The onward journey and remarkable rise are establishing MXene-based materials as multifaceted playgrounds for the technology-oriented explorations and are offering a tool-box for the ad hoc tailoring of advanced materials capable to effectively address current and future societal challenges. Unexpected applications have witnessed a tremendous growth owing to the material’s unique chemical and physical properties including, among others, optical, electrical, mechanical and thermal characteristics. Attaining an in-depth and critical understanding on the broadest arsenal of such unique and new properties as well as the synergistic effects of the assorted characteristics will play a pivotal role for new discoveries in both, research and industrial sectors. Herein, the current challenges, bottlenecks, controversies, as well as emerging opportunities are critically discussed by providing, in a single package, comprehensive insight into chemical and physical properties with a particular focus on their disruptive potential for technological applications. The key fundamental properties ranging from electrical, magnetic, thermal, mechanical, tribological to sensing features are elucidated to stimulate emerging opportunities and lucrative potentials with the ultimate goal being the technological exploitation of newfound materials and structures with targeted attributes. |
Czepa, W; Witomska, S; Samorì, P; Ciesielski, A A Graphene Oxide–Thioamide Polymer Hybrid for High-Performance Supercapacitor Electrodes Journal Article In: Small Sci., 3 (2300013), 2023. @article{Czepa2023, title = {A Graphene Oxide–Thioamide Polymer Hybrid for High-Performance Supercapacitor Electrodes}, author = {W. Czepa and S. Witomska and P. Samorì and A. Ciesielski}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/smsc.202300013}, year = {2023}, date = {2023-05-01}, journal = {Small Sci.}, volume = {3}, number = {2300013}, abstract = {The controlled chemical functionalization of graphene oxide (GO) represents a powerful strategy to finely tune its physical and chemical properties toward applications in energy storage. Herein, an unprecedented approach for the GO modification with thioamide-based polymers featuring numerous heteroatoms (S,N,O) is reported, which is instrumental for achieving superior electrochemical performance in symmetric supercapacitors. While the electrochemical investigations in aqueous electrolytes reveal specific capacitance of 221 F g−1 at 1 A g−1, the use of organic media allows the specific capacitance to be boosted up to 340 F g−1. Additionally, the increase of operating window yields energy densities as high as 94.4 Wh kg−1, thereby exceeding state-of-the-art performances of GO-based supercapacitors. Furthermore, the symmetric devices exhibit great robustness in both aqueous and organic electrolytes as evidenced by an excellent stability after 5000 working cycles (>98% in H2SO4 and >90% in TEABF4/ACN).}, keywords = {}, pubstate = {published}, tppubtype = {article} } The controlled chemical functionalization of graphene oxide (GO) represents a powerful strategy to finely tune its physical and chemical properties toward applications in energy storage. Herein, an unprecedented approach for the GO modification with thioamide-based polymers featuring numerous heteroatoms (S,N,O) is reported, which is instrumental for achieving superior electrochemical performance in symmetric supercapacitors. While the electrochemical investigations in aqueous electrolytes reveal specific capacitance of 221 F g−1 at 1 A g−1, the use of organic media allows the specific capacitance to be boosted up to 340 F g−1. Additionally, the increase of operating window yields energy densities as high as 94.4 Wh kg−1, thereby exceeding state-of-the-art performances of GO-based supercapacitors. Furthermore, the symmetric devices exhibit great robustness in both aqueous and organic electrolytes as evidenced by an excellent stability after 5000 working cycles (>98% in H2SO4 and >90% in TEABF4/ACN). |
Pandey, P; Fijahi, L; McIntosh, N; Turetta, N; Bardini, M; Giannini, S; Ruzié, C; Schweicher, G; Beljonne, D; Cornil, J; Samorì, P; Mas-Torrent, M; Geerts, Y H; Modena, E; Maini, L From synthesis to device fabrication: elucidating the structural and electronic properties of C7-BTBT-C7 Journal Article In: J. Mater. Chem. C, 2023, , 11 (7345–7355 ), 2023. @article{Pandey2023, title = {From synthesis to device fabrication: elucidating the structural and electronic properties of C7-BTBT-C7}, author = {P. Pandey and L. Fijahi and N. McIntosh and N. Turetta and M. Bardini and S. Giannini and C. Ruzié and G. Schweicher and D. Beljonne and J. Cornil and P. Samorì and M. Mas-Torrent and Y. H. Geerts and E. Modena and L. Maini}, url = {https://doi.org/10.1039/d3tc00434a}, year = {2023}, date = {2023-04-21}, journal = {J. Mater. Chem. C, 2023, }, volume = {11}, number = {7345–7355 }, abstract = {We report the polymorph investigation, crystallographic study and fabrication of organic field-effect transistors (OFETs) in solution-processed thin films of a prototypical organic semiconductor, i.e., 2,7-diheptylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (C7-BTBT-C7). We found that this molecule self-assembles solely into one type of stable crystal form, regardless of the experimental conditions employed when using conventional and non-conventional methods of crystallization. The integration of blends of C7-BTBT-C7 with polystyrene as active materials in OFETs fabricated using a solution shearing technique led to a field-effect mobility of 1.42 ± 0.45 cm2 V−1 s−1 in the saturation regime when a coating speed of 10 mm s−1 was employed. The intrinsic structural properties control the overlap of the frontier orbitals, thereby affecting the device performance. The interplay between the crystal packing, thin film morphology and uniformity and its impact on the device performance are reported.}, keywords = {}, pubstate = {published}, tppubtype = {article} } We report the polymorph investigation, crystallographic study and fabrication of organic field-effect transistors (OFETs) in solution-processed thin films of a prototypical organic semiconductor, i.e., 2,7-diheptylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (C7-BTBT-C7). We found that this molecule self-assembles solely into one type of stable crystal form, regardless of the experimental conditions employed when using conventional and non-conventional methods of crystallization. The integration of blends of C7-BTBT-C7 with polystyrene as active materials in OFETs fabricated using a solution shearing technique led to a field-effect mobility of 1.42 ± 0.45 cm2 V−1 s−1 in the saturation regime when a coating speed of 10 mm s−1 was employed. The intrinsic structural properties control the overlap of the frontier orbitals, thereby affecting the device performance. The interplay between the crystal packing, thin film morphology and uniformity and its impact on the device performance are reported. |
Ippolito, S; Urban, F; Zheng, W; Mazzarisi, O; Valentini, C; Kelly, A G; Gali, S M; Bonn, M; Beljonne, D; Corberi, F; Coleman, J N; Wang, H I; Samorì, P Unveiling Charge-Transport Mechanisms in Electronic Devices Based on Defect-Engineered MoS2 Covalent Networks Journal Article In: Adv. Mater., 35 (2211157), 2023. @article{Ippolito2023, title = {Unveiling Charge-Transport Mechanisms in Electronic Devices Based on Defect-Engineered MoS2 Covalent Networks}, author = {S. Ippolito and F. Urban and W. Zheng and O. Mazzarisi and C. Valentini and A. G. Kelly and S. M. Gali and M. Bonn and D. Beljonne and F. Corberi and J. N. Coleman and H. I. Wang and P. Samorì}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202211157}, year = {2023}, date = {2023-04-13}, journal = {Adv. Mater.}, volume = {35}, number = {2211157}, abstract = {Device performance of solution-processed 2D semiconductors in printed electronics has been limited so far by structural defects and high interflake junction resistance. Covalently interconnected networks of transition metal dichalcogenides potentially represent an efficient strategy to overcome both limitations simultaneously. Yet, the charge-transport properties in such systems have not been systematically researched. Here, the charge-transport mechanisms of printed devices based on covalent MoS2 networks are unveiled via multiscale analysis, comparing the effects of aromatic versus aliphatic dithiolated linkers. Temperature-dependent electrical measurements reveal hopping as the dominant transport mechanism: aliphatic systems lead to 3D variable range hopping, unlike the nearest neighbor hopping observed for aromatic linkers. The novel analysis based on percolation theory attributes the superior performance of devices functionalized with π-conjugated molecules to the improved interflake electronic connectivity and formation of additional percolation paths, as further corroborated by density functional calculations. Valuable guidelines for harnessing the charge-transport properties in MoS2 devices based on covalent networks are provided.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Device performance of solution-processed 2D semiconductors in printed electronics has been limited so far by structural defects and high interflake junction resistance. Covalently interconnected networks of transition metal dichalcogenides potentially represent an efficient strategy to overcome both limitations simultaneously. Yet, the charge-transport properties in such systems have not been systematically researched. Here, the charge-transport mechanisms of printed devices based on covalent MoS2 networks are unveiled via multiscale analysis, comparing the effects of aromatic versus aliphatic dithiolated linkers. Temperature-dependent electrical measurements reveal hopping as the dominant transport mechanism: aliphatic systems lead to 3D variable range hopping, unlike the nearest neighbor hopping observed for aromatic linkers. The novel analysis based on percolation theory attributes the superior performance of devices functionalized with π-conjugated molecules to the improved interflake electronic connectivity and formation of additional percolation paths, as further corroborated by density functional calculations. Valuable guidelines for harnessing the charge-transport properties in MoS2 devices based on covalent networks are provided. |
Zheng, H; Ou, C; Huang, X; Jiang, B; Li, W; Li, J; Han, X; Liu, C; Han, Z; Ji, T; Samorì, P; Zhang, L A Flexible, High-Voltage (>100 V) Generating Device Based on Zebra-Like Asymmetrical Photovoltaic Cascade Journal Article In: Adv. Mater., 35 (2209482 ), 2023. @article{Zheng2023, title = {A Flexible, High-Voltage (>100 V) Generating Device Based on Zebra-Like Asymmetrical Photovoltaic Cascade}, author = {H. Zheng and C. Ou and X. Huang and B. Jiang and W. Li and J. Li and X. Han and C. Liu and Z. Han and T. Ji and P. Samorì and L. Zhang}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/adma.202209482}, year = {2023}, date = {2023-03-09}, journal = {Adv. Mater.}, volume = {35}, number = {2209482 }, abstract = {The mutual conversion between light and electricity lies at the heart of optoelectronic and photonic applications. Maximization of the photoelectric conversion is a long-term goal that can be pursued via the fabrication of devices with ad-hoc architectures. In this framework, it is of utter importance to harvest and transform light irradiation into high electric potential in specific area for driving functional dielectrics that respond to pure electric field. Here, a nano-fabrication technology has been devised featuring double self-alignment that is applied to construct zebra-like asymmetric heterojunction arrays. Such nanostructured composite, which covers a surface area of 5 × 4 mm2 and contains 500 periodic repeating units, is capable of photo generating voltages as high as 140 V on a flexible substrate. This approach represents a leap over the traditional functionalization process based on simply embedding materials into devices by demonstrating the disruptive potential of integrating oriented nanoscale device components into meta-material.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The mutual conversion between light and electricity lies at the heart of optoelectronic and photonic applications. Maximization of the photoelectric conversion is a long-term goal that can be pursued via the fabrication of devices with ad-hoc architectures. In this framework, it is of utter importance to harvest and transform light irradiation into high electric potential in specific area for driving functional dielectrics that respond to pure electric field. Here, a nano-fabrication technology has been devised featuring double self-alignment that is applied to construct zebra-like asymmetric heterojunction arrays. Such nanostructured composite, which covers a surface area of 5 × 4 mm2 and contains 500 periodic repeating units, is capable of photo generating voltages as high as 140 V on a flexible substrate. This approach represents a leap over the traditional functionalization process based on simply embedding materials into devices by demonstrating the disruptive potential of integrating oriented nanoscale device components into meta-material. |
Pilato, S; Moffa, S; Siani, G; Diomede, F; Trubiani, O; Pizzicannella, J; Capista, D; Passacantando, M; Samorì, P; Fontana, A 3D Graphene Oxide-Polyethylenimine Scaffolds for Cardiac Tissue Engineering Journal Article In: Mater. Interfaces, 15 , pp. 14077–14088, 2023. @article{Pilato2023, title = {3D Graphene Oxide-Polyethylenimine Scaffolds for Cardiac Tissue Engineering}, author = {S. Pilato and S. Moffa and G. Siani and F. Diomede and O. Trubiani and J. Pizzicannella and D. Capista and M. Passacantando and P. Samorì and A. Fontana}, editor = {ACS Publcation}, url = {https://pubs.acs.org/doi/10.1021/acsami.3c00216}, year = {2023}, date = {2023-03-07}, journal = {Mater. Interfaces}, volume = {15}, pages = {14077–14088}, abstract = {The development of novel three-dimensional (3D) nanomaterials combining high biocompatibility, precise mechanical characteristics, electrical conductivity, and controlled pore size to enable cell and nutrient permeation is highly sought after for cardiac tissue engineering applications including repair of damaged heart tissues following myocardial infarction and heart failure. Such unique characteristics can collectively be found in hybrid, highly porous tridimensional scaffolds based on chemically functionalized graphene oxide (GO). By exploiting the rich reactivity of the GO’s basal epoxydic and edge carboxylate moieties when interacting, respectively, with NH2 and NH3+ groups of linear polyethylenimines (PEIs), 3D architectures with variable thickness and porosity can be manufactured, making use of the layer-by-layer technique through the subsequent dipping in GO and PEI aqueous solutions, thereby attaining enhanced compositional and structural control. The elasticity modulus of the hybrid material is found to depend on scaffold’s thickness, with the lowest value of 13 GPa obtained in samples containing the highest number of alternating layers. Thanks to the amino-rich composition of the hybrid and the established biocompatibility of GO, the scaffolds do not exhibit cytotoxicity; they promote cardiac muscle HL-1 cell adhesion and growth without interfering with the cell morphology and increasing cardiac markers such as Connexin-43 and Nkx 2.5. Our novel strategy for scaffold preparation thus overcomes the drawbacks associated with the limited processability of pristine graphene and low GO conductivity, and it enables the production of biocompatible 3D GO scaffolds covalently functionalized with amino-based spacers, which is advantageous for cardiac tissue engineering applications. In particular, they displayed a significant increase in the number of gap junctions compared to HL-1 cultured on CTRL substrates, which render them key components for repairing damaged heart tissues as well as being used for 3D in vitro cardiac modeling investigations.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The development of novel three-dimensional (3D) nanomaterials combining high biocompatibility, precise mechanical characteristics, electrical conductivity, and controlled pore size to enable cell and nutrient permeation is highly sought after for cardiac tissue engineering applications including repair of damaged heart tissues following myocardial infarction and heart failure. Such unique characteristics can collectively be found in hybrid, highly porous tridimensional scaffolds based on chemically functionalized graphene oxide (GO). By exploiting the rich reactivity of the GO’s basal epoxydic and edge carboxylate moieties when interacting, respectively, with NH2 and NH3+ groups of linear polyethylenimines (PEIs), 3D architectures with variable thickness and porosity can be manufactured, making use of the layer-by-layer technique through the subsequent dipping in GO and PEI aqueous solutions, thereby attaining enhanced compositional and structural control. The elasticity modulus of the hybrid material is found to depend on scaffold’s thickness, with the lowest value of 13 GPa obtained in samples containing the highest number of alternating layers. Thanks to the amino-rich composition of the hybrid and the established biocompatibility of GO, the scaffolds do not exhibit cytotoxicity; they promote cardiac muscle HL-1 cell adhesion and growth without interfering with the cell morphology and increasing cardiac markers such as Connexin-43 and Nkx 2.5. Our novel strategy for scaffold preparation thus overcomes the drawbacks associated with the limited processability of pristine graphene and low GO conductivity, and it enables the production of biocompatible 3D GO scaffolds covalently functionalized with amino-based spacers, which is advantageous for cardiac tissue engineering applications. In particular, they displayed a significant increase in the number of gap junctions compared to HL-1 cultured on CTRL substrates, which render them key components for repairing damaged heart tissues as well as being used for 3D in vitro cardiac modeling investigations. |
Peng, H; Huang, S; Montes-García, V; Pakulski, D; Guo, H; Richard, F; Zhuang, X; Samorì, P; Peng, CiesielskiH. A; Huang, S; Montes-García, V; Pakulski, D; Guo, H; Richard, F; Zhuang, X; Samorì, P; Ciesielski, A In: Angew. Chem. Int. , 62 (e202216136), 2023. @article{Peng2023b, title = {Supramolecular Engineering of Cathode Materials for Aqueous Zinc-ion Energy Storage Devices: Novel Benzothiadiazole Functionalized Two-Dimensional Olefin-Linked COFs}, author = {H. Peng and S. Huang and V. Montes-García and D. Pakulski and H. Guo and F. Richard and X. Zhuang and P. Samorì and A. CiesielskiH. Peng and S. Huang and V. Montes-García and D. Pakulski and H. Guo and F. Richard and X. Zhuang and P. Samorì and A. Ciesielski}, editor = {Wiley Online Library}, url = {https://doi.org/10.1002/anie.202216136}, year = {2023}, date = {2023-03-01}, journal = {Angew. Chem. Int. }, volume = {62}, number = {e202216136}, abstract = {Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance...}, keywords = {}, pubstate = {published}, tppubtype = {article} } Two-dimensional covalent organic frameworks (COFs) have emerged as promising materials for energy storage applications exhibiting enhanced electrochemical performance... |
Turetta, N; Danowski, W; Cusin, L; Livio, P A; Hallani, R; McCulloch, I; and S. Lara Avila, Samorì P A photo-responsive organic electrochemical transistor Journal Article In: J. Mater. Chem. C, 11 , pp. 7982–7988, 2023. @article{Turetta2023, title = {A photo-responsive organic electrochemical transistor}, author = {N. Turetta and W. Danowski and L. Cusin and P. A. Livio and R. Hallani and I. McCulloch and S. Lara Avila ,and P. Samorì}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d2tc05444b}, year = {2023}, date = {2023-02-28}, journal = {J. Mater. Chem. C}, volume = {11}, pages = {7982–7988}, abstract = {The design of novel organic electrochemical transistor (OECT) channel materials that can be controlled by a whole range of external stimuli is key towards the emergence of unprecedented technologies in bioelectronics. Like the established multiresponsive field-effect transistors, multiresponsive OECTs can in principle be realised via blending, by combining multiple components with each one imparting a specific function to the device. Here we report the first example of an optically switchable OECT which is capable of undergoing a reversible modulation of its ON current by up to 30% upon irradiation with UV and visible light. By investigating the electrical characteristics of the channel material, in conjunction with the electronic characterisation performed by a macroscopic Kelvin probe technique and photoemission yield spectroscopy in air, we gained distinct insight into the electrochemical doping process occurring within the blend upon light irradiation. Such a proof-of-concept work opens perspectives towards the implementation of complex neuromorphic operations and algorithms in OECTs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } The design of novel organic electrochemical transistor (OECT) channel materials that can be controlled by a whole range of external stimuli is key towards the emergence of unprecedented technologies in bioelectronics. Like the established multiresponsive field-effect transistors, multiresponsive OECTs can in principle be realised via blending, by combining multiple components with each one imparting a specific function to the device. Here we report the first example of an optically switchable OECT which is capable of undergoing a reversible modulation of its ON current by up to 30% upon irradiation with UV and visible light. By investigating the electrical characteristics of the channel material, in conjunction with the electronic characterisation performed by a macroscopic Kelvin probe technique and photoemission yield spectroscopy in air, we gained distinct insight into the electrochemical doping process occurring within the blend upon light irradiation. Such a proof-of-concept work opens perspectives towards the implementation of complex neuromorphic operations and algorithms in OECTs. |
Buriak, J M; Akinwande, D; Artzi, N; Brinker, C J; Burrows, C; Chan, W C W; Chen, C; Chen, X; Chhowalla, M; Chi, L; Chueh, W; Crudden, C M; Carlo, Di D; Glotzer, S C; Hersam, M C; Ho, D; Hu, T Y; Huang, J; Javey, A; Kamat, P V; Kim, I -D; Kotov, N A; Lee, T R; Lee, Y H; Li, Y; Liz-Marzán, L M; Mulvaney, P; Narang, P; Nordlander, P; Oklu, R; Parak, W J; Rogach, A L; Salanne, M; Samorì, P; Schaak, R E; Schanze, K S; Sekitani, T; Skrabalak, S; Sood, A K; Voets, I K; Wang, S; Wang, S; Wee, A T S; Ye, J Best Practices for Using AI When Writing Scientific Manuscripts – Caution, Care, and Consideration: Creative Science Depends on It Journal Article In: ACS Nano, 2023, ACS Nano (17), pp. 4091–4093, 2023. @article{Buriak2023, title = {Best Practices for Using AI When Writing Scientific Manuscripts – Caution, Care, and Consideration: Creative Science Depends on It}, author = {J. M. Buriak and D. Akinwande and N. Artzi and C. J. Brinker and C. Burrows and W. C. W. Chan and C. Chen and X. Chen and M. Chhowalla and L. Chi and W. Chueh and C. M. Crudden and D. Di Carlo and S. C. Glotzer and M. C. Hersam and D. Ho and T. Y. Hu and J. Huang and A. Javey and P. V. Kamat and I.-D. Kim and N. A. Kotov and T. R. Lee and Y. H. Lee and Y. Li and L. M. Liz-Marzán and P. Mulvaney and P. Narang and P. Nordlander and R. Oklu and W. J. Parak and A. L. Rogach and M. Salanne and P. Samorì and R. E. Schaak and K. S. Schanze and T. Sekitani and S. Skrabalak and A. K. Sood and I. K. Voets and S. Wang and S. Wang and A. T. S. Wee and J. Ye}, editor = {ACS Publcation}, url = {https://doi.org/10.1021/acsnano.3c01544}, year = {2023}, date = {2023-02-27}, journal = {ACS Nano, 2023}, volume = {ACS Nano}, number = {17}, pages = {4091–4093}, abstract = {Science is communicated through language. The media of language in science is multimodal, ranging from lecturing in classrooms, to informal daily discussions among scientists, to prepared talks at conferences, and, finally, to the pinnacle of science communication, the formal peer-reviewed publication. The arrival of language tools driven by artificial intelligence (AI), like ChatGPT, (1) has generated an explosion of interest globally. ChatGPT has set the record for the fastest growing user base of any application in history, with over 100 million active users in just two months, as of the end of January 2023. (2) ChatGPT is merely the first of many AI-based language tools, with announcements of more either in preparation or soon to be launched. (3−5) Many in scientific research and universities around the world have raised concerns of ChatGPT‘s potential to transform scientific communication (6) before we have had time to consider the ramifications of such a tool or verified that the text it generates is factually correct. The human-like quality of the text structure produced by ChatGPT can deceive readers into believing it is of human origin. (7) It is now apparent, however, that the generated text might be fraught with errors, can be shallow and superficial, and can generate false journal references and inferences. (8) More importantly, ChatGPT sometimes makes connections that are nonsensical and false. We have prepared a brief summary of some of the strengths and weaknesses of ChatGPT (and future AI language bots) and conclude with a set of our recommendations of best practices for scientists when using such tools at any stage of their research, particularly at the manuscript writing stage. (9,10) It is important to state that even among the authors here, there is a diversity of thought and opinion, and this editorial reflects the middle ground consensus. In its current incarnation, ChatGPT is merely an efficient language bot that generates text by linguistic connections. (11) It is, at present, “just a giant autocomplete machine”. (12) Since ChatGPT is the first of many models that will undoubtedly improve rapidly, within a few years we will almost certainly look back at ChatGPT like an old computer from the 1980s. It must be recognized that ChatGPT relies on its existing database and content and, at the time of writing of this editorial, fails to include information published or posted after 2021, thus restricting its utility when applied to the writing of up-to-date reviews, perspectives, and introductions. Therefore, for reviews and perspectives, ChatGPT is deficient due to its lack of analytical capabilities that scientists are expected to possess and the experiences that inform us.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Science is communicated through language. The media of language in science is multimodal, ranging from lecturing in classrooms, to informal daily discussions among scientists, to prepared talks at conferences, and, finally, to the pinnacle of science communication, the formal peer-reviewed publication. The arrival of language tools driven by artificial intelligence (AI), like ChatGPT, (1) has generated an explosion of interest globally. ChatGPT has set the record for the fastest growing user base of any application in history, with over 100 million active users in just two months, as of the end of January 2023. (2) ChatGPT is merely the first of many AI-based language tools, with announcements of more either in preparation or soon to be launched. (3−5) Many in scientific research and universities around the world have raised concerns of ChatGPT‘s potential to transform scientific communication (6) before we have had time to consider the ramifications of such a tool or verified that the text it generates is factually correct. The human-like quality of the text structure produced by ChatGPT can deceive readers into believing it is of human origin. (7) It is now apparent, however, that the generated text might be fraught with errors, can be shallow and superficial, and can generate false journal references and inferences. (8) More importantly, ChatGPT sometimes makes connections that are nonsensical and false. We have prepared a brief summary of some of the strengths and weaknesses of ChatGPT (and future AI language bots) and conclude with a set of our recommendations of best practices for scientists when using such tools at any stage of their research, particularly at the manuscript writing stage. (9,10) It is important to state that even among the authors here, there is a diversity of thought and opinion, and this editorial reflects the middle ground consensus. In its current incarnation, ChatGPT is merely an efficient language bot that generates text by linguistic connections. (11) It is, at present, “just a giant autocomplete machine”. (12) Since ChatGPT is the first of many models that will undoubtedly improve rapidly, within a few years we will almost certainly look back at ChatGPT like an old computer from the 1980s. It must be recognized that ChatGPT relies on its existing database and content and, at the time of writing of this editorial, fails to include information published or posted after 2021, thus restricting its utility when applied to the writing of up-to-date reviews, perspectives, and introductions. Therefore, for reviews and perspectives, ChatGPT is deficient due to its lack of analytical capabilities that scientists are expected to possess and the experiences that inform us. |
Valentini, C; Montes-García, V; Livio, P A; Chudziak, T; Raya, J; Ciesielski, A; Samorì, P Tuning the electrical properties of graphene oxide through low-temperature thermal annealing Journal Article In: Nanoscale, 15 , pp. 5743–5755 , 2023. @article{Valentini2023, title = {Tuning the electrical properties of graphene oxide through low-temperature thermal annealing}, author = {C. Valentini and V. Montes-García and P. A. Livio and T. Chudziak and J. Raya and A. Ciesielski and P. Samorì}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d2nr06091d}, year = {2023}, date = {2023-02-16}, journal = {Nanoscale}, volume = {15}, pages = {5743–5755 }, abstract = {During the last fifteen years, the reduction of electrically insulating graphene oxide (GO) through the elimination of oxygen containing functional groups and the restoration of sp2 conjugation yielding its conducting form, known as reduced graphene oxide (rGO), has been widely investigated as a scalable and low-cost method to produce materials featuring graphene-like characteristics. Among various protocols, thermal annealing represents an attractive green approach compatible with industrial processes. However, the high temperatures typically required to accomplish this process are energetically demanding and are incompatible with the use of plastic substrates often desired for flexible electronics applications. Here, we report a systematic study on the low-temperature annealing of GO by optimizing different annealing conditions, i.e., temperature, time, and reduction atmosphere. We show that the reduction is accompanied by structural changes of GO, which affect its electrochemical performance when used as an electrode material in supercapacitors. We demonstrate that thermally-reduced GO (TrGO) obtained under air or inert atmosphere at relatively low temperatures (<300 °C) exhibits low film resistivities (10−2–10−4 Ω m) combined with unaltered resistance after 2000 bending cycles when supported on plastic substrates. Moreover, it exhibits enhanced electrochemical characteristics with a specific capacitance of 208 F g−1 and a capacitance retention of >99% after 2000 cycles. The reported strategy is an important step forward toward the development of environmentally friendly TrGO for future electrical or electrochemical applications.}, keywords = {}, pubstate = {published}, tppubtype = {article} } During the last fifteen years, the reduction of electrically insulating graphene oxide (GO) through the elimination of oxygen containing functional groups and the restoration of sp2 conjugation yielding its conducting form, known as reduced graphene oxide (rGO), has been widely investigated as a scalable and low-cost method to produce materials featuring graphene-like characteristics. Among various protocols, thermal annealing represents an attractive green approach compatible with industrial processes. However, the high temperatures typically required to accomplish this process are energetically demanding and are incompatible with the use of plastic substrates often desired for flexible electronics applications. Here, we report a systematic study on the low-temperature annealing of GO by optimizing different annealing conditions, i.e., temperature, time, and reduction atmosphere. We show that the reduction is accompanied by structural changes of GO, which affect its electrochemical performance when used as an electrode material in supercapacitors. We demonstrate that thermally-reduced GO (TrGO) obtained under air or inert atmosphere at relatively low temperatures (<300 °C) exhibits low film resistivities (10−2–10−4 Ω m) combined with unaltered resistance after 2000 bending cycles when supported on plastic substrates. Moreover, it exhibits enhanced electrochemical characteristics with a specific capacitance of 208 F g−1 and a capacitance retention of >99% after 2000 cycles. The reported strategy is an important step forward toward the development of environmentally friendly TrGO for future electrical or electrochemical applications. |
Peng, H; Montes-García, V; Raya, J; Wang, H; Guo, H; Richard, F; Samorì, P; Ciesielski, A In: J. Mater. Chem. A, 11 , pp. 2718–2725, 2023. @article{Peng2023, title = {Supramolecular engineering of cathode materials for aqueous zinc-ion hybrid supercapacitors: novel thiophene-bridged donor–acceptor sp2 carbon-linked polymers}, author = {H. Peng and V. Montes-García and J. Raya and H. Wang and H. Guo and F. Richard and P. Samorì and A. Ciesielski}, editor = {Royal Society of Chemistry}, url = {https://doi.org/10.1039/d2ta09651j}, year = {2023}, date = {2023-01-18}, journal = {J. Mater. Chem. A}, volume = {11}, pages = {2718–2725}, abstract = {Rechargeable aqueous zinc-ion hybrid supercapacitors (Zn-HSCs) are promising candidates as large-scale energy storage devices owing to their high electrochemical performance, safety, long life, and low price. The development of nanostructured electrode materials featuring multiple active sites capable of interacting with Zn ions represents an efficient strategy to boost their electrochemical performance. In this work, we report for the first time the use of donor–acceptor carbon-linked conjugated polymers (DA-CCPs) as cathodes in aqueous Zn-HSCs. We have synthesized two novel DA-CCPs via Knoevenagel polymerization between electron-accepting 2,2′,2′′-(benzene-1,3,5-triyl)triacetonitrile and electron-donating 2,5-thiophene dicarboxaldehyde or [2,2′-bithiophene]-5,5′-dicarboxaldehyde, yielding DA-CCP-1 and DA-CCP-2, respectively. DA-CCP-2, which possesses an extra-thiophene unit in the backbone, exhibits improved electrochemical characteristics when compared to DA-CCP-1, and performance surpassing those of other reported cathode materials for aqueous Zn2+ energy storage systems. DA-CCP-1 and -2 based electrodes exhibited an outstanding energy density of 80.6 and 196.3 W h kg−1 respectively, representing the highest value ever reached for conjugated polymers to date. This study not only offers new perspectives for the rational design and precise synthesis of DA-CCPs but it also broadens the choice of cathodes for high-performance aqueous Zn-HSCs.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Rechargeable aqueous zinc-ion hybrid supercapacitors (Zn-HSCs) are promising candidates as large-scale energy storage devices owing to their high electrochemical performance, safety, long life, and low price. The development of nanostructured electrode materials featuring multiple active sites capable of interacting with Zn ions represents an efficient strategy to boost their electrochemical performance. In this work, we report for the first time the use of donor–acceptor carbon-linked conjugated polymers (DA-CCPs) as cathodes in aqueous Zn-HSCs. We have synthesized two novel DA-CCPs via Knoevenagel polymerization between electron-accepting 2,2′,2′′-(benzene-1,3,5-triyl)triacetonitrile and electron-donating 2,5-thiophene dicarboxaldehyde or [2,2′-bithiophene]-5,5′-dicarboxaldehyde, yielding DA-CCP-1 and DA-CCP-2, respectively. DA-CCP-2, which possesses an extra-thiophene unit in the backbone, exhibits improved electrochemical characteristics when compared to DA-CCP-1, and performance surpassing those of other reported cathode materials for aqueous Zn2+ energy storage systems. DA-CCP-1 and -2 based electrodes exhibited an outstanding energy density of 80.6 and 196.3 W h kg−1 respectively, representing the highest value ever reached for conjugated polymers to date. This study not only offers new perspectives for the rational design and precise synthesis of DA-CCPs but it also broadens the choice of cathodes for high-performance aqueous Zn-HSCs. |
2022 |
Miao, J; Wu, L; Bian, Z; Zhu, Q; Zhang, T; Pan, X; Hu, J; Xu, W; Wang, Y; Xu, Y; Yu, B; Ji, W; Zhang, X; Qiao, J; P. Samorì, Zhao Y A “Click” Reaction to Engineer MoS2 Field-Effect Transistors with Low Contact Resistance Journal Article In: ACS Nano, pp. 20647–20655, 2022. @article{Miao2023, title = {A “Click” Reaction to Engineer MoS2 Field-Effect Transistors with Low Contact Resistance}, author = {J. Miao and L. Wu and Z. Bian and Q. Zhu and T. Zhang and X. Pan and J. Hu and W. Xu and Y. Wang and Y. Xu and B. Yu and W. Ji and X. Zhang and J. Qiao and P. Samorì, Y. Zhao}, editor = {ACS Publcation}, url = {https://doi.org/10.1021/acsnano.2c07670}, year = {2022}, date = {2022-12-16}, journal = {ACS Nano}, pages = {20647–20655}, abstract = {Two-dimensional (2D) materials with the atomically thin thickness have attracted great interest in the post-Moore’s Law era because of their tremendous potential to continue transistor downscaling and offered advances in device performance at the atomic limit. However, the metal–semiconductor contact is the bottleneck in field-effect transistors (FETs) integrating 2D semiconductors as channel materials. A robust and tunable doping method at the source and drain region of 2D transistors to minimize the contact resistance is highly sought after. Here we report a stable carrier doping method via the mild covalent grafting of maleimides on the surface of 2D transition metal dichalcogenides. The chemisorbed interaction contributes to the efficient carrier doping without degrading the high-performance carrier transport. Density functional theory results further illustrate that the molecular functionalization leads to the mild hybridization and the negligible impact on the conduction bands of monolayer MoS2, avoiding the random scattering from the dopants. Differently from reported molecular treatments, our strategy displays high thermal stability (above 300 °C) and it is compatible with micro/nano processing technology. The contact resistance of MoS2 FETs can be greatly reduced by ∼12 times after molecular functionalization. The Schottky barrier of 44 meV is achieved on monolayer MoS2 FETs, demonstrating efficient charge injection between metal and 2D semiconductor. The mild covalent functionalization of molecules on 2D semiconductors represents a powerful strategy to perform the carrier doping and the device optimization.}, keywords = {}, pubstate = {published}, tppubtype = {article} } Two-dimensional (2D) materials with the atomically thin thickness have attracted great interest in the post-Moore’s Law era because of their tremendous potential to continue transistor downscaling and offered advances in device performance at the atomic limit. However, the metal–semiconductor contact is the bottleneck in field-effect transistors (FETs) integrating 2D semiconductors as channel materials. A robust and tunable doping method at the source and drain region of 2D transistors to minimize the contact resistance is highly sought after. Here we report a stable carrier doping method via the mild covalent grafting of maleimides on the surface of 2D transition metal dichalcogenides. The chemisorbed interaction contributes to the efficient carrier doping without degrading the high-performance carrier transport. Density functional theory results further illustrate that the molecular functionalization leads to the mild hybridization and the negligible impact on the conduction bands of monolayer MoS2, avoiding the random scattering from the dopants. Differently from reported molecular treatments, our strategy displays high thermal stability (above 300 °C) and it is compatible with micro/nano processing technology. The contact resistance of MoS2 FETs can be greatly reduced by ∼12 times after molecular functionalization. The Schottky barrier of 44 meV is achieved on monolayer MoS2 FETs, demonstrating efficient charge injection between metal and 2D semiconductor. The mild covalent functionalization of molecules on 2D semiconductors represents a powerful strategy to perform the carrier doping and the device optimization. |
