Qiwei Gu,Yuntao Jie,Jia Liu,Ying Wang,Linna Sha,Meiling Xu,Xi-Guang Han
Simultaneously optimizing the disparate active sites for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is a critical yet unmet challenge in bifunctional electrocatalyst design. Herein, we demonstrate a heterointerface-vacancy co-engineering strategy to construct VSe-NiSe2/CoSe2@C, in which a built-in electric field (BIEF) and abundant Se vacancies are synergistically integrated at the heterointerface. Operando Raman analysis combined with density functional theory (DFT) calculations confirms that the BIEF-vacancy synergy drives directional electron transfer from NiSe2 to CoSe2 through interfacial Ni-Se-Co bridging bonds, concurrently triggering surface self-reconstruction for enhanced OER and tailoring the adsorption energetics at Co sites (for HER) and Ni sites (for OER). Consequently, a two-electrode electrolyzer assembled with VSe-NiSe2/CoSe2@C achieves a current density of 10 mA cm-2 at a cell voltage of 1.62 V and maintains robust performance for more than 200 h. This study highlights heterointerface-vacancy co-engineering as a generalizable design principle for high-performance bifunctional transition metal selenide electrocatalysts.
{"title":"Heterointerface-Vacancy Co-Engineering of VSe-NiSe2/CoSe2@C for Efficient Bifunctional Overall Water Splitting","authors":"Qiwei Gu,Yuntao Jie,Jia Liu,Ying Wang,Linna Sha,Meiling Xu,Xi-Guang Han","doi":"10.1039/d6ta06513a","DOIUrl":"https://doi.org/10.1039/d6ta06513a","url":null,"abstract":"Simultaneously optimizing the disparate active sites for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is a critical yet unmet challenge in bifunctional electrocatalyst design. Herein, we demonstrate a heterointerface-vacancy co-engineering strategy to construct VSe-NiSe2/CoSe2@C, in which a built-in electric field (BIEF) and abundant Se vacancies are synergistically integrated at the heterointerface. Operando Raman analysis combined with density functional theory (DFT) calculations confirms that the BIEF-vacancy synergy drives directional electron transfer from NiSe2 to CoSe2 through interfacial Ni-Se-Co bridging bonds, concurrently triggering surface self-reconstruction for enhanced OER and tailoring the adsorption energetics at Co sites (for HER) and Ni sites (for OER). Consequently, a two-electrode electrolyzer assembled with VSe-NiSe2/CoSe2@C achieves a current density of 10 mA cm-2 at a cell voltage of 1.62 V and maintains robust performance for more than 200 h. This study highlights heterointerface-vacancy co-engineering as a generalizable design principle for high-performance bifunctional transition metal selenide electrocatalysts.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"10 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Taking the full advantage of silicon (Si) as anode material for rechargeable lithium-ion batteries (LIBs), while keeping Si mechanically stable is ambitious and challenging. The intrinsic volume change of Si particles of up to 400 % during the lithiation and delithiation processes hinders Si to fully replace conventional graphite in commercial LIBs. Copper silicides act as buffer for the stabilization of Si after the lithiation. These phases can be generated using flash-lamp annealing (FLA) at a sub-second time regime after the deposition of Si on copper (Cu). In this work, we evaluate the potential of the FLA to achieve a higher energy density and cycle ability for LIBs. The CuSi-anode is fabricated by combining magnetron sputtering and millisecond-range FLA. Subsequently, its structure was analyzed by X-ray diffraction. Cu3Si and Cu7Si are identified, where Cu3Si is the most abundant phase. Transmission-electron-microscopy-based analyses show insights into the Cu silicides formation on two different substrates (Cu foil and Cu deposited on a Si wafer) that are intended to be used in different LIB systems. Herein, the tensile stress induced by the Cu3Si phase at the Si/Cu interface is visualized. Elastic recoil detection analysis measurements confirm the catalysis effect in the formation of an oxide which strongly consumes the lithium inventory in the first cycle. The morphology of the Si and CuSi anodes is investigated using scanning electron microscopy imaging. Finally, the battery performance using the Si and CuSi anodes is demonstrated, and the mechanical stability of the structure of the Si and Cu silicides phases in the post-mortem is analyzed using X-ray diffraction and energy-dispersive X-ray spectroscopy.
{"title":"Si anode processing using flash-lamp annealing for lithium-ion batteries","authors":"Charaf Cherkouk,Tina Weigel,Marc Ferch,Robert Hahn,Thomas Köhler,Hartmut Stöcker,Annekatrin Delan,René Hübner,Frans Munnik,Christoph Folgner,Slawomir Prucnal,Jawaid Hussain,Shengqiang Zhou,Lars Rebohle","doi":"10.1039/d6ta02935c","DOIUrl":"https://doi.org/10.1039/d6ta02935c","url":null,"abstract":"Taking the full advantage of silicon (Si) as anode material for rechargeable lithium-ion batteries (LIBs), while keeping Si mechanically stable is ambitious and challenging. The intrinsic volume change of Si particles of up to 400 % during the lithiation and delithiation processes hinders Si to fully replace conventional graphite in commercial LIBs. Copper silicides act as buffer for the stabilization of Si after the lithiation. These phases can be generated using flash-lamp annealing (FLA) at a sub-second time regime after the deposition of Si on copper (Cu). In this work, we evaluate the potential of the FLA to achieve a higher energy density and cycle ability for LIBs. The CuSi-anode is fabricated by combining magnetron sputtering and millisecond-range FLA. Subsequently, its structure was analyzed by X-ray diffraction. Cu3Si and Cu7Si are identified, where Cu3Si is the most abundant phase. Transmission-electron-microscopy-based analyses show insights into the Cu silicides formation on two different substrates (Cu foil and Cu deposited on a Si wafer) that are intended to be used in different LIB systems. Herein, the tensile stress induced by the Cu3Si phase at the Si/Cu interface is visualized. Elastic recoil detection analysis measurements confirm the catalysis effect in the formation of an oxide which strongly consumes the lithium inventory in the first cycle. The morphology of the Si and CuSi anodes is investigated using scanning electron microscopy imaging. Finally, the battery performance using the Si and CuSi anodes is demonstrated, and the mechanical stability of the structure of the Si and Cu silicides phases in the post-mortem is analyzed using X-ray diffraction and energy-dispersive X-ray spectroscopy.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"153 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Alkaline water electrolysis coupled with an external magnetic field is gaining significant attention for its ability to enhance the kinetics of electrochemical reactions and reduce energy loss. However, uncertainties remain in explaining and correlating the role of magnetic-fielddriven ferrimagnetic and ferromagnetic interactions at interface in enhancing electrocatalytic performance. Here, a facile, one-step synthesis of self-supported ferrimagnetic (FiM) Nickel Cobaltite (NiCo 2 O 4 ) electrocatalyst on a ferromagnetic (FM) Nickel Foam (NF) substrate via a hydrothermal process, resulting in a nanostructured, flower-like nanoneedles. The developed electrocatalyst offered HER and OER overpotentials for 10 mA cm -2 current density (η 10 ) of ~ 207 and 296 mV, respectively, without any external magnetic field. However, the HER and OER overpotentials (η 10 ) significantly dropped to 168 and 272 mV, respectively, under a weak external static magnetic field of 35 mT. Thus, significant boosts are observed in its HER and OER with enhancements of ~ 178 % and ~ 540 % in current density, respectively, attributed to magnetic gradients at the FiM/FM interface and in the diamagnetic electrolyte, which induce FiM-FM exchange coupling and ultimately reduce the charge-transfer resistance of the electrode. Overall, this work highlights the synergy between magnetic electrocatalysts and magnetic substrates for energy-efficient overall alkaline water electrolysis.
{"title":"Magneto-Enhanced Alkaline Water Electrolysis with Self-Supported Ferrimagnetic NiCo 2 O 4 on Magnetic Substrate","authors":"Minakshi Sharma,Vijay K Singh,Ambesh Dixit","doi":"10.1039/d6ta06349g","DOIUrl":"https://doi.org/10.1039/d6ta06349g","url":null,"abstract":"Alkaline water electrolysis coupled with an external magnetic field is gaining significant attention for its ability to enhance the kinetics of electrochemical reactions and reduce energy loss. However, uncertainties remain in explaining and correlating the role of magnetic-fielddriven ferrimagnetic and ferromagnetic interactions at interface in enhancing electrocatalytic performance. Here, a facile, one-step synthesis of self-supported ferrimagnetic (FiM) Nickel Cobaltite (NiCo 2 O 4 ) electrocatalyst on a ferromagnetic (FM) Nickel Foam (NF) substrate via a hydrothermal process, resulting in a nanostructured, flower-like nanoneedles. The developed electrocatalyst offered HER and OER overpotentials for 10 mA cm -2 current density (η 10 ) of ~ 207 and 296 mV, respectively, without any external magnetic field. However, the HER and OER overpotentials (η 10 ) significantly dropped to 168 and 272 mV, respectively, under a weak external static magnetic field of 35 mT. Thus, significant boosts are observed in its HER and OER with enhancements of ~ 178 % and ~ 540 % in current density, respectively, attributed to magnetic gradients at the FiM/FM interface and in the diamagnetic electrolyte, which induce FiM-FM exchange coupling and ultimately reduce the charge-transfer resistance of the electrode. Overall, this work highlights the synergy between magnetic electrocatalysts and magnetic substrates for energy-efficient overall alkaline water electrolysis.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"28 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225860","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
High-performance photodetectors require balancing sensitivity, speed, and cost, yet polycrystalline perovskites suffer from ion migration and high trap density, limiting photodetection performance. Here, we report an ionic-liquid assisted isothermal space-confined method using the green solvent MAAC to grow high-quality single-crystal MAPbBr3 films. Integrated into a scanning photodetection system, the resultant photodetector exhibits robust operation even under intense background light interference. Under 520 nm excitation, it achieves a responsivity (R) of 978.25 A/W, an external quantum efficiency (EQE) of 2.33 × 105 %, a detectivity (D*) of 2.43 × 1012 Jones, and a fast response time of 101 μs, with excellent stability over 2000 s. This work demonstrates the potential of single-crystal halide perovskites for high-performance photodetection and provides a universal fabrication strategy.
{"title":"Isothermal Space-Confined Green-Solvent Growth of MAPbBr3 Single Crystals for High-Performance Photodetectors","authors":"Jiamian Wang,Zihui Ran,Wenlong Zong,Jiarong Zhang,Tianwei Song,Caixia Xu,Haibin Sun,Long Xu","doi":"10.1039/d6ta07237b","DOIUrl":"https://doi.org/10.1039/d6ta07237b","url":null,"abstract":"High-performance photodetectors require balancing sensitivity, speed, and cost, yet polycrystalline perovskites suffer from ion migration and high trap density, limiting photodetection performance. Here, we report an ionic-liquid assisted isothermal space-confined method using the green solvent MAAC to grow high-quality single-crystal MAPbBr3 films. Integrated into a scanning photodetection system, the resultant photodetector exhibits robust operation even under intense background light interference. Under 520 nm excitation, it achieves a responsivity (R) of 978.25 A/W, an external quantum efficiency (EQE) of 2.33 × 105 %, a detectivity (D*) of 2.43 × 1012 Jones, and a fast response time of 101 μs, with excellent stability over 2000 s. This work demonstrates the potential of single-crystal halide perovskites for high-performance photodetection and provides a universal fabrication strategy.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"12 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225853","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Formic acid dehydrogenation (FADH) is highly potent strategy for industrial-scale H2 production at near-ambient P, T, thus development of efficient heterogeneous catalysts capable of promoting FADH is a forward-looking challenge. Herein, we demonstrate a molecular surface engineering approach to tailor anatase-TiO2 quantum dots through covalent grafting of phosphonate ligands bearing either imidazolium (Im) or diphenylphosphine (Phos) functionalities. Controlled surface-functionalization was achieved via phosphonate anchoring using either hydrothermal or microwave-assisted grafting, enabling tuning of the organic-inorganic interface.Beyond serving as surface modifiers, the phosphonate ligands regulate the local chemical environment of TiO2 by modifying the interfacial electronic structure and the distribution of catalytically accessible surface sites. Using Fe(II) as the metal-catalytic center, optimized {TiO2-QD-Phos/Fe} hybrid catalyst, achieves FADH performance with TON = 4580 and TOF = 3915 h-1. Spectroscopic and structural data allow comprehension of the role of TiO2 quantum dot size, grafting methodology, and ligand functionality as the key-factors that dictate structure-activity relationships. This demonstrating that the catalytic performance of {TiO2-QD-Phos/Fe} and {TiO2-QD-Im/Fe} originate from a synergistic interplay between TiO2 surface chemistry and the molecular architecture of the grafted phosphonate ligands. This work establishes phosphonate ligand engineering as a versatile strategy for controlling oxide surface reactivity and provides a general design platform for developing high-performance heterogeneous catalysts for hydrogen generation from liquid organic hydrogen carriers.
{"title":"Phosphonate Surface Engineering of TiO2 Quantum Dots for Highly Efficient Formic Acid Dehydrogenation","authors":"Christos Dimitriou,Christos Gkatziouras,Elodie Gioan,Maria Louloudi,Johan Gilbert Alauzun,Yiannis Deligiannakis","doi":"10.1039/d6ta06531g","DOIUrl":"https://doi.org/10.1039/d6ta06531g","url":null,"abstract":"Formic acid dehydrogenation (FADH) is highly potent strategy for industrial-scale H2 production at near-ambient P, T, thus development of efficient heterogeneous catalysts capable of promoting FADH is a forward-looking challenge. Herein, we demonstrate a molecular surface engineering approach to tailor anatase-TiO2 quantum dots through covalent grafting of phosphonate ligands bearing either imidazolium (Im) or diphenylphosphine (Phos) functionalities. Controlled surface-functionalization was achieved via phosphonate anchoring using either hydrothermal or microwave-assisted grafting, enabling tuning of the organic-inorganic interface.Beyond serving as surface modifiers, the phosphonate ligands regulate the local chemical environment of TiO2 by modifying the interfacial electronic structure and the distribution of catalytically accessible surface sites. Using Fe(II) as the metal-catalytic center, optimized {TiO2-QD-Phos/Fe} hybrid catalyst, achieves FADH performance with TON = 4580 and TOF = 3915 h-1. Spectroscopic and structural data allow comprehension of the role of TiO2 quantum dot size, grafting methodology, and ligand functionality as the key-factors that dictate structure-activity relationships. This demonstrating that the catalytic performance of {TiO2-QD-Phos/Fe} and {TiO2-QD-Im/Fe} originate from a synergistic interplay between TiO2 surface chemistry and the molecular architecture of the grafted phosphonate ligands. This work establishes phosphonate ligand engineering as a versatile strategy for controlling oxide surface reactivity and provides a general design platform for developing high-performance heterogeneous catalysts for hydrogen generation from liquid organic hydrogen carriers.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"22 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225903","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Understanding the true active sites and structure-performance relationships of Cu-based catalysts in electrochemical nitrate reduction reaction (NO3RR) remains challenging due to the dynamic reconstruction of copper oxides under operating conditions. Herein, density functional theory calculations combined with ab initio molecular dynamics, surface Pourbaix analysis, and microkinetic simulations were employed to systematically investigate the coupled effects of catalyst reconstruction, applied potential, and pH on NO3RR over Cu2O-derived surfaces. Progressive reduction of Cu2O induces substantial structural reconstruction and generates a series of defect-rich surfaces with distinct active-site configurations. The reconstructed surfaces exhibit markedly different NO3RR mechanisms and pathway distributions, governed by the transformation behavior of key intermediates such as *NO2 + *OH. The results reveal that deeply reduced surfaces expose pentagonal defect sites and square-step sites that serve as the primary active centers for NO3RR. Importantly, NH3 selectivity is found to be predominantly determined by the active-site configuration, while the competition between NO3RR and the hydrogen evolution reaction is mainly regulated by the applied potential and pH. Moderate cathodic potentials under acidic conditions provide the optimal balance between catalytic activity and NO3RR competitiveness. This work establishes a comprehensive framework that explicitly incorporates catalyst reconstruction and operating conditions into mechanistic analysis, offering atomic-level insight into the origin of NO3RR performance on Cu2O-derived catalysts and guiding the rational design of efficient nitrate reduction electrocatalysts.
{"title":"Origins of NO3RR Activity and Selectivity on Cu2O-Derived Catalysts: Interplay of Oxidation States, Surface Reconstruction, and Reaction Conditions","authors":"Han Zhou,Neil Qiang Su","doi":"10.1039/d6ta07588f","DOIUrl":"https://doi.org/10.1039/d6ta07588f","url":null,"abstract":"Understanding the true active sites and structure-performance relationships of Cu-based catalysts in electrochemical nitrate reduction reaction (NO3RR) remains challenging due to the dynamic reconstruction of copper oxides under operating conditions. Herein, density functional theory calculations combined with ab initio molecular dynamics, surface Pourbaix analysis, and microkinetic simulations were employed to systematically investigate the coupled effects of catalyst reconstruction, applied potential, and pH on NO3RR over Cu2O-derived surfaces. Progressive reduction of Cu2O induces substantial structural reconstruction and generates a series of defect-rich surfaces with distinct active-site configurations. The reconstructed surfaces exhibit markedly different NO3RR mechanisms and pathway distributions, governed by the transformation behavior of key intermediates such as *NO2 + *OH. The results reveal that deeply reduced surfaces expose pentagonal defect sites and square-step sites that serve as the primary active centers for NO3RR. Importantly, NH3 selectivity is found to be predominantly determined by the active-site configuration, while the competition between NO3RR and the hydrogen evolution reaction is mainly regulated by the applied potential and pH. Moderate cathodic potentials under acidic conditions provide the optimal balance between catalytic activity and NO3RR competitiveness. This work establishes a comprehensive framework that explicitly incorporates catalyst reconstruction and operating conditions into mechanistic analysis, offering atomic-level insight into the origin of NO3RR performance on Cu2O-derived catalysts and guiding the rational design of efficient nitrate reduction electrocatalysts.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"4 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149218208","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Zhaoyang Zhang,Yanan Qiao,Xuemin Cao,Houde She,Ziqian Gao,Lei Wang,Jingwei Huang,Qizhao Wang
Photothermal CO2 hydrogenation synergistically integrates the merits of photo- and thermocatalysis, offering a compelling strategy for CO2 valorization. However, the intrinsic inertness of CO2, along with the convoluted multi-electron transfer pathways, imposes significant kinetic limitations on the methanation process. Herein, by mechanically grinding MnOx with ultrathin g-C3N4 that was uniformly pre-decorated with Ru nanoparticles, a type-II heterojunction photothermal catalyst, denoted as Ru-C3N4/MnOx, was successfully constructed. Under photothermal synergistic operation, the optimized composite catalyst delivered an outstanding CH4 yield of 586.7 µmol g−1 h−1 with an exceptionally high selectivity of 99.5%, representing 5.2-fold and 4.6-fold enhancements relative to those of 7Ru-C3N4 and pristine MnOx, respectively. Experimental investigation reveals that the type-II heterojunction facilitates the spatial separation of photogenerated charge carriers driven by a built-in interfacial electric field, thereby effectively suppressing deleterious electron–hole recombination. Meanwhile, the LSPR effect induced by the Ru nanoparticles enhances light harvesting and photothermal conversion efficiency, while the incorporation of MnOx further optimizes the interfacial charge migration pathways. The synergistic interplay among these three pivotal factors dramatically boosts both the catalytic activity and selectivity for the photothermal catalytic hydrogenation of CO2 to methane.
{"title":"Ru-CN/MnO type-II heterojunction photothermal catalysts for highly selective CO methanation","authors":"Zhaoyang Zhang,Yanan Qiao,Xuemin Cao,Houde She,Ziqian Gao,Lei Wang,Jingwei Huang,Qizhao Wang","doi":"10.1039/d6ta07173b","DOIUrl":"https://doi.org/10.1039/d6ta07173b","url":null,"abstract":"Photothermal CO2 hydrogenation synergistically integrates the merits of photo- and thermocatalysis, offering a compelling strategy for CO2 valorization. However, the intrinsic inertness of CO2, along with the convoluted multi-electron transfer pathways, imposes significant kinetic limitations on the methanation process. Herein, by mechanically grinding MnOx with ultrathin g-C3N4 that was uniformly pre-decorated with Ru nanoparticles, a type-II heterojunction photothermal catalyst, denoted as Ru-C3N4/MnOx, was successfully constructed. Under photothermal synergistic operation, the optimized composite catalyst delivered an outstanding CH4 yield of 586.7 µmol g−1 h−1 with an exceptionally high selectivity of 99.5%, representing 5.2-fold and 4.6-fold enhancements relative to those of 7Ru-C3N4 and pristine MnOx, respectively. Experimental investigation reveals that the type-II heterojunction facilitates the spatial separation of photogenerated charge carriers driven by a built-in interfacial electric field, thereby effectively suppressing deleterious electron–hole recombination. Meanwhile, the LSPR effect induced by the Ru nanoparticles enhances light harvesting and photothermal conversion efficiency, while the incorporation of MnOx further optimizes the interfacial charge migration pathways. The synergistic interplay among these three pivotal factors dramatically boosts both the catalytic activity and selectivity for the photothermal catalytic hydrogenation of CO2 to methane.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"53 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225813","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Nikita Rao,Pitabash Sahoo,P S V R A Kishor,Adarsh Pathiyath,Aslam Kunhi Mohamed,Souradeep Gupta,Amrit Venkatesh,Sheetal Kumar Jain
Alkali-activated binders (AABs) are low-carbon footprint alternatives to ordinary Portland cement. Accelerated carbonation can further reduce CO2 emissions while enhancing the binding properties of AABs. However, the atomic-scale structural consequences of this process remain poorly resolved, particularly in multi-precursor systems incorporating soilderived clay minerals. We used multinuclear ( 27Al, 29Si, 1H, 23Na, and 43Ca) solid-state nuclear magnetic resonance (NMR) in combination with X-ray diffraction and Infrared spectroscopy to track local structural changes as a function of material precursors and carbonation of AABs in their practical conditions. 27Al and 29Si solid-state NMR show a carbonation-induced conversion of Al(IV) to Al(VI) sites along with increased branching and disorder in soil containing AABs. 1H–27Al cross-polarization NMR identify the conversion as originating at Brønsted acid sites of this framework. 1H NMR confirms the generation of bicarbonate ions upon CO2 dissolution, establishing dissolved protons as the chemical trigger for Al re-coordination. 23Na and 43Ca NMR reveal the concurrent consumption of charge-balancing Ca2+ and Na+ through carbonate precipitation, which destabilizes lower-connectivity silicate sites and drives crosslinking to Q3 and Q3(1Al) species, as confirmed by 29Si and 29Si–27Al heteronuclear correlation experiments. These results establish a molecular mechanism for carbonation in soil-containing AABs and unravel the key structural transformations using solid-state NMR. These insights into carbon sequestration in AABs and its impact on the local structures are critical to their binding properties.
{"title":"Carbonation-Driven Al(IV) to Al(VI) Conversion and Network Restructuring in Natural Clay-Based Alkali-Activated Binders","authors":"Nikita Rao,Pitabash Sahoo,P S V R A Kishor,Adarsh Pathiyath,Aslam Kunhi Mohamed,Souradeep Gupta,Amrit Venkatesh,Sheetal Kumar Jain","doi":"10.1039/d6ta04544h","DOIUrl":"https://doi.org/10.1039/d6ta04544h","url":null,"abstract":"Alkali-activated binders (AABs) are low-carbon footprint alternatives to ordinary Portland cement. Accelerated carbonation can further reduce CO2 emissions while enhancing the binding properties of AABs. However, the atomic-scale structural consequences of this process remain poorly resolved, particularly in multi-precursor systems incorporating soilderived clay minerals. We used multinuclear ( 27Al, 29Si, 1H, 23Na, and 43Ca) solid-state nuclear magnetic resonance (NMR) in combination with X-ray diffraction and Infrared spectroscopy to track local structural changes as a function of material precursors and carbonation of AABs in their practical conditions. 27Al and 29Si solid-state NMR show a carbonation-induced conversion of Al(IV) to Al(VI) sites along with increased branching and disorder in soil containing AABs. 1H–27Al cross-polarization NMR identify the conversion as originating at Brønsted acid sites of this framework. 1H NMR confirms the generation of bicarbonate ions upon CO2 dissolution, establishing dissolved protons as the chemical trigger for Al re-coordination. 23Na and 43Ca NMR reveal the concurrent consumption of charge-balancing Ca2+ and Na+ through carbonate precipitation, which destabilizes lower-connectivity silicate sites and drives crosslinking to Q3 and Q3(1Al) species, as confirmed by 29Si and 29Si–27Al heteronuclear correlation experiments. These results establish a molecular mechanism for carbonation in soil-containing AABs and unravel the key structural transformations using solid-state NMR. These insights into carbon sequestration in AABs and its impact on the local structures are critical to their binding properties.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"499 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The increasing interest in environmentally friendly, efficient, and cost-effective products is reviving the potential of bio-based precursors as a primary source of carbon materials in sustainable energy applications. Chitosan is the second most abundant polymer in nature and is derived from the various sources of living organisms, especially from aquatic species. Chitosan has an inherent nitrogen content, various structural forms, and multiple functional groups. However, there are still more characteristic features as catalyst materials, including structure-activity, electronic properties, and electrochemical activity that need to be explored. This review aims to comprehensively emphasize the importance of material properties and the process involved in the conversion of chitosan into carbon, including its molecular structure and degree of deacetylation, thermal degradation, pyrolysis and activation strategies, and electrochemical energy conversion and storage applications. In addition, under the sustainability aspects, including eco-friendly material development, life cycle assessment, and the role of the circular economy, are discussed to highlight the significance of chitosan-derived carbon in sustainable energy systems. Overall, this review underscores the potential of chitosan-derived carbon as a promising sustainable electrode material for electrochemical energy systems, demonstrating how advanced materials engineering approaches can further enhance the catalytic performance towards clean energy technologies.
{"title":"From polymer to power: Chitosan-derived carbon materials for sustainable energy systems – Design strategies and emerging applications","authors":"Kannan Mohan,Vivekanandan Krishnaswamy Ezhilan,A. Annam Renita,Vijayakumar Natesan,Gayathri Kaliyannan,Revathi Nagarajan,Narayanamoorthy Bhuvanendran,Sabariswaran Kandasamy","doi":"10.1039/d6ta07352b","DOIUrl":"https://doi.org/10.1039/d6ta07352b","url":null,"abstract":"The increasing interest in environmentally friendly, efficient, and cost-effective products is reviving the potential of bio-based precursors as a primary source of carbon materials in sustainable energy applications. Chitosan is the second most abundant polymer in nature and is derived from the various sources of living organisms, especially from aquatic species. Chitosan has an inherent nitrogen content, various structural forms, and multiple functional groups. However, there are still more characteristic features as catalyst materials, including structure-activity, electronic properties, and electrochemical activity that need to be explored. This review aims to comprehensively emphasize the importance of material properties and the process involved in the conversion of chitosan into carbon, including its molecular structure and degree of deacetylation, thermal degradation, pyrolysis and activation strategies, and electrochemical energy conversion and storage applications. In addition, under the sustainability aspects, including eco-friendly material development, life cycle assessment, and the role of the circular economy, are discussed to highlight the significance of chitosan-derived carbon in sustainable energy systems. Overall, this review underscores the potential of chitosan-derived carbon as a promising sustainable electrode material for electrochemical energy systems, demonstrating how advanced materials engineering approaches can further enhance the catalytic performance towards clean energy technologies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"74 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225858","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Suryakant Singh,Leydi M. Moreno,Hemraj Dahiya,Juan Angel Gallego Organero,Pilar de la Cruz,Fernando Langa,Ganesh D. Sharma,Supravat Karak
Self-powered organic photodetectors (OPDs) capable of broadband near-infrared (NIR) detection, rapid response, and reliable optical signal processing are highly desirable for nextgeneration optoelectronic communication technologies, yet achieving these characteristics simultaneously remains challenging. Here, a molecularly engineered fused diketopyrrolopyrrole (F-DPP)-based non-fullerene acceptor known as LM-1 is synthesised and incorporated into a PM6:Y6 host bulk heterojunction blend to realize a high-performance advance MSIM type transient ternary OPD (T-OPD). The enhanced π-conjugation and molecular planarity of LM-1 broaden the absorption profile and extend the photoresponse into the deep-NIR region. Coupled with electric-double-layer formation at the semiconductor/ionic-liquid-gel interface, the resulting device enables efficient charge separation and displacement-current-driven photodetection under zero external bias. The selfpowered T-OPD demonstrates broadband UV-NIR photodetection up to 1060 nm, ultra-low dark current, high weak-light sensitivity, and well-distinguished bipolar transient photoresponse. Rapid switching dynamics with microsecond-scale response times, a maximum -3 dB cutoff frequency of 415.69 kHz, and a signal-to-noise ratio up to 55.8 dB are achieved. Furthermore, the dual-transparent-electrode architecture enables bidirectional photodetection and reliable optical communication using both on-off keying and four-level pulse-amplitude modulation (PAM-4) across the UV-NIR spectral range. This work demonstrates a synergistic molecular-device engineering strategy for realizing broadband, low-noise, and high-speed self-powered T-OPD, providing a versatile platform for advanced optical communication, intelligent sensing, and next-generation photonic technologies.
{"title":"A Novel Fused Diketopyrrolopyrrole Non-Fullerene Acceptor Enabled MSIM Ternary Organic Photodetector for Self-Powered Broadband UV-NIR Detection and High-Speed Multilevel Optical Communication","authors":"Suryakant Singh,Leydi M. Moreno,Hemraj Dahiya,Juan Angel Gallego Organero,Pilar de la Cruz,Fernando Langa,Ganesh D. Sharma,Supravat Karak","doi":"10.1039/d6ta06256c","DOIUrl":"https://doi.org/10.1039/d6ta06256c","url":null,"abstract":"Self-powered organic photodetectors (OPDs) capable of broadband near-infrared (NIR) detection, rapid response, and reliable optical signal processing are highly desirable for nextgeneration optoelectronic communication technologies, yet achieving these characteristics simultaneously remains challenging. Here, a molecularly engineered fused diketopyrrolopyrrole (F-DPP)-based non-fullerene acceptor known as LM-1 is synthesised and incorporated into a PM6:Y6 host bulk heterojunction blend to realize a high-performance advance MSIM type transient ternary OPD (T-OPD). The enhanced π-conjugation and molecular planarity of LM-1 broaden the absorption profile and extend the photoresponse into the deep-NIR region. Coupled with electric-double-layer formation at the semiconductor/ionic-liquid-gel interface, the resulting device enables efficient charge separation and displacement-current-driven photodetection under zero external bias. The selfpowered T-OPD demonstrates broadband UV-NIR photodetection up to 1060 nm, ultra-low dark current, high weak-light sensitivity, and well-distinguished bipolar transient photoresponse. Rapid switching dynamics with microsecond-scale response times, a maximum -3 dB cutoff frequency of 415.69 kHz, and a signal-to-noise ratio up to 55.8 dB are achieved. Furthermore, the dual-transparent-electrode architecture enables bidirectional photodetection and reliable optical communication using both on-off keying and four-level pulse-amplitude modulation (PAM-4) across the UV-NIR spectral range. This work demonstrates a synergistic molecular-device engineering strategy for realizing broadband, low-noise, and high-speed self-powered T-OPD, providing a versatile platform for advanced optical communication, intelligent sensing, and next-generation photonic technologies.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"8 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-10-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149225862","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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