Rechargeable non-aqueous lithium–oxygen (Li–O2) batteries, owing to their high specific capacity and energy density, are among the most promising next-generation energy storage systems. However, their practical application is hindered by sluggish electrochemical kinetics and high charge/discharge overpotentials, highlighting the need for novel catalysts. In this study, first-principles calculations were employed to theoretically investigate the catalytic potential of pristine, B-doped, N-doped, and BN co-doped graphenylene (GP) nanosheets as metal-free cathode electrocatalysts. Optimized geometries along two nucleation pathways (leading to Li4O4 and Li4O2) and free energy profiles were computed to elucidate mechanisms and predict final discharge products, revealing that Li4O4 formation is thermodynamically favored in all structures. Charge/discharge voltages lie within a safe range preventing electrolyte decomposition. Among the catalysts, B-BNGP exhibits enhanced stability compared to the other configurations and graphene, with the lowest discharge/charge overpotentials (0.280 and 0.293 V), making it the most efficient cathodic catalyst for the ORR/OER. Adsorption patterns in the rate-determining step (RDS) serve as overpotential descriptors, while reduced adsorption energy correlates with lower overpotential. Using B-BNGP as a reference, activation barriers for catalytic decomposition of Li2O2 and Li4O4 were 1.627 and 1.769 eV, respectively, significantly lower than that for Li2O2 decomposition on graphene (2.06 eV), yielding a 1.9 × 107-fold increase in the reaction rate. Additionally, B-BNGP can mitigate the tendency toward Li2CO3 formation and dimethyl sulfoxide (DMSO) electrolyte decomposition, thereby enhancing cycling reversibility. Electronic structure analysis confirms the conductivity of these structures, highlighting GP-based nanosheets as promising bifunctional cathodic electrocatalysts for non-aqueous Li–O2 batteries.
{"title":"Theoretical evaluation of pristine, single B- and N-doped, and BN co-doped graphenylene as metal-free cathode catalysts for nonaqueous Li–O2 batteries","authors":"Sima Roshan, Adel Reisi-Vanani","doi":"10.1039/d5ta09080f","DOIUrl":"https://doi.org/10.1039/d5ta09080f","url":null,"abstract":"Rechargeable non-aqueous lithium–oxygen (Li–O<small><sub>2</sub></small>) batteries, owing to their high specific capacity and energy density, are among the most promising next-generation energy storage systems. However, their practical application is hindered by sluggish electrochemical kinetics and high charge/discharge overpotentials, highlighting the need for novel catalysts. In this study, first-principles calculations were employed to theoretically investigate the catalytic potential of pristine, B-doped, N-doped, and BN co-doped graphenylene (GP) nanosheets as metal-free cathode electrocatalysts. Optimized geometries along two nucleation pathways (leading to Li<small><sub>4</sub></small>O<small><sub>4</sub></small> and Li<small><sub>4</sub></small>O<small><sub>2</sub></small>) and free energy profiles were computed to elucidate mechanisms and predict final discharge products, revealing that Li<small><sub>4</sub></small>O<small><sub>4</sub></small> formation is thermodynamically favored in all structures. Charge/discharge voltages lie within a safe range preventing electrolyte decomposition. Among the catalysts, B-BNGP exhibits enhanced stability compared to the other configurations and graphene, with the lowest discharge/charge overpotentials (0.280 and 0.293 V), making it the most efficient cathodic catalyst for the ORR/OER. Adsorption patterns in the rate-determining step (RDS) serve as overpotential descriptors, while reduced adsorption energy correlates with lower overpotential. Using B-BNGP as a reference, activation barriers for catalytic decomposition of Li<small><sub>2</sub></small>O<small><sub>2</sub></small> and Li<small><sub>4</sub></small>O<small><sub>4</sub></small> were 1.627 and 1.769 eV, respectively, significantly lower than that for Li<small><sub>2</sub></small>O<small><sub>2</sub></small> decomposition on graphene (2.06 eV), yielding a 1.9 × 10<small><sup>7</sup></small>-fold increase in the reaction rate. Additionally, B-BNGP can mitigate the tendency toward Li<small><sub>2</sub></small>CO<small><sub>3</sub></small> formation and dimethyl sulfoxide (DMSO) electrolyte decomposition, thereby enhancing cycling reversibility. Electronic structure analysis confirms the conductivity of these structures, highlighting GP-based nanosheets as promising bifunctional cathodic electrocatalysts for non-aqueous Li–O<small><sub>2</sub></small> batteries.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"3 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122398","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}
Boyun Wang, Na Ju, Zhigang Zhang, Dongxiang Li, Chen Yang, Suyan Niu, You Fu, Wenlong Zhang, Zilong Liu, Lei Shi, Guangwen Xu, Hongbin Sun
Electrolyte engineering is essential for advancing lithium-ion batteries (LIBs). Here, we introduce a carbonate-based inner-salt ionic liquid additive, ethylene carbonate-activated 1-methylimidazole (MI-EC), that markedly enhances rate capability and cycling stability. Molecular dynamics and electrochemical analyses show that MI-EC strongly coordinates with Li+, increasing the lithium-ion transference number. Density functional theory (DFT) calculations reveal its favorable electronic structure (LUMO: −0.82 eV; HOMO: −5.91 eV), which enables preferential interfacial reactions, stable SEI/CEI formation, and suppression of solvent decomposition. With only 1 wt% MI-EC (ME-10), the LFP‖Li half-cell achieves 95.8% capacity retention after 500 cycles at 0.5C (27% higher than that in baseline electrolyte, BE), a 100 mV charge/discharge voltage gap, and 18.8% higher capacity than in BE at 10C. Complementary graphite‖Li and LFP‖graphite cells also deliver superior capacity and rate performance. These findings establish carbonate-based inner-salt ionic liquid additives as a promising route toward durable, high-performance LIB electrolytes.
{"title":"Boosting lithium-ion battery performance: the role of a novel carbonate-based ionic liquid electrolyte additive","authors":"Boyun Wang, Na Ju, Zhigang Zhang, Dongxiang Li, Chen Yang, Suyan Niu, You Fu, Wenlong Zhang, Zilong Liu, Lei Shi, Guangwen Xu, Hongbin Sun","doi":"10.1039/d5ta08243a","DOIUrl":"https://doi.org/10.1039/d5ta08243a","url":null,"abstract":"Electrolyte engineering is essential for advancing lithium-ion batteries (LIBs). Here, we introduce a carbonate-based inner-salt ionic liquid additive, ethylene carbonate-activated 1-methylimidazole (MI-EC), that markedly enhances rate capability and cycling stability. Molecular dynamics and electrochemical analyses show that MI-EC strongly coordinates with Li<small><sup>+</sup></small>, increasing the lithium-ion transference number. Density functional theory (DFT) calculations reveal its favorable electronic structure (LUMO: −0.82 eV; HOMO: −5.91 eV), which enables preferential interfacial reactions, stable SEI/CEI formation, and suppression of solvent decomposition. With only 1 wt% MI-EC (ME-10), the LFP‖Li half-cell achieves 95.8% capacity retention after 500 cycles at 0.5C (27% higher than that in baseline electrolyte, BE), a 100 mV charge/discharge voltage gap, and 18.8% higher capacity than in BE at 10C. Complementary graphite‖Li and LFP‖graphite cells also deliver superior capacity and rate performance. These findings establish carbonate-based inner-salt ionic liquid additives as a promising route toward durable, high-performance LIB electrolytes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"48 22 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146115973","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}
Jinxiu Wang, Jianyi Zhang, Hongyu Zhao, Xuan Jia, Jinsheng Chen
Elucidating the mechanisms of coexisting SO2 and H2O, especially H2O’s dual function in aggravating or mitigating SO2 poisoning pathways, is pivotal for the rational design of high-performance, poison-resistant low-temperature SCR catalysts. This study compared the tolerance, sulfur-containing species, and reactive oxygen species of Fe2O3 and α-MnO2 chosen as model catalysts in SO2 alone versus a combined SO2 and H2O atmosphere, and unveils the distinct effect mechanisms of H2O on Fe2O3 and α-MnO2. That is, H2O aggravates SO2 poisoning on Fe2O3 while H2O mitigates SO2 poisoning on α-MnO2 catalyst in SCR reaction at 150–250 °C. After 50 min of poison exposure at 200 °C, the NOx conversion of α-MnO2 decreased from 94.0% to ~64.9% with SO2, whereas that remained high at 90.4% upon co-exposure to SO2 and H2O. The dominant sulfur-containing species formed are verified as ABS on Fe2O3 and MnSO4 on α-MnO2, respectively. H2O exacerbates SO2 poisoning on Fe2O3 via the competitive adsorption against reactants. However, H2O mitigates SO2 poisoning of α-MnO2 complexly by suppressing SO2 oxidation to form more sulfites and simultaneously activating surface lattice oxygen by protons from H2O dissociation, which generates abundant oxygen vacancies for converting O2 into reactive oxygen species. H2O exclusively activates lattice oxygen on α-MnO2, attributable to its higher surface lattice oxygen mobility than Fe2O3. This study reveals the intrinsic mechanism of the dual roles of H2O in SCR catalysts, providing new design strategies for developing low-temperature NH3-SCR catalysts with enhanced resistance to H2O and SO2 poisoning.
{"title":"Unveiling the distinct effect mechanisms of H2O: Aggravating and mitigating SO2 poisoning of Fe2O3 and α-MnO2 catalysts in low-temperature NH3-SCR","authors":"Jinxiu Wang, Jianyi Zhang, Hongyu Zhao, Xuan Jia, Jinsheng Chen","doi":"10.1039/d5ta09146b","DOIUrl":"https://doi.org/10.1039/d5ta09146b","url":null,"abstract":"Elucidating the mechanisms of coexisting SO2 and H2O, especially H2O’s dual function in aggravating or mitigating SO2 poisoning pathways, is pivotal for the rational design of high-performance, poison-resistant low-temperature SCR catalysts. This study compared the tolerance, sulfur-containing species, and reactive oxygen species of Fe2O3 and α-MnO2 chosen as model catalysts in SO2 alone versus a combined SO2 and H2O atmosphere, and unveils the distinct effect mechanisms of H2O on Fe2O3 and α-MnO2. That is, H2O aggravates SO2 poisoning on Fe2O3 while H2O mitigates SO2 poisoning on α-MnO2 catalyst in SCR reaction at 150–250 °C. After 50 min of poison exposure at 200 °C, the NOx conversion of α-MnO2 decreased from 94.0% to ~64.9% with SO2, whereas that remained high at 90.4% upon co-exposure to SO2 and H2O. The dominant sulfur-containing species formed are verified as ABS on Fe2O3 and MnSO4 on α-MnO2, respectively. H2O exacerbates SO2 poisoning on Fe2O3 via the competitive adsorption against reactants. However, H2O mitigates SO2 poisoning of α-MnO2 complexly by suppressing SO2 oxidation to form more sulfites and simultaneously activating surface lattice oxygen by protons from H2O dissociation, which generates abundant oxygen vacancies for converting O2 into reactive oxygen species. H2O exclusively activates lattice oxygen on α-MnO2, attributable to its higher surface lattice oxygen mobility than Fe2O3. This study reveals the intrinsic mechanism of the dual roles of H2O in SCR catalysts, providing new design strategies for developing low-temperature NH3-SCR catalysts with enhanced resistance to H2O and SO2 poisoning.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"3 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116007","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 stability of quantum dots (QDs) is primarily limited by photooxidation of their surface, and the adsorption of water and oxygen significantly affects this. Under photoexcitation, adsorbed H2O and O2 undergo photochemical reactions with the QD surface, thereby accelerating oxidative degradation. Therefore, minimizing water and oxygen adsorption is crucial for improving the inherent stability of QDs. Herein, we reveal that excess halide ions adsorbed on indium phosphide (InP) QDs promote water adsorption through synergistic coordinative interactions and hydrogen bonding between the surface halides and atmospheric water molecules, which substantially increase surface water coverage and severely deteriorate the stability of InP QDs. To address this challenge, we propose a two-step surface-engineering strategy: (i) removing excess surface halide ions to eliminate the main driving force for water adsorption, and (ii) constructing a SiO2@TiO2 composite passivation layer, where TiO2 fills the mesopores within the SiO2 matrix while modulating the interfacial hydrophobicity. The resulting QD@SiO2@TiO2 nanocomposite utilizes a synergistic mechanism of “halide removal-composite passivation”, significantly improving its environmental and photochemical stability. The white-light-emitting diodes (WLEDs) fabricated using this material exhibit a T85 lifetime exceeding 530 hours, highlighting its enormous potential in QD-based optoelectronic device applications.
{"title":"Halide Removal and SiO 2 @TiO 2 Composite Passivation: Enhancing InP QD Photooxidation Stability for WLEDs","authors":"Yuyuan Fu, Yujie Song, Qixin Weng, Wenda Zhang, Changsheng Cao, Yujie Song","doi":"10.1039/d5ta09502f","DOIUrl":"https://doi.org/10.1039/d5ta09502f","url":null,"abstract":"The stability of quantum dots (QDs) is primarily limited by photooxidation of their surface, and the adsorption of water and oxygen significantly affects this. Under photoexcitation, adsorbed H2O and O2 undergo photochemical reactions with the QD surface, thereby accelerating oxidative degradation. Therefore, minimizing water and oxygen adsorption is crucial for improving the inherent stability of QDs. Herein, we reveal that excess halide ions adsorbed on indium phosphide (InP) QDs promote water adsorption through synergistic coordinative interactions and hydrogen bonding between the surface halides and atmospheric water molecules, which substantially increase surface water coverage and severely deteriorate the stability of InP QDs. To address this challenge, we propose a two-step surface-engineering strategy: (i) removing excess surface halide ions to eliminate the main driving force for water adsorption, and (ii) constructing a SiO2@TiO2 composite passivation layer, where TiO2 fills the mesopores within the SiO2 matrix while modulating the interfacial hydrophobicity. The resulting QD@SiO2@TiO2 nanocomposite utilizes a synergistic mechanism of “halide removal-composite passivation”, significantly improving its environmental and photochemical stability. The white-light-emitting diodes (WLEDs) fabricated using this material exhibit a T85 lifetime exceeding 530 hours, highlighting its enormous potential in QD-based optoelectronic device applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"56 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116068","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}
Sabiha Sultana, Krzysztof Szczubiałka, Marcin Pisarek, Grzegorz D. Sulka, Karolina Syrek
Lignin, an underutilized lignocellulosic biomass often considered waste, is a rich source of fuel and aromatic chemicals. Utilizing lignin for sunlight-induced photocatalytic reactions to produce high-value bulk and fine chemicals is regarded as a bio-based economically viable strategy. Herein, we report a facile preparation strategy for a one-dimensional metal-doped nanostructured TiO2 photocatalyst aimed at the selective conversion of lignin into valuable chemicals. Specifically, we successfully synthesized and applied metal-doped anodized TiO2 nanotubes (NTs) to efficiently convert lignin into valuable chemical feedstock, with a focus on cleaving the β–O–4 linkage. Various metal dopants (Cr, Fe, Co, and Cu) were incorporated into TiO2 NTs to enhance charge separation, improve charge transfer efficiency, and increase the availability of active sites responsible for lignin bond cleavage. Optical and photoelectrochemical (PEC) analyses revealed slight band edge modulation, which facilitates the generation of active species essential for lignin conversion. Selective conversion to vanillin, a high-value chemical, was achieved, with Ti-Ox sites and the 1D nanotubular structure playing crucial roles in the process. Additionally, the reusability of the doped TiO2 systems and the distinct effects of different metal dopants on the photocatalytic process were thoroughly investigated. Overall, this study presents metal-doped TiO2 NTs as a promising approach for the efficient and selective conversion of lignin into valuable chemical feedstock, contributing to sustainability and bio-based resource utilization.
{"title":"Selective photocatalytic conversion of lignin via metal-doped anodic TiO2 nanotubes","authors":"Sabiha Sultana, Krzysztof Szczubiałka, Marcin Pisarek, Grzegorz D. Sulka, Karolina Syrek","doi":"10.1039/d5ta07356a","DOIUrl":"https://doi.org/10.1039/d5ta07356a","url":null,"abstract":"Lignin, an underutilized lignocellulosic biomass often considered waste, is a rich source of fuel and aromatic chemicals. Utilizing lignin for sunlight-induced photocatalytic reactions to produce high-value bulk and fine chemicals is regarded as a bio-based economically viable strategy. Herein, we report a facile preparation strategy for a one-dimensional metal-doped nanostructured TiO<small><sub>2</sub></small> photocatalyst aimed at the selective conversion of lignin into valuable chemicals. Specifically, we successfully synthesized and applied metal-doped anodized TiO<small><sub>2</sub></small> nanotubes (NTs) to efficiently convert lignin into valuable chemical feedstock, with a focus on cleaving the β–O–4 linkage. Various metal dopants (Cr, Fe, Co, and Cu) were incorporated into TiO<small><sub>2</sub></small> NTs to enhance charge separation, improve charge transfer efficiency, and increase the availability of active sites responsible for lignin bond cleavage. Optical and photoelectrochemical (PEC) analyses revealed slight band edge modulation, which facilitates the generation of active species essential for lignin conversion. Selective conversion to vanillin, a high-value chemical, was achieved, with Ti-O<small><sub><em>x</em></sub></small> sites and the 1D nanotubular structure playing crucial roles in the process. Additionally, the reusability of the doped TiO<small><sub>2</sub></small> systems and the distinct effects of different metal dopants on the photocatalytic process were thoroughly investigated. Overall, this study presents metal-doped TiO<small><sub>2</sub></small> NTs as a promising approach for the efficient and selective conversion of lignin into valuable chemical feedstock, contributing to sustainability and bio-based resource utilization.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"58 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122313","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}
Modern electronic devices with multifunctional capabilities have greatly improved everyday comfort and convenience. However, their frequent use often leads to both physical and chemical degradation, ultimately diminishing device longevity and reliability. In contrast, biological systems possess a remarkable self-healing ability that enables survival and adaptability in unpredictable environments, an attribute largely absent in conventional electronic devices. To overcome this limitation, integrating self-healing materials into device design presents a promising approach to extend operational lifespan and maintain mechanical integrity, functionality, and electrical performance. Drawing inspiration from nature, researchers have refined innovative self-healing materials and device architectures that significantly intensify the durability, resilience, and safety of energy-harvesting, sensing, and storage systems. This review highlights recent advancements in the development of self-healing materials tailored for energy-related and sensing applications over the past decade. It aims to furnish an extensive understanding of materials, mechanisms, and device-level implementations, shaping the future of robust, next-generation electronics. We hope this review offers valuable insights to guide future innovations in smart electronic skin and energy devices, where enhanced self-healing and sensing capabilities can be synergistically combined for practical, real-world applications.
{"title":"Smart self-healing polymers: innovations in material design and applications for electronic skin and energy devices","authors":"Sundararajan Ashok Kumar, Manoj Singh Yadav, Subrata Karmakar, Aniruddha Kundu, Vinodkumar Etacheri, Satyajit Ratha, Vijay Kumar Pal, Surjit Sahoo","doi":"10.1039/d5ta09101b","DOIUrl":"https://doi.org/10.1039/d5ta09101b","url":null,"abstract":"Modern electronic devices with multifunctional capabilities have greatly improved everyday comfort and convenience. However, their frequent use often leads to both physical and chemical degradation, ultimately diminishing device longevity and reliability. In contrast, biological systems possess a remarkable self-healing ability that enables survival and adaptability in unpredictable environments, an attribute largely absent in conventional electronic devices. To overcome this limitation, integrating self-healing materials into device design presents a promising approach to extend operational lifespan and maintain mechanical integrity, functionality, and electrical performance. Drawing inspiration from nature, researchers have refined innovative self-healing materials and device architectures that significantly intensify the durability, resilience, and safety of energy-harvesting, sensing, and storage systems. This review highlights recent advancements in the development of self-healing materials tailored for energy-related and sensing applications over the past decade. It aims to furnish an extensive understanding of materials, mechanisms, and device-level implementations, shaping the future of robust, next-generation electronics. We hope this review offers valuable insights to guide future innovations in smart electronic skin and energy devices, where enhanced self-healing and sensing capabilities can be synergistically combined for practical, real-world applications.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"58 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146115972","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}
Electrochemical hydrogen peroxide (H₂O₂) synthesis via the two-electron oxygen reduction reaction (2e⁻ ORR) offers a promising alternative to the traditional anthraquinone process. Herein, we report a silver-based single-atom catalyst Ag(I) complexed within a polymeric carbon nitride (PCN) sheet (Ag-PCN) as a highly selective and durable electrocatalyst for H₂O₂ production. Ag-PCN exhibited excellent H₂O₂ selectivity in 0.1 M KHCO₃ and demonstrated operational stability for over 60 hours at 0.25 V vs. RHE. Under accelerated stress testing in 3% H₂O₂ solution, Ag-PCN showed remarkable chemical durability with only 1% weight loss over one week. In contrast, pristine PCN, although also selective for H₂O₂, exhibited a 9% weight loss under the same conditions, underscoring the critical role of Ag(I) complexation in enhancing catalyst durability.Notably, Ag-PCN delivered enhanced faradaic efficiency after oxidative stress test, attributed to structural and chemical modifications induced during the stress test. Furthermore, Ag-PCN demonstrates superior thermal stability compared to PCN. Density functional theory (DFT) calculations on a model heptazine Ag(I) complex revealed that Ag(I) serves as an active site, facilitating OOH* intermediate binding and mediating charge transfer from the PCN framework to the adsorbed species. Overall, Ag-PCN presents a unique composition with excellent selectivity and robust chemical and thermal stability, making it a promising catalyst for electrochemical peroxide production.
通过双电子氧还原反应（2e - ORR）电化学合成过氧化氢（H₂O₂）为传统的蒽醌工艺提供了一个有前途的替代方案。本文中，我们报道了一种银基单原子催化剂Ag(I)在聚合物碳氮（PCN）片（Ag-PCN）内络合，作为一种高选择性和耐用的氢氧生成电催化剂。Ag-PCN在0.1 M KHCO₃中表现出优异的H₂O₂选择性，并且在0.25 V比RHE下表现出超过60小时的运行稳定性。在3% h2o2溶液中的加速应力测试中，Ag-PCN表现出显著的化学耐久性，一周内重量仅减少1%。相比之下，原始PCN虽然对H₂O₂也有选择性，但在相同的条件下，其重量减轻了9%，这强调了Ag(I)络合在提高催化剂耐久性方面的关键作用。值得注意的是，Ag-PCN在氧化应激测试后表现出更高的法拉第效率，这是由于在应激测试期间引起的结构和化学修饰。此外，Ag-PCN表现出比PCN更好的热稳定性。密度泛函理论（DFT）计算表明，Ag(I)作为一个活性位点，促进OOH*的中间结合，并介导电荷从PCN框架转移到被吸附的物质。总的来说，Ag-PCN具有独特的组成，具有优异的选择性和强大的化学和热稳定性，使其成为电化学过氧化氢生产的有前途的催化剂。
{"title":"Silver Single Atom in Polymeric Carbon Nitride as a Stable and Selective Oxygen Reduction Electrocatalyst towards Hydrogen Peroxide Synthesis","authors":"Akanksha Gupta, Manoj Shanmugasundaram, Shilendra Kumar Sharma, Sudip Chakraborty, David Zitoun","doi":"10.1039/d5ta05965h","DOIUrl":"https://doi.org/10.1039/d5ta05965h","url":null,"abstract":"Electrochemical hydrogen peroxide (H₂O₂) synthesis via the two-electron oxygen reduction reaction (2e⁻ ORR) offers a promising alternative to the traditional anthraquinone process. Herein, we report a silver-based single-atom catalyst Ag(I) complexed within a polymeric carbon nitride (PCN) sheet (Ag-PCN) as a highly selective and durable electrocatalyst for H₂O₂ production. Ag-PCN exhibited excellent H₂O₂ selectivity in 0.1 M KHCO₃ and demonstrated operational stability for over 60 hours at 0.25 V vs. RHE. Under accelerated stress testing in 3% H₂O₂ solution, Ag-PCN showed remarkable chemical durability with only 1% weight loss over one week. In contrast, pristine PCN, although also selective for H₂O₂, exhibited a 9% weight loss under the same conditions, underscoring the critical role of Ag(I) complexation in enhancing catalyst durability.Notably, Ag-PCN delivered enhanced faradaic efficiency after oxidative stress test, attributed to structural and chemical modifications induced during the stress test. Furthermore, Ag-PCN demonstrates superior thermal stability compared to PCN. Density functional theory (DFT) calculations on a model heptazine Ag(I) complex revealed that Ag(I) serves as an active site, facilitating OOH* intermediate binding and mediating charge transfer from the PCN framework to the adsorbed species. Overall, Ag-PCN presents a unique composition with excellent selectivity and robust chemical and thermal stability, making it a promising catalyst for electrochemical peroxide production.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"9 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122372","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}
In this work, a novel 2D-Bi2S3/1D-SnO2, n-n heterostructure thin film was employed as a pseudocapacitive photoanode for enhanced solar energy utilization, yielding a significant improvement in energy storage performance. The three–electrode system delivered an areal capacitance of 15.22 mF/cm2 in 1M Na2SO4 electrolyte at 0.2 mA/cm2 under 1 Sun illumination, achieving 33% enhancement compared to dark conditions. In addition, the fabricated Bi2S3/SnO2||PEDOT:PSS asymmetric photo-assisted electrochromic supercapacitor device exhibited maximum areal capacitance of 1.78 mF/cm2 at 0.06 mA/cm2, which represents 2.5-fold increase over its performance in the dark (0.70 mF/cm2 at 0.06 mA/cm2). Under illumination, the device also showed areal energy density (Ea) of 0.8 mWh/cm2 and areal power density (Pa) of 356 mW/cm2. The device maintained excellent cyclic stability, with capacitance retention of 82.2% and 77.2% at 0.2 mA/cm2 after 1000 GCD cycles under dark and illumination. Mechanistic investigations revealed that the intercalation/de-intercalation of Na+ ions into the 2D Bi2S3 (Bi2S3 + xNa+ + xe- ↔ NaxBi2S3) and SO42- ions into PEDOT:PSS chain during the charge-discharge process were facilitated by photon-induced redox activity and efficient charge separation by SnO2 nanorods, thereby improving energy storage capability. This study underscores the potential of novel heterostructure design and material combinations for the development of next-generation photo-rechargeable supercapacitors, paving the way for self-powered electronic devices.
{"title":"Unleashing potential of novel 2D-Bi2S3/1D-SnO2 heterostructure thin film anode for light-fostered asymmetric electrochromic supercapacitor","authors":"Manopriya Samtham, Aayushi Miglani, Ajay Patil, Venkatesh Dharavath, Santosh Bimli, Himanshu Srivastava, Ravindra Jangir, Yuan-Ron Ma Ma, Ram Janay Choudhary, Rupesh S. Devan","doi":"10.1039/d5ta09838f","DOIUrl":"https://doi.org/10.1039/d5ta09838f","url":null,"abstract":"In this work, a novel 2D-Bi2S3/1D-SnO2, n-n heterostructure thin film was employed as a pseudocapacitive photoanode for enhanced solar energy utilization, yielding a significant improvement in energy storage performance. The three–electrode system delivered an areal capacitance of 15.22 mF/cm2 in 1M Na2SO4 electrolyte at 0.2 mA/cm2 under 1 Sun illumination, achieving 33% enhancement compared to dark conditions. In addition, the fabricated Bi2S3/SnO2||PEDOT:PSS asymmetric photo-assisted electrochromic supercapacitor device exhibited maximum areal capacitance of 1.78 mF/cm2 at 0.06 mA/cm2, which represents 2.5-fold increase over its performance in the dark (0.70 mF/cm2 at 0.06 mA/cm2). Under illumination, the device also showed areal energy density (Ea) of 0.8 mWh/cm2 and areal power density (Pa) of 356 mW/cm2. The device maintained excellent cyclic stability, with capacitance retention of 82.2% and 77.2% at 0.2 mA/cm2 after 1000 GCD cycles under dark and illumination. Mechanistic investigations revealed that the intercalation/de-intercalation of Na+ ions into the 2D Bi2S3 (Bi2S3 + xNa+ + xe- ↔ NaxBi2S3) and SO42- ions into PEDOT:PSS chain during the charge-discharge process were facilitated by photon-induced redox activity and efficient charge separation by SnO2 nanorods, thereby improving energy storage capability. This study underscores the potential of novel heterostructure design and material combinations for the development of next-generation photo-rechargeable supercapacitors, paving the way for self-powered electronic devices.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"46 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146115971","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}
Fan Zhang, Meiting Gao, Yingying Lan, Jiake Wei, Zhongzhi Yuan, Wengang Lv, Wenlong Wang
Fluorinated carbon (CFx) stands out as a promising cathode material for lithium primary batteries, owing to its ultra-high specific capacity and energy density. However, the role of defects in CFx, which is crucial to shape its electrochemical properties, remains insufficiently explored, especially for different CFx forms such as layered fluorinated graphite (FG) and newly emerged fluorinated hard carbon (FHC) with disordered structure. This study systematically compares these two representative CFx materials in electronic structures and elucidates how distinct defect types regulate their electrochemical kinetics. Through comprehensive optical spectroscopy and structural characterizations, we revealed that FHC exhibits more pronounced excitation-energy dependent photoluminescence shifts, indicative of carbon-cluster-like defects. In contrast, FG displays optical signatures dominated by point-defect induced tail states. The fundamental differences in defect properties correlate well with cathodes’ electrochemical behaviour: FHC’s carbon-cluster defects leads to higher electrical conductivity, more favorable Li+ ion transport kinetics and higher operational voltages, while FG's point defects result in relatively increased electrochemical polarization and kinetic limitations. These findings establish a direct link between defect engineering and macroscopic battery performance, paving the way for rationally designing high performance CFx cathodes.
{"title":"Why Tail States Matter? Impact of Defect Types on the Electrochemical Kinetics of CFx Cathodes","authors":"Fan Zhang, Meiting Gao, Yingying Lan, Jiake Wei, Zhongzhi Yuan, Wengang Lv, Wenlong Wang","doi":"10.1039/d5ta09875k","DOIUrl":"https://doi.org/10.1039/d5ta09875k","url":null,"abstract":"Fluorinated carbon (CFx) stands out as a promising cathode material for lithium primary batteries, owing to its ultra-high specific capacity and energy density. However, the role of defects in CFx, which is crucial to shape its electrochemical properties, remains insufficiently explored, especially for different CFx forms such as layered fluorinated graphite (FG) and newly emerged fluorinated hard carbon (FHC) with disordered structure. This study systematically compares these two representative CFx materials in electronic structures and elucidates how distinct defect types regulate their electrochemical kinetics. Through comprehensive optical spectroscopy and structural characterizations, we revealed that FHC exhibits more pronounced excitation-energy dependent photoluminescence shifts, indicative of carbon-cluster-like defects. In contrast, FG displays optical signatures dominated by point-defect induced tail states. The fundamental differences in defect properties correlate well with cathodes’ electrochemical behaviour: FHC’s carbon-cluster defects leads to higher electrical conductivity, more favorable Li+ ion transport kinetics and higher operational voltages, while FG's point defects result in relatively increased electrochemical polarization and kinetic limitations. These findings establish a direct link between defect engineering and macroscopic battery performance, paving the way for rationally designing high performance CFx cathodes.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"89 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146115974","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}
Manoj Kumar Panjwani, Shah Muhammad Ahmadzai, Junjie Li, Zhipeng Luo, Ghada Eshaq, Ke Xiao, Huabin Zeng
The performance of atomically dispersed catalysts, especially single-atom catalysts (SACs) have attracted increasing attention due to their atomically dispersed active sites, which are closely related to the local electronic structure of their active sites. Although the introduction of heteroatoms, such as phosphorus, boron, or sulfur, can break the symmetric configuration of conventional transition metal-nitrogen (M-N4) sites, redistribute the charge density, and modulate the oxidation states of metal centers, systematic correlations between the dopant electronegativity, coordination-shell position, and reactive oxygen species (ROS) selectivity remain ambiguous. Mechanistic opinion suggests that the electronegativity mismatch between the dopant and the metal, as well as the dopant's spatial location, plays a crucial role in determining the charge-transfer polarity and, consequently, ROS selectivity. Based on the density functional theory, advanced spectroscopic techniques, and catalytic performance studies, this review proposes the guiding principles linking the characteristics of the dopants to ROS selectivity, which provides the conceptual basis for the rational design of next-generation SACs for selective PMS activation, and outline the major issues that remain in practice, such as long-term catalyst stability and catalyst scaling beyond laboratory conditions.
{"title":"Heteroatom Doping Strategies in Single-Atom Catalysts: Tuning Electronic Structure for Selective Peroxymonosulfate Activation","authors":"Manoj Kumar Panjwani, Shah Muhammad Ahmadzai, Junjie Li, Zhipeng Luo, Ghada Eshaq, Ke Xiao, Huabin Zeng","doi":"10.1039/d6ta00071a","DOIUrl":"https://doi.org/10.1039/d6ta00071a","url":null,"abstract":"The performance of atomically dispersed catalysts, especially single-atom catalysts (SACs) have attracted increasing attention due to their atomically dispersed active sites, which are closely related to the local electronic structure of their active sites. Although the introduction of heteroatoms, such as phosphorus, boron, or sulfur, can break the symmetric configuration of conventional transition metal-nitrogen (M-N4) sites, redistribute the charge density, and modulate the oxidation states of metal centers, systematic correlations between the dopant electronegativity, coordination-shell position, and reactive oxygen species (ROS) selectivity remain ambiguous. Mechanistic opinion suggests that the electronegativity mismatch between the dopant and the metal, as well as the dopant's spatial location, plays a crucial role in determining the charge-transfer polarity and, consequently, ROS selectivity. Based on the density functional theory, advanced spectroscopic techniques, and catalytic performance studies, this review proposes the guiding principles linking the characteristics of the dopants to ROS selectivity, which provides the conceptual basis for the rational design of next-generation SACs for selective PMS activation, and outline the major issues that remain in practice, such as long-term catalyst stability and catalyst scaling beyond laboratory conditions.","PeriodicalId":82,"journal":{"name":"Journal of Materials Chemistry A","volume":"1 1","pages":""},"PeriodicalIF":11.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116067","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：