Hydroxyl-yne click polymerization is a highly atom-economic and powerful tool for constructing sequence-controlled and structure-diverse unsaturated polymers. However, the cis/trans stereochemistry remains underdeveloped, thus lacking a stereodivergent synthesis of stereo-controlled polymers. Herein we first report the organocatalyzed stereo-controlled phenol-yne click polymerization of bio-derived diphenols and dipropiolates by judiciously changing the substrates, catalysts, and reaction solvents. Various sequence- and stereo-controlled poly(vinyl ether ester)s were effectively synthesized under mild reaction conditions, in which the trans content in the polymeric backbone can be proportionally altered in the range of 46~100%. More importantly, the bulk properties of these materials such as thermal (Td, 5% of 329~362 oC; Tg of 48~92 oC), mechanical (ultimate tensile strengths of 41~89 MPa, tensile moduli of 960~1991 MPa and elongations at break of 71~242%), and transport properties (oxygen transmission rates of 0.2~0.3 bar and water vapour transmission rates of 1.3~2.8 g mm m-2 day-1) can be tuned broadly. Moreover, the installed dynamic acetal moieties contribute to the excellent degradability and recyclability of these materials. This study provides an efficient and sustainable strategy for synthesizing stereo-regulated biopolymers with closed-loop recyclability, thereby expanding the chemical diversity of click polymers with structure-controlled and tailored properties.
{"title":"Stereo-controlled Phenol-yne Click Polymerization Towards High-performance Bioplastics with Closed-loop Recyclability","authors":"Wei Chen, Tong-Qiang Teng, Ming-Yang Yang, Tian-Jun Yue, Wei-Min Ren, Xiao-Bing Lu, Hui Zhou","doi":"10.1002/anie.202502416","DOIUrl":"https://doi.org/10.1002/anie.202502416","url":null,"abstract":"Hydroxyl-yne click polymerization is a highly atom-economic and powerful tool for constructing sequence-controlled and structure-diverse unsaturated polymers. However, the cis/trans stereochemistry remains underdeveloped, thus lacking a stereodivergent synthesis of stereo-controlled polymers. Herein we first report the organocatalyzed stereo-controlled phenol-yne click polymerization of bio-derived diphenols and dipropiolates by judiciously changing the substrates, catalysts, and reaction solvents. Various sequence- and stereo-controlled poly(vinyl ether ester)s were effectively synthesized under mild reaction conditions, in which the trans content in the polymeric backbone can be proportionally altered in the range of 46~100%. More importantly, the bulk properties of these materials such as thermal (Td, 5% of 329~362 oC; Tg of 48~92 oC), mechanical (ultimate tensile strengths of 41~89 MPa, tensile moduli of 960~1991 MPa and elongations at break of 71~242%), and transport properties (oxygen transmission rates of 0.2~0.3 bar and water vapour transmission rates of 1.3~2.8 g mm m-2 day-1) can be tuned broadly. Moreover, the installed dynamic acetal moieties contribute to the excellent degradability and recyclability of these materials. This study provides an efficient and sustainable strategy for synthesizing stereo-regulated biopolymers with closed-loop recyclability, thereby expanding the chemical diversity of click polymers with structure-controlled and tailored properties.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"125 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143713680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Tingqiang Yang, Matthias Boepple, Anne Hémeryck, Antoine Jay, Sara Karwounopoulos, Udo Weimar, Nicolae Barsan
Real-time detection of toxic and flammable H2S remains challenging for cost-effective semiconducting metal oxide (SMOX) sensors due to the insufficient focus on and inherently poor understanding of sulfur-poisoning effect. This research, focusing on SnO2 as a model for SMOX sensors, identifies the formation of sticky sulfite and sulfate surface species as root cause of poisoning through the detailed analyses of results obtained from operando DRIFTS experiments and DFT calculations. The formation of the poisoning species is highly energetically favorable. Meanwhile, the decomposition of sulfite and sulfate appears unfavorable at the typical operating temperature of 300 °C and is only feasible around the literature-reported 500°C. The sulfur poisoning effect is also likely to occur with SO2 and other sulfur-containing volatile organic compounds. Overcoming this issue is expected to require surface additives and/or alternative SMOX materials capable of providing different reaction pathways. The significance of metal-sulfur-oxygen chemistry extends beyond SMOX gas sensors to desulfurization catalysts, denitration catalysts, and solid oxide fuel cells.
{"title":"H2S Sensing with SnO2-Based Gas Sensors: Sulfur Poisoning Mechanism Revealed by Operando DRIFTS and DFT Calculations","authors":"Tingqiang Yang, Matthias Boepple, Anne Hémeryck, Antoine Jay, Sara Karwounopoulos, Udo Weimar, Nicolae Barsan","doi":"10.1002/anie.202504696","DOIUrl":"https://doi.org/10.1002/anie.202504696","url":null,"abstract":"Real-time detection of toxic and flammable H2S remains challenging for cost-effective semiconducting metal oxide (SMOX) sensors due to the insufficient focus on and inherently poor understanding of sulfur-poisoning effect. This research, focusing on SnO2 as a model for SMOX sensors, identifies the formation of sticky sulfite and sulfate surface species as root cause of poisoning through the detailed analyses of results obtained from operando DRIFTS experiments and DFT calculations. The formation of the poisoning species is highly energetically favorable. Meanwhile, the decomposition of sulfite and sulfate appears unfavorable at the typical operating temperature of 300 °C and is only feasible around the literature-reported 500°C. The sulfur poisoning effect is also likely to occur with SO2 and other sulfur-containing volatile organic compounds. Overcoming this issue is expected to require surface additives and/or alternative SMOX materials capable of providing different reaction pathways. The significance of metal-sulfur-oxygen chemistry extends beyond SMOX gas sensors to desulfurization catalysts, denitration catalysts, and solid oxide fuel cells.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"41 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143703583","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The coordination number (CN) in atomic cluster (AC) catalysts endows their catalytic performance with flexible tunability. However, the quantitative relationship between the coordination number (CN) and catalytic activity of atomic cluster (AC) catalysts remains ambiguity. Herein, inspired by the gardeners trimming plants branches to obtain ornamental value shape. We propose a “directional trimming” strategy to obtain a series of AC catalysts with wide range of Cl CN and establish an inverted volcano curve to explain the effect of CN on hydrogen evolution reaction (HER). Moreover, Pt/CB‐90 (moderate Cl CN of 3.7) exhibits the lowest overpotential of 22.94 mV at 10 mA cm‐2 and outstanding mass activity (25 times to commercial Pt/C). This proposed synthesis strategy fully utilizes the precursor atoms and is widely applicable. The reaction liquid can be reused up to 20 times to obtain 1130 mg catalysts without introducing any other chemicals. Additionally, Theoretical calculations highlight the appropriate Cl CN benefits the HER on Pt2 ACs. This fundamental understanding of the role of CN in catalytic activity offers valuable guidance to promote performance in various catalytic reactions.
{"title":"Simple \"Directional Trimming\" Strategy engineered Platinum Atomic Clusters with Controllable Coordination Numbers for Efficient Hydrogen Evolution","authors":"Fengkun Hao, Jing Zhong, Fengqian Hao, Shaorou Ke, Yanghong Li, Zhengyi Mao, Yunhu He, Tengshijie Gao, Linlin Wang, Shuohan Li, Minghao Fang, Zhaohui Huang, Xiaoxue Chang, Ruiwen Shao, Jian Lu, Xin Min","doi":"10.1002/anie.202504828","DOIUrl":"https://doi.org/10.1002/anie.202504828","url":null,"abstract":"The coordination number (CN) in atomic cluster (AC) catalysts endows their catalytic performance with flexible tunability. However, the quantitative relationship between the coordination number (CN) and catalytic activity of atomic cluster (AC) catalysts remains ambiguity. Herein, inspired by the gardeners trimming plants branches to obtain ornamental value shape. We propose a “directional trimming” strategy to obtain a series of AC catalysts with wide range of Cl CN and establish an inverted volcano curve to explain the effect of CN on hydrogen evolution reaction (HER). Moreover, Pt/CB‐90 (moderate Cl CN of 3.7) exhibits the lowest overpotential of 22.94 mV at 10 mA cm‐2 and outstanding mass activity (25 times to commercial Pt/C). This proposed synthesis strategy fully utilizes the precursor atoms and is widely applicable. The reaction liquid can be reused up to 20 times to obtain 1130 mg catalysts without introducing any other chemicals. Additionally, Theoretical calculations highlight the appropriate Cl CN benefits the HER on Pt2 ACs. This fundamental understanding of the role of CN in catalytic activity offers valuable guidance to promote performance in various catalytic reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702855","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Molecular glue (MG) degraders, small molecules with significant therapeutic potential for targeting undruggable proteins, are emerging as new modality in drug discovery. Profiling the E3 ligase interactome induced by MG degraders provides insights into their mechanism of action and identifies clinically relevant neo‐substrates for degradation, thereby offering new therapeutic opportunities. However, established methods face significant challenges in comprehensive and accurate profiling of MG degrader‐induced E3 ligase interactome. Herein, we introduce the concept of globally crosslinking profiling of the MG degrader‐induced E3 ligase interactome in living cells, achieved by integrating genetic code expansion technology with mass spectrometry‐based proteomics. Our approach presents an efficient and robust strategy for identifying neo‐substrates recruited to cereblon E3 ligase by the known degraders CC‐885 and DKY709, offering valuable insights for clinical evaluation and significantly expanding their target space. Moreover, we developed two novel MG degraders with potent anti‐proliferative effects on cancer cells, and application of our method identified neo‐substrates, revealing a previously unrecognized target landscape and advancing our understanding of E3 ligase–neo‐substrate interactions. Overall, our study provides a powerful tool for neo‐substrate identification and expanding target space of E3 ligase, opening new opportunities for developing next‐generation MG degraders to address the clinical challenge of undruggable targets.
{"title":"Crosslinking Profiling of Molecular Glue Degrader‐Induced E3 Ligase Interactome to Expand Target Space","authors":"Yali Xu, Wensi Zhao, Hui-Jun Nie, Jiamin Wang, Jingjing Fu, Hao Hu, Zihao Liu, Shengna Tao, Mingya Zhang, Yubo Zhou, Jia Li, Minjia Tan, Xiao-Hua Chen","doi":"10.1002/anie.202505053","DOIUrl":"https://doi.org/10.1002/anie.202505053","url":null,"abstract":"Molecular glue (MG) degraders, small molecules with significant therapeutic potential for targeting undruggable proteins, are emerging as new modality in drug discovery. Profiling the E3 ligase interactome induced by MG degraders provides insights into their mechanism of action and identifies clinically relevant neo‐substrates for degradation, thereby offering new therapeutic opportunities. However, established methods face significant challenges in comprehensive and accurate profiling of MG degrader‐induced E3 ligase interactome. Herein, we introduce the concept of globally crosslinking profiling of the MG degrader‐induced E3 ligase interactome in living cells, achieved by integrating genetic code expansion technology with mass spectrometry‐based proteomics. Our approach presents an efficient and robust strategy for identifying neo‐substrates recruited to cereblon E3 ligase by the known degraders CC‐885 and DKY709, offering valuable insights for clinical evaluation and significantly expanding their target space. Moreover, we developed two novel MG degraders with potent anti‐proliferative effects on cancer cells, and application of our method identified neo‐substrates, revealing a previously unrecognized target landscape and advancing our understanding of E3 ligase–neo‐substrate interactions. Overall, our study provides a powerful tool for neo‐substrate identification and expanding target space of E3 ligase, opening new opportunities for developing next‐generation MG degraders to address the clinical challenge of undruggable targets.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"93 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702856","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Ziliang Chen, Hongyuan Yang, J. Niklas Hausmann, Stefan Mebs, Viktor Hlukhyy, Holger Dau, Matthias Driess, Prashanth W. Menezes
Discovering novel oxygen evolution reaction (OER) (pre)catalysts with exceptional catalytic activity and long‐term stability is pivotal for advancing technologies aimed at decarbonization. In this study, we present the ternary Ba8Ni6Ge40 phase with a clathrate structure exhibiting remarkable performance in alkaline OER. When integrated into an alkaline water electrolyzer, this clathrate precatalyst achieves high stability under a sustained current density of ~550 mA cm–2 for 10 days. By combining in‐situ Raman spectroscopy, quasi in‐situ X‐ray absorption spectroscopy, and (micro)structural characterizations, we elucidate the complete electrochemical transformation of Ba8Ni6Ge40 forming ultrathin nanosheets composed of a porous and defective NiOOH nanostructure with maximized accessible active site exposure. Notably, a reversible phase transition mainly between Ni(OH)2 and NiOOH has also been established in the electrochemical redox process. Meanwhile, the successful application of the model Ba8Ni6Ge40 precatalyst represents a promising new class of functional inorganic materials for water electrolysis.
{"title":"Ba‐Ni‐Ge Clathrate Transformation Maximizes Active Site Utilization of Nickel for Enhanced Oxygen Evolution Performance","authors":"Ziliang Chen, Hongyuan Yang, J. Niklas Hausmann, Stefan Mebs, Viktor Hlukhyy, Holger Dau, Matthias Driess, Prashanth W. Menezes","doi":"10.1002/anie.202424743","DOIUrl":"https://doi.org/10.1002/anie.202424743","url":null,"abstract":"Discovering novel oxygen evolution reaction (OER) (pre)catalysts with exceptional catalytic activity and long‐term stability is pivotal for advancing technologies aimed at decarbonization. In this study, we present the ternary Ba8Ni6Ge40 phase with a clathrate structure exhibiting remarkable performance in alkaline OER. When integrated into an alkaline water electrolyzer, this clathrate precatalyst achieves high stability under a sustained current density of ~550 mA cm–2 for 10 days. By combining in‐situ Raman spectroscopy, quasi in‐situ X‐ray absorption spectroscopy, and (micro)structural characterizations, we elucidate the complete electrochemical transformation of Ba8Ni6Ge40 forming ultrathin nanosheets composed of a porous and defective NiOOH nanostructure with maximized accessible active site exposure. Notably, a reversible phase transition mainly between Ni(OH)2 and NiOOH has also been established in the electrochemical redox process. Meanwhile, the successful application of the model Ba8Ni6Ge40 precatalyst represents a promising new class of functional inorganic materials for water electrolysis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702666","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Lithium superionic conductors are pivotal for enabling all‐solid‐state batteries, which aim to replace liquid electrolytes and enhance safety. Herein, we report the discovery of an unprecedented lithium superionic conductor, Li21Ge8P3S34, featuring a novel structural type and a new composition in the Li–Ge–P–S system. This material exhibits high lithium ionic conductivity of approximately 1.0 mS cm−1 at 303 K with a low activation energy of 0.20(1) eV. Its unique crystal structure was elucidated using three‐dimensional electron diffraction (3D ED) and further refined through combined powder X‐ray and neutron diffraction analyses. The structure consists of alternating two‐dimensional slabs: one of corner‐sharing GeS4 tetrahedra and the other of isolated PS4 tetrahedra, enabling efficient lithium‐ion transport through a tetrahedrally interconnected network of 1D, 2D, and 3D diffusion pathways. This distinctive structural motif provides a novel design strategy for next‐generation solid electrolytes, broadening the structural landscape of lithium superionic conductors. With further advancements in compositional tuning and interfacial engineering, Li21Ge8P3S34 could contribute to the development of high‐performance all‐solid‐state batteries.
{"title":"Li21Ge8P3S34: New Lithium Superionic Conductor with Unprecedented Structural Type","authors":"Jihun Roh, Saleh Gholam, Namgyu Do, Alicia Manjón-Sanz, Joke Hadermann, Seung-Tae Hong","doi":"10.1002/anie.202500732","DOIUrl":"https://doi.org/10.1002/anie.202500732","url":null,"abstract":"Lithium superionic conductors are pivotal for enabling all‐solid‐state batteries, which aim to replace liquid electrolytes and enhance safety. Herein, we report the discovery of an unprecedented lithium superionic conductor, Li21Ge8P3S34, featuring a novel structural type and a new composition in the Li–Ge–P–S system. This material exhibits high lithium ionic conductivity of approximately 1.0 mS cm−1 at 303 K with a low activation energy of 0.20(1) eV. Its unique crystal structure was elucidated using three‐dimensional electron diffraction (3D ED) and further refined through combined powder X‐ray and neutron diffraction analyses. The structure consists of alternating two‐dimensional slabs: one of corner‐sharing GeS4 tetrahedra and the other of isolated PS4 tetrahedra, enabling efficient lithium‐ion transport through a tetrahedrally interconnected network of 1D, 2D, and 3D diffusion pathways. This distinctive structural motif provides a novel design strategy for next‐generation solid electrolytes, broadening the structural landscape of lithium superionic conductors. With further advancements in compositional tuning and interfacial engineering, Li21Ge8P3S34 could contribute to the development of high‐performance all‐solid‐state batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702852","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Organic semiconductors with intramolecular noncovalent interactions are promising hole transport materials (HTMs) for efficient and stable perovskite solar cells (PSCs), but the effects of different types of noncovalent bonds on the properties of HTMs are rarely reported. Here, three thiazolo[5,4‐d]thiazole (TzTz)‐based HTMs with different side chains were developed. Compared with alkyl side chains, functional side chains can improve the crystallinity and charge transport ability of HTMs by forming intramolecular noncovalent interactions. However, the steric hindrance of S···O in TzTzTPA‐SO distorted the molecular skeleton, leading to edge‐on stacking and local aggregation of film. Fortunately, TzTzTPA‐NH with intramolecular hydrogen bond showed high planarity, proper crystallinity and preferred stacking orientation. Consequently, a remarkable power conversion efficiency (PCE) of 24.2% with a nice long‐term stability was achieved by dopant‐free TzTzTPA‐NH‐based PSCs, which is superior to the doped Spiro‐OMeTAD‐based PSCs. In addition, TzTzTPA‐NH is well used as HTM in wide‐bandgap PSCs and perovskite/organic tandem solar cells (TSCs). Encouragingly, the TSCs based on TzTzTPA‐NH achieved an excellent PCE of 25.4%, which is the highest PCE of n‐i‐p perovskite/organic TSCs. This work clearly illustrates the effect of intramolecular noncovalent interactions on the properties of HTMs, and provides guidance for designing high‐performance dopant‐free HTMs in PSCs.
{"title":"Management of Intramolecular Noncovalent Interactions in Dopant‐Free Hole Transport Materials for High‐Performance Perovskite Solar Cells","authors":"Gang Xie, Qifan Xue, Haojia Ding, Aihui Liang, Jiaxin Liu, Yonglong Yang, Jing Wang, Xunfan Liao, Yonggang Min, Yiwang Chen","doi":"10.1002/anie.202504144","DOIUrl":"https://doi.org/10.1002/anie.202504144","url":null,"abstract":"Organic semiconductors with intramolecular noncovalent interactions are promising hole transport materials (HTMs) for efficient and stable perovskite solar cells (PSCs), but the effects of different types of noncovalent bonds on the properties of HTMs are rarely reported. Here, three thiazolo[5,4‐d]thiazole (TzTz)‐based HTMs with different side chains were developed. Compared with alkyl side chains, functional side chains can improve the crystallinity and charge transport ability of HTMs by forming intramolecular noncovalent interactions. However, the steric hindrance of S···O in TzTzTPA‐SO distorted the molecular skeleton, leading to edge‐on stacking and local aggregation of film. Fortunately, TzTzTPA‐NH with intramolecular hydrogen bond showed high planarity, proper crystallinity and preferred stacking orientation. Consequently, a remarkable power conversion efficiency (PCE) of 24.2% with a nice long‐term stability was achieved by dopant‐free TzTzTPA‐NH‐based PSCs, which is superior to the doped Spiro‐OMeTAD‐based PSCs. In addition, TzTzTPA‐NH is well used as HTM in wide‐bandgap PSCs and perovskite/organic tandem solar cells (TSCs). Encouragingly, the TSCs based on TzTzTPA‐NH achieved an excellent PCE of 25.4%, which is the highest PCE of n‐i‐p perovskite/organic TSCs. This work clearly illustrates the effect of intramolecular noncovalent interactions on the properties of HTMs, and provides guidance for designing high‐performance dopant‐free HTMs in PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"215 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702854","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dongrun Yang, Chen Liu, Xuan-Wen Gao, Zhiwei Zhao, Qinfen Gu, Yutong Long, Qingsong Lai, Hong Chen, Zhaomeng Liu, Wen-Bin Luo
Manganese-based layer-structured oxide materials are considered as one of the most competitive cathode materials for sodium-ion batteries due to their low cost and efficient sodium intercalation chemistry. Their electrochemical performance, however, is hindered by mechanical and chemical failures stemming from weak interlayer interactions, the Jahn-Teller effect of Mn3+ and unstable surfaces. To address these issues, a quenching method was employed to fabricate a robust multiphase structure with a fluorine and dislocation-rich surface. Through the accumulation of dislocations and the interlocking of multiphase structures, the mechanical stability of the material during (de)sodiation processes is enhanced, while the surface fluorine anchoring further strengthens the chemical stability. Even after 200 cycles at 0.5 C and 1 C within the voltage range of 1.5-4.5 V, the designed composite material P2/P3/O3-Na0.89Ni0.3Mn0.55Cu0.1Ti0.05O1.94F0.06 exhibits impressive capacity retention rates of 87.17% and 90.4%, respectively. This work exemplifies the important role of simultaneous design of mechano-chemically coupled materials for the development of high performances cathode materials.
{"title":"Constructing Mechanical-Chemical Stability via Multiphase Riveting and Interface Optimization towards Layer-structured Oxide Cathode Material","authors":"Dongrun Yang, Chen Liu, Xuan-Wen Gao, Zhiwei Zhao, Qinfen Gu, Yutong Long, Qingsong Lai, Hong Chen, Zhaomeng Liu, Wen-Bin Luo","doi":"10.1002/anie.202500939","DOIUrl":"https://doi.org/10.1002/anie.202500939","url":null,"abstract":"Manganese-based layer-structured oxide materials are considered as one of the most competitive cathode materials for sodium-ion batteries due to their low cost and efficient sodium intercalation chemistry. Their electrochemical performance, however, is hindered by mechanical and chemical failures stemming from weak interlayer interactions, the Jahn-Teller effect of Mn3+ and unstable surfaces. To address these issues, a quenching method was employed to fabricate a robust multiphase structure with a fluorine and dislocation-rich surface. Through the accumulation of dislocations and the interlocking of multiphase structures, the mechanical stability of the material during (de)sodiation processes is enhanced, while the surface fluorine anchoring further strengthens the chemical stability. Even after 200 cycles at 0.5 C and 1 C within the voltage range of 1.5-4.5 V, the designed composite material P2/P3/O3-Na0.89Ni0.3Mn0.55Cu0.1Ti0.05O1.94F0.06 exhibits impressive capacity retention rates of 87.17% and 90.4%, respectively. This work exemplifies the important role of simultaneous design of mechano-chemically coupled materials for the development of high performances cathode materials.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"61 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Mengyu Liu, Weirong Li, Zhongxiang Peng, Xingxin Shao, Jun Liu, Lixiang Wang
Device performance of photodiode-type short-wavelength infrared (SWIR) organic photodetectors (OPDs) is largely limited by poor exciton dissociation. In this work, we reported that downshifted highest occupied molecular orbital energy level (EHOMO) and increased electrostatic potential (ESP) of electron acceptor lead to improved exciton dissociation and consequently enhanced SWIR OPD device performance. Tetramers of thiophene-fused 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (TF-BODIPY) unit represent a new kind of electron acceptors with SWIR photoresponse. By endcapping the TF-BODIPY tetramer with electron-deficient pentafluorophenyl groups, we downshift the EHOMO of the electron acceptor by 0.06 eV and increase the ESP of the electron acceptor by 89 meV. As a result, the OPD devices of the electron acceptor exhibit SWIR photoresponse in the wavelength range of 0.3–1.3 μm with a maximum specific detectivity (D*) of 1.04[[EQUATION]]1012 Jones and a responsivity (R) of 0.16 A/W at 1.12 μm. This performance is among the highest reported for SWIR OPDs.
{"title":"Electron Acceptors Based on Resonant N—B←N Unit with Improved Exciton Dissociation for High-Performance Short-Wavelength Infrared Organic Photodetectors","authors":"Mengyu Liu, Weirong Li, Zhongxiang Peng, Xingxin Shao, Jun Liu, Lixiang Wang","doi":"10.1002/anie.202506116","DOIUrl":"https://doi.org/10.1002/anie.202506116","url":null,"abstract":"Device performance of photodiode-type short-wavelength infrared (SWIR) organic photodetectors (OPDs) is largely limited by poor exciton dissociation. In this work, we reported that downshifted highest occupied molecular orbital energy level (EHOMO) and increased electrostatic potential (ESP) of electron acceptor lead to improved exciton dissociation and consequently enhanced SWIR OPD device performance. Tetramers of thiophene-fused 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (TF-BODIPY) unit represent a new kind of electron acceptors with SWIR photoresponse. By endcapping the TF-BODIPY tetramer with electron-deficient pentafluorophenyl groups, we downshift the EHOMO of the electron acceptor by 0.06 eV and increase the ESP of the electron acceptor by 89 meV. As a result, the OPD devices of the electron acceptor exhibit SWIR photoresponse in the wavelength range of 0.3–1.3 μm with a maximum specific detectivity (D*) of 1.04[[EQUATION]]1012 Jones and a responsivity (R) of 0.16 A/W at 1.12 μm. This performance is among the highest reported for SWIR OPDs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"99 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702883","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Electron donors that can be excited to higher energy states through light absorption can achieve oxidation potentials as low as -3.0 V (vs. SCE). However, ground-state organic electron transfer reagents operating at such potentials remain underdeveloped, often necessitating multi-step syntheses and elevated reaction temperatures for activation. The longer lifetime of ground-state reagents is an advantage compared to most photoexcited single-electron reductants, which typically have relatively short lifetimes. In this study, catalytically generated phosphine oxide radical anions derived from phosphines and water applying redox catalysis are introduced as highly efficient single-electron reductants. The in situ generated radical anions are capable of reducing electron rich aryl chlorides at potentials as low as -3.3 V (vs. SCE). Cyclic voltammetry studies and DFT calculations provide valuable insights into the behavior of these phosphorus-based ground-state electron donors. These findings do not only expand the chemistry of phosphoranyl radicals but also unlock the potential of in situ generated organic ground state electron donors that reach potentials comparable to elemental potassium.
{"title":"Photocatalytic Generation of a Ground-State Electron Donor through Water Activation","authors":"Maxim-Aleksa Wiethoff, Lena Lezius, Armido Studer","doi":"10.1002/anie.202501757","DOIUrl":"https://doi.org/10.1002/anie.202501757","url":null,"abstract":"Electron donors that can be excited to higher energy states through light absorption can achieve oxidation potentials as low as -3.0 V (vs. SCE). However, ground-state organic electron transfer reagents operating at such potentials remain underdeveloped, often necessitating multi-step syntheses and elevated reaction temperatures for activation. The longer lifetime of ground-state reagents is an advantage compared to most photoexcited single-electron reductants, which typically have relatively short lifetimes. In this study, catalytically generated phosphine oxide radical anions derived from phosphines and water applying redox catalysis are introduced as highly efficient single-electron reductants. The in situ generated radical anions are capable of reducing electron rich aryl chlorides at potentials as low as -3.3 V (vs. SCE). Cyclic voltammetry studies and DFT calculations provide valuable insights into the behavior of these phosphorus-based ground-state electron donors. These findings do not only expand the chemistry of phosphoranyl radicals but also unlock the potential of in situ generated organic ground state electron donors that reach potentials comparable to elemental potassium.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143702884","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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