Angewandte Chemie International Edition最新文献_第7页

Homochiral Helical Poly(thiophene)s Accessed via Living Catalyst-Transfer Polymerization

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-03 DOI: 10.1002/anie.202502104

Matthew Hannigan, Jada Sampson, Lasya Damaraju, Marcus Weck

{"title":"Homochiral Helical Poly(thiophene)s Accessed via Living Catalyst-Transfer Polymerization","authors":"Matthew Hannigan, Jada Sampson, Lasya Damaraju, Marcus Weck","doi":"10.1002/anie.202502104","DOIUrl":"https://doi.org/10.1002/anie.202502104","url":null,"abstract":"Synthetic helical polymers form compact, ordered, and inherently chiral structures, enabling their uses in biomimetic applications as well as catalysis. A challenge in using synthetic helical polymers, however, is their tendency to be sensitive to pH and the presence of nucleophiles, Lewis-acids, or metal ions. We report a strategy to overcome these shortcomings by adapting catalyst-transfer polymerization, a living chain-growth polymerization typically used to access linear conjugated polymers, for the synthesis of helical poly(thiophene)s. We demonstrate that the helical poly(thiophene)s can be synthesized with a single helicity, incorporated into block copolymers, and functionalized at the chain-ends, enabling further conjugation and functionalization. The helical poly(thiophene)s are stable to a variety of conditions, providing benefits over other helical polymers which contain sensitive imine or carbonyl-based functional groups. We anticipate that the ability to access homochiral, heterotelechelic helical conjugated polymers and copolymers will enable new uses of these materials in optoelectronics as well as in applications for mimicking biomacromolecules and other polymers with precisely defined sequences.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532435","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}

引用次数: 0

In-Cell Fast Photochemical Oxidation Interrogates the Native Structure of Integral Membrane Proteins

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-03 DOI: 10.1002/anie.202424779

Jie Sun, Mierziati Saimi, Don Rempel, Qing Cao, Mengqi L. Chang, Weikai Li, Michael L. Gross

引用次数: 0

Redox-Activated Near Infrared/Short-Wave Infrared Emissive Chromophores: Synthesis of Triphenylamine-Appended Pyrazinacenes

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-03 DOI: 10.1002/anie.202504564

Gary James Richards, Kazushi Nakada, Keita Aoki, Tomoki Jitsukata, Kana Hashimoto, Toshiki Tajima, Ryusuke Mizoguchi, Ayumi Ishii, Jonathan P. Hill, Akiko Hori

{"title":"Redox-Activated Near Infrared/Short-Wave Infrared Emissive Chromophores: Synthesis of Triphenylamine-Appended Pyrazinacenes","authors":"Gary James Richards, Kazushi Nakada, Keita Aoki, Tomoki Jitsukata, Kana Hashimoto, Toshiki Tajima, Ryusuke Mizoguchi, Ayumi Ishii, Jonathan P. Hill, Akiko Hori","doi":"10.1002/anie.202504564","DOIUrl":"https://doi.org/10.1002/anie.202504564","url":null,"abstract":"Organic dyes showing absorbance and fluorescence in the near infrared and short-wave infrared regions are attractive for a variety of applications. Redox-coupled reversible switching of absorbance or fluorescence implies enhanced functionality of such dyes, especially where large changes in photophysical properties across the redox process can be realized. Here, we report the synthesis of two new pyrazinacenes containing four and five fused pyrazine units, appended with electron-donor triphenylamine groups, and redox-coupled switching of their photophysical properties. In their reduced state, the compounds show absorbance and fluorescence in the visible region. Reversible shifts in absorbance and fluorescence from the visible to the near infrared or even short-wave infrared regions are observed upon chemical and electrochemical oxidations. Such large redox-coupled shifts in photophysical properties are unprecedented for a redox process that affects only a single, six-membered ring in which both reduced and oxidized states consist of neutral, closed-shell species. The compounds show high fluorescence quantum yields in their reduced states, and oxidized species show fluorescence quantum yields that compare well with existing near infrared and short-wave infrared active fluorescent dyes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"18 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539183","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}

引用次数: 0

Mechanistic Insights into H2O Dissociation in Overall Photo-/Electro-Catalytic CO2 Reduction

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-03 DOI: 10.1002/anie.202425195

Minzhi Ma, Yuanxing Fang, Zeai Huang, Sixin Wu, Weiwei He, Suxiang Ge, Zhi Zheng, Ying Zhou, Wenjun Fa, Xinchen Wang

{"title":"Mechanistic Insights into H2O Dissociation in Overall Photo-/Electro-Catalytic CO2 Reduction","authors":"Minzhi Ma, Yuanxing Fang, Zeai Huang, Sixin Wu, Weiwei He, Suxiang Ge, Zhi Zheng, Ying Zhou, Wenjun Fa, Xinchen Wang","doi":"10.1002/anie.202425195","DOIUrl":"https://doi.org/10.1002/anie.202425195","url":null,"abstract":"Photo-/electro-catalytic CO2 reduction with H2O to produce fuels and chemicals offers a dual solution to address both environmental and energy challenges. For a long time, catalyst design in this reaction system has primarily focused on optimizing reduction sites to improve the efficiency or guide the reaction pathway of the CO2 reduction half-reaction. However, less attention has been paid to designing activation sites for H2O to modulate the H2O dissociation half-reaction. Yet, the rate-determining step in overall CO2 reduction is the latter, as it influences the evolution direction and formation energy of carbon-containing intermediates through the proton-coupled electron transfer process. Herein, we summarize the mechanism of the H2O dissociation half-reaction in modulating CO2 reduction performance based on cutting-edge research. These analyses aim to uncover the potential regulatory mechanisms by which H2O activation influences CO2 reduction pathways and conversion efficiency, and to establish a mechanism-structure-performance relationship that can guide the design and development of high-efficiency catalytic materials. A summary of advanced characterization techniques for investigating the dissociation mechanism of H2O is presented. We also discuss the challenges and offer perspectives on the future design of activation sites to improve the performance of photo-/electro-catalytic CO2 reduction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"55 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532316","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}

引用次数: 0

Size Effect of Surface Defects Dictates Reactivity for Nitrogen Electrofixation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-03 DOI: 10.1002/anie.202425112

Yuntong Sun, Gonggong Lu, Zhiqi Wang, Xuheng Li, Yinghao Li, Nicole L. D. Sui, Wenjun Fan, Ao Wang, Bo Yuan, Junjie Wang, Jong-Min Lee

{"title":"Size Effect of Surface Defects Dictates Reactivity for Nitrogen Electrofixation","authors":"Yuntong Sun, Gonggong Lu, Zhiqi Wang, Xuheng Li, Yinghao Li, Nicole L. D. Sui, Wenjun Fan, Ao Wang, Bo Yuan, Junjie Wang, Jong-Min Lee","doi":"10.1002/anie.202425112","DOIUrl":"https://doi.org/10.1002/anie.202425112","url":null,"abstract":"Electrocatalytic nitrogen reduction reaction (eNRR) offers a sustainable pathway for ammonia (NH3) production. Defect engineering has emerged as a promising strategy to enhance eNRR activity; however, it can concurrently amplify the competing hydrogen evolution reaction (HER), posing challenges for achieving high selectivity. Herein, VOx with systematically tuned defect sizes was engineered to establish a structure–activity relationship between defect size and eNRR performance. In-situ spectroscopy and theoretical calculations reveal that medium-sized defects (VOx-MD, 1-2 nm) provide an optimal electronic environment for enhanced N2 adsorption and activation while maintaining sufficient spatial flexibility to facilitate efficient hydrogenation and suppress HER. Consequently, VOx-MD exhibits outstanding eNRR performance, achieving an NH3 yield rate of 81.94 ± 1.45 μg h–1 mg–1 and a Faradaic efficiency of 31.97 ± 0.75% at -0.5 V (vs. RHE). These findings highlight the critical role of defect size in governing eNRR activity and selectivity, offering a scalable strategy for the rational design of advanced electrocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532340","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}

引用次数: 0

Unveil the Failure of Alkali Ion-Sulfur Aqueous Batteries: Resolving Water Migration by Coordination Regulation

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-03 DOI: 10.1002/anie.202503138

Xiaoyu Yu, Yutong Feng, Jiazhuang Tian, Xin Liu, Boya Wang, Yanyan Zhang, Tengsheng Zhang, Gaoyang Li, Xinran Li, Hongrun Jin, Wanhai Zhou, Wei Li, Zhiyuan Zeng, Laiquan Li, Dongyuan Zhao, Dongliang Chao

{"title":"Unveil the Failure of Alkali Ion-Sulfur Aqueous Batteries: Resolving Water Migration by Coordination Regulation","authors":"Xiaoyu Yu, Yutong Feng, Jiazhuang Tian, Xin Liu, Boya Wang, Yanyan Zhang, Tengsheng Zhang, Gaoyang Li, Xinran Li, Hongrun Jin, Wanhai Zhou, Wei Li, Zhiyuan Zeng, Laiquan Li, Dongyuan Zhao, Dongliang Chao","doi":"10.1002/anie.202503138","DOIUrl":"https://doi.org/10.1002/anie.202503138","url":null,"abstract":"Sulfur aqueous battery (SAB) is promising owing to its high theoretical capacity and cost competitiveness. Although decoupled electrolyte design has successfully endowed transition metal ion-SABs with customizability to achieve high energy density, its effectiveness in alkali ion-SABs remains problematic. Here, we identify for the first time an intractable phenomenon of alkali-ion-driven water migration between decoupled electrolytes through ex-situ NMR, which is recognized as the origin of the irreversible sulfur redox reactions. To address the challenge, we propose an alkali-ion-H2O-poor coordination strategy to effectively regulate water migration by incorporating low molecular polarity index (MPI) anions. In-situ Raman, synchrotron spectroscopy, and molecule dynamic simulations reveal that the repulsion of low MPI anions to water effectively disrupts the hydration patterns around the alkali cations, and thereby minimizes the concomitant water migration. The elaborated Na+-SAB achieved an ultrahigh capacity of 1634 mAh g−1 (97.7% sulfur utilization) and prolonged stability over 500 cycles. Furthermore, the versatility of alkali-ion-H2O-poor coordination strategy is further substantiated in Li+-SAB and K+-SAB batteries, boosting the scope of following SAB systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"86 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532436","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}

引用次数: 0

Digital-Twin-Assisted Insights into Irreversible Capacity and Activation Strategy Power High-Loading Solid-State Batteries

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-02 DOI: 10.1002/anie.202502169

Yecai Sun, Yanbin Ning, Zhuomin Qiang, Lizhi Xiang, Qingsong Liu, Chaoqun Zhang, Guoce Quan, Yan Zhang, Biao Deng, Geping Yin, Tiefeng Liu, Jiajun Wang, Shuaifeng Lou

{"title":"Digital-Twin-Assisted Insights into Irreversible Capacity and Activation Strategy Power High-Loading Solid-State Batteries","authors":"Yecai Sun, Yanbin Ning, Zhuomin Qiang, Lizhi Xiang, Qingsong Liu, Chaoqun Zhang, Guoce Quan, Yan Zhang, Biao Deng, Geping Yin, Tiefeng Liu, Jiajun Wang, Shuaifeng Lou","doi":"10.1002/anie.202502169","DOIUrl":"https://doi.org/10.1002/anie.202502169","url":null,"abstract":"In solid-state lithium-ion batteries (SSLIBs), the fraction of active materials involved in electrode electrochemistry reduces with the increase of electrode thickness. Conventional wisdom suggests that the degree of reaction linearly decreases toward the current-collector as that in the lithium-ion batteries, which is, however, limited by the high difficulty of experimental capture of operando transport of charge & mass. Electrode dynamics simulations can provide space visualization but are usually based on assumed or simplified models. Herein, we build digital-twin electrodes with digital-space voxel microstructure based on synchrotron tomography, which transforms the electrode architecture from real space to digital space for the construction of precision models. From the digital-model-driven simulation, we find an interesting “lithium trapping” effect, stemming from susceptible lithium stuck in the solid electrolyte, triggers an inadequate reaction of the intermediate region of electrodes but not near current-collector region. Then, we construct locally accelerated ion paths activating the lithium trapping, indicating that this strategy can significantly guide the sustainable battery design for next-generation energy storage.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532439","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}

引用次数: 0

Exploiting Anti-site Defects in FeWN2 Nanosheets for Enol Electrooxidation Coupled with H2 Evolution at a Large Current Density

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-02 DOI: 10.1002/anie.202500678

Zheng-Jie Chen, Qiting Shao, Jiajing Wu, Jian Zheng, Shida Bao, Lili Zhang, Tao Zhang, Xuexia Lan, Yuanmiao Sun, Jing Peng, Dawei Wang, Hui-Ming Cheng

{"title":"Exploiting Anti-site Defects in FeWN2 Nanosheets for Enol Electrooxidation Coupled with H2 Evolution at a Large Current Density","authors":"Zheng-Jie Chen, Qiting Shao, Jiajing Wu, Jian Zheng, Shida Bao, Lili Zhang, Tao Zhang, Xuexia Lan, Yuanmiao Sun, Jing Peng, Dawei Wang, Hui-Ming Cheng","doi":"10.1002/anie.202500678","DOIUrl":"https://doi.org/10.1002/anie.202500678","url":null,"abstract":"Hydrogen production from biomass electrooxidation offers a promising alternative to water electrolysis by lowering the anodic oxidation barrier and producing valuable chemicals. However, current biomass electrooxidation systems have difficulties in achieving an industrial-scale current density due to the difficulty in cleaving high-energy C-H and O-H bonds. Here, we report a ternary layer nitride FeWN2 electrocatalyst with abundant anti-site defects (ASDs), which significantly improves its electrocatalytic performance for ascorbic acid (AA) oxidation. The catalyst works at a remarkable current density of 2.5 A cm-2 at 0.69 V (vs. RHE) and achieves 4 A cm-2 at 1.12 V in a two-electrode electrolyzer at 60°C with 100% Faraday efficiency for H2 production. Theoretical calculations reveal that W atoms near antipodal Fe sites replenish the electron density of Fe, maintaining moderate Fe-DHA adsorption strength induced by ASDs that achieve superior catalytic efficiency for AA-to-DHA conversion This study provides new insight for developing high-performance organic oxidation catalysts with ASDs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"90 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-03-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143532444","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}

引用次数: 0

Self-Assembled Monolayer of N-Heterocyclic Carbene as a Primer in a Dual-Layer Coating for Corrosion Protection on Iron N-Heterocyclic Carbene 的自组装单层作为双层涂层的底层，用于保护铁免受腐蚀

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-02 DOI: 10.1002/anie.202422879

Linoy Amar, Rajarshi Mondal, Omer Blumen, Lihi Rekanati, Iris Berg, Sara Harpaz, Daniel Sharon, Elad Gross

引用次数: 0

Electrocatalytic Hydrogenation of Olefins

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-03-02 DOI: 10.1002/anie.202501215

Qingquan Lu, Ping Hu, Wentao Xu, Lang Tian, Hance Zhu, Fabao Li, Xiaotian Qi

引用次数: 0