Angewandte Chemie International Edition最新文献_第3页

Unveiling the Dual Role of Oxophilic Cr⁴⁺ in Cr-Cu₂O Nanosheet Arrays for Enhanced Nitrate Electroreduction to Ammonia. 揭示 Cr-Cu2O 纳米片阵列中亲氧 Cr4+ 在增强硝酸盐电还原成氨方面的双重作用

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-11-07 DOI: 10.1002/anie.202411796

Kai Zhang, Bo Li, Fengchen Guo, Nigel Graham, Wenhui He, Wenzheng Yu

{"title":"Unveiling the Dual Role of Oxophilic Cr4+ in Cr-Cu2O Nanosheet Arrays for Enhanced Nitrate Electroreduction to Ammonia.","authors":"Kai Zhang, Bo Li, Fengchen Guo, Nigel Graham, Wenhui He, Wenzheng Yu","doi":"10.1002/anie.202411796","DOIUrl":"10.1002/anie.202411796","url":null,"abstract":"Cuprous oxide (Cu2O)-based catalysts present a promising activity for the electrochemical nitrate (NO3 -) reduction to ammonia (eNO3RA), but the electrochemical instability of Cu+ species may lead to an unsatisfactory durability, hindering the exploration of the structure-performance relationship. Herein, we propose an efficient strategy to stabilize Cu+ through the incorporation of Cr4+ into the Cu2O matrix to construct a Cr4+-O-Cu+ network structure. In situ and quasi-in situ characterizations reveal that the Cu+ species are well maintained via the strong Cr4+-O-Cu+ interaction that inhibits the leaching of lattice oxygen. Importantly, in situ generated Cr3+-O-Cu+ from Cr4+-O-Cu+ is identified as a dual-active site for eNO3RA, wherein the Cu+ sites are responsible for the activation of N-containing intermediates, while the assisting Cr3+ centers serve as the electron-proton mediators for rapid water dissociation. Theoretical investigations further demonstrated that the metastable state Cr3+-O-Cu+ favors the conversion from the endoergic hydrogenation of the key *ON intermediate to an exoergic reaction in an ONH pathway, and facilitates the subsequent NH3 desorption with a low energy barrier. The superior eNO3RA with a maximum 91.6 % Faradaic efficiency could also be coupled with anodic sulfion oxidation to achieve concurrent NH3 production and sulfur recovery with reduced energy input.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202411796"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142405749","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

Proton Relays in Molecular Catalysis for Hydrogen Evolution and Oxidation: Lessons From the Mimicry of Hydrogenases and Electrochemical Kinetic Analyses. 氢气进化和氧化分子催化中的质子中继：从模仿氢化酶和电化学动力学分析中汲取的教训。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-11-18 DOI: 10.1002/anie.202413910

Matthieu Haake, Bertrand Reuillard, Murielle Chavarot-Kerlidou, Cyrille Costentin, Vincent Artero

{"title":"Proton Relays in Molecular Catalysis for Hydrogen Evolution and Oxidation: Lessons From the Mimicry of Hydrogenases and Electrochemical Kinetic Analyses.","authors":"Matthieu Haake, Bertrand Reuillard, Murielle Chavarot-Kerlidou, Cyrille Costentin, Vincent Artero","doi":"10.1002/anie.202413910","DOIUrl":"10.1002/anie.202413910","url":null,"abstract":"The active sites of metalloenzymes involved in small molecules activation often contain pendant bases that act as proton relay promoting proton-coupled electron-transfer processes. Here we focus on hydrogenases and on the reactions they catalyze, i. e. the hydrogen evolution and oxidation reactions. After a short description of these enzymes, we review some of the various biomimetic and bioinspired molecular systems that contain proton relays. We then provide the formal electrochemical framework required to decipher the key role of such proton relay to enhance catalysis in a single direction and discuss the few systems active for H2 evolution for which quantitative kinetic data are available. We finally highlight key parameters required to reach bidirectional catalysis (both hydrogen evolution and hydrogen oxidation catalyzed) and then transition to reversible catalysis (both reactions catalyzed in a narrow potential range) as well as illustrate these features on few systems from the literature.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202413910"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142646475","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

Hydrazine-Catalysed Ring-Opening Metathesis Polymerization Of Cyclobutenes. 肼催化的环丁烯开环 Metathesis 聚合反应。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-10-22 DOI: 10.1002/anie.202413093

Julian S Kellner-Rogers, Jesse H Hsu, Ivan Keresztes, Brett P Fors, Tristan H Lambert

引用次数: 0

Solvent-Engineering-Assisted Ligand Exchange Strategy for High-Efficiency AgBiS₂ Quantum Dot Solar Cells. 用于高效 AgBiS2 量子点太阳能电池的溶剂工程辅助配体交换策略。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-10-22 DOI: 10.1002/anie.202412590

Qixuan Zhong, Bin Zhao, Yongqiang Ji, Qiuyang Li, Xiaoyu Yang, Mingyu Chu, Yiqi Hu, Lei Li, Shunde Li, Hongyu Xu, Haoming Yan, Tianyu Huang, Peng Chen, Hao-Hsin Chen, Zhangyuchang Lu, Yiming Huangfu, Jiang Wu, Dengke Wang, Ning Wang, Muhan Cao, Qihuang Gong, Rui Zhu, Lichen Zhao

{"title":"Solvent-Engineering-Assisted Ligand Exchange Strategy for High-Efficiency AgBiS2 Quantum Dot Solar Cells.","authors":"Qixuan Zhong, Bin Zhao, Yongqiang Ji, Qiuyang Li, Xiaoyu Yang, Mingyu Chu, Yiqi Hu, Lei Li, Shunde Li, Hongyu Xu, Haoming Yan, Tianyu Huang, Peng Chen, Hao-Hsin Chen, Zhangyuchang Lu, Yiming Huangfu, Jiang Wu, Dengke Wang, Ning Wang, Muhan Cao, Qihuang Gong, Rui Zhu, Lichen Zhao","doi":"10.1002/anie.202412590","DOIUrl":"10.1002/anie.202412590","url":null,"abstract":"As the initial synthesized colloidal quantum dots (CQDs) are generally capped with insulating ligands, ligand exchange strategies are essential in the fabrication of CQD films for solar cells, which can regulate the surface chemical states of CQDs to make them more suitable for thin-film optoelectronic devices. However, uncontrollable surface adsorption of water molecules during the ligand exchange process introduces new defect sites, thereby impairing the resultant device performance, which attracts more efforts devoted to it but remains a puzzle. Here, we develop a solvent-engineering-assisted ligand exchange strategy to revamp the surface adsorption, improve the exchange efficiency, and modulate the surface chemistry for the environmentally friendly lead-free silver bismuth disulfide (AgBiS2) CQDs. The optimized AgBiS2 CQD solar cells deliver an outstanding champion power conversion efficiency (PCE) of up to 8.95 % and improved long-term stability. Our strategy is less environment-dependent and can produce solar cells with negligible performance variance for several batches across several months. Our work demonstrates the critical role of solvents for ligand exchange in the surface chemistry of CQDs and the realization of high-performance photovoltaic devices in a highly reproducible manner.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412590"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142046015","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

Regiodivergent Functionalization of Protected and Unprotected Carbohydrates using Photoactive 4-Tetrafluoropyridinylthio Fragment as an Adaptive Activating Group. 使用光活性 4-Tetrafluoropyridinylthio 片段作为自适应活化基团，对受保护和未受保护的碳水化合物进行 Regiodivergent 功能化。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-10-24 DOI: 10.1002/anie.202412436

Shen Cao, Haobo Zhang, Mingshuo Chen, Niming Zhu, Beibei Zhan, Peng Xu, Xiaoping Chen, Biao Yu, Xiaheng Zhang

引用次数: 0

Polymerization-induced Chiral Self-assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures. 聚合诱导手性自组装，用于不对称超结构的原位构建、调制、放大和应用。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-10-29 DOI: 10.1002/anie.202414332

Xiaoxiao Cheng, Wei Zhang

{"title":"Polymerization-induced Chiral Self-assembly for the In situ Construction, Modulation, Amplification and Applications of Asymmetric Suprastructures.","authors":"Xiaoxiao Cheng, Wei Zhang","doi":"10.1002/anie.202414332","DOIUrl":"10.1002/anie.202414332","url":null,"abstract":"In the polymerization-induced chiral self-assembly (PICSA) process, chiral functional monomers undergo spontaneous supramolecular self-assembly and asymmetric stacking during living polymerization, leading to the in situ generation of chiroptical polymer assemblies characterized by diverse morphologies. The PICSA strategy facilitates precise control and manipulation of both non-covalent supramolecular helices and covalent macromolecular helices within aggregated cores, thereby driving significant advancements in fields such as chiral recognition materials, asymmetric catalysts, nonlinear optical materials, and ferroelectric liquid crystals (LC). This minireview summarizes recent developments in the in situ chiroptical construction and modulation associated with the PICSA methodology. Furthermore, it seeks to elucidate emerging PICSA systems founded on various living polymerization mechanisms, exploring hierarchical chirality transfer processes and the pathway complexities in both equilibrium and non-equilibrium conditions. This minireview also presents several illustrative examples that demonstrate the practical applications of chiral polymer materials synthesized through the PICSA approach, thereby illuminating future opportunities in this innovative field.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202414332"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142118494","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

Selective Catalytic Combustion of Hydrogen under Aerobic Conditions on Na₂WO₄/SiO₂. 有氧条件下氢气在 Na2WO4/SiO2 上的选择性催化燃烧。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-10-29 DOI: 10.1002/anie.202412932

Elijah R Kipp, Javier Garcia-Barriocanal, Aditya Bhan

{"title":"Selective Catalytic Combustion of Hydrogen under Aerobic Conditions on Na2WO4/SiO2.","authors":"Elijah R Kipp, Javier Garcia-Barriocanal, Aditya Bhan","doi":"10.1002/anie.202412932","DOIUrl":"10.1002/anie.202412932","url":null,"abstract":"Na2WO4/SiO2, a material known to catalyze alkane selective oxidation including the oxidative coupling of methane (OCM), is demonstrated to catalyze selective hydrogen combustion (SHC) with >97 % selectivity in mixtures with several hydrocarbons (CH4, C2H6, C2H4, C3H6, C6H6) in the presence of gas-phase dioxygen at 883-983 K. Hydrogen combustion rates exhibit a near-first-order dependence on H2 partial pressure and are zero-order in H2O and O2 partial pressures. Mechanistic studies at 923 K using isotopically-labeled reagents demonstrate the kinetic relevance of H-H dissociation and absence of O-atom recombination. In situ X-ray diffraction (XRD) and W LIII-edge X-ray absorption spectroscopy (XAS) studies demonstrate, respectively, a loss of Na2WO4 crystallinity and lack of second-shell coordination with respect to W6+ cations below 923 K; benchmark experiments show that alkali cations must be present for the material to be selective for hydrogen combustion, but that materials containing Na alone have much lower combustion rates (per gram Na) than those containing Na and W. These data suggest a synergy between Na and W in a disordered phase at temperatures below the bulk melting point of Na2WO4 (971 K) during SHC catalysis. The Na2WO4/SiO2 SHC catalyst maintains stable combustion rates at temperatures ca. 100 K higher than redox-active SHC catalysts and could potentially enable enhanced olefin yields in tandem operation of reactors combining alkane dehydrogenation with SHC processes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412932"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142118496","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

Interface-Triggered Spin-Magnetic Effect in Rare Earth Intraparticle Heterostructured Nanoalloys for Boosting Hydrogen Evolution. 稀土微粒内异质结构纳米合金中的界面触发自旋磁效应促进氢气进化

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-10-25 DOI: 10.1002/anie.202412591

Hengjun Liu, Yong Jiang, Qingqing Li, Guangtong Hai, Chao Gu, Yaping Du

{"title":"Interface-Triggered Spin-Magnetic Effect in Rare Earth Intraparticle Heterostructured Nanoalloys for Boosting Hydrogen Evolution.","authors":"Hengjun Liu, Yong Jiang, Qingqing Li, Guangtong Hai, Chao Gu, Yaping Du","doi":"10.1002/anie.202412591","DOIUrl":"10.1002/anie.202412591","url":null,"abstract":"Rare earth (RE) elements are attractive for spin-magnetic modulation due to their unique 4 f electron configuration and strong orbital couplings. Alloying RE with conventional 3d transition-metal (TM) is promising for the fabrication of advanced spin catalysts yet remains much difficulties in preparation, which leads to the mysteries of spin-magnetic effect between RE and 3d TM on catalysis. Here we define a solid-phase synthetic protocol for creating RE-3d TM-noble metal integrated intraparticle heterostructured nanoalloys (IHAs) with distinct Gd and Co interface within the entire Rh framework, denoted as RhCo-RhGd IHAs. They exhibit interface-triggered antiferromagnetic interaction, which can induce electron redistribution and regulate spin polarization. Theoretical calculations further reveal that active sites around the heterointerface with weakened spin polarization optimize the adsorption and dissociation of H2O, thus promoting alkaline hydrogen evolution catalysis. The RhCo-RhGd IHAs show a small overpotential of 11.3 mV at 10 mA cm-2, as well as remarkable long-term stability, far superior to previously reported Rh-based catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412591"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142102493","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

Thermally-Stable Single-Site Pd on CeO₂ Catalyst for Selective Amination of Phenols to Aromatic Amines without External Hydrogen. 热稳定的 CeO2 单位钯催化剂，用于在无外加氢的情况下将苯酚选择性胺化为芳香胺。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-11-06 DOI: 10.1002/anie.202412062

Yaqin Wang, Bingfeng Chen, Lina Li, Xuelei Mei, Yucheng Gu, Haihong Wu, Mingyuan He, Buxing Han

{"title":"Thermally-Stable Single-Site Pd on CeO2 Catalyst for Selective Amination of Phenols to Aromatic Amines without External Hydrogen.","authors":"Yaqin Wang, Bingfeng Chen, Lina Li, Xuelei Mei, Yucheng Gu, Haihong Wu, Mingyuan He, Buxing Han","doi":"10.1002/anie.202412062","DOIUrl":"10.1002/anie.202412062","url":null,"abstract":"Developing a new route to produce aromatic amines as key chemicals from renewable phenols is a benign alternative to current fossil-based routes like nitroaromatic hydrogenation, but is challenging because of the high dissociation energy of the Ar-OH bond and difficulty in controlling side reactions. Herein, an aerosolizing-pyrolysis strategy was developed to prepare high-density single-site cationic Pd species immobilized on CeO2 (Pd1/CeO2) with excellent sintering resistance. The obtained Pd1/CeO2 catalysts achieved remarkable selectivity of important aromatic amines (yield up to 76.2 %) in the phenols amination with amines without external hydrogen sources, while Pd nano-catalysts mainly afforded phenyl-ring-saturation products. The excellent catalytic properties of the Pd1/CeO2 are closely related to high-loading Pd single-site catalysts with abundant surface defect sites and suitable acid-base properties. This report provides a sustainable route for producing aromatic amines from renewable feedstocks.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202412062"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142306742","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

Pairing Oxygen Reduction and Water Oxidation for Dual-Pathway H₂O₂ Production. 氧还原与水氧化配对，实现双途径 H2O2 生产。

IF 16.1 1区化学

Angewandte Chemie International Edition Pub Date : 2024-12-20 Epub Date: 2024-11-06 DOI: 10.1002/anie.202414417

Xin Sun, Jindi Yang, Xiangkang Zeng, Lijun Guo, Chuanbiao Bie, Zhuyuan Wang, Kaige Sun, Aloka Kumar Sahu, Mike Tebyetekerwa, Thomas E Rufford, Xiwang Zhang

{"title":"Pairing Oxygen Reduction and Water Oxidation for Dual-Pathway H2O2 Production.","authors":"Xin Sun, Jindi Yang, Xiangkang Zeng, Lijun Guo, Chuanbiao Bie, Zhuyuan Wang, Kaige Sun, Aloka Kumar Sahu, Mike Tebyetekerwa, Thomas E Rufford, Xiwang Zhang","doi":"10.1002/anie.202414417","DOIUrl":"10.1002/anie.202414417","url":null,"abstract":"Hydrogen peroxide (H2O2) is a crucial chemical applied in various industry sectors. However, the current industrial anthraquinone process for H2O2 synthesis is carbon-intensive. With sunlight and renewable electricity as energy inputs, photocatalysis and electrocatalysis have great potential for green H2O2 production from oxygen (O2) and water (H2O). Herein, we review the advances in pairing two-electron O2 reduction and two-electron H2O oxidation reactions for dual-pathway H2O2 synthesis. The basic principles, paired redox reactions, and catalytic device configurations are introduced initially. Aligning with the energy input, the latest photocatalysts, electrocatalysts, and photo-electrocatalysts for dual-pathway H2O2 production are discussed afterward. Finally, we outlook the research opportunities in the future. This minireview aims to provide insights and guidelines for the broad community who are interested in catalyst design and innovative technology for on-site H2O2 synthesis.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":" ","pages":"e202414417"},"PeriodicalIF":16.1,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142277494","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