Angewandte Chemie International Edition最新文献_第3页

Facile (Z)-Selective Synthesis of β,γ-Unsaturated Ketones by a Silicon-based Olefination Strategy. 硅基烯烃法合成β，γ-不饱和酮类化合物

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202517069

Daniya Aynetdinova,Jakub Brześkiewicz,Nikolaos Skoulikas,Nuno Maulide

引用次数: 0

Integrative Ni1-Px Catalytic Pairs for Low-Concentration CO2 Electroreduction. 集成Ni1-Px催化对低浓度CO2电还原。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202518003

Xiuwen Shi,Xiongyi Liang,Lingyue Liu,Fangxin Hu,Yuhang Liu,Yuhang Jin,Yang Yu,Tingting Zhao,Pingping Wang,Jie Ding,Xiao Cheng Zeng,Bin Liu,Hong Bin Yang

{"title":"Integrative Ni1-Px Catalytic Pairs for Low-Concentration CO2 Electroreduction.","authors":"Xiuwen Shi,Xiongyi Liang,Lingyue Liu,Fangxin Hu,Yuhang Liu,Yuhang Jin,Yang Yu,Tingting Zhao,Pingping Wang,Jie Ding,Xiao Cheng Zeng,Bin Liu,Hong Bin Yang","doi":"10.1002/anie.202518003","DOIUrl":"https://doi.org/10.1002/anie.202518003","url":null,"abstract":"The electrochemical CO2 reduction reaction (CO2RR) powered by renewable electricity offers a promising approach for sustainable carbon utilization. However, under industrially relevant low CO2 concentrations (5-15 vol.%), the efficiency and selectivity of electrochemical CO2RR are significantly constrained by the limited CO2 supply and the competitive hydrogen evolution reaction (HER). Herein, we report integrative Ni1-Px catalytic pairs (Ni1-Px/ICPs) that exhibit super CO2-to-CO conversion efficiency under low-concentration CO2 conditions. In situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) and X-ray absorption spectroscopy (XAS) measurements show that P incorporation modulates the electrochemical microenvironment and accelerates reaction kinetics. H/D isotopic substitution experiments and theoretical calculations unveil a mechanistic transition from an Eley-Rideal to Langmuir-Hinshelwood pathway, enabled by cooperative adsorption on adjacent Ni and P sites. Notably, a hydrogen-bonded six-membered Ni-C-O-H-O-P-Ni ring forms between adsorbed CO2 and H2O, facilitating proton-coupled electron transfer and lowering the reaction barrier. This unique adsorption motif enhances CO2 activation, suppresses HER, and enables efficient CO generation at low CO2 concentrations. Our findings show the importance of atomically dispersed catalytic pairs for advancing carbon utilization and overcoming selectivity challenges in electrochemical hydrogenation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"108 1","pages":"e202518003"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145351478","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

Breaking Diffusion Limit in Ester-Flame-Proof Na-Ion Electrolytes Through Solvent Coordination Chemistry. 溶剂配位化学突破酯-隔爆钠离子电解质的扩散极限。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202512950

Jidao Li,Junli Long,He Du,Jingshu Wang,Wenlong Zhao,Hao Gong,Wenhong Zou,Feng Wang,Jie Shi,Yanyan Zhang,Zhengshuai Bai,Oleksandr I Malyi,Yuxin Tang

{"title":"Breaking Diffusion Limit in Ester-Flame-Proof Na-Ion Electrolytes Through Solvent Coordination Chemistry.","authors":"Jidao Li,Junli Long,He Du,Jingshu Wang,Wenlong Zhao,Hao Gong,Wenhong Zou,Feng Wang,Jie Shi,Yanyan Zhang,Zhengshuai Bai,Oleksandr I Malyi,Yuxin Tang","doi":"10.1002/anie.202512950","DOIUrl":"https://doi.org/10.1002/anie.202512950","url":null,"abstract":"Traditional electrolyte systems are struggle to meet practical needs for high performance of sodium-ion batteries (SIBs) due to their limited functionality. The design of electrolytes today relies largely on expensive trial-and-error methodologies and intricate solvent-structure engineering, in which various additives and solvents are arbitrarily used without any reasonable selection rules. Motivated by this, we herein establish a descriptor-guided framework centered on solvent oxidative stability and Na+-solvent coordination chemistry to identify intrinsically flame-proof, ester-based electrolytes that overcome conventional diffusion limits. By screening a number of fluorinated phosphate and cyclic carbonate candidates, the electrolytes with the comprehensive properties, including the electrolyte desolvation processes, oxidation resistance, and flame retardancy, were successfully designed and synthesized, thereby realizing intrinsic flameproofing with fast-charging capability. Impressively, our optimized electrolytes sustain over 98% capacity retention for 350 cycles at 1.0 C with a Coulombic efficiency of nearly 100% when deployed in Na3V2(PO4)3 (NVP) cells, whereas benchmark carbonate systems fail within a few tens of cycles. By linking the explicit performance descriptors of solvent electronic structure and ion-solvent coordination, this work delivers a rational pathway to flame-proof and high-rate SIB electrolytes, breaking the long-standing diffusion limit and brute-force screening.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"138 1","pages":"e202512950"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145351482","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

Optical Switching of Catalytic Pathways for Hydrogen Generation via Light-Handedness Control on Chiral Nanostructures. 手性纳米结构的光手性控制催化制氢途径的光开关。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202517047

Qingli Wang,Jiahong Liu,Shouyuan Li,Shuaikun Ji,Caiwei Zhang,Junting Wang,Jiatao Zhang,Yiou Wang

{"title":"Optical Switching of Catalytic Pathways for Hydrogen Generation via Light-Handedness Control on Chiral Nanostructures.","authors":"Qingli Wang,Jiahong Liu,Shouyuan Li,Shuaikun Ji,Caiwei Zhang,Junting Wang,Jiatao Zhang,Yiou Wang","doi":"10.1002/anie.202517047","DOIUrl":"https://doi.org/10.1002/anie.202517047","url":null,"abstract":"Precise optical control over catalytic pathways remains a major challenge in solar-driven hydrogen production. Here, we report a reversible light-handedness-dependent switching mechanism between photocatalysis and photothermal catalysis using a standard Au@CdS nanocatalyst functionalized with chiral cysteine ligands. The switching behavior is governed by the interplay of chemical chirality and circularly polarized light, mediated by the chirality-induced spin selectivity effect. When the handedness of circularly polarized light matches the catalyst's chirality, spin-polarized carriers are efficiently transferred, favoring photocatalysis. In contrast, mismatched conditions suppress charge transfer, enhance recombination, and induce localized heating, shifting the reaction toward photothermal catalysis. Tuning the handedness of circularly polarized light to mismatch the catalyst chirality induces a significant photothermal effect, with temperatures reaching 343 K and hydrogen evolution rates of up to 4.8 mmol g-1 h-1, doubling the performance in the matched case. This study introduces a light-handedness-controlled catalytic switch that enables dynamic modulation between two reaction modes using the same chiral catalyst, advancing our mechanistic understanding of spin-dependent photothermal phenomena and establishing a versatile platform for optically tunable solar fuel production. The interaction of chemical and optical chirality offers a novel approach to designing next-generation photocatalysts that can be tailored for energy conversion.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"73 1","pages":"e202517047"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145351762","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

Complete Recycling of Polyester Wastes with Dialkyl Carbonates. 用碳酸二烷基酯完全回收聚酯废料。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202518885

Rongxiang Li,Wei Zeng,Yanfei Zhao,Guoxuan Li,Jiaju Fu,Fengtao Zhang,Yusi Wang,Hui Zhang,Minhao Tang,Daolan Liu,Runyao Zhao,Buxing Han,Zhimin Liu

{"title":"Complete Recycling of Polyester Wastes with Dialkyl Carbonates.","authors":"Rongxiang Li,Wei Zeng,Yanfei Zhao,Guoxuan Li,Jiaju Fu,Fengtao Zhang,Yusi Wang,Hui Zhang,Minhao Tang,Daolan Liu,Runyao Zhao,Buxing Han,Zhimin Liu","doi":"10.1002/anie.202518885","DOIUrl":"https://doi.org/10.1002/anie.202518885","url":null,"abstract":"Chemical and biological recycling of spent polyesters is of great significance for solving problems caused by their accumulation, but generally suffering from requirements for high temperature, specific catalysts or enzymes, and incomplete depolymerization in most cases. Here, we report a novel strategy for complete depolymerization of polyesters (e.g., poly(ethylene terephthalate), PET) with dialkyl carbonates (e.g., dimethyl carbonate, DMC) into monomers over halide salts (e.g., tetrabutylammonium chloride, [N4444]Cl) under mild conditions. We demonstrate that PET can be completely degraded into dimethyl terephthalate (DMT) using DMC over [N4444]Cl at temperatures of 80∼120 °C. Based on this reaction, we have achieved highly efficient and complete depolymerization of PET in various PET blend textiles into DMT while preserving the structural integrity of other components including natural and synthetic components. Mechanistic studies reveal the key role of methoxy anion derived from DMC in cleaving the acyl C─O bond of polyesters. Techno-economic assessment for recycling of spent PET wastes demonstrates excellent economic profit.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":"e202518885"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145351810","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

Access to Inherently and Centrally Chiral Calix[4]Arenes via Rhodium-Catalyzed C─H Activation and Insertion into Diverse Olefins and Alkynes. 通过铑催化的C─H活化和插入到各种烯烃和炔烃中获得固有和中心手性杯芳烃。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202520283

Yunfei Yao,Fen Wang,Xiao-Xi Li,Ruijie Mi,Xingwei Li

引用次数: 0

Steam-Activated Lattice Oxygen Enhances Interfacial Redox Stability for Low-Temperature N2O Decomposition over Rh/CeO2. 蒸汽活化的点阵氧在Rh/CeO2上增强低温N2O分解的界面氧化还原稳定性。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202517403

Ningqiang Zhang,Chenxi He,Yuan Jing,Yucheng Qian,Yuan Qin,Hong Lin,Minami Obuchi,Ryo Toyoshima,Hiroshi Kondoh,Kohei Oka,Lingcong Li,Akihiko Anzai,Takashi Toyao,Ken-Ichi Shimizu

{"title":"Steam-Activated Lattice Oxygen Enhances Interfacial Redox Stability for Low-Temperature N2O Decomposition over Rh/CeO2.","authors":"Ningqiang Zhang,Chenxi He,Yuan Jing,Yucheng Qian,Yuan Qin,Hong Lin,Minami Obuchi,Ryo Toyoshima,Hiroshi Kondoh,Kohei Oka,Lingcong Li,Akihiko Anzai,Takashi Toyao,Ken-Ichi Shimizu","doi":"10.1002/anie.202517403","DOIUrl":"https://doi.org/10.1002/anie.202517403","url":null,"abstract":"Activation of surface lattice oxygen is crucial for enabling low-temperature catalytic oxidation reactions. While earlier studies have hinted that steam treatment could enhance the activity of lattice oxygen in CeO2 supported catalysts, the mechanistic understanding remains superficial. Here, we unravel the origin and role of steam-activated lattice oxygen in promoting low-temperature N2O decomposition. Using a combination of isotope-labeled steam (H2 18O), in situ ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), and in situ X-ray absorption spectroscopy (XAS), we provide direct evidence that high-temperature steam induces lattice oxygen activation at the Rh-CeO2 interface. These activated oxygen species facilitate oxygen desorption and enhance the redox cycling stability of Rh and Ce species, dramatically improving catalytic activity at low temperatures. Our findings reveal a previously overlooked pathway for surface lattice oxygen activation and offer mechanistic insights to guide the rational design of efficient low-temperature redox catalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":"e202517403"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145339322","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

Elucidating Ligand-Dependent Selectivities in Pd-Catalyzed C-H Activations. 阐明pd催化的C-H活化中配体依赖的选择性。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202507500

Fritz Deufel,Monika Ravi,Manuel van Gemmeren

{"title":"Elucidating Ligand-Dependent Selectivities in Pd-Catalyzed C-H Activations.","authors":"Fritz Deufel,Monika Ravi,Manuel van Gemmeren","doi":"10.1002/anie.202507500","DOIUrl":"https://doi.org/10.1002/anie.202507500","url":null,"abstract":"Achieving regioselectivity in C-H activation remains a major challenge. Controlling or even reversing the regioisomeric outcome through the choice of ligand is even harder to achieve, let alone to predict. In this study, we investigated ligand effects in the regioselective Pd-catalyzed alkynylation of thiophenes using multivariate linear regression to build predictive models that offer deeper insight into the structural factors driving regioselectivity and enabled the discovery of a more selective ligand. Combining experimental and DFT studies, we propose a Curtin-Hammett scenario between the C-H activation and migratory insertion as the origin of the ligand-controlled selectivities. A detailed investigation of solvent effects uncovered an inadequate description of solvent-solute dispersion interactions by implicit solvation models. The crucial role of the solvent in substrate coordination is further evidenced by an inverse solvent kinetic isotope effect. Additionally, the often poorly understood role of silver was scrutinized, showing that it serves to mitigate a detrimental side reaction. This study provides generalizable insights for the computational description of challenging regio- and stereoselectivities and is expected to aid future mechanistic investigations in Pd-catalyzed C-H activation that holistically consider the role of all reaction components.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"200 1","pages":"e202507500"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145339315","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

Empowering Chemistry Experts with Large Language Models for Literature Interpretation in Single-Atom Catalysis Toward Advanced Oxidation. 授权化学专家与大语言模型的文献解释在单原子催化向高级氧化。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202520525

Jing-Hang Wu,Ran Shi,Xiao Zhou,Liang Zhang,Kong Chen,Han-Qing Yu,Yuen Wu

{"title":"Empowering Chemistry Experts with Large Language Models for Literature Interpretation in Single-Atom Catalysis Toward Advanced Oxidation.","authors":"Jing-Hang Wu,Ran Shi,Xiao Zhou,Liang Zhang,Kong Chen,Han-Qing Yu,Yuen Wu","doi":"10.1002/anie.202520525","DOIUrl":"https://doi.org/10.1002/anie.202520525","url":null,"abstract":"Large language models (LLMs) hold considerable promise for large-scale data extraction from scientific literatures for catalyst design and practical optimization. Yet, turning such outputs into reliable, formalized chemical knowledge would heavily rely on domain expertise rather than end-to-end automation. Herein, we present a human-in-the-loop workflow integrating LLM-facilitated structured data extraction with iterative, expert-guided curation and analysis. As a proof of concept, we take single-atom catalysts (SACs) for advanced oxidation processes (AOPs) as an example, enabling efficient data extraction, rigorous curation, and statistically driven interpretation. Thus, we uncover the key correlations among metal types, coordination environments, reaction substances, and catalytic performance, providing deeper mechanism insights into SAC-driven AOPs. In contrast to fully automated, end-to-end models, our approach relies on human-driven optimization at multiple stages, and underscores human insight as central to understand LLM outputs. By introducing human-driven prompt refinement, model comparison, and expert-led analysis, our method ensures that human cognition remains central to interpreting LLM outputs and converting structured data into reliable scientific knowledge. Our work addresses the limitations inherent in fully automated, end-to-end methodologies and effectively bridges the gap between structured outputs and catalytically meaningful insights.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"138 1","pages":"e202520525"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145351811","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

Linkage Multi-functionalization in Covalent Organic Frameworks via Criss-Cross 1,3-Dipolar Cycloaddition. 通过交叉1,3-偶极环加成在共价有机框架中的连锁多功能化。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-23 DOI: 10.1002/anie.202511708

Hui-Hui Sun,Xi-Jun Wen,Zhi-Bei Zhou,Qiao-Yan Qi,Peng-Ju Tian,Xin Zhao

{"title":"Linkage Multi-functionalization in Covalent Organic Frameworks via Criss-Cross 1,3-Dipolar Cycloaddition.","authors":"Hui-Hui Sun,Xi-Jun Wen,Zhi-Bei Zhou,Qiao-Yan Qi,Peng-Ju Tian,Xin Zhao","doi":"10.1002/anie.202511708","DOIUrl":"https://doi.org/10.1002/anie.202511708","url":null,"abstract":"Introducing functional groups to skeletons of covalent organic frameworks (COFs) is fundamentally important to create specific properties and functions for this class of crystalline porous polymers. The strategy of multi-functionalization could introduce multiple functional groups in one-step but has rarely been developed for polymers. Herein, we report a novel linkage conversion strategy which could simultaneously install multiple functional groups into a single site of azine-linked COFs. This strategy is based on criss-cross 1,3-dipolar cycloaddition reaction between azine linkages in COFs and multifarious alkynes carrying different functional groups. Its general applicability and high efficiency have been demonstrated by the successful construction of more than 10 COFs with widespread functional groups, for which homo-type and hetero-type functional groups could be introduced. This study provides a general and powerful tool to introduce highly dense functional groups into nanopores of COFs, enabling the further exploration of their applications bestowed by the functional groups.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":"e202511708"},"PeriodicalIF":16.6,"publicationDate":"2025-10-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145351815","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