{"title":"Electrochemical Alkyne Semi-Hydrogenation via Proton-Coupled Electron Transfer on Cu(111) Surface.","authors":"Shangfeng Tang,Na Guo,Cheng Chen,Bingqing Yao,Xuan Liu,Chi Ma,Qiyuan Liu,Shan Ren,Chi He,Bin Liu,Xinzhe Li","doi":"10.1002/anie.202510192","DOIUrl":"https://doi.org/10.1002/anie.202510192","url":null,"abstract":"Electrocatalytic alkyne semi-hydrogenation (EASH) powered by renewable electricity using water as a hydrogen donor provides a sustainable alternative to conventional thermocatalysis. However, the current EASH systems predominantly follow hydrogen atom transfer (HAT) pathways, which are prone to over-hydrogenation and at the same time compete with the hydrogen evolution reaction. In this work, we report a proton-coupled electron transfer (PCET) mechanism enabled on Cu(111) surface for highly efficient and selective EASH. Well-defined two-dimensional Cu nanosheets with exposed (111) facets achieve > 98% selectivity for electrochemical semi-hydrogenation of 4-aminophenylacetylene to 4-vinylphenylamine in a membrane electrode assembly reactor. The Cu nanosheets can also efficiently remove 1%-8% alkyne impurities in alkene and exhibit broad substrate scope, stereoselectivity, as well as operational stability. In situ Raman spectroscopy measurements reveal that, during the PCET-mediated EASH, the covalent adsorption of alkynes and their conversion to weakly bound planar intermediates facilitate the EASH process and suppress over-hydrogenation. Interfacial K+-structured and linearly hydrogen-bonded water species further enhance EASH selectivity via proton supply and steric modulation. Radical scavenging and kinetic isotope effect studies, along with theoretical calculations, corroborate a PCET-dominated mechanism on Cu(111) surface. This work establishes a PCET-driven paradigm for selective hydrogenation beyond the conventional HAT pathways.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"8 1","pages":"e202510192"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769561","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}
{"title":"Continuous Photocatalytic Acetylene Conversion to Ethylene in Liquid Under Ambient Conditions.","authors":"Xiaojia Lei,Chao Lei,Xuxu Wang,Wenqian Chen,Qian Guo,Yongyou Hu,Jianbo Liu,Tiefeng Wang,Binbin Huang","doi":"10.1002/anie.202511422","DOIUrl":"https://doi.org/10.1002/anie.202511422","url":null,"abstract":"Ethylene is a basic building block for polymer synthesis, but its purification from petroleum-based processes (e.g., thermo-catalytic acetylene hydrogenation) and its production from coal-based processes (e.g., Fischer-Tropsch synthesis) normally require high temperature, high pressure, and gaseous hydrogen. Here, we report a continuous ethylene photosynthesis approach as a new platform technology that enables highly efficient and selective conversion of acetylene to ethylene in liquid under mild conditions. This platform technology is compatible with a wide range of solvents, catalysts, and hydrogen sources. Using Pd/mpg-C3N4 as the model photocatalyst, a complete conversion of acetylene was achieved with high ethylene selectivity (>93%) under the continuous flow of either a pure acetylene stream or a crude ethylene stream containing acetylene impurity. The process performance remained stable for at least 72 h. Physical, theoretical, and in situ spectroscopy investigations showed that the photocatalytic acetylene hydrogenation follows the proton-coupled electron transfer (PCET) and atomic hydrogen-mediated indirect electron transfer pathways with proton as the hydrogen source. The technoeconomic analysis (TEA) demonstrated that this photocatalytic approach has large profitable margins for both ethylene purification and ethylene production processes. This study provides a green and sustainable technology for both petrochemical (ethylene purification) and coal-chemical (ethylene production) industries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":"e202511422"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769563","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}
{"title":"Phase Transition-Induced Regulation of Room Temperature Phosphorescence and Delayed Fluorescence in Doping System.","authors":"Chenxiao Li,Yuteng Feng,Yue Feng,Yuehui Lin,Na Wang,Kun Liu,Qiuzhuo Dong,Chengguang Huang,Huifang Shi,Kang Shen,Wei Yao,Huili Ma,Zhongfu An,Wei Huang","doi":"10.1002/anie.202510781","DOIUrl":"https://doi.org/10.1002/anie.202510781","url":null,"abstract":"Switching between triplet-involved room temperature phosphorescence (RTP) and delayed fluorescence (DF) is pivotal for advancing molecular encryption application but remains a significant challenge in multicomponent material systems. In this study, we successfully realized the selective modulation of RTP and DF emissions in a donor-acceptor doping system by inducing conformational changes in the donor through solid-liquid transition. In the solid state, the donor adopts a highly twisted quasi-axial conformation, which effectively suppresses non-radiative decay, resulting in efficient green RTP. In contrast, in the liquid state, the donor transitions to a relatively planar conformation, forming the intermolecular charge transfer state with the acceptor, significantly reducing the energy gap between the lowest singlet and triplet excited states, thereby facilitating reverse intersystem crossing (RISC) and generating yellow DF. Furthermore, the coexistence of multiple emissive triplet states demonstrates promising applications in information encryption, ink-free rewritable paper, and thermal sensing.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":"e202510781"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769564","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}
Kai Lan,Cefei Zhang,Yifei Li,Changwei Hu,Zhishan Su,Chuyang Cheng
{"title":"Strain Energy Prompted Tunable Aggregation-Induced Emission Property of Tetraphenylethylene.","authors":"Kai Lan,Cefei Zhang,Yifei Li,Changwei Hu,Zhishan Su,Chuyang Cheng","doi":"10.1002/anie.202507763","DOIUrl":"https://doi.org/10.1002/anie.202507763","url":null,"abstract":"Organic molecules exhibiting aggregation-induced emission (AIE) have attracted considerable attention due to their exceptional solid-state luminescent properties. Understanding the AIE mechanism has been a focal point of both theoretical and experimental research. While conical intersection (CI) dynamics on potential energy surfaces (PESs) have emerged as a key factor in elucidating the AIE mechanism, modulating the accessibility to CI to regulate the non-radiative decay pathways remains a substantial challenge. Here we propose a new strategy leveraging strain energy introduced by cycloparaphenylenes (CPPs) to tune the AIE property of tetraphenylethylene (TPE). We synthesized and characterized a series of TPE-incorporated CPPs with varying sizes and endo/exo vinyl moieties. The photophysical properties and AIE behavior of these strained TPE-CPPs were meticulously examined. Endo-TPE-CPPs exhibit AIE, while Exo-TPE-CPPs do not, opposite to strain-free TPE macrocycles. The luminescence of Endo-TPE-CPPs and Exo-TPE-CPPs can be further tuned by adjusting the number of phenylene units in the loop. Their excited-state dynamics were investigated using density functional theory (DFT) calculation and time-resolved absorption spectroscopy. The strain energy induces structural distortion of TPE, stabilizing or elevating the transition state (TS), thereby regulating the accessibility to CI and enabling tunable AIE properties. These findings provide new insights for designing AIE molecules.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":"e202507763"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769867","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}
John M Bennett,Andrew R Bortz,Zheyuan Wang,Muhammed Fastheem,Rudi Fasan
{"title":"Chemoenzymatic Skeletal Editing of Natural Product Scaffolds via P450-Controlled Site-Selective Ring Expansion at Aliphatic C─H Sites.","authors":"John M Bennett,Andrew R Bortz,Zheyuan Wang,Muhammed Fastheem,Rudi Fasan","doi":"10.1002/anie.202512576","DOIUrl":"https://doi.org/10.1002/anie.202512576","url":null,"abstract":"Methods for introducing subtle modifications at the level of single atoms/bonds (\"skeletal editing\") are highly desirable in organic and medicinal chemistry, owing to their potential for fine-tuning the structure and biological activity of organic molecules. Here, we report a chemoenzymatic strategy for enabling the skeletal editing of organic frameworks via ring expansion at the level of one or more aliphatic (methylene) C─H sites, as achieved through the synergistic combination of P450-mediated site-selective oxidation with subsequent Baeyer-Villiger rearrangement or ketone homologation. Combining this approach with engineered P450 catalysts exhibiting divergent regioselectivity enabled the expeditious synthesis of a panel of ring-expanded analogs of various complex natural product substrates. Importantly, the skeletal modification was found to drastically altered the anticancer activity of some of these compounds. By the direct targeting of aliphatic C─H sites with tunable site-selectivity, this strategy provides a powerful tool to rapidly access skeletally edited derivatives of natural products and other bioactive molecules for applications in drug discovery and chemical biology.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"28 1","pages":"e202512576"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769567","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}
{"title":"A Natural Oxygen-Harvesting Electrode Enables Aeration-Free Electrochemical Advanced Oxidation for In Situ Water Remediation.","authors":"Sijin Zuo,Geyi Zheng,Dailin Yang,Juan Wang","doi":"10.1002/anie.202513329","DOIUrl":"https://doi.org/10.1002/anie.202513329","url":null,"abstract":"Electro-Fenton treatment through the two-electron oxygen reduction reaction (2e- ORR) offers an effective approach for degrading persistent organic pollutants (POPs) in water; however, aeration is always required to overcome the low solubility of oxygen in water, ensuring adequate oxygen availability for the 2e- ORR to generate H2O2 and facilitate its transport for activation into hydroxyl radicals. The aeration energy consumption can reach tens of times higher than the energy required for the electrochemical reactions themselves. To address this, we developed an aeration-free dual-cathode system featuring a natural oxygen-harvesting electrode (NOHE). The NOHE's superhydrophobic and microporous structure effectively captures and utilizes anode-generated oxygen for H2O2 synthesis (957.1 mg gcat -1) without external aeration. By decoupling H2O2 generation and activation into separate cathodes, the system optimizes both processes independently, achieving superior efficiency. This design demonstrated rapid removal of bisphenol AF (BPAF) in saline environments, achieving 98% mineralization and exhibiting excellent operational stability over 90 h continuous use. By eliminating energy-intensive aeration, our approach may open the avenue for a scalable, sustainable solution for in situ water remediation, with broad applicability in diverse aquatic environments.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"58 1","pages":"e202513329"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769570","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}
{"title":"Coordinating the Competitive Adsorption of Organic and OH- to Accelerate Electrooxidation Kinetics of Biomass-Derived Nucleophiles.","authors":"Baojun Long,Mingyu Yang,Yuchan Li,Wenqing Li,Dong He,Zunjian Ke,Xiangheng Xiao","doi":"10.1002/anie.202508095","DOIUrl":"https://doi.org/10.1002/anie.202508095","url":null,"abstract":"Elaborating electrooxidation mechanisms of biomass molecules on transition-metal-based electrodes is crucial to designing high-performance active sites. Herein, we unveiled the direct oxidation mechanism of three electrode models, Co4N, CoO, and Co4N-CoO, in which the adsorptions of OH- and glycerol on the electrodes were competitive. The adsorption of glycerol on Co4N was quite strong but weak on CoO, whereas the CoO preferred to adsorb OH- species. The one-sided adsorption properties of surface reactants led to the sluggish electrooxidation kinetics of organics on Co4N and CoO. Constructing Co4N-CoO heterointerfaces significantly balanced the one-sided adsorption features. Due to the moderate OH- and glycerol adsorptions on Co4N-CoO, the OH- was mainly used to activate glycerol rather than trigger the oxidative reconstruction of materials to form high-valence OER sites. Consequently, the Co4N-CoO showed excellent glycerol oxidation properties. The Co4N-CoO delivered a lower Tafel slope of 178 mV dec-1 while achieving a high formate yield rate of 29.40 mmol cm-2 h-1. Furthermore, the Faradaic efficiency (FE) of formate was maintained above 90% in a 120-h electrolysis. In situ Raman and attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) experiments and DFT simulations unraveled that the improved GOR performance was mainly ascribed to the balanced co-adsorptions of OH- and organics on Co4N-CoO interfaces.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"30 1","pages":"e202508095"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769573","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}
{"title":"A Photoregulated Peptidase Mimic","authors":"Monochura Saha, Palash Jana, Subhajit Bandyopadhyay","doi":"10.1002/anie.202509194","DOIUrl":"https://doi.org/10.1002/anie.202509194","url":null,"abstract":"Proteases and peptidases play crucial roles in numerous biological processes. These enzymes bind to protein substrates and hydrolyze peptide bonds, resulting in the cleavage of proteins and peptides into smaller fragments. This study reports on a small‐molecule light activated peptidase (SLAP) enzyme mimic featuring a glucose‐linked photoswitch‐imidazole triad, where peptidase activity can be controlled by light by tuning the distance between the basic imidazole residue, the reaction center, and the sugar moiety, that provides a binding site for the substrate and also takes a role in stabilizing the transition state. The <jats:italic>cis</jats:italic> isomer exhibited a ∼300‐fold increase in catalytic activity compared to its inactive <jats:italic>trans</jats:italic> counterpart with a model amide‐substrate. Catalytic hydrolysis was studied with small molecules, FRET‐based substrates, and large cellular proteins. The light‐controlled peptidase activity opens new possibilities for protein degradation in biological systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144770019","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}
{"title":"Metallic Ni as Electron Acceptor Modulates the Redox of Catalytic Centers at Activated Ni0/Ni(OH)2 Heterojunctions for Efficient Ethanol Electrooxidation.","authors":"Ruixing Du,Bin Wu,Weiling Tan,Yuchen Lei,Yunchuan Tu,Chalachew Mebrahtu,Zuohuan Chen,Shulong Li,Zuhui Zhou,Zhenchen Tang,Huanhao Chen,Shiming Chen,Long Chen,Jian-Jun Wang,Xiaofeng Shi,Yifan Ye,Dingsheng Wang,Regina Palkovits,Wei Zhao,Feng Zeng","doi":"10.1002/anie.202510285","DOIUrl":"https://doi.org/10.1002/anie.202510285","url":null,"abstract":"The coproduction of high-value-added acetate and hydrogen fuel by ethanol-assisted water electrolysis is significant, but the efficiency of ethanol electrooxidation (EOR) is hindered both by sluggish kinetics, primarily dictated by the redox properties of the catalyst. Therefore, the development of efficient EOR electrocatalysts has to target optimized redox properties. Herein, a Ni0/Ni(OH)2 heterostructure was synthesized by inducing a shift from hydrophilic to hydrophobic properties on the electrode surface during electrochemical deposition. The electrocatalyst enabled a current density of 573.7 mA cm-2 at 1.37 V versus RHE for EOR with a solar-to-hydrogen conversion efficiency of 14.4% when coupled to a commercial solar panel. Experimental and theoretical results disclosed that the incorporation of Ni0 facilitates the ethanol to acetate kinetics through enhanced Ni2+ to Ni3+ conversion. The strategy, combining hydrogen production with the synthesis of value-added products, enhances economic viability compared to conventional water electrolysis, underscoring its promise for practical implementation.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":"e202510285"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769568","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}
Lu Wei,Likang Lv,Tong Han,Peiqi Chu,Yuxi Liu,Zhenxia Zhao,Hongxing Dai,Suping Cui,Yaoyao Zhao,Jiguang Deng
{"title":"Impact of Coordination Environment for Designing Ru-Based Alloy Catalysts for Ammonia Decomposition.","authors":"Lu Wei,Likang Lv,Tong Han,Peiqi Chu,Yuxi Liu,Zhenxia Zhao,Hongxing Dai,Suping Cui,Yaoyao Zhao,Jiguang Deng","doi":"10.1002/anie.202513385","DOIUrl":"https://doi.org/10.1002/anie.202513385","url":null,"abstract":"Alloying is an effective strategy to modulate a metal catalyst's electronic structure and optimize its performance, but developing a fundamental design principle has been challenging due to the geometric and electronic disturbance between the active atom and its microenvironment. We introduce a descriptor, coordination impact, which combines ligand and structural effects to quantify the influence of neighboring atoms on the electronic structure of the adsorption site. Using first-principles simulations, microkinetic model and experimental data, we thoroughly examine the catalytic performance of RuM alloys for ammonia decomposition using this descriptor. The microenvironment influences the activity of adsorption site by modulating the orbital interaction between the active site and adsorbate. The descriptor follows a volcano-shaped relationship with reaction rates, consistent with Sabatier principle, and the predicted rates are experimentally validated.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":"e202513385"},"PeriodicalIF":16.6,"publicationDate":"2025-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144769865","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}