ACS Catalysis 最新文献_第4页

Synthesis of α-Chlorocarbonyls through Kharasch-Type Addition and Cotelomerization Driven by Photoredox/Cobalt Dual Catalysis 光氧化还原/钴双催化催化下kharasch型加成和共端粒合成α-氯羰基

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-30 DOI: 10.1021/acscatal.6c06753

Asuka Tonomura, Shotaro Shibutani, Kazunori Nagao, Hirohisa Ohmiya

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From α,β-Unsaturated Amide to Enamide: Intramolecular Alkene Translocation via Iridium-Catalyzed Transfer Hydrogenation 从α，β-不饱和酰胺到烯酰胺：通过铱催化转移氢化的分子内烯烃易位

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-29 DOI: 10.1021/acscatal.6c05353

Yin Xu, Zhi-Zhou Pan, Guangbin Dong

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Enantioselective Scandium-Catalyzed Benzylic C−H Addition of Tertiary Anilines to Alkenes 叔苯胺在钪催化下对映选择性C−H加成烯烃

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-07 DOI: 10.1021/acscatal.6c05658

Xiangli Feng, Jiao Zhang, Qianlin Sun, Gen Luo, Xin Xu

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Rewiring Electrocatalytic Nitrate Reduction with Single-Atom-Based Dual Active Sites at the Water-Energy Nexus 水-能关系中单原子双活性位点电催化硝酸还原的研究

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-06 DOI: 10.1021/acscatal.6c06060

Xialiang Jiang, Wen Lu, Haochen Ma, Mingzhu Zhou, Jiaheng Teng, Leihong Zhao, Hongjun Lin, Bisheng Li

{"title":"Rewiring Electrocatalytic Nitrate Reduction with Single-Atom-Based Dual Active Sites at the Water-Energy Nexus","authors":"Xialiang Jiang, Wen Lu, Haochen Ma, Mingzhu Zhou, Jiaheng Teng, Leihong Zhao, Hongjun Lin, Bisheng Li","doi":"10.1021/acscatal.6c06060","DOIUrl":"10.1021/acscatal.6c06060","url":null,"abstract":"Nitrate electroreduction links water purification with ammonia production, but its use is still limited by sluggish proton-coupled electron transfer, poor product selectivity, and competition from the hydrogen evolution reaction. Single-atom-based dual active sites (SADASCs) address these constraints by coupling atomically dispersed metal centres with adjacent single atoms, clusters, or nanoparticles. Such coupled motifs regulate adsorption, charge redistribution, intermediate stabilisation, hydrogen supply, and product release in a step-specific manner. This review discusses electrocatalytic nitrate reduction according to its elementary sequence: nitrate adsorption and activation, initial N–O bond cleavage, nitrite conversion, deep NOx hydrogenation, active-hydrogen regulation, product desorption, and catalyst reconstruction. SADASCs are then classified into single-atom/single-atom, single-atom/cluster, and single-atom/nanoparticle architectures, with emphasis on how dual-site coupling overcomes the limitations of isolated single atoms. Key challenges in stability, operando identification, selectivity control, benchmarking, matrix tolerance, and device integration are also summarized. This perspective provides design principles for dual-site catalysts that can promote nitrate valorization under complex aquatic conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19829–19845"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092019","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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Kinetic Resolution of Ferrocenyl Halide Racemates via Palladium/Chiral Norbornene Cooperative Catalysis 钯/降冰片烯协同催化下二茂铁卤化物外消旋物的动力学拆分

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-15 DOI: 10.1021/acscatal.6c05029

Dan Ye, Lan Zhou, Shuang Deng, Huimin Li, Yabin Zhang, Qianghui Zhou, Hong-Gang Cheng

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The Cu(210)/ZnO Interface: The Operando Active Sites for Industrial Water-Gas Shift Catalysis Cu(210)/ZnO界面：工业水气转换催化的操作活性位点

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-28 DOI: 10.1021/acscatal.6c05264

Hongbo Zhao, Qingli Tang, Beien Zhu, Yi Gao

{"title":"The Cu(210)/ZnO Interface: The Operando Active Sites for Industrial Water-Gas Shift Catalysis","authors":"Hongbo Zhao, Qingli Tang, Beien Zhu, Yi Gao","doi":"10.1021/acscatal.6c05264","DOIUrl":"10.1021/acscatal.6c05264","url":null,"abstract":"Copper nanoparticles (NPs) supported on a ZnO substrate represent a textbook catalytic system for industrial applications. However, the atomic identity of their active sites remains obscured by the “pressure gap” between surface science and industrial catalysis. Using multiscale structure reconstruction modeling, we elucidate the energetic driving forces behind the shape evolution of Cu NPs, demonstrating that high CO chemical potentials under realistic industrial pressures (PCO > 1 bar) induce a drastic in situ morphological restructuring. Crucially, this structural evolution remains highly robust under operando water-gas shift reaction (WGSR) conditions with coexisting CO and H2O, where the Cu NPs preferentially expose previously overlooked open (210) facets, while the conventionally emphasized stepped or Cu(111) vicinal facets virtually vanish. Integrating density functional calculations with microkinetic simulations, we reveal that the self-generated Cu(210)/ZnO interfaces exhibit enhanced catalytic activity for the WGSR, profoundly reducing the reaction barriers of the rate-determining steps while accelerating the overall turnover kinetics. Our simulated turnover frequencies quantitatively align with experimental benchmarks, establishing the Cu(210)/ZnO interface, rather than traditional models, as the authentic active site. These findings shift the paradigm of Cu/ZnO catalysis from static surface models to environment-adaptive interfacial evolution under realistic working conditions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20419–20429"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149090643","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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A Redox-Active Iron Azo-Pyridine Complex for Aqueous H2 Evolution and H2 Oxidation: From Mechanism to Devices 一种具有氧化还原活性的铁偶氮吡啶配合物：从机理到装置

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-05 DOI: 10.1021/acscatal.6c03030

Thinles Dolkar, Naseer Ahmad Shah, Vaibhav Trivedi, Saptarshi Ghosh Dastider, Manodip Pal, Tannu Kaushik, Krishnakanta Mondal, Goutam K. Lahiri, Arnab Dutta

{"title":"A Redox-Active Iron Azo-Pyridine Complex for Aqueous H2 Evolution and H2 Oxidation: From Mechanism to Devices","authors":"Thinles Dolkar, Naseer Ahmad Shah, Vaibhav Trivedi, Saptarshi Ghosh Dastider, Manodip Pal, Tannu Kaushik, Krishnakanta Mondal, Goutam K. Lahiri, Arnab Dutta","doi":"10.1021/acscatal.6c03030","DOIUrl":"10.1021/acscatal.6c03030","url":null,"abstract":"The efficient and reversible interconversion of protons and molecular hydrogen is essential for commercially viable hydrogen energy systems. Natural hydrogenases catalyze this process with unmatched efficiency but lack operational stability outside biological conditions. Inspired by their catalytic activity, a water-soluble nonheme iron complex, Fe(pap)3(ClO4)2 (pap = 2-(phenylazo)pyridine), has been developed as a molecular catalyst exhibiting bifunctional homogeneous hydrogen evolution (HER) and hydrogen oxidation (HOR) activity in aqueous media. The complex achieves a turnover number of ∼800 for HOR and delivers HER with ∼90% Faradaic efficiency at overpotentials near 150 mV, maintaining activity under mild conditions. Ligand redox activity facilitates electron and proton transfer, enabling efficient HER and HOR. Beyond mechanistic relevance, the catalyst is integrated into a prototype fuel cell and electrolyzer. In HOR fuel cell mode, an open-circuit voltage of 0.98 V and a peak power density of 0.87 mW·cm–2 is observed, while in a separate PEM electrolyzer operated in HER mode, sustained hydrogen evolution is observed under acidic conditions. This study highlights the potential of nonheme molecular iron catalysts to enable translation of molecular electrocatalysis toward device-relevant hydrogen conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"19956–19971"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092023","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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Molecular Activation of MoS2 Photocatalysts Enables Direct Reduction of Atmospheric CO2 二硫化钼光催化剂的分子活化实现了大气CO2的直接还原

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-30 DOI: 10.1021/acscatal.6c04428

Heying Li, Hao Liu, Zhenyu Zhang, Bingjie Guo, Zihao Huang, Weiqi Mao, Haitao Sun, Guiling Shi, Jingxiang Zhao, Congmin Wang, Kaihong Chen

{"title":"Molecular Activation of MoS2 Photocatalysts Enables Direct Reduction of Atmospheric CO2","authors":"Heying Li, Hao Liu, Zhenyu Zhang, Bingjie Guo, Zihao Huang, Weiqi Mao, Haitao Sun, Guiling Shi, Jingxiang Zhao, Congmin Wang, Kaihong Chen","doi":"10.1021/acscatal.6c04428","DOIUrl":"10.1021/acscatal.6c04428","url":null,"abstract":"The production of solar fuels directly from atmospheric CO2 remains a long-standing goal, primarily because catalysts perform poorly under highly dilute CO2 (approximately 420 ppm) and in the presence of oxygen. Herein, we report a molecular activation strategy that simultaneously enriches the local CO2 concentration and tunes the electronic structure of active sites by integrating basic organic ligands into cobalt-doped MoS2 (MoS2:Co). Density functional theory (DFT) calculations reveal that ligand basicity governs both CO2 adsorption capacity and metal–ligand interactions, enabling precise control over catalytic activity. This synergy, achieved by integrating a ligand of moderate basicity, i.e., 2-methylimidazole (2-MIm), onto the surface of MoS2:Co, results in an over 1800-fold enhancement in formic acid production with >99% selectivity in pure water and without sacrificial agents. Notably, the system can also operate under ambient air and natural sunlight, producing formic acid continuously for five days without external CO2 supply. In situ spectroscopy and DFT calculations underlie the essential role of 2-MIm in enhancing CO2 reduction kinetics by modulating the electronic structure of Co dopants, facilitating electron transfer, and stabilizing intermediates. By effectively bypassing the need for energy-intensive direct air capture, this work establishes a robust and viable pathway for developing decentralized solar refineries that convert air directly into solar fuels.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20078–20088"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092085","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

Uncovering Functional Distant Mutations by Ultrahigh-Throughput Screening of Dehalogenases 通过超高通量筛选脱卤酶发现功能性远端突变

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-10-02 DOI: 10.1021/acscatal.6c03694

Hana Faldynova, David Kovar, Ankit Jain, Michaela Slanska, Marek Martinek, Andreas Jakob, Marie Sulova, Michal Vasina, Joan Planas-Iglesias, Sergio M. Marques, Naina Verma, Pavel Vanacek, David Damborsky, Christoffel P. S. Badenhorst, Tomas Buryska, Flora W. Y. Chiu, Marika Majerova, Tana Kohutekova, Petr Kouba, Nela Sendlerova, Andrew J. deMello, Jiri Damborsky, Josef Sivic, Uwe T. Bornscheuer, David Bednar, Stanislav Mazurenko, Lenka Hernychova, Martin Marek, Petr Klan, Stavros Stavrakis, Zbynek Prokop

{"title":"Uncovering Functional Distant Mutations by Ultrahigh-Throughput Screening of Dehalogenases","authors":"Hana Faldynova, David Kovar, Ankit Jain, Michaela Slanska, Marek Martinek, Andreas Jakob, Marie Sulova, Michal Vasina, Joan Planas-Iglesias, Sergio M. Marques, Naina Verma, Pavel Vanacek, David Damborsky, Christoffel P. S. Badenhorst, Tomas Buryska, Flora W. Y. Chiu, Marika Majerova, Tana Kohutekova, Petr Kouba, Nela Sendlerova, Andrew J. deMello, Jiri Damborsky, Josef Sivic, Uwe T. Bornscheuer, David Bednar, Stanislav Mazurenko, Lenka Hernychova, Martin Marek, Petr Klan, Stavros Stavrakis, Zbynek Prokop","doi":"10.1021/acscatal.6c03694","DOIUrl":"10.1021/acscatal.6c03694","url":null,"abstract":"Conformational dynamics play a central role in enzyme function by controlling substrate access and productive binding. Yet, mutations that beneficially modulate these properties are difficult to identify. Here, we used ultrahigh-throughput fluorescence-activated droplet sorting (FADS) with a bulky fluorogenic substrate derived from coumarin (COU-3) to impose steric selection pressure on the haloalkane dehalogenase LinB. Screening a focused library yielded five single substitutions located 11.5–15.5 Å from the catalytic center. Variant I138N showed a fourfold increase in catalytic efficiency towards COU-3 through reduced KM and increased kcat, associated with increased cap-domain flexibility and facilitated substrate entry. In contrast, variant P208S markedly reduced substrate inhibition and shifted specificity towards bulkier iodinated haloalkanes by reshaping its tunnel environment. Integrated kinetic and structural analyses revealed that screening with bulky substrates directs selection towards distal regions controlling substrate access and unproductive binding. These findings demonstrate that combining ultrahigh-throughput FADS with focused library design can reveal dynamic mechanisms of enzyme adaptation that remain challenging to anticipate using conventional rational-design approaches.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20001–20014"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092089","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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Enabling Data-Efficient Machine Learning through Multi-Target Training Set Design via Greedy Neighborhood Coverage 通过贪婪邻域覆盖的多目标训练集设计实现数据高效机器学习

IF 13.6 1区化学

ACS Catalysis Pub Date : 2026-10-16 Epub Date: 2026-09-28 DOI: 10.1021/acscatal.6c04894

Jakob A. Meckes, Jiang Yi He, Jolene P. Reid

{"title":"Enabling Data-Efficient Machine Learning through Multi-Target Training Set Design via Greedy Neighborhood Coverage","authors":"Jakob A. Meckes, Jiang Yi He, Jolene P. Reid","doi":"10.1021/acscatal.6c04894","DOIUrl":"10.1021/acscatal.6c04894","url":null,"abstract":"Machine learning is increasingly used to guide asymmetric catalysis, but each enantioselectivity measurement remains experimentally expensive. Prior work established that predictive accuracy in these datasets is dominated by reactions that are structurally similar to the target, motivating neighborhood-restricted models, such as radius-based random forests (RaRF). However, realistic screening campaigns require predictions for many related targets simultaneously (e.g., 20–50 reactions in a scope), and selecting training data independently for each target can be redundant because target neighborhoods overlap. Here, we frame multi-target training set design as a neighborhood multi-coverage problem, where the goal is to select a compact shared set of experiments such that each target retains at least one neighbor within a given similarity radius in reaction fingerprint space. We introduce MT-RaRF, a greedy neighborhood-coverage algorithm that prioritizes candidate experiments that satisfy the remaining local-neighbor needs of underserved targets while exploiting overlap among neighborhoods. Across several previously curated asymmetric catalysis datasets, MT-RaRF can use only a fraction of the experiments required by independent RaRF while maintaining comparable mean absolute errors. Systematic comparisons across similarity radii, training budgets, and target-set distributions establish practical guidelines for prospective use: MT-RaRF is most effective when locality is enforced, experimental budgets are limited, and target panels contain overlapping neighborhoods. MT-RaRF therefore makes locality-driven models practical and affordable for multi-target screening in asymmetric catalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 20","pages":"20235–20246"},"PeriodicalIF":13.6,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149092278","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