Nature Catalysis最新文献_第5页

Coupled cation–electron transfer at the Pt(111)/perfluoro-sulfonic acid ionomer interface and its impact on the oxygen reduction reaction kinetics Pt(111)/全氟磺酸离聚体界面阳离子-电子耦合转移及其对氧还原反应动力学的影响

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-13 DOI: 10.1038/s41929-024-01279-1

Kaiyue Zhao, Mingchuan Luo, Yongfan Zhang, Xiaoxia Chang, Bingjun Xu

{"title":"Coupled cation–electron transfer at the Pt(111)/perfluoro-sulfonic acid ionomer interface and its impact on the oxygen reduction reaction kinetics","authors":"Kaiyue Zhao, Mingchuan Luo, Yongfan Zhang, Xiaoxia Chang, Bingjun Xu","doi":"10.1038/s41929-024-01279-1","DOIUrl":"10.1038/s41929-024-01279-1","url":null,"abstract":"Electrochemical interfaces between polymer electrolytes and electrodes are central to electrochemical devices in the global transition towards renewable energy. Here we show that the adsorption and desorption of sulfonates in Nafion on Pt(111) involve distinct elementary steps, with the latter proceeding through a coupled cation–electron transfer. Adsorbed sulfonates not only block a fraction of surface Pt sites but, more importantly, generate two additional types of surface adsorbate, OHNafion and ONafion, which exhibit distinct kinetic properties from adsorbed OH and O on bare Pt(111), respectively. The impact of the adsorption of sulfonate groups in Nafion on the activity of the oxygen reduction reaction (ORR) on Pt cannot be rationalized by existing thermodynamic descriptors. The reduced ORR activity on the Nafion-covered Pt(111) is caused by the kinetically hindered *O→*OH conversion and *OH reduction on sites close to adsorbed sulfonates. The understanding of electrochemical interfaces between polymer electrolytes and metal electrodes, which is critical to many practical devices, remains limited. Now, the interaction between Nafion’s sulfonate groups and platinum and its impact on the oxygen reduction reaction is studied in detail, and a distinct coupled cation–electron transfer mechanism is identified.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 1","pages":"46-57"},"PeriodicalIF":42.8,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968209","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

Organic electrolyte cations promote non-aqueous CO2 reduction by mediating interfacial electric fields 有机电解质阳离子通过介面电场促进非水CO2还原

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-10 DOI: 10.1038/s41929-024-01278-2

Jon-Marc McGregor, Jay T. Bender, Amanda S. Petersen, Louise Cañada, Jan Rossmeisl, Joan F. Brennecke, Joaquin Resasco

{"title":"Organic electrolyte cations promote non-aqueous CO2 reduction by mediating interfacial electric fields","authors":"Jon-Marc McGregor, Jay T. Bender, Amanda S. Petersen, Louise Cañada, Jan Rossmeisl, Joan F. Brennecke, Joaquin Resasco","doi":"10.1038/s41929-024-01278-2","DOIUrl":"10.1038/s41929-024-01278-2","url":null,"abstract":"The electrochemical reduction of CO2 is sensitive to the microenvironment surrounding catalytic active sites. Although the impact of changing electrolyte composition on rates has been studied intensively in aqueous electrolytes, less is known about the influence of the electrochemical environment in non-aqueous solvents. Here we demonstrate that organic alkylammonium cations influence catalytic performance in non-aqueous media and describe a physical model that rationalizes these observations. Using results from kinetic, spectroscopic and computational techniques, we argue that the strength of the electric field at the catalyst surface is sensitive to the molecular identity of the organic cation in the electrolyte. This is true irrespective of solvent, electrolyte ionic strength or electrolyte anion. Our results suggest that changes in the interfacial electric field strength can be attributed to differences in the cation–electrode distance. Changes in the electric field strength affect CO formation rates as they modify the energetics of the kinetically relevant CO2 activation step. Electrolyte cations have been shown to have a strong impact on reactivity in electrocatalytic CO2 reduction. However, most studies have been performed in an aqueous environment. Here the effect of various alkylammonium cations on CO2 reduction in aprotic solvents is investigated, with the interfacial electric field induced by the cations shown to be a dominant factor.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 1","pages":"79-91"},"PeriodicalIF":42.8,"publicationDate":"2025-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142961389","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

Confined hot-pressurized water in Brønsted-acidic beta zeolite speeds up the O-demethylation of guaiacol br ønsted-酸性β沸石中的密闭热压水加速愈创木酚的O去甲基化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-09 DOI: 10.1038/s41929-024-01282-6

Massimo Bocus, Elias Van Den Broeck, Xian Wu, Mathias Bal, Jeroen Bomon, Louis Vanduyfhuys, Bert F. Sels, Bert U. W. Maes, Veronique Van Speybroeck

{"title":"Confined hot-pressurized water in Brønsted-acidic beta zeolite speeds up the O-demethylation of guaiacol","authors":"Massimo Bocus, Elias Van Den Broeck, Xian Wu, Mathias Bal, Jeroen Bomon, Louis Vanduyfhuys, Bert F. Sels, Bert U. W. Maes, Veronique Van Speybroeck","doi":"10.1038/s41929-024-01282-6","DOIUrl":"10.1038/s41929-024-01282-6","url":null,"abstract":"Biorefinery technologies that convert lignin into platform chemicals are essential to reduce our future dependence on fossil resources. In these technologies, a key process is the acid-catalysed O-demethylation of guaiacol derivatives in hot-pressurized water using Brønsted mineral acids or microporous zeolites. The fundamental understanding of how hydronium ions behave in a confined environment versus bulk is still limited. Here we investigate the O-demethylation of guaiacol in hot-pressurized water with HCl or H-BEA zeolite catalysts to elucidate the impact of zeolite microporosity on reaction mechanisms and rates. Operando molecular simulations combined with experimental kinetic studies reveal that, regardless of the catalyst type, O-demethylation follows a concerted O-activated SN2 mechanism. The reaction rate is higher in the zeolite due to more active, under-coordinated hydronium ions. Additionally, the molecular organization of solvent and reactants around the confined active site plays a crucial role in modulating the association of the reacting species and the reaction kinetics. Understanding the interplay between solvent, reactant and catalyst is important to advance towards upgrading biomass into useful products, but the process remains challenging. Now a study on guaiacol demethylation in water highlights the substantial shift in catalytic behaviour that occurs when moving from bulk water to the confined space within zeolite channels.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 1","pages":"33-45"},"PeriodicalIF":42.8,"publicationDate":"2025-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142937423","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

Site- and enantioselective allylic and propargylic C–H oxidation enabled by copper-based biomimetic catalysis 位和对映选择性烯丙基和丙炔C-H氧化由铜基仿生催化实现

IF 42.8 1区化学

Nature Catalysis Pub Date : 2025-01-08 DOI: 10.1038/s41929-024-01276-4

Honggang Zhang, Yibo Zhou, Tilong Yang, Jingui Wu, Pinhong Chen, Zhenyang Lin, Guosheng Liu

{"title":"Site- and enantioselective allylic and propargylic C–H oxidation enabled by copper-based biomimetic catalysis","authors":"Honggang Zhang, Yibo Zhou, Tilong Yang, Jingui Wu, Pinhong Chen, Zhenyang Lin, Guosheng Liu","doi":"10.1038/s41929-024-01276-4","DOIUrl":"10.1038/s41929-024-01276-4","url":null,"abstract":"Methods for direct enantioselective oxidation of C(sp3)–H bonds will revolutionize the preparation of chiral alcohols and their derivatives. Enzymatic catalysis, which uses key metal-oxo species to facilitate efficient hydrogen atom abstraction, has evolved as a highly selective approach for C–H oxidation in biological systems. Despite its effectiveness, reproducing this function and achieving high stereoselectivity in biomimetic catalysts has proven to be a daunting task. Here we present a copper-based biomimetic catalytic system that achieves highly efficient asymmetric sp3 C–H oxidation with C–H substrates as the limiting reagent. A Cu(II)-bound tert-butoxy radical is responsible for the site-selective C–H bond cleavage, which resembles the active site of copper-based enzymes for C–H oxidation. The developed method has been successfully accomplished with good functional group compatibility and exceptionally high site- and enantioselectivity, which is applicable for the late-stage oxidation of bioactive compounds. The efficiency of enantioselective sp3 C–H bond oxidation using small synthetic catalysts is usually limited. Now a catalytic system involving a Cu(II)-bound tert-butoxy radical for site-selective C–H bond cleavage achieves allylic and propargylic sp3 C–H oxidation with the C–H substrates as the limiting reagent.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 1","pages":"58-66"},"PeriodicalIF":42.8,"publicationDate":"2025-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142936391","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

Publisher Correction: Parahydrogen-enhanced magnetic resonance identification of intermediates in [Fe]-hydrogenase catalysis [Fe]-氢化酶催化中间体的对氢增强磁共振鉴定

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-23 DOI: 10.1038/s41929-024-01285-3

Lukas Kaltschnee, Andrey N. Pravdivtsev, Manuel Gehl, Gangfeng Huang, Georgi L. Stoychev, Christoph Riplinger, Maximilian Keitel, Frank Neese, Jan-Bernd Hövener, Alexander A. Auer, Christian Griesinger, Seigo Shima, Stefan Glöggler

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[Fe]-hydrogenase intermediates revealed [Fe]-氢化酶中间体的发现

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01274-6

Sven T. Stripp

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Photoelectrochemical asymmetric catalysis 光电化学不对称催化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01260-y

Chong Huang, Peng Xiong, Xiao-Li Lai, Hai-Chao Xu

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One zeolite for multiple Fe species 一种沸石可用于多种铁

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01272-8

Yulong Shan, Hong He

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Photobiocatalysis with non-haem iron enzymes for enantioselective radical transformations 非血红素铁酶对映选择性自由基转化的光生物催化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01263-9

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The STRENDA Biocatalysis Guidelines for cataloguing metadata 元数据编目的STRENDA生物催化指南

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01261-x

Stephan Malzacher, Dominik Meißner, Jan Range, Zvjezdana Findrik Blažević, Katrin Rosenthal, John M. Woodley, Roland Wohlgemuth, Peter Wied, Bernd Nidetzky, Robert T. Giessmann, Kridsadakorn Prakinee, Pimchai Chaiyen, Andreas S. Bommarius, Johann M. Rohwer, Rodrigo O. M. A. de Souza, Peter J. Halling, Jürgen Pleiss, Carsten Kettner, Dörte Rother

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