Nature Catalysis最新文献_第3页

Generating alkyl carbanions for organic synthesis 有机合成用烷基碳离子的生成

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01264-8

Sergio González-Granda, Corey R. J. Stephenson

引用次数: 0

Alkali metal cations act as homogeneous cocatalysts for the oxygen reduction reaction in aqueous electrolytes 碱金属阳离子是水溶液中氧还原反应的均相助催化剂

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01241-1

Sang Gu Ji, Minho M. Kim, Man Ho Han, Junsic Cho, Yoosang Son, Young Yong Kim, Jaeyoung Jeong, Zee Hwan Kim, Keun Hwa Chae, Hyung-Suk Oh, Hyungjun Kim, Chang Hyuck Choi

{"title":"Alkali metal cations act as homogeneous cocatalysts for the oxygen reduction reaction in aqueous electrolytes","authors":"Sang Gu Ji, Minho M. Kim, Man Ho Han, Junsic Cho, Yoosang Son, Young Yong Kim, Jaeyoung Jeong, Zee Hwan Kim, Keun Hwa Chae, Hyung-Suk Oh, Hyungjun Kim, Chang Hyuck Choi","doi":"10.1038/s41929-024-01241-1","DOIUrl":"10.1038/s41929-024-01241-1","url":null,"abstract":"Alkali metal cations (AM+) exhibit high solubility and ionic conductivity, making them optimal components in aqueous electrolytes. Despite the conventional belief that AM+ are chemically inert spectators, the strong dependence of electrocatalysis on AM+ has recently provoked debates about their unforeseen catalytic role. However, conclusive evidence is still lacking. Here we demonstrate that AM+ can couple with reaction intermediates and determine kinetics as homogeneous cocatalysts in aqueous conditions, for the alkaline oxygen reduction reaction on a carbon catalyst. In situ X-ray absorption spectroscopy reveals a change in the electronic structure of Na+ from its hydrated state on a charged electrode. In situ Raman spectroscopy further identifies that this change is due to the formation of water-unstable NaO2 as a key intermediate in OOH− production. Together with theoretical calculations, this finding enunciates the counterintuitive cocatalytic role of AM+ in aqueous environments, highlighting the exigency of refined interface design principles for better electrocatalysis. Alkali cations in electrolytes are commonly considered chemically inert species, but their role has recently been called into question. Now, using in situ spectroscopy and molecular dynamics simulations, it is shown that alkali cations couple with intermediates in the oxygen reduction reaction, acting as cocatalysts.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1330-1338"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858064","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

Polymer-decorated bacteria for cascade catalysis 用于级联催化的聚合物修饰细菌

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01273-7

Andrea Belluati, Nico Bruns

引用次数: 0

Methanotrophic catalysis for methane oxidation to formaldehyde 甲烷氧化生成甲醛的甲烷营养催化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01252-y

引用次数: 0

An unsung hero in electrochemistry 电化学领域的无名英雄

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01265-7

Yang-Fan Xu, Xiangfeng Chen, Xiangdong Yao

引用次数: 0

Merging photoredox with metalloenzymatic catalysis for enantioselective decarboxylative C(sp3)‒N3 and C(sp3)‒SCN bond formation 合并光氧化还原与金属酶催化对映选择性脱羧C(sp3) -N3和C(sp3) -SCN键形成

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-20 DOI: 10.1038/s41929-024-01257-7

Jinyan Rui, Xinpeng Mu, Jordi Soler, Jared C. Paris, Yisong Guo, Marc Garcia-Borràs, Xiongyi Huang

{"title":"Merging photoredox with metalloenzymatic catalysis for enantioselective decarboxylative C(sp3)‒N3 and C(sp3)‒SCN bond formation","authors":"Jinyan Rui, Xinpeng Mu, Jordi Soler, Jared C. Paris, Yisong Guo, Marc Garcia-Borràs, Xiongyi Huang","doi":"10.1038/s41929-024-01257-7","DOIUrl":"10.1038/s41929-024-01257-7","url":null,"abstract":"The scope of nature’s catalytic abilities has been expanded by recent advancements in biocatalysis to include synthetic transformations with no biological equivalent. However, these newly introduced catalytic functions represent only a small fraction of reactions utilized in synthetic catalysis. Here we present a biocatalytic platform that combines photoredox and metalloenzymatic catalysis for enantioselective radical transformations. Under green light irradiation, the eosin Y photocatalyst enables 4-hydroxyphenylpyruvate dioxygenases to catalyse enantioselective decarboxylative azidation and thiocyanation of N-hydroxyphthalimide esters. The final optimized variant obtained through directed evolution can afford diverse chiral organic azide and thiocyanate compounds with up to 77% yield, 385 total turnovers and 94% enantiomeric excess. Mechanistic studies show that the eosin Y catalyst mediates the generation of both C(sp3) radical and Fe(III)‒N3/Fe(III)‒NCS intermediate, leading to efficient enantioselective C‒N3 and C‒SCN bond formation in the enzyme active site. These findings establish an adaptable biocatalytic platform for introducing abiological metallophotoredox catalysis into biology. Decarboxylative azidation is a valuable transformation in organic chemistry, but a biocatalytic equivalent remained elusive. Now merging photoredox with metalloenzymatic catalysis enables the enantioselective decarboxylative radical azidation and thiocyanation of N-hydroxyphthalimide esters.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1394-1403"},"PeriodicalIF":42.8,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142858194","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

Earth-abundant electrocatalysts for acidic oxygen evolution 用于酸性氧进化的地球富集电催化剂

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-17 DOI: 10.1038/s41929-024-01266-6

Rendian Wan, Tenghui Yuan, Liuchen Wang, Bing Li, Meilin Liu, Bote Zhao

{"title":"Earth-abundant electrocatalysts for acidic oxygen evolution","authors":"Rendian Wan, Tenghui Yuan, Liuchen Wang, Bing Li, Meilin Liu, Bote Zhao","doi":"10.1038/s41929-024-01266-6","DOIUrl":"10.1038/s41929-024-01266-6","url":null,"abstract":"Proton-exchange membrane water electrolysis is a promising technology for green hydrogen production, but its widespread commercialization is hindered by the high cost and scarcity of precious-metal-based catalysts for the oxygen evolution reaction (OER). Recent progress has been made in developing low-cost, earth-abundant electrocatalysts for the acidic OER, but little is known about degradation pathways. This makes the design of active and robust catalysts challenging. Here we review recent advances in the design of earth-abundant catalysts for the acidic OER, examining the degradation mechanisms from the device level to the catalyst electronic structure level, and highlighting the relevant characterization techniques. We discuss the thermodynamic and kinetic stability of the catalysts and present a quantitative comparative analysis of electrochemical data to evaluate different materials and design strategies for catalysts. We also examine the performance of the catalysts in proton-exchange membrane water electrolysers and conclude with a discussion of the key scientific challenges and future perspectives in the field. Proton-exchange membrane water electrolysers often rely on scarce iridium or ruthenium catalysts at the anode, as many low-cost, earth-abundant catalysts cannot withstand the harsh operational conditions. This Review discusses the state of the art in earth-abundant water oxidation catalysts and examines their degradation mechanisms at multiple levels.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1288-1304"},"PeriodicalIF":42.8,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832610","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

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 : 2024-12-13 DOI: 10.1038/s41929-024-01262-w

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

{"title":"Parahydrogen-enhanced magnetic resonance identification of intermediates in [Fe]-hydrogenase catalysis","authors":"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","doi":"10.1038/s41929-024-01262-w","DOIUrl":"10.1038/s41929-024-01262-w","url":null,"abstract":"Hydrogenases are widespread metalloenzymes used for the activation and production of molecular hydrogen. Understanding the catalytic mechanism of hydrogenases can help to establish industrial (bio)catalytic hydrogen production and conversion. Here we show the observation of so-far undetectable intermediates of [Fe]-hydrogenase in its catalytic cycle. We observed these intermediates by applying a signal-enhancing NMR technique based on parahydrogen. Molecular hydrogen occurs as orthohydrogen or parahydrogen, depending on its nuclear spin state. We found that catalytic conversion of parahydrogen by the [Fe]-hydrogenase leads to notably enhanced NMR signals (parahydrogen-induced polarization, PHIP). The observed signals encode information about how the [Fe]-hydrogenase binds hydrogen during catalysis. Our data support models of the catalytic mechanism that involve the formation of a hydride at the iron centre. Moreover, PHIP enabled studying the binding kinetics. This work demonstrates the hitherto unexploited power of PHIP to study catalytic mechanisms of hydrogenases. The catalytic mechanism of [Fe]-hydrogenases is not well understood. Now a signal-enhanced nuclear magnetic resonance method based on parahydrogen is introduced to study [Fe]-hydrogenase under turnover conditions in situ, revealing intermediates of the catalytic cycle.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1417-1429"},"PeriodicalIF":42.8,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01262-w.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142815516","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering living cells with polymers for recyclable photoenzymatic catalysis 工程活细胞的聚合物可回收光酶催化

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-11 DOI: 10.1038/s41929-024-01259-5

Jian Ning, Zhiyong Sun, René Hübner, Henrik Karring, Morten Frendø Ebbesen, Mathias Dimde, Changzhu Wu

{"title":"Engineering living cells with polymers for recyclable photoenzymatic catalysis","authors":"Jian Ning, Zhiyong Sun, René Hübner, Henrik Karring, Morten Frendø Ebbesen, Mathias Dimde, Changzhu Wu","doi":"10.1038/s41929-024-01259-5","DOIUrl":"10.1038/s41929-024-01259-5","url":null,"abstract":"Engineering cell membranes for catalysis is challenging due to their inherent complexity. Here we introduce a polymeric strategy to overcome these challenges by chemically modifying cell membranes with catalytic polymers, enabling robust, recyclable and photoenzymatic catalysis. Through a one-step in situ atom transfer radical polymerization on living Escherichia coli cells, polymers are generated to protect the cells from environmental stressors while facilitating chemoenzymatic synthesis by integrating catalytic polymers with intracellular enzymes. As a proof of concept, a photoenzymatic cascade with an anthraquinone-based polymer and benzaldehyde lyase is demonstrated, converting benzyl alcohol into benzoin and achieving bioconversion yields that are 15 times higher than controls. Additionally, cells serve as large biological scaffolds for polymers, enabling recycling of macromolecular catalysts. A recyclable chemoenzymatic system incorporating an organometallic polymer with intracellular enzymes is also presented. Our versatile, straightforward approach offers a technology platform for engineering cell membranes for cascade synthesis, with broad implications for synthetic chemistry, polymer chemistry and biotechnology. Compatibility issues often limit chemoenzymatic systems. Now it is shown that the proximity between catalytic polymers grafted from the membrane of microorganisms and intracellular heterologous enzymes enhances the reaction rates of a photoenzymatic system, while the coating increases the stability.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1404-1416"},"PeriodicalIF":42.8,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804820","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

Concerted methane fixation at ambient temperature and pressure mediated by an alcohol oxidase and Fe-ZSM-5 catalytic couple 乙醇氧化酶和Fe-ZSM-5催化偶联介导的常温常压甲烷协同固定

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-12-04 DOI: 10.1038/s41929-024-01251-z

Daniel J. Lundberg, Jimin Kim, Yu-Ming Tu, Cody L. Ritt, Michael S. Strano

{"title":"Concerted methane fixation at ambient temperature and pressure mediated by an alcohol oxidase and Fe-ZSM-5 catalytic couple","authors":"Daniel J. Lundberg, Jimin Kim, Yu-Ming Tu, Cody L. Ritt, Michael S. Strano","doi":"10.1038/s41929-024-01251-z","DOIUrl":"10.1038/s41929-024-01251-z","url":null,"abstract":"Anthropogenic methane emissions, particularly from diffuse and dilute sources, pose a significant challenge for oxidation and valorization as existing methane oxidation routes rely on high temperatures or pressures. Here we report the catalytic coupling of alcohol oxidase with the iron-modified ZSM-5 (Fe-ZSM-5) zeolite catalyst, creating a tandem methanotrophic system that partially oxidizes methane at ambient temperatures and pressures. Methane reacts at Fe-ZSM-5 to produce methanol, which is then oxidized at the enzyme to formaldehyde and hydrogen peroxide. The latter subsequently reacts back at Fe-ZSM-5 and oxidizes methane in a catalytic couple. We show that methane-to-formaldehyde selectivity can exceed 90% at room temperature. The generated formaldehyde was rapidly incorporated into a growing urea polymer, with a material growth rate exceeding 5.0 mg gcat−1 h−1, which matches or exceeds the growth rates of many methanotrophic organisms. This work presents a sustainable route for methane oxidation, driven by oxygen in the air under ambient conditions, producing high-value polymers and valorizing methane emission streams. The development of catalytic systems for sequestering anthropogenic methane emissions from the atmosphere could potentially reduce global warming. Now, coupling the enzyme alcohol oxidase with an inorganic zeolite generates formaldehyde from methane under ambient conditions with 90% selectivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 12","pages":"1359-1371"},"PeriodicalIF":42.8,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142763638","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