Nature Catalysis最新文献_第10页

Bioproduction from methanol 甲醇的生物生产

IF 37.8 1区化学

Nature Catalysis Pub Date : 2024-05-29 DOI: 10.1038/s41929-024-01164-x

Jan Lukas Krüsemann, Steffen N. Lindner

引用次数: 0

Tunable layered Mn oxides for oxygen electrocatalysis 用于氧电催化的可调谐层状锰氧化物

IF 37.8 1区化学

Nature Catalysis Pub Date : 2024-05-29 DOI: 10.1038/s41929-024-01144-1

Eric Liu, Drew Higgins

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Intermetallic synergy in platinum–cobalt electrocatalysts for selective C–O bond cleavage 选择性 C-O 键裂解铂钴电催化剂中的金属间协同作用

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-05-28 DOI: 10.1038/s41929-024-01165-w

Ruizhi Wu, Qinglei Meng, Jiang Yan, Zhanrong Zhang, Bingfeng Chen, Huizhen Liu, Jing Tai, Guikai Zhang, Lirong Zheng, Jing Zhang, Buxing Han

{"title":"Intermetallic synergy in platinum–cobalt electrocatalysts for selective C–O bond cleavage","authors":"Ruizhi Wu, Qinglei Meng, Jiang Yan, Zhanrong Zhang, Bingfeng Chen, Huizhen Liu, Jing Tai, Guikai Zhang, Lirong Zheng, Jing Zhang, Buxing Han","doi":"10.1038/s41929-024-01165-w","DOIUrl":"10.1038/s41929-024-01165-w","url":null,"abstract":"Catalysts with tailored structures are crucial to determine the selectivity of chemical reactions. However, the design of catalyst structures for the selective cleavage of hydroxylic C–O(H) bonds while retaining etheric C–O(R) bonds remains a challenge and needs to be comprehensively explored. Here we report a series of mesoporous-carbon-supported platinum–cobalt (Pt–Co) bimetallic electrocatalysts in which different intermetallic interactions between Pt and Co species result in different hydrodeoxygenation and hydrogenation routes. Notably, Pt nanoparticles decorated with Co single atoms afford the selective cleavage of the C–O(H) bond in guaiacol and other lignin derivatives adjacent to an etheric C–O(R) bond with ether selectivities of >72.1%, and also work extensively for various other substrates with different substituents. This work highlights that a thorough understanding of the structure–performance relationship is crucial to rationally design and construct suitable catalysts with tailored sites for desired catalytic reactions. Being able to selectively derive desired compounds from biomass feedstock is very challenging. Now the selectivity of Pt–Co catalysts for the electroreduction of guaiacol and other lignin-derived substrates is shown to depend on the Co speciation and preferential C–OH cleavage can be obtained, retaining the C–OR group.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 6","pages":"702-718"},"PeriodicalIF":42.8,"publicationDate":"2024-05-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141159546","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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Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations 调节非水环境中的水氢键，控制其在电化学转化中的反应活性

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-05-24 DOI: 10.1038/s41929-024-01162-z

Reginaldo J. Gomes, Ritesh Kumar, Hannah Fejzić, Bidushi Sarkar, Ishaan Roy, Chibueze V. Amanchukwu

{"title":"Modulating water hydrogen bonding within a non-aqueous environment controls its reactivity in electrochemical transformations","authors":"Reginaldo J. Gomes, Ritesh Kumar, Hannah Fejzić, Bidushi Sarkar, Ishaan Roy, Chibueze V. Amanchukwu","doi":"10.1038/s41929-024-01162-z","DOIUrl":"10.1038/s41929-024-01162-z","url":null,"abstract":"Electrochemical carbon dioxide reduction (CO2R) can provide a sustainable route to produce fuels and chemicals; however, CO2R selectivity is frequently impaired by the competing hydrogen evolution reaction (HER), even for small concentrations of water. Here we tune water solvation and dynamics within a series of aprotic solvents featuring different functional groups and physicochemical properties to modulate HER activity and CO2R selectivity. We show that one can extend the HER onset potential by almost 1 V by confining water within a strong hydrogen bond network. We then achieve nearly 100% CO Faradaic efficiency at water concentrations as high as 3 M with a gold catalyst. Furthermore, under mildly acidic conditions, we sustain nearly 100% Faradaic efficiency towards CO with no carbonate losses over long-term electrolysis with an earth-abundant zinc catalyst. Our work provides insights to control water’s reactivity and reveals descriptors to guide electrolyte design for important electrochemical transformations. Electroreduction of CO2 competes with the hydrogen evolution reaction; thus, controlling water’s activity to exclusively act as a proton donor is a desirable yet challenging goal. Now the behaviour of water in aprotic solvents is shown to depend on the solvent’s donor ability, which can modulate the hydrogen bond network and in turn promote the desired reactivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 6","pages":"689-701"},"PeriodicalIF":42.8,"publicationDate":"2024-05-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141091864","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

Edge sites dominate the hydrogen evolution reaction on platinum nanocatalysts 铂纳米催化剂上的氢进化反应以边缘位为主

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-05-22 DOI: 10.1038/s41929-024-01156-x

Zhihong Huang, Tao Cheng, Aamir Hassan Shah, Guangyan Zhong, Chengzhang Wan, Peiqi Wang, Mengning Ding, Jin Huang, Zhong Wan, Sibo Wang, Jin Cai, Bosi Peng, Haotian Liu, Yu Huang, William A. Goddard III, Xiangfeng Duan

{"title":"Edge sites dominate the hydrogen evolution reaction on platinum nanocatalysts","authors":"Zhihong Huang, Tao Cheng, Aamir Hassan Shah, Guangyan Zhong, Chengzhang Wan, Peiqi Wang, Mengning Ding, Jin Huang, Zhong Wan, Sibo Wang, Jin Cai, Bosi Peng, Haotian Liu, Yu Huang, William A. Goddard III, Xiangfeng Duan","doi":"10.1038/s41929-024-01156-x","DOIUrl":"10.1038/s41929-024-01156-x","url":null,"abstract":"Platinum nanocatalysts facilitate the hydrogen evolution reaction (HER) for renewable chemical fuel generation. These nanostructures encompass diverse surface sites, including (111) and (100) facets and edge sites between them. Identifying the exact active sites is essential for optimal catalyst design, but remains challenging. Here, combining electrical transport spectroscopy (ETS) with reactive force field (ReaxFF) calculations, we profile hydrogen adsorption on platinum nanowires and reveal two distinct peaks: one at 0.20 VRHE for (111) and (100) facets and one at 0.038 VRHE for edge sites. Concurrent ETS and cyclic voltammetry show that edge site adsorption coincides with the onset of the HER, indicating the critical role of edge sites. ReaxFF molecular dynamics calculations confirm lower activation barriers for the HER at edge sites, with two to four orders of magnitude higher turnover frequencies. ETS in alkaline media reveals substantially suppressed hydrogen adsorption on edge sites, contributing to the more sluggish HER kinetics. These findings resolve the elusive role of different sites on platinum surfaces, offering critical insights for HER catalyst design. Pt is the most active catalyst for the hydrogen evolution reaction in acidic media, but the precise nature of its active sites remains elusive. Now electrical transport spectroscopy and molecular dynamics are combined to map the hydrogen adsorption sites on Pt nanowires and reveal the much higher activity of (111)/(100) edge sites.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 6","pages":"678-688"},"PeriodicalIF":42.8,"publicationDate":"2024-05-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141079255","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

Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite 用 MFI 沸石中的亚纳米 Rh 簇进行区域选择性加氢甲酰化反应

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-05-15 DOI: 10.1038/s41929-024-01155-y

Xiaomeng Dou, Tao Yan, Lixiang Qian, Huaming Hou, Miguel Lopez-Haro, Carlo Marini, Giovanni Agostini, Debora M. Meira, Xiangjie Zhang, Liang Zhang, Zhi Cao, Lichen Liu

{"title":"Regioselective hydroformylation with subnanometre Rh clusters in MFI zeolite","authors":"Xiaomeng Dou, Tao Yan, Lixiang Qian, Huaming Hou, Miguel Lopez-Haro, Carlo Marini, Giovanni Agostini, Debora M. Meira, Xiangjie Zhang, Liang Zhang, Zhi Cao, Lichen Liu","doi":"10.1038/s41929-024-01155-y","DOIUrl":"10.1038/s41929-024-01155-y","url":null,"abstract":"Achieving the regioselective hydroformylation of linear α-olefins to linear aldehydes using solid catalysts with regioselectivities comparable to the corresponding homogeneous process is a great challenge in the chemical industry. Despite the tremendous efforts devoted to this research topic, most of the reported heterogeneous metal catalysts still give considerably lower regioselectivities than well-established homogeneous metal catalysts. Here we show the design of efficient Rh-zeolite catalysts, in which subnanometre Rh clusters are selectively confined in the sinusoidal ten-membered-ring channels of MFI zeolite, for the hydroformylation of long-chain linear α-olefins (C6–C12) into linear aldehydes with very high linear-to-branched aldehyde ratios (up to 400). The exceptional catalytic performances result from the involvement of the MFI zeolite framework as a rigid solid ligand that accommodates subnanometre Rh clusters in the sinusoidal channels of the MFI zeolite. Olefin hydroformylation is traditionally performed with homogeneous catalysts. Here the authors introduce a heterogeneous system based on zeolite-confined Rh clusters that is characterized by high efficiency for the hydroformylation of C6–C12 terminal olefins into linear aldehydes with high selectivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 6","pages":"666-677"},"PeriodicalIF":42.8,"publicationDate":"2024-05-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140925100","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

C–heteroatom coupling with electron-rich aryls enabled by nickel catalysis and light 通过镍催化和光，实现 C-杂原子与富电子芳基的耦合

IF 42.8 1区化学

Nature Catalysis Pub Date : 2024-05-07 DOI: 10.1038/s41929-024-01160-1

Shengyang Ni, Riya Halder, Dilgam Ahmadli, Edward J. Reijerse, Josep Cornella, Tobias Ritter

{"title":"C–heteroatom coupling with electron-rich aryls enabled by nickel catalysis and light","authors":"Shengyang Ni, Riya Halder, Dilgam Ahmadli, Edward J. Reijerse, Josep Cornella, Tobias Ritter","doi":"10.1038/s41929-024-01160-1","DOIUrl":"10.1038/s41929-024-01160-1","url":null,"abstract":"Nickel photoredox catalysis has resulted in a rich development of transition-metal-catalysed transformations for carbon–heteroatom bond formation. By harnessing light energy, the transition metal can attain oxidation states that are difficult to achieve through thermal chemistry in a catalytic manifold. For example, nickel photoredox reactions have been reported for both the synthesis of anilines and aryl ethers from aryl(pseudo)halides. However, oxidative addition to simple nickel systems is often sluggish in the absence of special, electron-rich ligands, leading to catalyst decomposition. Electron-rich aryl electrophiles therefore currently fall outside the scope of many transformations in the field. Here we provide a conceptual solution to this problem and demonstrate nickel-catalysed C–heteroatom bond-forming reactions of arylthianthrenium salts, including amination, oxygenation, sulfuration and halogenation. Because the redox properties of arylthianthrenium salts are primarily dictated by the thianthrenium, oxidative addition of highly electron-rich aryl donors can be unlocked using simple NiCl2 under light irradiation to form the desired C‒heteroatom bonds. Photoredox-catalysed coupling of electron-rich aryl electrophiles based on simple nickel salts usually suffers from a slow oxidative addition. Now, it is shown that thianthrenation leads to more favourable redox properties of the substrates, alleviating this problem in carbon–heteroatom bond-forming reactions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 6","pages":"733-741"},"PeriodicalIF":42.8,"publicationDate":"2024-05-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.com/articles/s41929-024-01160-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140845391","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

Biocatalytic, enantioenriched primary amination of tertiary C–H bonds 三级 C-H 键的生物催化对映体一级胺化反应

IF 37.8 1区化学

Nature Catalysis Pub Date : 2024-05-03 DOI: 10.1038/s41929-024-01149-w

Runze Mao, Shilong Gao, Zi-Yang Qin, Torben Rogge, Sophia J. Wu, Zi-Qi Li, Anuvab Das, K. N. Houk, Frances H. Arnold

{"title":"Biocatalytic, enantioenriched primary amination of tertiary C–H bonds","authors":"Runze Mao, Shilong Gao, Zi-Yang Qin, Torben Rogge, Sophia J. Wu, Zi-Qi Li, Anuvab Das, K. N. Houk, Frances H. Arnold","doi":"10.1038/s41929-024-01149-w","DOIUrl":"10.1038/s41929-024-01149-w","url":null,"abstract":"Intermolecular functionalization of tertiary C–H bonds to construct fully substituted stereogenic carbon centres represents a formidable challenge: without the assistance of directing groups, state-of-the-art catalysts struggle to introduce chirality to racemic tertiary sp3-carbon centres. Direct asymmetric functionalization of such centres is a worthy reactivity and selectivity goal for modern biocatalysis. Here we present an engineered nitrene transferase (P411-TEA-5274), derived from a bacterial cytochrome P450, that is capable of aminating tertiary C–H bonds to provide chiral α-tertiary primary amines with high efficiency (up to 2,300 total turnovers) and selectivity (up to >99% enantiomeric excess). The construction of fully substituted stereocentres with methyl and ethyl groups underscores the enzyme’s remarkable selectivity. A comprehensive substrate scope study demonstrates the biocatalyst’s compatibility with diverse functional groups and tertiary C–H bonds. Mechanistic studies explain how active-site residues distinguish between the enantiomers and enable the enzyme to perform this transformation with excellent enantioselectivity. Direct stereoselective amination of tertiary C–H bonds without the assistance of directing groups is a challenging task in synthetic organic chemistry. Now a nitrene transferase is engineered to aminate tertiary C–H bonds with high enantioselectivity, providing direct access to valuable chiral α-tertiary primary amines.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 5","pages":"585-592"},"PeriodicalIF":37.8,"publicationDate":"2024-05-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140821088","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

Author Correction: Epistasis arises from shifting the rate-limiting step during enzyme evolution of a β-lactamase 作者更正：β-内酰胺酶酶进化过程中限速步骤的移动产生了外显子效应

IF 37.8 1区化学

Nature Catalysis Pub Date : 2024-05-02 DOI: 10.1038/s41929-024-01170-z

Christopher Fröhlich, H. Adrian Bunzel, Karol Buda, Adrian J. Mulholland, Marc W. van der Kamp, Pål J. Johnsen, Hanna-Kirsti S. Leiros, Nobuhiko Tokuriki

引用次数: 0

Catalytic atroposelective synthesis 催化丙选择性合成

IF 37.8 1区化学

Nature Catalysis Pub Date : 2024-04-30 DOI: 10.1038/s41929-024-01138-z

Shao-Hua Xiang, Wei-Yi Ding, Yong-Bin Wang, Bin Tan

{"title":"Catalytic atroposelective synthesis","authors":"Shao-Hua Xiang, Wei-Yi Ding, Yong-Bin Wang, Bin Tan","doi":"10.1038/s41929-024-01138-z","DOIUrl":"10.1038/s41929-024-01138-z","url":null,"abstract":"Atropisomeric architectures are increasingly encountered in modern materials and medicinally important compounds. More importantly, they are now a characteristic of broadly useful chiral ligands and organocatalysts. Over the past decade, substantial advancements have been made in enhancing the accessibility of major classes of atropisomers through the refinement of existing strategies and the introduction of contemporary concepts for catalytic atroposelective synthesis. This synthetic capability enables the expansion of chemical space and facilitates the preparation of valuable atropisomeric scaffolds. Here we review the state of the art in the asymmetric synthesis of atropisomers with the help of selected examples. Focus will be placed on the strategies that have emerged rapidly in recent years, and that are characterized by high versatility and modularity. Additionally, the incorporation of emerging synthetic tools and representative scaffolds are discussed, alongside future directions in this research domain. Atropisomerism is an expanding target of asymmetric catalysis. In this Review, recent advances in atroposelective synthesis under catalytic control are highlighted with a focus on general strategies that provide high versatility and modularity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"7 5","pages":"483-498"},"PeriodicalIF":37.8,"publicationDate":"2024-04-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"140814377","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