Nature Catalysis最新文献

Metalloradical-driven enzymatic CO2 reduction by a dynamic Ni–Fe cluster 金属自由基驱动的动态Ni-Fe簇酶促CO2还原

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-08-01 DOI: 10.1038/s41929-025-01388-5

Yudhajeet Basak, Christian Lorent, Jae-Hun Jeoung, Ingo Zebger, Holger Dobbek

{"title":"Metalloradical-driven enzymatic CO2 reduction by a dynamic Ni–Fe cluster","authors":"Yudhajeet Basak, Christian Lorent, Jae-Hun Jeoung, Ingo Zebger, Holger Dobbek","doi":"10.1038/s41929-025-01388-5","DOIUrl":"https://doi.org/10.1038/s41929-025-01388-5","url":null,"abstract":"Carbon monoxide dehydrogenases (CODHs) selectively catalyse the reversible reduction of CO2 to CO and water. The catalytic centre of CODHs contains a unique [NiFe4(OH)(µ3-S)4] cluster whose role in activating and converting CO2 is poorly understood. Here we reveal the structures of all catalytically relevant oxidation states with and without substrates and products bound. We show that the Ni–Fe cluster combines a rigid Fe–S core with a dynamic Ni(I/II)–Fe(II) dyad. The redox-active element is the Ni ion, cycling between square-planar Ni(II) and T-shaped Ni(I) states with metalloradical character, the latter serving as the nucleophile for CO2 activation. The Fe(II) ion switches between two positions, the one preceding CO2 activation is close to Ni(I) with a potential Ni(I)–Fe(II) interaction and the other binds the substrates CO2 and water. We demonstrate how the Ni–Fe cluster creates an efficient CO2 reduction catalyst and provides a blueprint for the design of novel catalysts based on abundant transition metals.<figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"721 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144756649","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

Behind the curtain 幕后

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01394-7

引用次数: 0

Tethered oxygen turns methane into methanol 束缚氧将甲烷转化为甲醇

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01381-y

Aditya Prajapati

引用次数: 0

A copper enzyme for Lewis acid biocatalysis 用于路易斯酸生物催化的铜酶

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01353-2

Franco Della-Felice, Gerard Roelfes

引用次数: 0

A radical way to ethylene 乙烯的自由基生成方法

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01382-x

Luka Ðorđević, Francesca Arcudi

引用次数: 0

Semiconductors in pores 孔隙中的半导体

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01385-8

Zhuo Jiang, Xiaofan Shi, Hexiang Deng

引用次数: 0

Biocompatible Lossen rearrangement 生物相容性Lossen重排

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01391-w

Jan-Stefan Völler

{"title":"Biocompatible Lossen rearrangement","authors":"Jan-Stefan Völler","doi":"10.1038/s41929-025-01391-w","DOIUrl":"https://doi.org/10.1038/s41929-025-01391-w","url":null,"abstract":"Now, Stephen Wallace and colleagues report this chemistry in the presence of microbial cells and interface it with plastic degradation and microbial metabolism to synthesize valuable compounds from waste. The researchers started their investigation by designing a screening experiment. For this purpose, an auxotrophic Escherichia coli (E. coli) strain that is unable to produce para-aminobenzoate (PABA), which is essential for its growth, was selected. Then the Lossen rearrangement substrate 1 and potential catalysts were supplied to the microbial culture medium. The idea was that this would allow the screen for a biocompatible, non-toxic catalyst that is able to convert 1 into PABA by measuring cell growth (pictured). The highest optical densities were measured when ferroin, Fe(acac)3, and FeCl2 were supplemented. Surprisingly, robust growth was also observed for cells without the addition of these external catalysts in the presence of 1. By testing each component of the culture medium, it was discovered that the reaction was catalysed by phosphate. The authors reasoned that phosphate is likely the catalyst in all cases observed in their screen, but that ferroin, Fe(acac)3, and FeCl2 further improve growth by increasing the Fe availability in E. coli. Then, the authors showed that 1 can be synthesized from terephthalic acid, a depolymerization monomer of PET plastic. Moreover, a plasmid was incorporated into E. coli harbouring genes that encode enzymes to convert PABA into paracetamol. In this way, the researchers highlighted a synthetic route to synthesize a valuable compound from plastic waste.The Lossen rearrangement could be applied in the future to more substrates and catalytic cascades in different biological contexts. In such cases it might be useful to consider the uptake mechanisms of the Lossen rearrangement substrates and products by the distinct cells and consequentially perform the Lossen rearrangement preferentially in the culture medium or intracellularly.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"66 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-07-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144694270","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

Biomimetic aldol reaction of glycinate 甘氨酸的仿生醛醇反应

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-24 DOI: 10.1038/s41929-025-01383-w

Luca Bernardi

引用次数: 0

Cobalt hydride-mediated photocatalytic semihydrogenation of acetylene impurities for continuous-flow production of polymer-grade ethylene 钴氢化介导乙炔杂质光催化半加氢连续流生产聚合级乙烯

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-22 DOI: 10.1038/s41929-025-01380-z

Haojie Dai, Yuhan Wang, Kailin Wang, Hao Kang, Xiangyang Chen, Bei Ding, Xudan Chen, Ying Du, Lize Dong, Wen Zhong, Ning Sun, Pengyu Liu, Chunyang Yu, Jingyuan Ma, Fei Song, Yongfeng Hu, Shan Tang, Yannan Liu, Wenfeng Jiang, Yuanhai Su, Jun Li, Yongfeng Zhou

{"title":"Cobalt hydride-mediated photocatalytic semihydrogenation of acetylene impurities for continuous-flow production of polymer-grade ethylene","authors":"Haojie Dai, Yuhan Wang, Kailin Wang, Hao Kang, Xiangyang Chen, Bei Ding, Xudan Chen, Ying Du, Lize Dong, Wen Zhong, Ning Sun, Pengyu Liu, Chunyang Yu, Jingyuan Ma, Fei Song, Yongfeng Hu, Shan Tang, Yannan Liu, Wenfeng Jiang, Yuanhai Su, Jun Li, Yongfeng Zhou","doi":"10.1038/s41929-025-01380-z","DOIUrl":"https://doi.org/10.1038/s41929-025-01380-z","url":null,"abstract":"The semihydrogenation of acetylene impurities in crude ethylene streams to produce polymer-grade ethylene is important for the polyethylene industry. Photocatalytic reduction offers a promising solution in terms of sustainability. However, the current state of photocatalytic acetylene semihydrogenation systems has shown limited activity. Here we report a metal-catalysed hydrogen atom transfer pathway to promote photocatalytic acetylene semihydrogenation via rapid formation of cobalt hydride species. Applying a N,N′-bis(salicylidene)ethylenediamine cobalt catalyst with an electron-donating ligand that energetically favours cobalt hydride formation in pure acetylene yields excellent acetylene-to-ethylene reduction performance with near-unity selectivity, a turnover number of 29,401 and a turnover frequency of 2.14 s−1. Most importantly, we engineered a continuous-flow photoreactor, by which crude ethylene containing 1.10 vol% acetylene can be steadily converted into polymer-grade ethylene continuously over 50 h.<figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"14 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-07-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144678209","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

Controlling hydrocarbon chain growth and degree of branching in CO2 electroreduction on fluorine-doped nickel catalysts 含氟镍催化剂对CO2电还原过程中烃链生长及支化程度的控制

IF 37.8 1区化学

Nature Catalysis Pub Date : 2025-07-17 DOI: 10.1038/s41929-025-01370-1

Yingqing Ou, Lu Liu, Ranga Rohit Seemakurthi, Futian You, Haibin Ma, Javier Pérez-Ramírez, Núria López, Boon Siang Yeo

{"title":"Controlling hydrocarbon chain growth and degree of branching in CO2 electroreduction on fluorine-doped nickel catalysts","authors":"Yingqing Ou, Lu Liu, Ranga Rohit Seemakurthi, Futian You, Haibin Ma, Javier Pérez-Ramírez, Núria López, Boon Siang Yeo","doi":"10.1038/s41929-025-01370-1","DOIUrl":"https://doi.org/10.1038/s41929-025-01370-1","url":null,"abstract":"Nickel-based materials can facilitate the electrocatalytic CO2 reduction (CO2R) reaction to generate hydrocarbons up to C6. Here we show that fluorine doping alters the nature of the Ni active sites, which proves instrumental in tuning the selectivity of the CO2R. We interrogate the CO2R reaction mechanism using intermediate surrogates, including aldehydes, alkyl iodides and acetylene. Aldehydes are electroreduced to alcohols and deoxygenated intermediates. Among the latter, unsaturated hydrocarbon intermediates (RCH2−x*, where the asterisk represents surface-bound species and x = 1 or 2) reacting with *CO dictate chain propagation, modulated by competitive C–C coupling and C–H hydrogenation reactions. Compound branching in the hydrocarbons initiates from *CO coupling with two *CH2 species, and the branch-to-linear hydrocarbon ratio can be doubled using a pulsed potential strategy. An inverse H/D kinetic isotope effect promotes deuterated hydrocarbon formation with a Faradaic efficiency of 22.2%. This work reveals mechanisms and strategies for the conversion of CO2 into linear and branched hydrocarbons, thus advancing electrosynthetic fuel development.<figure></figure>","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"676 1","pages":""},"PeriodicalIF":37.8,"publicationDate":"2025-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144645256","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