Nature Catalysis最新文献

{"title":"Unveiling the reconstruction of copper bimetallic catalysts during CO2 electroreduction","authors":"Intae Kim, Gi-Baek Lee, Sungin Kim, Hyun Dong Jung, Ji-Yong Kim, Taemin Lee, Hyesung Choi, Jaeyeon Jo, Geosan Kang, Sang-Ho Oh, Woosuck Kwon, Deokgi Hong, Hyoung Gyun Kim, Yujin Lee, Unggi Kim, Hyeontae Kim, Miyoung Kim, Seoin Back, Jungwon Park, Young-Chang Joo, Dae-Hyun Nam","doi":"10.1038/s41929-025-01368-9","DOIUrl":"10.1038/s41929-025-01368-9","url":null,"abstract":"Efficient electrocatalysts should provide optimal binding sites for intermediates under operating conditions. Atomic rearrangements in catalysts during electrochemical CO2 reduction reaction (CO2RR) alter the original structures of active sites. Here we report a general principle for understanding and predicting the reconstruction of Cu bimetallic catalysts during CO2RR in terms of selective dissolution–redeposition. We categorize the reconstruction trends of Cu bound to a secondary metal (X, where X = Ag, Fe, Zn or Pd) according to the oxophilicity and miscibility of Cu and X. Cross-sectional microscopy analysis of gas diffusion electrodes reveals that the surface states of reconstructed Cu–X are determined by atomic miscibility. We find that CO2RR intermediates alter elemental preferences for dissolution, shifting them away from oxophilicity-governed behaviour and leading to selective Cu dissolution–redeposition in Cu–X. This reconstruction affects spillover in CO2RR, controlling the selectivities of ethylene/ethanol and C1/C2 products. We also develop a methodology for the control of reconstruction dynamics. Our findings provide insights into designing catalysts that undergo reconstruction during electrolysis. Reconstruction of Cu catalysts under electrochemical CO2 reduction conditions is a well-reported phenomenon. Here the reconstruction of bimetallic Cu–X catalysts is investigated to reveal the roles of atomic miscibility and intermediate binding on surface reconstruction and the resulting effects on product selectivity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"697-713"},"PeriodicalIF":44.6,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622315","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}

{"title":"Enantioselective Pd-catalysed nucleophilic C(sp3)–H (radio)fluorination","authors":"Nikita Chekshin, Luo-Yan Liu, D. Quang Phan, David J. Donnelly, Yuxin Ouyang, Kap-Sun Yeung, Jennifer X. Qiao, Jin-Quan Yu","doi":"10.1038/s41929-025-01366-x","DOIUrl":"10.1038/s41929-025-01366-x","url":null,"abstract":"Despite increasing demand for chiral fluorinated organic molecules, enantioselective C–H fluorination remains among the most challenging and sought-after transformations in organic synthesis. Furthermore, utilizing nucleophilic sources of fluorine is especially desirable for 18F-radiolabelling. To date, methods for enantioselective nucleophilic fluorination of inert C(sp3)–H bonds remain unknown. Here we report our design and development of a palladium-based catalytic system bearing bifunctional monoprotected amino sulfonamide ligands which enabled highly regio- and enantioselective nucleophilic β-C(sp3)–H fluorination of synthetically important amides and lactams, commonly present in medicinal targets. The enantioenriched fluorinated products can be rapidly converted to corresponding chiral amines and ketones which are building blocks for a wide range of bioactive scaffolds. Mechanistic studies suggest that the C–F bond formation proceeds via outer-sphere reductive elimination with direct incorporation of fluoride, which was applied to late-stage 18F-radiolabelling of pharmaceutical derivatives using [18F]KF. Enantioselective catalytic C(sp3)–H fluorination has been limited to electrophilic fluorine sources. Now chiral palladium catalysts bearing amino sulfonamide ligands enable enantioselective incorporation of nucleophilic fluoride into unactivated aliphatic C–H bonds with demonstrated applications to 18F-radiolabelling using [18F]KF.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"678-687"},"PeriodicalIF":44.6,"publicationDate":"2025-07-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144622313","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}

{"title":"Ligand binding to a Ni–Fe cluster orchestrates conformational changes of the CO-dehydrogenase–acetyl-CoA synthase complex","authors":"Jakob Ruickoldt, Julian Kreibich, Thomas Bick, Jae-Hun Jeoung, Benjamin R. Duffus, Silke Leimkühler, Holger Dobbek, Petra Wendler","doi":"10.1038/s41929-025-01365-y","DOIUrl":"10.1038/s41929-025-01365-y","url":null,"abstract":"Catalytic metal clusters play critical roles in important enzymatic pathways such as carbon fixation and energy conservation. However, how ligand binding to the active-site metal regulates conformational changes critical for enzyme function is often not well understood. One carbon fixation pathway that relies heavily on metalloenzymes is the reductive acetyl-coenzyme A (acetyl-CoA) pathway. In this study, we investigated the catalysis of the last step of the reductive acetyl-CoA pathway by the CO-dehydrogenase (CODH)–acetyl-CoA synthase (ACS) complex from Carboxydothermus hydrogenoformans, focusing on how ligand binding to the nickel atom in the active site affects the conformational equilibrium of the enzyme. We captured six intermediate states of the enzyme by cryo-electron microscopy, with resolutions of 2.5–1.9 Å, and visualized reaction products bound to cluster A (an Ni,Ni-[4Fe4S] cluster) and identified several previously uncharacterized conformational states of CODH–ACS. The structures demonstrate how substrate binding controls conformational changes in the ACS subunit to prepare for the next catalytic step. The CO dehydrogenase–acetyl-coenzyme A synthase complex produces acetyl-coenzyme A from CO2, but its structural dynamics during catalysis remain unresolved. Now cryo-EM maps of six intermediate states reveal how ligand binding to a Ni–Fe cluster orchestrates the conformational changes of the complex during catalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"657-667"},"PeriodicalIF":44.6,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01365-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603724","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}

{"title":"Reticular copper dual sites embedded with semiconductor particles for selective CO2-to-C2H4 photoreduction","authors":"Qixin Zhou, Yan Guo, Yongfa Zhu","doi":"10.1038/s41929-025-01369-8","DOIUrl":"10.1038/s41929-025-01369-8","url":null,"abstract":"Dual sites, positioned through atomically precise proximity coordination for C–C coupling, serve as an exemplary platform for CO2-to-C2H4 conversion. Nonetheless, their surface-only distribution results in inefficient photogenerated electron injection via long-range migration from the bulk phase, leading to inadequate site charge to drive the consecutive electron transfers for C2H4 synthesis. Here we demonstrate a reticular dual-site photocatalyst design by embedding semiconductor units (TiO2, polymeric carbon nitride or WO3·H2O) within ligand-defective copper-based metal–organic frameworks (CuBTC-D/PC). This system demonstrates a 75.5% selectivity in converting CO2 to C2H4 with H2O as the electron donor. The reticular copper dual sites facilitate short-range photogenerated electron transfer from the photocatalyst to active sites, ensuring a sufficient electron concentration for all elementary steps in C2H4 conversion. Enhanced electron injection allows for high C2H4 selectivity even under low-intensity irradiation (~0.4 Sun), demonstrating suitability for solar-driven applications. This work establishes the feasibility of CO2 photoreduction to C2H4 as a primary product, providing insights into multi-electron CO2 photoreduction. The formation of multi-carbon products in photocatalytic CO2 reduction has been limited by the supply of sufficient excited electrons to C–C coupling active sites. Here Cu2 sites introduced into metal–organic frameworks with semiconductor photocatalyst-filled pores allow multi-electron transfer and improved solar efficiency towards C2H4.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"728-739"},"PeriodicalIF":44.6,"publicationDate":"2025-07-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144603723","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}

{"title":"Asymmetric biomimetic aldol reaction of glycinate enables highly efficient synthesis of chiral β-hydroxy-α-amino acid derivatives","authors":"Hanyu Liang, Peng Ren, Lei Wang, Dongchen Cai, Sheng Gong, Siqi Liu, Xiao Xiao, Kuiling Ding, Baoguo Zhao","doi":"10.1038/s41929-025-01364-z","DOIUrl":"10.1038/s41929-025-01364-z","url":null,"abstract":"Efficient biomimetic reactions provide a powerful platform for producing bioactive chiral compounds. Chiral β-hydroxy-α-amino acids display exceptionally high bioactivity and are key functional components of many marketed drugs. However, the efficient synthesis of chiral β-hydroxy-α-amino acids remains a long-standing challenge for both chemical and biological syntheses. Chemical synthesis is problematic due to low step- and atom-efficiencies, high costs and environmental hazards. The enzymatic aldol reaction of glycine can make β-hydroxy-α-amino acids in one step, but it is constrained by issues such as limited substrate scope, unsatisfactory stereoselectivity and low conversion. Here we have successfully realized the biomimetic aldol reaction of glycinate with aldehydes, using 0.01–1.0 mol% of a chiral pyridoxal as the catalyst to produce a remarkably broad range of chiral β-hydroxy-α-amino esters. Moreover, a high-diversity parallel asymmetric synthesis has also been tested using over 1,100 aldehydes and it yielded over 1,700 chiral β-hydroxy-α-amino acid esters, demonstrating its important potential for drug innovation. Chemical synthesis of chiral β-hydroxy-α-amino acids usually requires multiple steps. Now a biomimetic enantioselective aldol reaction of glycinate and aldehydes catalysed by a chiral pyridoxal has been achieved, providing efficient access to a large number of chiral β-hydroxy-α-amino esters.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"668-677"},"PeriodicalIF":44.6,"publicationDate":"2025-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144594013","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}

{"title":"High-selectivity room-temperature partial oxidation of methane to methanol enabled by electrochemical oxygen promotion on IrO2 catalysts","authors":"Cheolho Kim, Jaehyun Lee, Sungwoo Lee, Wonho Jung, Heewon Min, Jiyun Choi, Sungwon Kim, Yong Tae Kim, Jinwon Lee, Jong Suk Yoo, Jun Hyuk Moon","doi":"10.1038/s41929-025-01363-0","DOIUrl":"10.1038/s41929-025-01363-0","url":null,"abstract":"The electrochemical conversion of methane into value-added chemicals offers a sustainable solution for utilizing abundant methane resources, yet achieving high selectivity for partial oxidation remains challenging. Here we demonstrate that employing an IrO2 catalyst with CO32− as an oxygen source enables efficient and selective electrochemical methane-to-methanol conversion at room temperature. Adsorption and dissociation of CO32− on IrO2(110) surfaces generates abundant active oxygen species, facilitating methane activation through surface-bound methoxy intermediates and thereby substantially enhancing methanol selectivity. Optimal conditions for methanol production are achieved within a potential range where interference from the competing oxygen evolution reaction is minimized, reaching a maximum methanol production rate of approximately 11.1 mmol gcat−1 h−1 at 1.50 versus the reversible hydrogen electrode under continuous operation. Process modelling indicates an approximately 50% reduction in carbon emissions compared to conventional methanol production methods, emphasizing the sustainability and practical potential of this electrochemical methane oxidation approach. The electrochemical oxidation of methane is a promising process but controlling its selectivity for a partial oxidation product such as methanol is very challenging. Now a strategy to convert methane into methanol with high selectivity is demonstrated, using an IrO2 catalyst and CO32− in the electrolyte as the oxygen source.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"688-696"},"PeriodicalIF":44.6,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144566589","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}

{"title":"Steering oxygen-centred radicals with ground-state ene-reductases for enantioselective intermolecular hydroalkoxylations","authors":"Bin Chen, Qiaoyu Zhang, Jinhai Yu, Beibei Zhao, Ran Ge, Zihan Zhang, Ding Luo, Binju Wang, Xiaoqiang Huang","doi":"10.1038/s41929-025-01372-z","DOIUrl":"10.1038/s41929-025-01372-z","url":null,"abstract":"Enzymes are emerging as promising catalysts for selective radical transformations. However, non-natural radical-type enzymatic catalysis is currently limited to utilizing C-, N- and S-centred radical species. Alkoxy radicals are recognized as versatile intermediates with high reactivity, typically engaging in reactivity modes such as hydrogen atom transfer, β-scission processes and intramolecular addition to alkenes. Enantioselective intermolecular alkoxy radical addition to alkenes remained unknown. Here we develop a biocatalytic strategy based on engineered ene-reductases that facilitate the radical hydroalkoxylation of oxygen-centred radicals with alkenes. A single, ground-state ene-reductase adeptly controls the biocompatible generation of O-radicals, the follow-up intermolecular O-radical addition to alkenes and the final prochiral C-radical termination, achieving high chemo- and enantioselectivity (both enantiomers are obtained separately with different enzymes). Mechanistic experiments, including computational simulations, reveal that the radical enzymatic reaction initiates via a ground-state single-electron transfer and elucidate the origins of enantiodiscrimination of the overall reaction. The intermolecular addition of O-centred radicals to alkenes is a challenging endeavour in synthetic chemistry. Now ene-reductases are used to tame reactive O-radicals for intermolecular and enantioselective radical hydroalkoxylation involving a ground-state single-electron radical mechanism.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"740-748"},"PeriodicalIF":44.6,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144566509","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}

{"title":"Unlocking Lewis acid catalysis in non-haem enzymes for an abiotic ene reaction","authors":"Xinpeng Mu, Xinyuan Ji, Xiahe Chen, Hongli Wu, Jinyan Rui, Xin Hong, Madison M. Worth, Abigail D. Reitz, Lucie T. M. Goldberg, Marc Garcia-Borràs, Sarah L. J. Michel, Yunfang Yang, Xiongyi Huang","doi":"10.1038/s41929-025-01350-5","DOIUrl":"10.1038/s41929-025-01350-5","url":null,"abstract":"Lewis acid catalysis is a powerful tool in organic synthesis. However, biocatalytic Lewis acid catalysis has been limited in its reaction scope and diversity, constraining its synthetic utility. In this study, we expand the scope of biocatalytic Lewis acid catalysis by integrating abiotic ene reactions into metalloenzymatic catalysis. We found that substituting the iron centre with copper enabled SadA, a non-haem iron hydroxylase from Burkholderia ambifaria, to catalyse abiotic Conia-ene reactions. A high-throughput screening platform based on fluorogenic click chemistry was developed to optimize this abiotic transformation. Using this platform, directed evolution was used to generate variants that produced a range of Conia-ene cyclization products with stereogenic quaternary carbon centres, achieving up to 99% yield, 250 total turnovers and 99% enantiomeric excess. Mechanistic studies suggested that the reaction proceeded through a dual activation mechanism, where the Cu(II) centre activated both the ketoester and alkyne moieties. The scope of Lewis acid catalysis mediated by enzymes is low compared with the range of reactions it drives in organic synthesis. Now the substitution of the iron centre with copper, and the subsequent directed evolution, enabled a non-haem iron hydroxylase to efficiently catalyse asymmetric abiotic Conia-ene cyclizations.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"635-644"},"PeriodicalIF":44.6,"publicationDate":"2025-07-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144566508","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}

{"title":"Addendum: Au/ZSM-5 catalyses the selective oxidation of CH4 to CH3OH and CH3COOH using O2","authors":"Guodong Qi, Thomas E. Davies, Ali Nasrallah, Mala A. Sainna, Alexander G. R. Howe, Richard J. Lewis, Matthew Quesne, C. Richard A. Catlow, David J. Willock, Bingqing Yao, Qian He, Donald Bethell, Mark J. Howard, Barry A. Murrer, Brian Harrison, Christopher J. Kiely, Xingling Zhao, Feng Deng, Jun Xu, Graham J. Hutchings","doi":"10.1038/s41929-025-01362-1","DOIUrl":"10.1038/s41929-025-01362-1","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 7","pages":"749-751"},"PeriodicalIF":44.6,"publicationDate":"2025-06-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01362-1.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144500382","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}

{"title":"Operando probing dynamic migration of copper carbonyl during electrocatalytic CO2 reduction","authors":"Yao Yang, Julian Feijóo, Marc Figueras-Valls, Chubai Chen, Chuqiao Shi, Maria V. Fonseca Guzman, Yves Murhabazi Maombi, Shikai Liu, Pulkit Jain, Valentín Briega-Martos, Zhengxing Peng, Yu Shan, Geonhui Lee, Michael Rebarchik, Lang Xu, Christopher J. Pollock, Jianbo Jin, Nathan E. Soland, Cheng Wang, Miquel B. Salmeron, Zhu Chen, Yimo Han, Manos Mavrikakis, Peidong Yang","doi":"10.1038/s41929-025-01359-w","DOIUrl":"10.1038/s41929-025-01359-w","url":null,"abstract":"Single crystals and shape-controlled nanocrystals are well known to exhibit facet-dependent catalytic properties. However, few studies have investigated how those nanocrystals evolve and (de)activate during reactions, calling for the development of nanoscale time-resolved operando methods. In this context, we have designed Cu nanocubes as a model system to elucidate the underlying driving force of dynamic nanocatalyst reconstruction during the CO2 reduction reaction (CO2RR). Operando electrochemical liquid-cell scanning transmission electron microscopy (EC-STEM) and synchrotron-based X-ray spectroscopy reveal the size- and potential-dependent complete transformation from (100)-oriented Cu@Cu2O nanocubes to polycrystalline metallic Cu nanograins under CO2RR conditions. In addition, machine learning-assisted operando four-dimensional STEM reveals that large Cu nanograins derived from nanocubes form mainly crystalline domains, while their smaller counterparts are more amorphous due to faster evolution kinetics. In situ Raman spectroscopy and density functional theory calculations suggest that CO drives the ejection of single Cu atoms, resulting in few-nanometre Cu clusters and the surface migration of highly mobile copper carbonyl (Cu–CO) species. Combined, these multimodal operando methods and theoretical approaches pave the way for understanding the complex structural evolution of energy-related nanocatalysts under electrochemical conditions. Understanding how copper nanoparticles evolve under electrochemical conditions is crucial for the development of selective CO2 reduction electrocatalysts. Here the authors prepare well-defined nanocrystals and use advanced operando imaging and spectroscopic techniques to reveal the Cu–CO species-driven dynamic evolution of Cu electrodes.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 6","pages":"579-594"},"PeriodicalIF":44.6,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144479010","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}