Nature Catalysis最新文献

{"title":"Ligand-mediated radical orientation enables asymmetric cyanation of unstabilized alkyl C-radicals","authors":"Xin Chen, Wenzheng Fan, Junfeng Wang, Pinhong Chen, Guosheng Liu","doi":"10.1038/s41929-026-01573-0","DOIUrl":"10.1038/s41929-026-01573-0","url":null,"abstract":"Transition metal-catalysed enantioselective radical transformations have emerged as powerful tools for the synthesis of chiral molecules, and a range of methods have been developed. However, most of these successful reactions are effective for resonance-stabilized radicals; in sharp contrast, achieving precise stereocontrol over highly reactive, unstabilized alkyl radicals remains a major challenge, with very few successful examples. Here we establish a ligand-mediated radical orientation strategy that enables the highly enantioselective cyanation of such transient intermediates via copper catalysis. The chiral BoxOH ligand engages in dynamic hydrogen bonding with various remote functional groups on the radical species, strategically reshaping the reaction energy landscape and overcoming the inherently barrierless radical coupling process to dictate stereoselectivity. Consequently, this method enables the direct asymmetric cyano-functionalization of unactivated alkenes and inert sp3 C–H bonds, expanding asymmetric radical reactions beyond stabilized intermediates and providing a platform for the enantioselective functionalization of abundant chemical feedstocks. Reactions involving transient, unstabilized alkyl C-radicals generally suffer from poor enantioselectivity. Here the authors describe a method for the highly enantioselective cyanation of C-radicals via copper catalysis, enabled by a ligand-mediated radical orientation strategy.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"773-781"},"PeriodicalIF":48.3,"publicationDate":"2026-07-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148432540","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":"Publisher Correction: Atomically precise layer-by-layer titration of perovskite oxides reveals the termination-specific reactivity in oxygen electrocatalysis","authors":"Hongyang Su, Jie Zheng, Wenxiang Mu, Zixuan Guan, Pei Wang, Ziyun Zhang, Fanqi Meng, Xiaoying Yan, Peng Liu, Guiping Ji, Tianxiang Nan, Hui Zhang, Yidan Cao, Zhi Liu, Yuan-Hua Lin, Wei-Xue Li, William C. Chueh, Sulei Hu, Di Chen","doi":"10.1038/s41929-026-01590-z","DOIUrl":"10.1038/s41929-026-01590-z","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 8","pages":"924-924"},"PeriodicalIF":48.3,"publicationDate":"2026-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-026-01590-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148432541","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":"Triple energy transfer-enabled dearomative cycloaddition/rearrangement cascade of bicyclic azaarenes to structurally complex products","authors":"Preeti Chahar, Utpal Kundu, Subhabrata Dutta, Niklas Hölter, Florian Boser, Fabian M. Hugel, Luca Stadtmann, Constantin G. Daniliuc, Frank Glorius","doi":"10.1038/s41929-026-01566-z","DOIUrl":"10.1038/s41929-026-01566-z","url":null,"abstract":"Pyridine-fused, C(sp3)-rich bridged frameworks are privileged scaffolds in natural products and pharmaceutical compounds, yet their synthesis remains a formidable challenge due to prevailing step-intensive routes. Energy transfer (EnT)-catalysed dearomative cycloadditions offer a milder approach to increase saturation in feedstock (hetero)arenes. Current methods exploiting the 1,4-biradical reactivity of bicyclic azaarenes mainly focus on [4+2] cycloadditions. However, achieving higher-order cycloadditions, such as [4+n] (n > 2), to construct pyridine-fused/bridged motifs, remains challenging. Here we report a cascade reaction combining a higher-order dearomative [5+4] photocycloaddition of bicyclic azaarenes and vinyl cyclopropanes with a formal [3,3]-sigmatropic rearrangement and a subsequent [2+2] photocycloaddition. This triple EnT-catalysed cascade provides a mild, one-pot protocol for efficiently accessing complex pyridine-fused/bridged pentacyclic motifs with excellent selectivity. Notably, the EnT-mediated formal [3,3]-sigmatropic rearrangement unveils a mechanistic paradigm in photochemical cascades. Mechanistic experiments and density functional theory studies support involvement of three sequential EnT steps, rationalizing the origin of regioselectivity and diastereoselectivity. Energy transfer (EnT) catalysed dearomative cycloadditions of bicyclic azaarenes are largely limited to [4+2] pathways, with higher-order cycloadditions being difficult to achieve. Now, the authors circumvent this limitation by establishing a higher-order cycloaddition followed by cascades. This triple EnT-enabled [5+4]/[3,3]/[2+2] cascade with vinyl cyclopropanes enables one-pot access to complex pyridine-fused, bridged pentacycles scaffolds that are widely embedded in bioactive molecules, but whose synthesis has remained challenging owing to scarcity of efficient strategies.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"750-760"},"PeriodicalIF":48.3,"publicationDate":"2026-07-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-026-01566-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148432555","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":"Copper-catalysed carbon monoxide electrolysis under dynamic operation","authors":"Wanyu Deng, Ahryeon Lee, Soonho Kwon, Zhaoxi Wang, Yifei Xu, Siyang Xing, Bingjun Xu, Ryan Rasmussen, William Andrew Goddard III, Feng Jiao","doi":"10.1038/s41929-026-01574-z","DOIUrl":"10.1038/s41929-026-01574-z","url":null,"abstract":"Electrochemical reduction of carbon monoxide (CO) into valuable multicarbon products offers a promising pathway for carbon utilization. However, most CO electrolysers are developed for steady-state operation, whereas integration with intermittent renewable electricity may pose technical challenges. Here we show that repeated cycling between power-on and power-off modes rapidly degrades copper(Cu)-based cathodes, either through carbonate accumulation under CO-rich conditions or oxidation to Cu2O under Ar environments. To circumvent these Cu degradation issues, we introduce a controlled power-down strategy where the Cu cathode is kept at a slightly more negative potential than open-circuit potential, effectively preventing carbonate formation and Cu oxidation. This strategy enables stable dynamic operation of a CO electrolyser for more than 750 h without any significant performance loss. Techno-economic analysis indicates that dynamic operation can lower the acetic acid production cost by up to 26%, leveraging periods of lower electricity prices and thus improving viability for integrating with intermittent renewable electricity. The intermittent production of renewable electricity can have practical implications for renewable-driven electrocatalytic reactions. Here electrocatalytic CO reduction on Cu-based cathodes is investigated under power-on/power-off cycles, exposing mechanisms of deactivation and suggesting strategies to improve stability under these conditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 8","pages":"823-833"},"PeriodicalIF":48.3,"publicationDate":"2026-07-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148409218","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":"Alkali metal cation impurities stabilize Cu+ in oxide-derived copper for CO2 electrolysis","authors":"Haesol Kim, Seunghoon Lee, Jihoon Son, Hansol Choi, Junsic Cho, Baptiste Gault, Won-Hyoung Lee, Benedikt Paul Klein, Cheolho Jeon, Joonhee Moon, Da Hye Won, Dae-Hyun Nam, Gyeongwon Kang, Hyeyoung Shin, Se-Ho Kim, Chang Hyuck Choi","doi":"10.1038/s41929-026-01571-2","DOIUrl":"10.1038/s41929-026-01571-2","url":null,"abstract":"Electrocatalysts often undergo dynamic phase transitions during electrochemical operation, which introduce structural and chemical complexities that obscure the fundamental origins of their catalytic performance. Oxide-derived Cu (OD-Cu), produced by the electrochemical reduction of Cu oxide, exemplifies this challenge and continues to prompt debate regarding the nature of its high activity in CO2 electrolysis. Here, using cryogenic atom probe tomography, we show the formation of nanoscale Na+-containing microstructures within OD-Cu, originating from phase transitions of Cu oxide in a NaHCO3 electrolyte. Comparative studies with Na+-free OD-Cu and pulsed electrolysis identify a strong correlation between Na+ impurity incorporation and enhanced CO2 electrolysis activity. Complementary in situ Raman spectroscopy studies further confirm that these extrinsic impurities stabilize labile yet catalytically active Cu+ species. Overall, our findings elucidate the pivotal role of Na+ impurities and provide mechanistic insights to guide the rational design of synthetic and operational strategies for more efficient CO2 valorization. Oxide-derived copper is known to display high activity in electrocatalytic CO2 reduction to multicarbon products; however, the mechanism behind this remains unresolved. Here cryogenic atom probe tomography reveals the formation of microstructures containing alkali cations from the electrolyte that correlate with activity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 8","pages":"812-822"},"PeriodicalIF":48.3,"publicationDate":"2026-07-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148409223","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":"Bifunctional molecular additives enable efficient oxygen reduction reaction on platinum electrodes in the presence of strongly binding anions","authors":"Kaiyue Zhao, Linke Fu, Zelong Qiao, Yuke Li, Chaoran Huang, Bingyuan Chen, Zihan Jin, Xiaoqing Cao, Junrong Zheng, Shaojun Guo, Dapeng Cao, Xiaoxia Chang, Bingjun Xu","doi":"10.1038/s41929-026-01569-w","DOIUrl":"10.1038/s41929-026-01569-w","url":null,"abstract":"Rational design of electrode–electrolyte interfaces is central to achieving an efficient oxygen reduction reaction (ORR) in proton-exchange membrane fuel cells. Here we demonstrate that 7-alkyltheophyllines are a group of bifunctional molecular additives capable of enhancing ORR activity on Pt(111) in the presence of strongly binding anions, for example, sulfonate in Nafion and phosphate, by enhancing intrinsic ORR kinetics and suppressing the specific adsorption of anions. Single-crystal voltammetric analysis and computational investigations reveal that the enhanced intrinsic ORR kinetics by adsorbed 7-alkyltheophyllines stems from facilitating the reduction of *O to *OH, which is a kinetically important step in the ORR on Pt surfaces. Mechanistic insights regarding the molecular additives gained on Pt(111) are shown to be valid on polycrystalline Pt. Finally, the practical relevance of this discovery is demonstrated by substantial performance enhancements in proton-exchange membrane fuel cells with Pt/C catalysts modified by 7-ethyltheophylline, highlighting the transferability of fundamental insights. The specific binding of anions, including those present in ionomer binders, to the Pt surface imposes substantial limitations on performance in electrocatalytic oxygen reduction reactions. Here organic additives are shown to improve reaction kinetics on single-crystalline Pt surfaces, translating into improved performance in fuel cells when using commercial Pt/C catalysts.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"761-772"},"PeriodicalIF":48.3,"publicationDate":"2026-07-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148385819","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":"Rapid screening platform for peptide prenyltransferases to diversify pseudo-natural prenylated peptides","authors":"Sumika Inoue \u0000 (, ), Shunya Matsushita \u0000 (, ), Sayaka Ito \u0000 (, ), Marin Yokomine \u0000 (, ), Masayuki Satake \u0000 (, ), Chikako Okada \u0000 (, ), Keisuke Hamada \u0000 (, ), Yuchen Zhang \u0000 (, ), Risa Ohta \u0000 (, ), Taro Shiraishi \u0000 (, ), Hiroaki Suga \u0000 (, ), Masahiro Okada \u0000 (, ), Toru Sengoku \u0000 (, ), Yuki Goto \u0000 (, )","doi":"10.1038/s41929-026-01560-5","DOIUrl":"10.1038/s41929-026-01560-5","url":null,"abstract":"Peptide lipidation can enhance stability and permeability, yet biocatalysts for late-stage, site- and mode-selective modification remain limited. Here we established a streamlined activity-profiling system that rapidly assesses peptide-prenylating activities using an artificial substrate set. Screening 19 recombinant, putative cyanobactin prenyltransferases (PTases) uncovered 14 active enzymes with diverse catalytic properties, including five previously unreported modes of prenylation, bifunctionality towards Trp/Tyr and expanded donor utilization such as farnesylation. Co-crystal structures of seven PTases reveal how subtle active-site changes enable dual substrate recognition and accommodation of bulkier donors, highlighting the evolutionary diversification of catalytic functions. The enzymes tolerate non-native substrates, enabling late-stage, site- and mode-selective lipidation to construct pseudo-natural peptides. Together, these findings expand the enzymatic and mechanistic landscape of cyanobactin PTases, enlarging their functional repertoire and revealing the structural principles that govern the diversification of peptide prenylation chemistry. Late-stage peptide lipidation remains limited by the scarcity of broadly useful late-stage biocatalysts. Now a rapid screening platform reveals 14 cyanobactin prenyltransferases with diverse reaction patterns, prenyl donor scope and structures that support combinatorial peptide lipidation.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"699-710"},"PeriodicalIF":48.3,"publicationDate":"2026-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148385835","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":"Unveiling solid electrolyte interphase dynamics in electrochemical lithium-mediated ammonia synthesis via operando Raman spectroscopy","authors":"Antonia Herzog, Haldrian Iriawan, Louis Ah, Yang Shao-Horn","doi":"10.1038/s41929-026-01562-3","DOIUrl":"10.1038/s41929-026-01562-3","url":null,"abstract":"During electrochemical lithium-mediated nitrogen reduction to ammonia (LiNRR), the formation and function of the solid electrolyte interphase (SEI) remain poorly understood. Here operando Raman spectroscopy yielding realistic ammonia Faradaic efficiencies in tetrahydrofuran-based lithium perchlorate (LiClO4) and lithium bis(fluorosulfonyl)imide (LiFSI) electrolytes reveals how SEI composition and dynamics govern ammonia synthesis. By systematically probing the interaction between N2, ethanol and electroplated Li, we find that ethanol, beyond acting as a proton donor, actively reshapes the SEI via lithium ethoxide formation, thereby enabling N2 activation. Tuning the electrolyte composition shows that higher conversion to NH3 correlated with SEIs enriched in lithium alkoxides and LiOH, which enhanced the reactivity of the Li surface towards N2 and H+. Our results highlight the SEI as a key regulator of N2, H+ and Li+, tunable by electrolyte additives, providing design principles for efficient ammonia electrosynthesis. Understanding the role of solid electrolyte interphase (SEI) under reaction conditions is crucial to improving the efficiency of electrochemical lithium-mediated N2 reduction. Here, operando Raman spectroscopy is used to investigate the effect of electrolyte, proton donor and gas environments on SEI composition and its resultant performance and stability.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"711-726"},"PeriodicalIF":48.3,"publicationDate":"2026-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148385822","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 the Cu-catalysed asymmetric radical azidation of N-heterobenzylic sites through rational ligand design","authors":"Yifan Lei, Zitong Chen, Hongyou Guo, Qiyang Yuan, Aoping Zhu, Zixin Zhang, Yuhongxu Bai, Xiaotian Qi, Caiyou Chen","doi":"10.1038/s41929-026-01563-2","DOIUrl":"10.1038/s41929-026-01563-2","url":null,"abstract":"Transition-metal-catalysed asymmetric radical functionalization of N-heteroarene derivatives remains a substantial challenge. The asymmetric azidation of N-heteroarene derivatives remains unattainable with current catalytic systems, probably due to catalyst poisoning. Here we develop a strong chelating tridentate PyAP ligand, which allows the formation of the mono-azido Cu(II) intermediate and further prevents the successive binding of N-heteroarenes that might lead to catalyst poisoning. Thus, the Cu/PyAP catalytic system shows excellent reactivity, together with high enantioselectivity induced by the chiral environment close to the metal centre. Mechanistic studies and density functional theory calculations suggest that the asymmetric azidation proceeds through an intramolecular homolytic substitution pathway, with the pyridyl alkyl radical bound to Cu. The Cu/PyAP catalytic system realizes both the asymmetric azido difunctionalization of N-heteroaryl ethylenes and the azidation of the N-heterobenzyl halides in high yield and enantiomeric excess, thereby expediting the synthesis of various chiral drugs, natural products and bioactive compounds featuring the chiral azido N-heteroarene motif. Current effective methods for the transition-metal-catalysed asymmetric radical functionalization of N-heteroarene derivatives remain scarce. Here the authors present a Cu/PyAP catalytic system that realizes the asymmetric azido difunctionalization of N-heteroaryl ethylenes and the azidation of N-heterobenzyl halides.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"727-738"},"PeriodicalIF":48.3,"publicationDate":"2026-06-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148385820","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":"Atomically precise layer-by-layer titration of perovskite oxides reveals the termination-specific reactivity in oxygen electrocatalysis","authors":"Hongyang Su, Jie Zheng, Wenxiang Mu, Zixuan Guan, Pei Wang, Ziyun Zhang, Fanqi Meng, Xiaoying Yan, Peng Liu, Guiping Ji, Tianxiang Nan, Hui Zhang, Yidan Cao, Zhi Liu, Yuan-Hua Lin, Wei-Xue Li, William C. Chueh, Sulei Hu, Di Chen","doi":"10.1038/s41929-026-01561-4","DOIUrl":"10.1038/s41929-026-01561-4","url":null,"abstract":"Understanding how atomic-scale surface structures govern catalytic pathways is central to advancing electrocatalysis yet remains poorly resolved in complex oxides. Here we develop an in situ titration platform integrating atomic layer-by-layer titration with reactivity quantification to dissect elevated-temperature oxygen incorporation reactions on (La0.5Sr0.5)FeO3−δ. We reveal a volcano-shaped correlation between oxygen incorporation reaction activity and SrO termination layers, and find that a single-layer SrO termination maximizes performance. Microkinetic modelling and theoretical calculations reveal a rate-determining step shift with surface termination. The single-layer SrO termination optimally balances oxygen dissociation, incorporation and subsurface diffusion by modulating charge transfer and steric constraints. This platform paves the way to quantitatively correlate catalytic activity with surface atomic structures, offering atomically precise surface engineering methodologies for designing high-performance electrocatalysts in energy and environmental applications. Surface composition governs the catalytic performance of any given material but in mixed oxides it can be particularly challenging to determine this with atomic precision. Now by means of in situ layer-by-layer titration it is shown that single-layer SrO termination maximizes oxygen incorporation on (La0.5Sr0.5)FeO3−δ perovskite.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"9 7","pages":"739-749"},"PeriodicalIF":48.3,"publicationDate":"2026-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148336494","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}