Substituted cyclohexanes are ubiquitous motifs in bioactive molecules. Thermodynamically disfavoured substituted cyclohexane scaffolds can significantly enhance both the biological activity and pharmacokinetic properties of potential drugs. However, achieving stereoselective cross-coupling for the synthesis of these structures with precise kinetic control remains a challenge. Here we present a modular reductive cross-coupling reaction that enables the stereoselective synthesis of thermodynamically disfavoured substituted cyclohexanes, employing simple alkenes as coupling partners. Mechanistically, the exceptional stereochemistry of this reaction is governed by a Heck-type migratory insertion step. The utility of this method is also demonstrated through the concise synthesis of bioactive molecules. Thermodynamically disfavoured substituted cyclohexane compounds often display superior physical and bioactive properties to their isomeric counterparts. Now their synthesis is achieved by Ni-catalysed coupling of substituted methylenecyclohexanes with electrophiles under kinetic control.
{"title":"A stereoselective reductive cross-coupling reaction with kinetic control","authors":"Zhenpeng Shen, Hongjin Shi, Yangyang Li, Xiangyu Zhang, Xiaotian Qi, Guoyin Yin","doi":"10.1038/s41929-025-01440-4","DOIUrl":"10.1038/s41929-025-01440-4","url":null,"abstract":"Substituted cyclohexanes are ubiquitous motifs in bioactive molecules. Thermodynamically disfavoured substituted cyclohexane scaffolds can significantly enhance both the biological activity and pharmacokinetic properties of potential drugs. However, achieving stereoselective cross-coupling for the synthesis of these structures with precise kinetic control remains a challenge. Here we present a modular reductive cross-coupling reaction that enables the stereoselective synthesis of thermodynamically disfavoured substituted cyclohexanes, employing simple alkenes as coupling partners. Mechanistically, the exceptional stereochemistry of this reaction is governed by a Heck-type migratory insertion step. The utility of this method is also demonstrated through the concise synthesis of bioactive molecules. Thermodynamically disfavoured substituted cyclohexane compounds often display superior physical and bioactive properties to their isomeric counterparts. Now their synthesis is achieved by Ni-catalysed coupling of substituted methylenecyclohexanes with electrophiles under kinetic control.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1241-1249"},"PeriodicalIF":44.6,"publicationDate":"2025-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145455582","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}
Pub Date : 2025-11-05DOI: 10.1038/s41929-025-01430-6
Negin Orouji, Jeffrey A. Bennett, Richard B. Canty, Long Qi, Shijing Sun, Paulami Majumdar, Chong Liu, Núria López, Neil M. Schweitzer, John R. Kitchin, Hongliang Xin, Milad Abolhasani
Catalysis is essential to modern chemical manufacturing and environmental sustainability. Yet, traditional catalyst discovery remains slow, resource-intensive and constrained by human-centred trial-and-error workflows. The integration of artificial intelligence (AI), robotics and high-throughput experimentation into self-driving laboratories (SDLs) presents a transformative approach for accelerating catalyst discovery and optimization. SDLs combine automated synthesis and testing platforms, data infrastructures and AI-guided decision-making to enable information-rich experimentation and the fast-tracked generation of scientific knowledge. However, in our view, realizing the full potential of SDLs requires sustained human oversight to ensure rigorous data curation, validate machine-generated hypotheses and establish benchmarks to mitigate AI-related errors. This Perspective outlines core SDL components, including hardware, computational modelling and AI-guided decision-making. We discuss challenges in data availability, integration of computational and experimental workflows and scalable platforms. Finally, we outline immediate opportunities to broaden the adoption of autonomous experimentation in catalysis. The rise of artificial intelligence together with advances in robotics is leading a surge of interest in self-driving laboratories. This Perspective discusses self-driving laboratories for catalysis while arguing that, to achieve their full potential, human oversight is required.
{"title":"Autonomous catalysis research with human–AI–robot collaboration","authors":"Negin Orouji, Jeffrey A. Bennett, Richard B. Canty, Long Qi, Shijing Sun, Paulami Majumdar, Chong Liu, Núria López, Neil M. Schweitzer, John R. Kitchin, Hongliang Xin, Milad Abolhasani","doi":"10.1038/s41929-025-01430-6","DOIUrl":"10.1038/s41929-025-01430-6","url":null,"abstract":"Catalysis is essential to modern chemical manufacturing and environmental sustainability. Yet, traditional catalyst discovery remains slow, resource-intensive and constrained by human-centred trial-and-error workflows. The integration of artificial intelligence (AI), robotics and high-throughput experimentation into self-driving laboratories (SDLs) presents a transformative approach for accelerating catalyst discovery and optimization. SDLs combine automated synthesis and testing platforms, data infrastructures and AI-guided decision-making to enable information-rich experimentation and the fast-tracked generation of scientific knowledge. However, in our view, realizing the full potential of SDLs requires sustained human oversight to ensure rigorous data curation, validate machine-generated hypotheses and establish benchmarks to mitigate AI-related errors. This Perspective outlines core SDL components, including hardware, computational modelling and AI-guided decision-making. We discuss challenges in data availability, integration of computational and experimental workflows and scalable platforms. Finally, we outline immediate opportunities to broaden the adoption of autonomous experimentation in catalysis. The rise of artificial intelligence together with advances in robotics is leading a surge of interest in self-driving laboratories. This Perspective discusses self-driving laboratories for catalysis while arguing that, to achieve their full potential, human oversight is required.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1135-1145"},"PeriodicalIF":44.6,"publicationDate":"2025-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145441152","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}
Pub Date : 2025-11-03DOI: 10.1038/s41929-025-01436-0
Zhi Zou, Indrek Kalvet, Boris Lozhkin, Elinor Morris, Kailin Zhang, Dongping Chen, Marco L. Ernst, Xiang Zhang, David Baker, Thomas R. Ward
Artificial metalloenzymes present a promising avenue for abiotic catalysis within living systems. However, their in vivo application is currently limited by critical challenges, particularly in selecting suitable protein scaffolds capable of binding abiotic cofactors and maintaining catalytic activity in complex media. Here we address these limitations by introducing an artificial metathase—an artificial metalloenzyme designed for ring-closing metathesis—for whole-cell biocatalysis. Our approach integrates a tailored metal cofactor into a hyper-stable, de novo-designed protein. By combining computational design with genetic optimization, a binding affinity (KD ≤ 0.2 μM) between the protein scaffold and cofactor is achieved through supramolecular anchoring. Directed evolution of the artificial metathase yielded variants exhibiting excellent catalytic performance (turnover number ≥1,000) and biocompatibility. This work represents a pronounced leap in the de novo design and in cellulo engineering of artificial metalloenzymes, paving the way for abiological catalysis in living systems. The creation of artificial metalloenzymes compatible with complex biological settings could enable broad applications. Now a de novo-designed artificial metalloenzyme containing an abiological ruthenium cofactor is reported and optimized for ring-closing metathesis in the cytoplasm of whole cells.
{"title":"De novo design and evolution of an artificial metathase for cytoplasmic olefin metathesis","authors":"Zhi Zou, Indrek Kalvet, Boris Lozhkin, Elinor Morris, Kailin Zhang, Dongping Chen, Marco L. Ernst, Xiang Zhang, David Baker, Thomas R. Ward","doi":"10.1038/s41929-025-01436-0","DOIUrl":"10.1038/s41929-025-01436-0","url":null,"abstract":"Artificial metalloenzymes present a promising avenue for abiotic catalysis within living systems. However, their in vivo application is currently limited by critical challenges, particularly in selecting suitable protein scaffolds capable of binding abiotic cofactors and maintaining catalytic activity in complex media. Here we address these limitations by introducing an artificial metathase—an artificial metalloenzyme designed for ring-closing metathesis—for whole-cell biocatalysis. Our approach integrates a tailored metal cofactor into a hyper-stable, de novo-designed protein. By combining computational design with genetic optimization, a binding affinity (KD ≤ 0.2 μM) between the protein scaffold and cofactor is achieved through supramolecular anchoring. Directed evolution of the artificial metathase yielded variants exhibiting excellent catalytic performance (turnover number ≥1,000) and biocompatibility. This work represents a pronounced leap in the de novo design and in cellulo engineering of artificial metalloenzymes, paving the way for abiological catalysis in living systems. The creation of artificial metalloenzymes compatible with complex biological settings could enable broad applications. Now a de novo-designed artificial metalloenzyme containing an abiological ruthenium cofactor is reported and optimized for ring-closing metathesis in the cytoplasm of whole cells.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1208-1219"},"PeriodicalIF":44.6,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01436-0.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145427399","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}
Radical repositioning, a transformative strategy for activating remote C–C/C–H bonds through the relocation of unpaired electrons, remains unexplored in biological systems. Recent advances in photogenerated nitrogen-centred radicals (NCRs) have enabled radical 1,2- to 1,n-translocations for organic synthesis, but achieving stereochemical control over the repositioned prochiral radicals is challenging. Here we introduce a visible light-promoted, thiamine-dependent radical biocatalytic system that leverages NCR-triggered radical repositioning for the enantioselective acylation of remote C–C/C–H bonds. Synergistic single-electron transfer and thiamine cofactor-mediated biocatalysis enables the generation of NCRs, which translocate to remote carbon-centred radicals via 1,n-hydrogen atom transfer or C–C fragmentation, and facilitates the subsequent radical cross-coupling within the active site, producing diverse chiral nitriles and amides with a remote carbonyl group (43 examples with a δ-, ε-, ζ- or η-position relative to the N atom) in good-to-excellent enantiomeric ratios (up to 99.5:0.5). This strategy couples radical repositioning and enzymes to unlock the selective functionalization of remote C–H/C–C bonds. Radical repositioning to activate remote bonds is underdeveloped in synthetic biocatalysis. Now a photobiocatalytic system couples light-driven single-electron transfer and the relocation of unpaired electrons to activate remote C–C and C–H bonds for enzymatically controlled enantioselective acylation.
{"title":"Photobiocatalytic radical repositioning for enantioselective acylation of remote C–C/C–H bonds","authors":"Yang Ming, Zhouping Wu, Yuanyuan Xu, Yao Chen, Zhongqiu Xing, Xichao Peng, Jianlin Chun, Hailong Sun, Jiayu Wu, Yu Zheng, Ling Jiang, Xiaoqiang Huang","doi":"10.1038/s41929-025-01435-1","DOIUrl":"10.1038/s41929-025-01435-1","url":null,"abstract":"Radical repositioning, a transformative strategy for activating remote C–C/C–H bonds through the relocation of unpaired electrons, remains unexplored in biological systems. Recent advances in photogenerated nitrogen-centred radicals (NCRs) have enabled radical 1,2- to 1,n-translocations for organic synthesis, but achieving stereochemical control over the repositioned prochiral radicals is challenging. Here we introduce a visible light-promoted, thiamine-dependent radical biocatalytic system that leverages NCR-triggered radical repositioning for the enantioselective acylation of remote C–C/C–H bonds. Synergistic single-electron transfer and thiamine cofactor-mediated biocatalysis enables the generation of NCRs, which translocate to remote carbon-centred radicals via 1,n-hydrogen atom transfer or C–C fragmentation, and facilitates the subsequent radical cross-coupling within the active site, producing diverse chiral nitriles and amides with a remote carbonyl group (43 examples with a δ-, ε-, ζ- or η-position relative to the N atom) in good-to-excellent enantiomeric ratios (up to 99.5:0.5). This strategy couples radical repositioning and enzymes to unlock the selective functionalization of remote C–H/C–C bonds. Radical repositioning to activate remote bonds is underdeveloped in synthetic biocatalysis. Now a photobiocatalytic system couples light-driven single-electron transfer and the relocation of unpaired electrons to activate remote C–C and C–H bonds for enzymatically controlled enantioselective acylation.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1198-1207"},"PeriodicalIF":44.6,"publicationDate":"2025-11-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145427398","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}
Pub Date : 2025-10-31DOI: 10.1038/s41929-025-01438-y
Shengyang Ni, Alexios Stamoulis, Vanessa A. Béland, Josep Cornella
The Heck reaction, which is widely used for the construction of C‒C bonds, is a cornerstone of modern organic synthesis. Traditionally, this transformation relies on transition metal catalysts, whose frontier d-orbitals cement the mechanism and scope of the reaction. Here we present a conceptually distinct Heck-type coupling strategy that replaces transition metals with a photoactive bismuth complex, marking an advance in main group catalysis. This approach leverages the distinctive electronic and photophysical properties of bismuth, providing a reimagined reaction pathway. The bismuth catalyst undergoes a photo-induced ligand-to-metal charge transfer processes, unmasking a Bi(II) species capable of halogen atom transfer (XAT) processes with alkyl iodides. The multifaceted redox-dependent photophysical properties of the bismuth catalyst facilitate the coupling of aryl and alkyl electrophiles with styrenes through an intricate interplay of mechanistic steps. The method provides a mechanistic blueprint for accessing coveted Bi(II) species, offering an alternative to transition metal catalysis in organic synthesis. The Heck reaction is widely used in modern organic chemistry. Here the authors provide an alternative approach to common transition-metal catalysis, leveraging access to Bi(II) species thanks to bismuth’s photophysical properties.
{"title":"Bismuth-photocatalysed Heck-type coupling with alkyl and aryl electrophiles","authors":"Shengyang Ni, Alexios Stamoulis, Vanessa A. Béland, Josep Cornella","doi":"10.1038/s41929-025-01438-y","DOIUrl":"10.1038/s41929-025-01438-y","url":null,"abstract":"The Heck reaction, which is widely used for the construction of C‒C bonds, is a cornerstone of modern organic synthesis. Traditionally, this transformation relies on transition metal catalysts, whose frontier d-orbitals cement the mechanism and scope of the reaction. Here we present a conceptually distinct Heck-type coupling strategy that replaces transition metals with a photoactive bismuth complex, marking an advance in main group catalysis. This approach leverages the distinctive electronic and photophysical properties of bismuth, providing a reimagined reaction pathway. The bismuth catalyst undergoes a photo-induced ligand-to-metal charge transfer processes, unmasking a Bi(II) species capable of halogen atom transfer (XAT) processes with alkyl iodides. The multifaceted redox-dependent photophysical properties of the bismuth catalyst facilitate the coupling of aryl and alkyl electrophiles with styrenes through an intricate interplay of mechanistic steps. The method provides a mechanistic blueprint for accessing coveted Bi(II) species, offering an alternative to transition metal catalysis in organic synthesis. The Heck reaction is widely used in modern organic chemistry. Here the authors provide an alternative approach to common transition-metal catalysis, leveraging access to Bi(II) species thanks to bismuth’s photophysical properties.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1232-1240"},"PeriodicalIF":44.6,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01438-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145405105","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}
Ionic interactions between DNA phosphates and positively charged amino acid residues in aqueous environments are ubiquitous and essential across all biological systems. Such interactions are readily disrupted by polar solvents according to Coulomb’s law, which accounts for the predominant use of non-polar or weakly polar organic solvents in chiral phosphate-mediated asymmetric organocatalysis. This intriguing discrepancy prompted us to exploit the possibility of conducting asymmetric catalysis in water with intrinsically chiral and abundant DNA phosphates. Here we experimentally and computationally demonstrate that DNA phosphates play a critical role in rate acceleration and stereoinduction through ion-pairing interactions with cationic reagents, featuring a cation-dependent dynamic and adaptive nature of the DNA catalyst rarely seen in highly specific enzymatic systems. The application of DNA phosphates to mediate asymmetric reactions is underdeveloped in synthetic chemistry. Now, DNA phosphates are designed to catalyse enantioselective fluorination, Mannich and photo-induced cross-dehydrogenative coupling reactions in water driven by ion-pairing interactions.
{"title":"DNA phosphates are effective catalysts for asymmetric ion-pairing catalysis in water","authors":"Zhaoyang Li, Yang Zheng, Qi Zhao, Yihan Li, Adon Yap, Xinglong Zhang, Ru-Yi Zhu","doi":"10.1038/s41929-025-01437-z","DOIUrl":"10.1038/s41929-025-01437-z","url":null,"abstract":"Ionic interactions between DNA phosphates and positively charged amino acid residues in aqueous environments are ubiquitous and essential across all biological systems. Such interactions are readily disrupted by polar solvents according to Coulomb’s law, which accounts for the predominant use of non-polar or weakly polar organic solvents in chiral phosphate-mediated asymmetric organocatalysis. This intriguing discrepancy prompted us to exploit the possibility of conducting asymmetric catalysis in water with intrinsically chiral and abundant DNA phosphates. Here we experimentally and computationally demonstrate that DNA phosphates play a critical role in rate acceleration and stereoinduction through ion-pairing interactions with cationic reagents, featuring a cation-dependent dynamic and adaptive nature of the DNA catalyst rarely seen in highly specific enzymatic systems. The application of DNA phosphates to mediate asymmetric reactions is underdeveloped in synthetic chemistry. Now, DNA phosphates are designed to catalyse enantioselective fluorination, Mannich and photo-induced cross-dehydrogenative coupling reactions in water driven by ion-pairing interactions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1220-1231"},"PeriodicalIF":44.6,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145404976","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}
Pub Date : 2025-10-31DOI: 10.1038/s41929-025-01434-2
Jin Zhu, Qiaoyu Zhang, Tao Gu, Binbin Chen, Mingzhe Ma, Xiaoyu Wang, Xiao Liu, Mingjie Ma, Binju Wang, Yajie Wang
Established strategies for enantioselective hydroalkylation for C(sp3)–C(sp3) bond formation usually require prefunctionalized substrates as radical precursors in both transition-metal and photoenzymatic catalysis. Here, based on a sequential proton transfer/electron transfer strategy, we show a cooperative photoenzymatic system consisting of a flavin-dependent ‘ene’-reductase and an organophotoredox catalyst fluorescein (FI) to achieve atom-economic enantiodivergent hydroalkylation of electron-deficient C(sp3)–H with olefins. Mechanistic studies revealed a pathway for radical intermediate formation via excited-state FI*-induced single-electron oxidation of carbanions under alkaline conditions. The overall catalytic efficiency is enhanced by the electron transfer between FMNox and FI−•, while the stereoselectivity is controlled by ene-reductases through enantioselective hydrogen atom transfer. We anticipate that this mode of photoenzymatic catalysis will inspire new pathways for generating free radical intermediates and foster innovative strategies for achieving photoenzymatic new-to-nature reactions. Constructing C(sp3)–C(sp3) bonds using non-prefunctionalized substrates as radical precursors is challenging. Now an ene-reductase and an organophotoredox catalyst work together to enable the enantiodivergent hydroalkylation of electron-deficient C(sp3)–H bonds via radical intermediates generated from carbanions.
{"title":"Atom-economic enantioselective photoenzymatic radical hydroalkylation via single-electron oxidation of carbanions","authors":"Jin Zhu, Qiaoyu Zhang, Tao Gu, Binbin Chen, Mingzhe Ma, Xiaoyu Wang, Xiao Liu, Mingjie Ma, Binju Wang, Yajie Wang","doi":"10.1038/s41929-025-01434-2","DOIUrl":"10.1038/s41929-025-01434-2","url":null,"abstract":"Established strategies for enantioselective hydroalkylation for C(sp3)–C(sp3) bond formation usually require prefunctionalized substrates as radical precursors in both transition-metal and photoenzymatic catalysis. Here, based on a sequential proton transfer/electron transfer strategy, we show a cooperative photoenzymatic system consisting of a flavin-dependent ‘ene’-reductase and an organophotoredox catalyst fluorescein (FI) to achieve atom-economic enantiodivergent hydroalkylation of electron-deficient C(sp3)–H with olefins. Mechanistic studies revealed a pathway for radical intermediate formation via excited-state FI*-induced single-electron oxidation of carbanions under alkaline conditions. The overall catalytic efficiency is enhanced by the electron transfer between FMNox and FI−•, while the stereoselectivity is controlled by ene-reductases through enantioselective hydrogen atom transfer. We anticipate that this mode of photoenzymatic catalysis will inspire new pathways for generating free radical intermediates and foster innovative strategies for achieving photoenzymatic new-to-nature reactions. Constructing C(sp3)–C(sp3) bonds using non-prefunctionalized substrates as radical precursors is challenging. Now an ene-reductase and an organophotoredox catalyst work together to enable the enantiodivergent hydroalkylation of electron-deficient C(sp3)–H bonds via radical intermediates generated from carbanions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1188-1197"},"PeriodicalIF":44.6,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145404977","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}
Pub Date : 2025-10-27DOI: 10.1038/s41929-025-01429-z
Wenjie Li, Muwen Yang, Zhiheng Zhao, Ming Zhao, Rong Ye, Bing Fu, Peng Chen
Many vital electrocatalytic transformations hinge on reactive surface metal–hydrogen intermediates (M–H*), yet the low concentration and transient nature of such intermediates present formidable challenges to in-depth investigation. Here we use single-molecule super-resolution reaction imaging to directly probe surface palladium–hydrogen (Pd–H*) intermediates on individual palladium nanocubes during electrocatalytic hydrogen evolution. Our approach visualizes hydrogen spillover from palladium to the surrounding substrate surface over hundreds of nanometres away and dissects substantial inter- and intraparticle heterogeneity. Through Gaussian-broadening kinetic analysis, we reveal that ensemble-averaged measurements systematically overestimate the stability of Pd–H*. Moreover, we resolve three subpopulations of palladium nanocubes with distinct reactivity features, uncovering critical correlations between intermediate stability, hydrogenation reactivity and transition-state properties. Our findings highlight the necessity of single-particle resolution for capturing the intrinsic complexity of electrocatalysts; our approach is also broadly applicable to interrogate surface-reactive intermediates across a wide array of electrocatalytic pathways. Probing transient intermediates and deriving subsequent mechanistic and kinetic analyses is very challenging. Now, Pd–H* intermediates on palladium nanocubes are identified at the single-particle level by means of single-molecule reaction imaging, evidencing intra- and interparticle heterogeneity and hydrogen spillover events.
{"title":"Single-molecule reaction mapping uncovers diverse behaviours of electrocatalytic surface Pd–H intermediates","authors":"Wenjie Li, Muwen Yang, Zhiheng Zhao, Ming Zhao, Rong Ye, Bing Fu, Peng Chen","doi":"10.1038/s41929-025-01429-z","DOIUrl":"10.1038/s41929-025-01429-z","url":null,"abstract":"Many vital electrocatalytic transformations hinge on reactive surface metal–hydrogen intermediates (M–H*), yet the low concentration and transient nature of such intermediates present formidable challenges to in-depth investigation. Here we use single-molecule super-resolution reaction imaging to directly probe surface palladium–hydrogen (Pd–H*) intermediates on individual palladium nanocubes during electrocatalytic hydrogen evolution. Our approach visualizes hydrogen spillover from palladium to the surrounding substrate surface over hundreds of nanometres away and dissects substantial inter- and intraparticle heterogeneity. Through Gaussian-broadening kinetic analysis, we reveal that ensemble-averaged measurements systematically overestimate the stability of Pd–H*. Moreover, we resolve three subpopulations of palladium nanocubes with distinct reactivity features, uncovering critical correlations between intermediate stability, hydrogenation reactivity and transition-state properties. Our findings highlight the necessity of single-particle resolution for capturing the intrinsic complexity of electrocatalysts; our approach is also broadly applicable to interrogate surface-reactive intermediates across a wide array of electrocatalytic pathways. Probing transient intermediates and deriving subsequent mechanistic and kinetic analyses is very challenging. Now, Pd–H* intermediates on palladium nanocubes are identified at the single-particle level by means of single-molecule reaction imaging, evidencing intra- and interparticle heterogeneity and hydrogen spillover events.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 11","pages":"1159-1168"},"PeriodicalIF":44.6,"publicationDate":"2025-10-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145382245","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}
Pub Date : 2025-10-24DOI: 10.1038/s41929-025-01414-6
Héctor Soria-Carrera, Job Boekhoven
A study demonstrates that fully synthetic molecules can undergo self-replication, mutation and selection — hallmarks of Darwinian evolution — without relying on DNA or proteins.
{"title":"Catalyst optimization through synthetic Darwinian evolution","authors":"Héctor Soria-Carrera, Job Boekhoven","doi":"10.1038/s41929-025-01414-6","DOIUrl":"10.1038/s41929-025-01414-6","url":null,"abstract":"A study demonstrates that fully synthetic molecules can undergo self-replication, mutation and selection — hallmarks of Darwinian evolution — without relying on DNA or proteins.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 10","pages":"979-980"},"PeriodicalIF":44.6,"publicationDate":"2025-10-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145371937","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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