Pub Date : 2025-12-22DOI: 10.1038/s41929-025-01461-z
Nitish Govindarajan, An T. Chu, Christopher Hahn, Yogesh Surendranath
Electrocatalysts enable the efficient interconversion of electrical and chemical energy for the sustainable production of fuels and chemicals. Here we highlight the importance of developing electrochemical adsorption isotherms to demystify complex reaction mechanisms and rationalize catalytic activity.
{"title":"The overlooked role of adsorption isotherms in electrocatalysis","authors":"Nitish Govindarajan, An T. Chu, Christopher Hahn, Yogesh Surendranath","doi":"10.1038/s41929-025-01461-z","DOIUrl":"10.1038/s41929-025-01461-z","url":null,"abstract":"Electrocatalysts enable the efficient interconversion of electrical and chemical energy for the sustainable production of fuels and chemicals. Here we highlight the importance of developing electrochemical adsorption isotherms to demystify complex reaction mechanisms and rationalize catalytic activity.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1254-1259"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808781","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 : 2025-12-22DOI: 10.1038/s41929-025-01458-8
Cong Xiao, Wen-Jing Xiao
Energy transfer photocatalysis typically requires expensive metal complexes or specific synthetic photosensitizers with particular triplet energies. Nitroarenes now emerge as powerful, sustainable alternatives, with their catalytic efficiency governed by excited-state geometry rather than only by energy matching, enabling efficient alkene isomerizations and cycloadditions.
{"title":"Nitroarenes as energy transfer catalysts","authors":"Cong Xiao, Wen-Jing Xiao","doi":"10.1038/s41929-025-01458-8","DOIUrl":"10.1038/s41929-025-01458-8","url":null,"abstract":"Energy transfer photocatalysis typically requires expensive metal complexes or specific synthetic photosensitizers with particular triplet energies. Nitroarenes now emerge as powerful, sustainable alternatives, with their catalytic efficiency governed by excited-state geometry rather than only by energy matching, enabling efficient alkene isomerizations and cycloadditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1260-1261"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808782","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 : 2025-12-22DOI: 10.1038/s41929-025-01457-9
Jianbin Li, Ding Zhang, Zhennan Hu, Zehao Yuan
Photocatalysis has become a cornerstone in modern organic synthesis due to its ability to generate and manage reactive radical intermediates, thus facilitating diverse chemical processes under mild conditions. A critical yet often overlooked aspect of photocatalysis is the dynamic transformation of photocatalysts into their active forms during reactions, which fundamentally governs their reactivity, selectivity and reaction outcome. Here we term this class of catalysts ‘transformer photocatalysts’, which undergo various activation pathways such as reductive activation, acid coordination, radical substitution and deconstructive processes. By categorizing selected examples based on these activation mechanisms, we aim to highlight the typical activation modes of some common photocatalysts and elucidate the underlying principles that guide the formation and behaviour of these active species. We hope that these mechanistic insights will provide a foundation for broadening the horizon of photocatalysis and developing photocatalysts tailored to organic transformations, thus inspiring further research in photochemistry and beyond. Photocatalysis enables many appealing synthetic reactions to proceed under mild conditions. This Review focuses on structural and electronic changes of photocatalysts, potentially resulting in frequently neglected active species that facilitate catalysis.
{"title":"Illuminating the transformation of photocatalysts in light-driven organic synthesis","authors":"Jianbin Li, Ding Zhang, Zhennan Hu, Zehao Yuan","doi":"10.1038/s41929-025-01457-9","DOIUrl":"10.1038/s41929-025-01457-9","url":null,"abstract":"Photocatalysis has become a cornerstone in modern organic synthesis due to its ability to generate and manage reactive radical intermediates, thus facilitating diverse chemical processes under mild conditions. A critical yet often overlooked aspect of photocatalysis is the dynamic transformation of photocatalysts into their active forms during reactions, which fundamentally governs their reactivity, selectivity and reaction outcome. Here we term this class of catalysts ‘transformer photocatalysts’, which undergo various activation pathways such as reductive activation, acid coordination, radical substitution and deconstructive processes. By categorizing selected examples based on these activation mechanisms, we aim to highlight the typical activation modes of some common photocatalysts and elucidate the underlying principles that guide the formation and behaviour of these active species. We hope that these mechanistic insights will provide a foundation for broadening the horizon of photocatalysis and developing photocatalysts tailored to organic transformations, thus inspiring further research in photochemistry and beyond. Photocatalysis enables many appealing synthetic reactions to proceed under mild conditions. This Review focuses on structural and electronic changes of photocatalysts, potentially resulting in frequently neglected active species that facilitate catalysis.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1268-1280"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808783","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 : 2025-12-22DOI: 10.1038/s41929-025-01455-x
Boon Siang Yeo
Electrocatalytic CO2 reduction on Cu is typically studied at room temperature and pressure, producing mostly C1 and C2 products (short carbon chains). High-temperature experiments above 125 °C now reveal a carbon-chain growth mechanism akin to the thermally driven Fischer–Tropsch reaction, resulting in the production of C1–C5 hydrocarbons.
{"title":"Growing the carbon chain","authors":"Boon Siang Yeo","doi":"10.1038/s41929-025-01455-x","DOIUrl":"10.1038/s41929-025-01455-x","url":null,"abstract":"Electrocatalytic CO2 reduction on Cu is typically studied at room temperature and pressure, producing mostly C1 and C2 products (short carbon chains). High-temperature experiments above 125 °C now reveal a carbon-chain growth mechanism akin to the thermally driven Fischer–Tropsch reaction, resulting in the production of C1–C5 hydrocarbons.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1266-1267"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808788","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 : 2025-12-22DOI: 10.1038/s41929-025-01468-6
Marcal Capdevila-Cortada
{"title":"Shifting both ways on ceria","authors":"Marcal Capdevila-Cortada","doi":"10.1038/s41929-025-01468-6","DOIUrl":"10.1038/s41929-025-01468-6","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1252-1252"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808785","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 : 2025-12-22DOI: 10.1038/s41929-025-01459-7
Christina N. Wiswell, David K. Tanas, Mitchell P. Croatt
Direct conversion of carboxylic acids to nitriles is desirable but thermodynamically uphill. Here, a bioinspired process utilizes magnesium and palladium co-catalysts and urea as a nitrogen source.
{"title":"Practical conversion of carboxylic acids to nitriles","authors":"Christina N. Wiswell, David K. Tanas, Mitchell P. Croatt","doi":"10.1038/s41929-025-01459-7","DOIUrl":"10.1038/s41929-025-01459-7","url":null,"abstract":"Direct conversion of carboxylic acids to nitriles is desirable but thermodynamically uphill. Here, a bioinspired process utilizes magnesium and palladium co-catalysts and urea as a nitrogen source.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1262-1263"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808786","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 : 2025-12-22DOI: 10.1038/s41929-025-01469-5
Benjamin Martindale
{"title":"Shining light using the dark","authors":"Benjamin Martindale","doi":"10.1038/s41929-025-01469-5","DOIUrl":"10.1038/s41929-025-01469-5","url":null,"abstract":"","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1253-1253"},"PeriodicalIF":44.6,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145808787","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 : 2025-12-18DOI: 10.1038/s41929-025-01454-y
Manpreet Kaur, Sourav Rej, Jan Navrátil, Eva Yazmin Santiago, Michal Otyepka, Stefano Livraghi, Lorenzo Mino, Štěpán Kment, Zhikang Xu, Haibo Zhu, Paolo Fornasiero, Alexander O. Govorov, Piotr Błoński, Alberto Naldoni
Upgrading biomass feedstock into higher-value chemicals is central to improve the sustainability of the chemical industry and to reduce its dependence on fossil raw materials. Heterogeneous photocatalysts are promising for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a biomass-derived molecular platform for biopolymers, but their FDCA selectivity is negligible without the aid of a base. Here we present a plasmonic photocatalyst integrating TiN nanocubes and bimetallic RuPt nanoparticles that in base-free conditions exhibits complete HMF conversion and selective FDCA formation due to an unconventional mechanism of molecular oxygen activation. This unique reactivity is enhanced by both photothermal heating and hot electrons, whose contribution is confirmed by kinetic isotopic effect experiments. Density functional theory calculations support a scenario in which the activated nanoparticle–oxygen complex facilitates the rate-determining step and enables an improved FDCA selectivity. Our results demonstrate the potential of plasmonic photocatalysts in the catalytic transformation of biomass. Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O2 and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.
{"title":"Near-infrared plasmonic activation of molecular oxygen for selective oxidation of biomass derivatives","authors":"Manpreet Kaur, Sourav Rej, Jan Navrátil, Eva Yazmin Santiago, Michal Otyepka, Stefano Livraghi, Lorenzo Mino, Štěpán Kment, Zhikang Xu, Haibo Zhu, Paolo Fornasiero, Alexander O. Govorov, Piotr Błoński, Alberto Naldoni","doi":"10.1038/s41929-025-01454-y","DOIUrl":"10.1038/s41929-025-01454-y","url":null,"abstract":"Upgrading biomass feedstock into higher-value chemicals is central to improve the sustainability of the chemical industry and to reduce its dependence on fossil raw materials. Heterogeneous photocatalysts are promising for the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a biomass-derived molecular platform for biopolymers, but their FDCA selectivity is negligible without the aid of a base. Here we present a plasmonic photocatalyst integrating TiN nanocubes and bimetallic RuPt nanoparticles that in base-free conditions exhibits complete HMF conversion and selective FDCA formation due to an unconventional mechanism of molecular oxygen activation. This unique reactivity is enhanced by both photothermal heating and hot electrons, whose contribution is confirmed by kinetic isotopic effect experiments. Density functional theory calculations support a scenario in which the activated nanoparticle–oxygen complex facilitates the rate-determining step and enables an improved FDCA selectivity. Our results demonstrate the potential of plasmonic photocatalysts in the catalytic transformation of biomass. Selective oxidation of biomass-derived precursors has been reported but requires elevated temperatures and pressures of O2 and strongly alkaline conditions. This study develops an antenna–reactor plasmonic photocatalyst (RuPt on TiN) for the selective conversion of HMF to FDCA using near-infrared irradiation in the absence of base.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1370-1381"},"PeriodicalIF":44.6,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01454-y.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145771399","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}
Pub Date : 2025-12-17DOI: 10.1038/s41929-025-01453-z
Martin Rihtaršič, Byeongseok Kweon, Piotr T. Błyszczyk, Alessandro Ruffoni, Enrique M. Arpa, Daniele Leonori
Energy transfer (EnT) catalysis enables the selective population of triplet excited states without previous singlet excitation, thus eliminating the need for high-energy irradiation. Traditionally, EnT catalysis has been approached by developing specific photosensitizers with triplet energies (ET) that match those of the targeted substrates. Here we introduce an alternative approach to EnT using widely available nitroarenes as photocatalysts. Our findings reveal that their catalytic efficiency is governed by the localization of their excited state rather than ET. Specifically, 3π,π* nitroarenes, where the excitation is centred on the aromatic core rather than the nitro group, exhibit superior catalytic performance compared with their 3n,π* counterparts. We have demonstrated the utility of this concept for nitroarene photocatalysis in contra-thermodynamic E-to-Z alkene isomerization and [2 + 2] cycloadditions. Additionally, we use the energetic descriptor ΔETT as easy tool to distinguish the preferential population of 3n,π* versus 3π,π* triplet states and therefore accelerate the identification of novel photosensitizers. Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.
{"title":"Excited-state configuration controls the ability of nitroarenes to act as energy transfer catalysts","authors":"Martin Rihtaršič, Byeongseok Kweon, Piotr T. Błyszczyk, Alessandro Ruffoni, Enrique M. Arpa, Daniele Leonori","doi":"10.1038/s41929-025-01453-z","DOIUrl":"10.1038/s41929-025-01453-z","url":null,"abstract":"Energy transfer (EnT) catalysis enables the selective population of triplet excited states without previous singlet excitation, thus eliminating the need for high-energy irradiation. Traditionally, EnT catalysis has been approached by developing specific photosensitizers with triplet energies (ET) that match those of the targeted substrates. Here we introduce an alternative approach to EnT using widely available nitroarenes as photocatalysts. Our findings reveal that their catalytic efficiency is governed by the localization of their excited state rather than ET. Specifically, 3π,π* nitroarenes, where the excitation is centred on the aromatic core rather than the nitro group, exhibit superior catalytic performance compared with their 3n,π* counterparts. We have demonstrated the utility of this concept for nitroarene photocatalysis in contra-thermodynamic E-to-Z alkene isomerization and [2 + 2] cycloadditions. Additionally, we use the energetic descriptor ΔETT as easy tool to distinguish the preferential population of 3n,π* versus 3π,π* triplet states and therefore accelerate the identification of novel photosensitizers. Photoexcited nitroarenes are traditionally consumed as reactive intermediates in transformations. Now, it is shown that simple and cheap nitroarenes can be used as energy transfer photocatalysts in reactions such as E-to-Z alkene isomerization and [2 + 2] intramolecular cycloadditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 12","pages":"1361-1369"},"PeriodicalIF":44.6,"publicationDate":"2025-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01453-z.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145765589","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}