Pub Date : 2025-08-28DOI: 10.1038/s41929-025-01404-8
Congjun Yu, Linda Yiu, Zining Zhang, Guangbin Dong
Directing group-based strategies have proven highly effective for site-selective functionalization of π bonds in alkenes and carbonyls, as well as C–H and C–C bonds, but have yet to be demonstrated for unactivated aromatic π-systems. Meanwhile, catalytic hydrogenation of arenes to their corresponding saturated carbo- or heterocycles offers a straightforward approach to increase molecular three-dimensionality and sp3 carbon content in pharmaceutical compounds; however, it remains challenging to achieve site-selective dearomatization among electronically and sterically unbiased arenes. Here we report a Ru-catalysed directed arene saturation, which selectively reduces the aryl group adjacent to the directing moiety. Remarkably, a number of easily reducible functional groups are compatible with the mild reaction conditions. The preliminary mechanistic study reveals a homogeneous catalysis process and the potential involvement of an η6-arene-ruthenium intermediate. The synthetic utility of this method is demonstrated in the streamlined synthesis of cis-atovaquone, gram-scale reactions and late-stage saturation of complex bioactive compounds. Directing group strategies for selective dearomatization of unactivated aromatic π-systems have remained elusive. Now a homogeneous ruthenium catalyst, aided by a removable directing group, enables the site-selective hydrogenation of less reactive arene moieties in polyaryl compounds.
{"title":"Site-selective Ru-catalysed saturation of unactivated arenes via directed 6π activation","authors":"Congjun Yu, Linda Yiu, Zining Zhang, Guangbin Dong","doi":"10.1038/s41929-025-01404-8","DOIUrl":"10.1038/s41929-025-01404-8","url":null,"abstract":"Directing group-based strategies have proven highly effective for site-selective functionalization of π bonds in alkenes and carbonyls, as well as C–H and C–C bonds, but have yet to be demonstrated for unactivated aromatic π-systems. Meanwhile, catalytic hydrogenation of arenes to their corresponding saturated carbo- or heterocycles offers a straightforward approach to increase molecular three-dimensionality and sp3 carbon content in pharmaceutical compounds; however, it remains challenging to achieve site-selective dearomatization among electronically and sterically unbiased arenes. Here we report a Ru-catalysed directed arene saturation, which selectively reduces the aryl group adjacent to the directing moiety. Remarkably, a number of easily reducible functional groups are compatible with the mild reaction conditions. The preliminary mechanistic study reveals a homogeneous catalysis process and the potential involvement of an η6-arene-ruthenium intermediate. The synthetic utility of this method is demonstrated in the streamlined synthesis of cis-atovaquone, gram-scale reactions and late-stage saturation of complex bioactive compounds. Directing group strategies for selective dearomatization of unactivated aromatic π-systems have remained elusive. Now a homogeneous ruthenium catalyst, aided by a removable directing group, enables the site-selective hydrogenation of less reactive arene moieties in polyaryl compounds.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"931-938"},"PeriodicalIF":44.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910713","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 : 2025-08-28DOI: 10.1038/s41929-025-01402-w
Jia-Yong Zhang, Ji-Jun Chen, Boming Shen, Jia-Heng Fang, Xuan-Yi Du, Ning-Yuan Yang, Chang-Jiang Yang, Wei-Long Liu, Fu Liu, Zhong-Liang Li, Qiang-Shuai Gu, Zhe Dong, Peiyuan Yu, Xin-Yuan Liu
The cross-coupling of bulky electrophiles and nucleophiles to form sterically congested molecules is a challenging issue in modern synthetic chemistry. Among them, chiral hindered dialkyl ethers are one class of valuable motifs, but the catalytic asymmetric synthesis of such motifs from readily available tertiary alcohols and racemic electrophiles remains underexplored. Challenges arise from the steric hindrance of both reactants, the difficulty in enantiodiscriminating the three substituents of tertiary electrophiles and the low nucleophilicity of bulky alcohols. Here we show the copper-catalysed enantioconvergent radical O-alkylation of diverse alcohols with racemic α-tertiary haloamides to access enantioenriched hindered dialkyl ethers. Successful realization of this strategy relies on the development of anionic N,N,N-ligands with a side arm to form coordinatively saturated key Cu(iii) intermediates, therefore exerting remarkable chemo- and enantioselectivity. The synthetic potential is showcased by the late-stage functionalization and stereodivergent synthesis of four stereoisomers of a product with two stereocentres. The O-alkylation of tertiary alcohols with racemic tertiary electrophiles to access chiral hindered dialkyl ethers has remained elusive. Now this synthetic challenge has been accomplished by copper-catalysed C–O cross-coupling between tertiary haloamides and alcohols using designed ligands.
{"title":"Copper-catalysed enantioconvergent O-alkylation of alcohols with racemic α-tertiary haloamides to access enantioenriched hindered dialkyl ethers","authors":"Jia-Yong Zhang, Ji-Jun Chen, Boming Shen, Jia-Heng Fang, Xuan-Yi Du, Ning-Yuan Yang, Chang-Jiang Yang, Wei-Long Liu, Fu Liu, Zhong-Liang Li, Qiang-Shuai Gu, Zhe Dong, Peiyuan Yu, Xin-Yuan Liu","doi":"10.1038/s41929-025-01402-w","DOIUrl":"10.1038/s41929-025-01402-w","url":null,"abstract":"The cross-coupling of bulky electrophiles and nucleophiles to form sterically congested molecules is a challenging issue in modern synthetic chemistry. Among them, chiral hindered dialkyl ethers are one class of valuable motifs, but the catalytic asymmetric synthesis of such motifs from readily available tertiary alcohols and racemic electrophiles remains underexplored. Challenges arise from the steric hindrance of both reactants, the difficulty in enantiodiscriminating the three substituents of tertiary electrophiles and the low nucleophilicity of bulky alcohols. Here we show the copper-catalysed enantioconvergent radical O-alkylation of diverse alcohols with racemic α-tertiary haloamides to access enantioenriched hindered dialkyl ethers. Successful realization of this strategy relies on the development of anionic N,N,N-ligands with a side arm to form coordinatively saturated key Cu(iii) intermediates, therefore exerting remarkable chemo- and enantioselectivity. The synthetic potential is showcased by the late-stage functionalization and stereodivergent synthesis of four stereoisomers of a product with two stereocentres. The O-alkylation of tertiary alcohols with racemic tertiary electrophiles to access chiral hindered dialkyl ethers has remained elusive. Now this synthetic challenge has been accomplished by copper-catalysed C–O cross-coupling between tertiary haloamides and alcohols using designed ligands.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"919-930"},"PeriodicalIF":44.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910716","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 : 2025-08-28DOI: 10.1038/s41929-025-01411-9
Liang Huang, Ge Gao, Jiwu Zhao, William L. Roberts, Xu Lu
Electrochemical upcycling of captured CO2 under high pressure holds significant potential to bridge between CO2 emissions and hydrocarbon commodities, yet it remains underexplored. Here we convert gas-phase high-pressure captured CO2 into ethylene (C2H4) using a high-pressure membrane electrode assembly equipped with In/Cu catalysts, affording up to 85% Faradaic efficiency and 750 mA cm−2 partial current density under 20 bar. Theoretical calculations and operando studies link enhanced C–C coupling to the pressure-modulated *CO adsorption configuration and elevated CO2 coverage. High pressure also mitigates salt precipitation by relocating bicarbonate formation to the catalyst–membrane interface, enabling stable electrolysis for over 1,500 h at 600 mA cm−2. As a proof of concept, by recapturing residual CO2, the system delivers industrial-grade 99.9% purity C2H4, creating an opportunity to turn the otherwise costly CO2 capture into a profit. Energy analysis suggests that directly valorizing high-pressure captured CO2, instead of depressurizing and repressurizing, is essential to minimize energy consumption. Electrocatalytic CO2 conversion offers opportunities for producing sustainable fuels and chemicals, but achieving strong performance with realistic CO2 sources remains a challenge. Here a system is designed to use high-pressure captured CO2, and achieves 85% Faradaic efficiency and high-purity C2H4 for over 1,500 h.
在高压下对捕获的二氧化碳进行电化学升级回收，在二氧化碳排放和碳氢化合物产品之间具有巨大的桥梁潜力，但仍未得到充分开发。在这里，我们使用配备In/Cu催化剂的高压膜电极组件将气相高压捕获的CO2转化为乙烯（C2H4），在20 bar下提供高达85%的法拉第效率和750 mA cm - 2的分电流密度。理论计算和operando研究将增强的C-C耦合与压力调制的*CO吸附配置和提高的CO2覆盖率联系起来。高压还通过将碳酸氢盐重新定位到催化剂-膜界面来减轻盐的沉淀，从而在600毫安厘米−2下稳定电解超过1500小时。作为概念验证，通过重新捕获残留的二氧化碳，该系统提供了纯度为99.9%的工业级C2H4，从而创造了将原本昂贵的二氧化碳捕获转化为利润的机会。能源分析表明，直接对高压捕获的二氧化碳进行增压，而不是减压和再增压，对于最大限度地减少能源消耗至关重要。
{"title":"Electrocatalytic upcycling of high-pressure captured CO2 to ethylene","authors":"Liang Huang, Ge Gao, Jiwu Zhao, William L. Roberts, Xu Lu","doi":"10.1038/s41929-025-01411-9","DOIUrl":"10.1038/s41929-025-01411-9","url":null,"abstract":"Electrochemical upcycling of captured CO2 under high pressure holds significant potential to bridge between CO2 emissions and hydrocarbon commodities, yet it remains underexplored. Here we convert gas-phase high-pressure captured CO2 into ethylene (C2H4) using a high-pressure membrane electrode assembly equipped with In/Cu catalysts, affording up to 85% Faradaic efficiency and 750 mA cm−2 partial current density under 20 bar. Theoretical calculations and operando studies link enhanced C–C coupling to the pressure-modulated *CO adsorption configuration and elevated CO2 coverage. High pressure also mitigates salt precipitation by relocating bicarbonate formation to the catalyst–membrane interface, enabling stable electrolysis for over 1,500 h at 600 mA cm−2. As a proof of concept, by recapturing residual CO2, the system delivers industrial-grade 99.9% purity C2H4, creating an opportunity to turn the otherwise costly CO2 capture into a profit. Energy analysis suggests that directly valorizing high-pressure captured CO2, instead of depressurizing and repressurizing, is essential to minimize energy consumption. Electrocatalytic CO2 conversion offers opportunities for producing sustainable fuels and chemicals, but achieving strong performance with realistic CO2 sources remains a challenge. Here a system is designed to use high-pressure captured CO2, and achieves 85% Faradaic efficiency and high-purity C2H4 for over 1,500 h.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"968-976"},"PeriodicalIF":44.6,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910714","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 : 2025-08-25DOI: 10.1038/s41929-025-01403-9
The response of a well-defined Cu pre-catalyst surface to dynamic pulsed electrocatalytic CO2 reduction conditions is unveiled using a correlated spatially resolved spectro-microscopy approach. The observed structural changes are key to understanding the increased selectivity towards ethanol and ethylene under these conditions.
{"title":"Linking surface modifications of Cu(100) to selectivity during dynamic CO2 electroreduction","authors":"","doi":"10.1038/s41929-025-01403-9","DOIUrl":"10.1038/s41929-025-01403-9","url":null,"abstract":"The response of a well-defined Cu pre-catalyst surface to dynamic pulsed electrocatalytic CO2 reduction conditions is unveiled using a correlated spatially resolved spectro-microscopy approach. The observed structural changes are key to understanding the increased selectivity towards ethanol and ethylene under these conditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"870-871"},"PeriodicalIF":44.6,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901485","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 : 2025-08-22DOI: 10.1038/s41929-025-01384-9
Junting Dong, Chang Yu, Jieshan Qiu
Coupled electrocatalytic reactions are of great potential for cost-effective co-production of hydrogen and fine chemicals, yet engineering of catalysts, conditions and cell architectures are still key to delivering this technology at scale. Now, a case study shows the efficient production of 2,5-furandicarboxylic acid enabled by a liquid-cooled kilowatt-scale electrolyser.
{"title":"Redesigning electrolysers in coupled electrolysis","authors":"Junting Dong, Chang Yu, Jieshan Qiu","doi":"10.1038/s41929-025-01384-9","DOIUrl":"10.1038/s41929-025-01384-9","url":null,"abstract":"Coupled electrocatalytic reactions are of great potential for cost-effective co-production of hydrogen and fine chemicals, yet engineering of catalysts, conditions and cell architectures are still key to delivering this technology at scale. Now, a case study shows the efficient production of 2,5-furandicarboxylic acid enabled by a liquid-cooled kilowatt-scale electrolyser.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 8","pages":"755-757"},"PeriodicalIF":44.6,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901543","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 : 2025-08-22DOI: 10.1038/s41929-025-01386-7
Olga A. Esakova, Squire J. Booker
The radical S-adenosylmethionine (SAM) enzyme, AbmM, catalyses a replacement of the ring oxygen of a sugar with sulfur. However, how this reaction takes place is unknown. Now, an [Fe4S4] cluster is shown to have a dual role in catalysis. It functions in the reductive cleavage of SAM and is the donor of the appended sulfur atom.
{"title":"Iron–sulfur cluster with double duty","authors":"Olga A. Esakova, Squire J. Booker","doi":"10.1038/s41929-025-01386-7","DOIUrl":"10.1038/s41929-025-01386-7","url":null,"abstract":"The radical S-adenosylmethionine (SAM) enzyme, AbmM, catalyses a replacement of the ring oxygen of a sugar with sulfur. However, how this reaction takes place is unknown. Now, an [Fe4S4] cluster is shown to have a dual role in catalysis. It functions in the reductive cleavage of SAM and is the donor of the appended sulfur atom.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 8","pages":"758-759"},"PeriodicalIF":44.6,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901681","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 : 2025-08-22DOI: 10.1038/s41929-025-01395-6
Hao-Fei Geng, Yi-Fan Bao, Xiang Wang, Bin Ren
The evolution of local microenvironments at copper electrodes during the electrochemical CO reduction reaction has long been overlooked. In situ electrochemical surface-enhanced Raman spectroscopy now reveals that the dynamic restructuring of interfacial water resulting from increased local alkalinity enhances the acetate selectivity of this reaction.
{"title":"The critical role of local microenvironments","authors":"Hao-Fei Geng, Yi-Fan Bao, Xiang Wang, Bin Ren","doi":"10.1038/s41929-025-01395-6","DOIUrl":"10.1038/s41929-025-01395-6","url":null,"abstract":"The evolution of local microenvironments at copper electrodes during the electrochemical CO reduction reaction has long been overlooked. In situ electrochemical surface-enhanced Raman spectroscopy now reveals that the dynamic restructuring of interfacial water resulting from increased local alkalinity enhances the acetate selectivity of this reaction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 8","pages":"753-754"},"PeriodicalIF":44.6,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901680","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 : 2025-08-20DOI: 10.1038/s41929-025-01387-6
Liviu C. Tănase, Mauricio J. Prieto, Lucas de Souza Caldas, Aarti Tiwari, Fabian Scholten, Philipp Grosse, Andrea Martini, Janis Timoshenko, Thomas Schmidt, Beatriz Roldan Cuenya
Subjecting copper to short anodic pulses during the electrocatalytic reduction of carbon dioxide (CO2RR) has been shown to improve the activity and selectivity towards hydrocarbons and alcohols. Nonetheless, the nature of the active sites is still unclear. Here the evolution of the morphology, chemical state and crystal structure of Cu(100) exposed to potential pulses during the CO2RR was resolved by a combination of spectroscopy, microscopy and diffraction methods applied concurrently. Under anodic potential pulses, (n10) facets were formed. Moreover, alternating anodic to cathodic potential pulses during the CO2RR also lead to the stabilization of copper oxide species located either at the surface or directly underneath ultrathin metallic copper layers, depending on the specific pulse potential treatment applied. Both findings are key for the enhanced ethylene and ethanol production reported during pulsed CO2RR. Anodic pulsing during electrocatalytic CO2 reduction has been shown to enhance activity and selectivity towards hydrocarbons and alcohols on copper yet the nature of the active sites remains unclear. Here, correlated spectro-microscopy in a quasi in situ experimental set-up provides information on the formation of specific facets and oxidation states under reactive conditions.
{"title":"Morphological and chemical state effects in pulsed CO2 electroreduction on Cu(100) unveiled by correlated spectro-microscopy","authors":"Liviu C. Tănase, Mauricio J. Prieto, Lucas de Souza Caldas, Aarti Tiwari, Fabian Scholten, Philipp Grosse, Andrea Martini, Janis Timoshenko, Thomas Schmidt, Beatriz Roldan Cuenya","doi":"10.1038/s41929-025-01387-6","DOIUrl":"10.1038/s41929-025-01387-6","url":null,"abstract":"Subjecting copper to short anodic pulses during the electrocatalytic reduction of carbon dioxide (CO2RR) has been shown to improve the activity and selectivity towards hydrocarbons and alcohols. Nonetheless, the nature of the active sites is still unclear. Here the evolution of the morphology, chemical state and crystal structure of Cu(100) exposed to potential pulses during the CO2RR was resolved by a combination of spectroscopy, microscopy and diffraction methods applied concurrently. Under anodic potential pulses, (n10) facets were formed. Moreover, alternating anodic to cathodic potential pulses during the CO2RR also lead to the stabilization of copper oxide species located either at the surface or directly underneath ultrathin metallic copper layers, depending on the specific pulse potential treatment applied. Both findings are key for the enhanced ethylene and ethanol production reported during pulsed CO2RR. Anodic pulsing during electrocatalytic CO2 reduction has been shown to enhance activity and selectivity towards hydrocarbons and alcohols on copper yet the nature of the active sites remains unclear. Here, correlated spectro-microscopy in a quasi in situ experimental set-up provides information on the formation of specific facets and oxidation states under reactive conditions.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 9","pages":"881-890"},"PeriodicalIF":44.6,"publicationDate":"2025-08-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.nature.comhttps://www.nature.com/articles/s41929-025-01387-6.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901711","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 : 2025-08-19DOI: 10.1038/s41929-025-01396-5
Qiliang Liu, Wenxing Yang
Non-covalent interactions between the electrocatalyst surface and its electrolyte play a vital role in shaping the microenvironments of electrochemical interfaces. Yet, direct spectroscopic investigation of these interactions and their catalytic effects has remained elusive in electrocatalysis research. Here, using in situ Raman spectroscopy, we resolve a universal change of interfacial water structure at electrified Cu surfaces during alkaline CO reduction reaction. An intricate non-covalent interaction between interfacial water and surface hydroxyl (OHad) was recognized through a proposed OHad···M+(H2O)n complex, with M+ representing electrolyte cations. On exposure to catalytic potentials, these non-covalent complexes evolve into local OH−···M+(H2O)n species residing within the electrical double layer and favour CO reduction reaction into acetate over other C2 products. These results demonstrate the crucial roles of non-covalent interactions in determining the activity of surface reactions, whose existence and rational design may offer opportunities for future fine control of electrocatalysis processes. Understanding the interplay between the catalyst surface and its microenvironment is important for the development of electrocatalysis. Here, in situ Raman spectroscopy is used to resolve the interactions between copper, surface-adsorbed hydroxyl, electrolyte cations and interfacial water during electrocatalytic CO reduction.
{"title":"Resolving non-covalent interactions between surface hydroxyl on Cu and interfacial water in alkaline CO electroreduction","authors":"Qiliang Liu, Wenxing Yang","doi":"10.1038/s41929-025-01396-5","DOIUrl":"10.1038/s41929-025-01396-5","url":null,"abstract":"Non-covalent interactions between the electrocatalyst surface and its electrolyte play a vital role in shaping the microenvironments of electrochemical interfaces. Yet, direct spectroscopic investigation of these interactions and their catalytic effects has remained elusive in electrocatalysis research. Here, using in situ Raman spectroscopy, we resolve a universal change of interfacial water structure at electrified Cu surfaces during alkaline CO reduction reaction. An intricate non-covalent interaction between interfacial water and surface hydroxyl (OHad) was recognized through a proposed OHad···M+(H2O)n complex, with M+ representing electrolyte cations. On exposure to catalytic potentials, these non-covalent complexes evolve into local OH−···M+(H2O)n species residing within the electrical double layer and favour CO reduction reaction into acetate over other C2 products. These results demonstrate the crucial roles of non-covalent interactions in determining the activity of surface reactions, whose existence and rational design may offer opportunities for future fine control of electrocatalysis processes. Understanding the interplay between the catalyst surface and its microenvironment is important for the development of electrocatalysis. Here, in situ Raman spectroscopy is used to resolve the interactions between copper, surface-adsorbed hydroxyl, electrolyte cations and interfacial water during electrocatalytic CO reduction.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 8","pages":"843-852"},"PeriodicalIF":44.6,"publicationDate":"2025-08-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123703","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 : 2025-08-18DOI: 10.1038/s41929-025-01392-9
Rong Xia, Yiqing Chen, Yuxin Chang, Heejong Shin, Huajie Ze, Hengzhou Liu, Pengfei Ou, Roham Dorakhan, Sungjin Park, Panos Papangelakis, Zunmin Guo, Eduardo G. Machado, Marcio V. Reboucas, Mohsen Nikkhoo, Ricardo G. A. Duarte, Daojin Zhou, Yuan Liu, Weiyan Ni, Cong Tian, Yuanjun Chen, Christine Yu, Omar K. Farha, Ke Xie, Edward H. Sargent
Current ethylene glycol (EG) production generates 46 million metric tons of CO2 equiv. emission annually. While electrified synthesis could decarbonize this process, existing ethylene oxidation systems suffer from high energy consumption resulting from excessive voltages. Here we identify, with the aid of in situ photoluminescence spectroscopy, an increased pH at the membrane–anode interface within a membrane–electrode assembly electrolyser and find that it arises due to hydroxide counter-migration across the membrane. To address this challenge, we integrate cathodic electrochemical carbon capture to reduce hydroxide flux and develop RuSnOx catalysts that favour *Cl over *OH adsorption, facilitating chloride-mediated ethylene oxidation. The system achieves 94% Faradaic efficiency for ethylene-to-EG conversion and 91% CO2 capture efficiency from a 10% CO2 stream, sequestering 0.60 tonnes CO2 per tonne of EG produced from ethylene. This approach results in an estimated carbon intensity of 0.133 tonnes CO2 equiv. per tonne EG, compared with the global average of 1.2 tonnes CO2 equiv. per tonne EG. Current industrial methods of ethylene glycol production generate substantial CO2 emissions. Here electrocatalytic ethylene-to-ethylene glycol conversion is coupled to electrochemical CO2 capture, decreasing carbon intensity by an order of magnitude.
{"title":"Electrosynthesis of ethylene glycol from ethylene coupled with CO2 capture","authors":"Rong Xia, Yiqing Chen, Yuxin Chang, Heejong Shin, Huajie Ze, Hengzhou Liu, Pengfei Ou, Roham Dorakhan, Sungjin Park, Panos Papangelakis, Zunmin Guo, Eduardo G. Machado, Marcio V. Reboucas, Mohsen Nikkhoo, Ricardo G. A. Duarte, Daojin Zhou, Yuan Liu, Weiyan Ni, Cong Tian, Yuanjun Chen, Christine Yu, Omar K. Farha, Ke Xie, Edward H. Sargent","doi":"10.1038/s41929-025-01392-9","DOIUrl":"10.1038/s41929-025-01392-9","url":null,"abstract":"Current ethylene glycol (EG) production generates 46 million metric tons of CO2 equiv. emission annually. While electrified synthesis could decarbonize this process, existing ethylene oxidation systems suffer from high energy consumption resulting from excessive voltages. Here we identify, with the aid of in situ photoluminescence spectroscopy, an increased pH at the membrane–anode interface within a membrane–electrode assembly electrolyser and find that it arises due to hydroxide counter-migration across the membrane. To address this challenge, we integrate cathodic electrochemical carbon capture to reduce hydroxide flux and develop RuSnOx catalysts that favour *Cl over *OH adsorption, facilitating chloride-mediated ethylene oxidation. The system achieves 94% Faradaic efficiency for ethylene-to-EG conversion and 91% CO2 capture efficiency from a 10% CO2 stream, sequestering 0.60 tonnes CO2 per tonne of EG produced from ethylene. This approach results in an estimated carbon intensity of 0.133 tonnes CO2 equiv. per tonne EG, compared with the global average of 1.2 tonnes CO2 equiv. per tonne EG. Current industrial methods of ethylene glycol production generate substantial CO2 emissions. Here electrocatalytic ethylene-to-ethylene glycol conversion is coupled to electrochemical CO2 capture, decreasing carbon intensity by an order of magnitude.","PeriodicalId":18845,"journal":{"name":"Nature Catalysis","volume":"8 8","pages":"833-842"},"PeriodicalIF":44.6,"publicationDate":"2025-08-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145123640","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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