Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Here...Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Herein,the key roles of Nafion for CO_(2)RR were systematically studied on Cu nanoparticles(NPs)electrocatalyst.We found that Nafion modifier not only inhibit hydrogen evolution reaction(HER)by decreasing the accessibility of H_(2)O from electrolyte to Cu NPs,and increase the CO_(2)concentration at electrocatalyst interface for enhancing the CO_(2)mass transfer process,but also activate CO_(2)molecule by Lewis acid-base interaction between Nafion and CO_(2)to accelerate the formation of^(*)CO,which favor of C–C coupling for boosting C_(2)product generation.Owing to these features,the HER selectivity was suppressed from 40.6%to 16.8%on optimal Cu@Nafion electrode at-1.2 V versus reversible hydrogen electrode(RHE),and as high as 73.5%faradaic efficiencies(FEs)of C_(2)products were achieved at the same applied potential,which was 2.6 times higher than that on bare Cu electrode(~28.3%).In addition,Nafion also contributed to the long-term stability by hinder Cu NPs morphology reconstruction.Thus,this work provides insights into the impact of Nafion on electrocatalytic CO_(2)RR performance.展开更多
The electrochemical reduction of CO_(2)to multi-carbon(C_(2+))products is a promising strategy for sustainable fuel and chemical production and CO_(2)emission mitigation.However,optimizing^(*)CO intermediate generatio...The electrochemical reduction of CO_(2)to multi-carbon(C_(2+))products is a promising strategy for sustainable fuel and chemical production and CO_(2)emission mitigation.However,optimizing^(*)CO intermediate generation and utilization in complex multi-electron systems is crucial for the C_(2)products,but it remains challenging.Herein,we synthesize a yolk-shell structured Cu@HCS catalyst via hydrothermal synthesis coupled with high-temperature calcination,featuring a unique copper core and hollow carbon shell nanostructure.This architecture significantly enhances the selectivity toward C_(2)products during electrocatalytic CO_(2)reduction.The optimized Cu@HCS-2-800 catalyst achieves a Faradaic efficiency(FE)of 69.7%for C_(2)products at-1.4 V vs.reversible hydrogen electrode(RHE),markedly surpassing the 30.1%FE of conventional Cu/xc-72 catalyst.Furthermore,the yolk-shell configuration suppresses hydrogen evolution,ensuring superior stability during prolonged operation.In situ attenuated total reflectance-surface enhanced infrared absorption spectroscopy(ATR-SEIRAS)and density functional theory(DFT)analysis reveal that the Cu@HCS-2-800 catalyst leverages spatial confinement effects to retard CO diffusion and promote CO re-adsorption,thereby elevating^(*)CO intermediate coverage to enhance C-C coupling.This work underscores the pivotal role of nanoscale spatial confinement in advancing CO_(2)electroreduction performance and provides a guidance for designing advanced catalysts with tailored microenvironment.展开更多
基金financially supported by the Natural Science Foundation of Guangdong Province (2022A1515012359)the National Natural Science Foundation of China (21902121)+1 种基金the STU Scientific Research Foundation for Talents (NTF21020)the 2020 Li Ka Shing Foundation Cross-Disciplinary Research Grant (2020LKSFG09A)。
文摘Nafion as a universal polymer ionomer was widely applied for nanocatalysts electrode preparation.However,the effect of Nafion on electrocatalytic performance was often overlooked,especially for CO_(2)electrolysis.Herein,the key roles of Nafion for CO_(2)RR were systematically studied on Cu nanoparticles(NPs)electrocatalyst.We found that Nafion modifier not only inhibit hydrogen evolution reaction(HER)by decreasing the accessibility of H_(2)O from electrolyte to Cu NPs,and increase the CO_(2)concentration at electrocatalyst interface for enhancing the CO_(2)mass transfer process,but also activate CO_(2)molecule by Lewis acid-base interaction between Nafion and CO_(2)to accelerate the formation of^(*)CO,which favor of C–C coupling for boosting C_(2)product generation.Owing to these features,the HER selectivity was suppressed from 40.6%to 16.8%on optimal Cu@Nafion electrode at-1.2 V versus reversible hydrogen electrode(RHE),and as high as 73.5%faradaic efficiencies(FEs)of C_(2)products were achieved at the same applied potential,which was 2.6 times higher than that on bare Cu electrode(~28.3%).In addition,Nafion also contributed to the long-term stability by hinder Cu NPs morphology reconstruction.Thus,this work provides insights into the impact of Nafion on electrocatalytic CO_(2)RR performance.
基金supported by the National Natural Science Foundation of China(No.21902121)Natural Science Foundation of Guangdong Province(Nos.2022A1515012359 and 2025A1515011015)+1 种基金STU Scientific Research Foundation for Talents(NO.NTF21020)the 2020 Li Ka Shing Foundation Cross-Disciplinary Research Grant(No.2020LKSFG09A).
文摘The electrochemical reduction of CO_(2)to multi-carbon(C_(2+))products is a promising strategy for sustainable fuel and chemical production and CO_(2)emission mitigation.However,optimizing^(*)CO intermediate generation and utilization in complex multi-electron systems is crucial for the C_(2)products,but it remains challenging.Herein,we synthesize a yolk-shell structured Cu@HCS catalyst via hydrothermal synthesis coupled with high-temperature calcination,featuring a unique copper core and hollow carbon shell nanostructure.This architecture significantly enhances the selectivity toward C_(2)products during electrocatalytic CO_(2)reduction.The optimized Cu@HCS-2-800 catalyst achieves a Faradaic efficiency(FE)of 69.7%for C_(2)products at-1.4 V vs.reversible hydrogen electrode(RHE),markedly surpassing the 30.1%FE of conventional Cu/xc-72 catalyst.Furthermore,the yolk-shell configuration suppresses hydrogen evolution,ensuring superior stability during prolonged operation.In situ attenuated total reflectance-surface enhanced infrared absorption spectroscopy(ATR-SEIRAS)and density functional theory(DFT)analysis reveal that the Cu@HCS-2-800 catalyst leverages spatial confinement effects to retard CO diffusion and promote CO re-adsorption,thereby elevating^(*)CO intermediate coverage to enhance C-C coupling.This work underscores the pivotal role of nanoscale spatial confinement in advancing CO_(2)electroreduction performance and provides a guidance for designing advanced catalysts with tailored microenvironment.
