Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenv...Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenvironments.Herein,we synthesize CeO_(2)with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag_(2)O nanoparticles(Ag_(2)O/Vo-CeO_(2)).Vo-CeO_(2)acts as a multifunctional modulator,regulating both the reaction microenvironment and the electronic structure of Ag sites,thereby boosting CO_(2)reduction(CO_(2)RR)efficiency.Its strong CO_(2)adsorption and H_(2)O dissociation capabilities facilitate the supply of CO_(2)and active^(*)H species to Ag sites.The electron-withdrawing effect of VoCeO_(2)induces polarization at interfacial Ag sites,generating Agd+species that enhance CO_(2)affinity and activation.Moreover,the electronic coupling between Vo-CeO_(2)and Ag upshifts the d-band center of Ag,optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step.Ag_(2)O/Vo-CeO_(2)delivers a consistently high Faraday efficiency(FE)of over 99% for CO production even at industrially current density(up to 365 mA cm^(-2)herein),and the operational potential window spans an astonishing 1700 m V(FE>95%).The unprecedented activity,which overcomes the trade-off between the selectivity and current density for CO_(2)RR,outperforms state-of-the-art Ag-based catalysts reported to date.These findings offer a promising pathway to develop robust CO_(2)RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation.展开更多
基金the support of this research by the Nat ional Natural Science Foundation of China(22179035)the Hei-longjiang Provincial Natural Science Foundation Joint Fund Cultivation Project(PL2024B012)the Fundamental Research Funds for the Universities of Heilongjiang Province(2023-KYYWF-1440)。
文摘Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenvironments.Herein,we synthesize CeO_(2)with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag_(2)O nanoparticles(Ag_(2)O/Vo-CeO_(2)).Vo-CeO_(2)acts as a multifunctional modulator,regulating both the reaction microenvironment and the electronic structure of Ag sites,thereby boosting CO_(2)reduction(CO_(2)RR)efficiency.Its strong CO_(2)adsorption and H_(2)O dissociation capabilities facilitate the supply of CO_(2)and active^(*)H species to Ag sites.The electron-withdrawing effect of VoCeO_(2)induces polarization at interfacial Ag sites,generating Agd+species that enhance CO_(2)affinity and activation.Moreover,the electronic coupling between Vo-CeO_(2)and Ag upshifts the d-band center of Ag,optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step.Ag_(2)O/Vo-CeO_(2)delivers a consistently high Faraday efficiency(FE)of over 99% for CO production even at industrially current density(up to 365 mA cm^(-2)herein),and the operational potential window spans an astonishing 1700 m V(FE>95%).The unprecedented activity,which overcomes the trade-off between the selectivity and current density for CO_(2)RR,outperforms state-of-the-art Ag-based catalysts reported to date.These findings offer a promising pathway to develop robust CO_(2)RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation.
