Elastic strain in Cu catalysts enhances their selectivity for the electrochemical CO_(2)reduction reaction(eCO_(2)RR),particularly toward the formation of multicarbon(C_(2+))products.However,the reasons for this selec...Elastic strain in Cu catalysts enhances their selectivity for the electrochemical CO_(2)reduction reaction(eCO_(2)RR),particularly toward the formation of multicarbon(C_(2+))products.However,the reasons for this selectivity and the effect of catalyst precursors have not yet been clarified.Hence,we employed a redox strategy to induce strain on the surface of Cu nanocrystals.Oxidative transformation was employed to convert Cu nanocrystals to CuxO nanocrystals;these were subsequently electrochemically reduced to form Cu catalysts,while maintaining their compressive strain.Using a flow cell configuration,a current density of 1 A/cm^(2)and Faradaic efficiency exceeding 80%were realized for the C_(2+)products.The selectivity ratio of C_(2+)/C1 was also remarkable at 9.9,surpassing that observed for the Cu catalyst under tensile strain by approximately 7.6 times.In-situ Raman and infrared spectroscopy revealed a decrease in the coverage of K+ion-hydrated water(K·H_(2)O)on the compressively strained Cu catalysts,consistent with molecular dynamics simulations and density functional theory calculations.Finite element method simulations confirmed that reducing the coverage of coordinated K·H_(2)O water increased the probability of intermediate reactants interacting with the surface,thereby promoting efficient C–C coupling and enhancing the yield of C_(2+)products.These findings provide valuable insights into targeted design strategies for Cu catalysts used in the eCO_(2)RR.展开更多
基金supported by the National Natural Science Foundation of China(92266107 and 22101182)the Shccig-Qinling Program(2021JLM-27)+6 种基金the Shaanxi Fundamental Science Research Project in the fields of Mathematics and Physics(22JSQ008)the China Postdoctoral Science Foundation(2022M722506)the Fundamental Research Funds for the Central UniversitiesChina Manned Space Station ProgramShenzhen Science and TechnologyProgram(JCYJ20210324095202006)Shaanxi Province Natural Science Basic Research Program(2024JC-YBQN-0394)QinChuangYuan Scientist and Engineer Program(2022KXJ175HZ)。
文摘Elastic strain in Cu catalysts enhances their selectivity for the electrochemical CO_(2)reduction reaction(eCO_(2)RR),particularly toward the formation of multicarbon(C_(2+))products.However,the reasons for this selectivity and the effect of catalyst precursors have not yet been clarified.Hence,we employed a redox strategy to induce strain on the surface of Cu nanocrystals.Oxidative transformation was employed to convert Cu nanocrystals to CuxO nanocrystals;these were subsequently electrochemically reduced to form Cu catalysts,while maintaining their compressive strain.Using a flow cell configuration,a current density of 1 A/cm^(2)and Faradaic efficiency exceeding 80%were realized for the C_(2+)products.The selectivity ratio of C_(2+)/C1 was also remarkable at 9.9,surpassing that observed for the Cu catalyst under tensile strain by approximately 7.6 times.In-situ Raman and infrared spectroscopy revealed a decrease in the coverage of K+ion-hydrated water(K·H_(2)O)on the compressively strained Cu catalysts,consistent with molecular dynamics simulations and density functional theory calculations.Finite element method simulations confirmed that reducing the coverage of coordinated K·H_(2)O water increased the probability of intermediate reactants interacting with the surface,thereby promoting efficient C–C coupling and enhancing the yield of C_(2+)products.These findings provide valuable insights into targeted design strategies for Cu catalysts used in the eCO_(2)RR.
