The electrochemical carbon dioxide reduction reaction(CO_(2)RR)to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming.However,the selective CO_(2)reduction to C_...The electrochemical carbon dioxide reduction reaction(CO_(2)RR)to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming.However,the selective CO_(2)reduction to C_(2)products remains challenge.Cu-based catalyst with the specific Cu^(0)and Cu^(+)sites is important to generate C_(2)products.This work used nitrogen(N)to tune amounts of Cu^(0)and Cu^(+)sites in Cu_(2)O catalysts and improve C_(2)-product conversion.The controllable Cu^(0)/Cu^(+)ratio of Cu_(2)O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment.The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu^(0)/Cu^(+)ratio.The optimal Cu^(0)/Cu^(+)ratio was determined as 0.43 for selective electroreduction CO_(2)to ethylene.X-ray spectroscopy and density functional theory(DFT)calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of N–Cu bond and stabilize Cu^(+),resulting in a 92.3%reduction in the potential energy change for^(∗)CO-^(∗)CO dimerization.This study is inspiring in designing high performance electrocatalysts for CO_(2)conversion.展开更多
基金supported by“Pioneer”and“Leading Goose”R&D Program of Zhejiang(Nos.2022C03146 and 2023C03017)the National Natural Science Foundation of China(Nos.U23A20677 and 22022610)+1 种基金Zhejiang Provincial Natural Science Foundation of China(No.LDT23E06015B06)the National Funded Postdoctoral Researcher Program of China(No.GZC20232363).
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR)to high value-added fuels or chemicals driven by the renewable energy is promising to alleviate global warming.However,the selective CO_(2)reduction to C_(2)products remains challenge.Cu-based catalyst with the specific Cu^(0)and Cu^(+)sites is important to generate C_(2)products.This work used nitrogen(N)to tune amounts of Cu^(0)and Cu^(+)sites in Cu_(2)O catalysts and improve C_(2)-product conversion.The controllable Cu^(0)/Cu^(+)ratio of Cu_(2)O catalyst from 0.16 to 15.19 was achieved by adjusting the N doping amount using NH3/Ar plasma treatment.The major theme of this work was clarifying a volcano curve of the ethylene Faraday efficiency as a function of the Cu^(0)/Cu^(+)ratio.The optimal Cu^(0)/Cu^(+)ratio was determined as 0.43 for selective electroreduction CO_(2)to ethylene.X-ray spectroscopy and density functional theory(DFT)calculations were employed to elucidate that the strong interaction between N and Cu increased the binding energy of N–Cu bond and stabilize Cu^(+),resulting in a 92.3%reduction in the potential energy change for^(∗)CO-^(∗)CO dimerization.This study is inspiring in designing high performance electrocatalysts for CO_(2)conversion.
