Designing catalysts with highly active,selectivity,and stability for electrocatalytic CO_(2)to formate is currently a severe challenge.Herein,we developed an electronic structure engineering on carbon nano frameworks ...Designing catalysts with highly active,selectivity,and stability for electrocatalytic CO_(2)to formate is currently a severe challenge.Herein,we developed an electronic structure engineering on carbon nano frameworks embedded with nitrogen and sulfur asymmetrically dual-coordinated indium active sites toward the efficient electrocatalytic CO_(2)reduction reaction.As expected,atomically dispersed In-based catalysts with In-S_(1)N_(3)atomic interface with asymmetrically coordinated exhibited high efficiency for CO_(2)reduction reaction(CO_(2)RR)to formate.It achieved a maximum Faradaic efficiency(FE)of 94.3%towards formate generation at−0.8 V vs.reversible hydrogen electrode(RHE),outperforming that of catalysts with In-S2N2 and In-N4 atomic interface.And at a potential of−1.10 V vs.RHE,In-S_(1)N_(3)achieves an impressive Faradaic efficiency of 93.7%in flow cell.The catalytic performance of In-S_(1)N_(3)sites was confirmed to be enhanced through in-situ X-ray absorption near-edge structure(XANES)measurements under electrochemical conditions.Our discovery provides the guidance for performance regulation of main group metal catalysts toward CO_(2)RR at atomic scale.展开更多
Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light abso...Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light absorption of photocatalysts,however,most of the developed photocatalysts still suffer from low photocatalytic performance due to the limited active site(s)and fast recombination of photogenerated charge carriers.In this work,atomically dispersed main group magnesium(Mg)is introduced onto CdS monodispersed nanospheres,which greatly enhances the photocatalytic hydrogen evolution reaction.The photocatalytic hydrogen evolution reaction rate reaches 30.6 mmol·gcatalyst^(-1)·h^(-1),which is about 11.8 and 2.5 times that of pure CdS and Pt(2 wt.%)-CdS.The atomically dispersed Mg on CdS acts as an electron sink to trap photogenerated electrons,and at the same time,greatly reduces the Gibbs free energy of hydrogen evolution reaction(HER)and accelerates HER.展开更多
基金the Anhui Provincial Department of Education(No.KJ2021A1125)the National Natural Science Foundation of China(No.12374390)+1 种基金Ningbo 3315 Innovative Teams Program(No.2019A-14-C)the member of Youth Innovation Promotion Association Foundation of CAS,China(No.2023310).
文摘Designing catalysts with highly active,selectivity,and stability for electrocatalytic CO_(2)to formate is currently a severe challenge.Herein,we developed an electronic structure engineering on carbon nano frameworks embedded with nitrogen and sulfur asymmetrically dual-coordinated indium active sites toward the efficient electrocatalytic CO_(2)reduction reaction.As expected,atomically dispersed In-based catalysts with In-S_(1)N_(3)atomic interface with asymmetrically coordinated exhibited high efficiency for CO_(2)reduction reaction(CO_(2)RR)to formate.It achieved a maximum Faradaic efficiency(FE)of 94.3%towards formate generation at−0.8 V vs.reversible hydrogen electrode(RHE),outperforming that of catalysts with In-S2N2 and In-N4 atomic interface.And at a potential of−1.10 V vs.RHE,In-S_(1)N_(3)achieves an impressive Faradaic efficiency of 93.7%in flow cell.The catalytic performance of In-S_(1)N_(3)sites was confirmed to be enhanced through in-situ X-ray absorption near-edge structure(XANES)measurements under electrochemical conditions.Our discovery provides the guidance for performance regulation of main group metal catalysts toward CO_(2)RR at atomic scale.
基金We are grateful for the financial support from the Natural Science Foundation of China(51979081)Fundamental Research Funds for the Central Universities(No.B200202103)+2 种基金Ministry of Education of Singapore(Tier 1:RG4/20 and Tier 2:MOET2EP10120-0002)Agency for Science,Technology and Research(AME IRG:A20E5c0080)PAPD。
文摘Photoabsorption charge separation/transfer and surface reaction are the three main factors influencing the efficiency of photocatalysis.Band structure engineering has been extensively applied to improve the light absorption of photocatalysts,however,most of the developed photocatalysts still suffer from low photocatalytic performance due to the limited active site(s)and fast recombination of photogenerated charge carriers.In this work,atomically dispersed main group magnesium(Mg)is introduced onto CdS monodispersed nanospheres,which greatly enhances the photocatalytic hydrogen evolution reaction.The photocatalytic hydrogen evolution reaction rate reaches 30.6 mmol·gcatalyst^(-1)·h^(-1),which is about 11.8 and 2.5 times that of pure CdS and Pt(2 wt.%)-CdS.The atomically dispersed Mg on CdS acts as an electron sink to trap photogenerated electrons,and at the same time,greatly reduces the Gibbs free energy of hydrogen evolution reaction(HER)and accelerates HER.
基金supported by the National Natural Science Foundation(51772283,22072140)the Fundamental Research Funds for the Central Universities(WK2060000032)the Hong Kong Scholars Program(XJ2019022)。
