摘要
The oxygen atom coordination inducing the structure reconstruction of the catalytic site is identified and recognized ambiguously,which is related to accurately declare the mechanism in a dynamic catalytic process.Herein,we demonstrated that the reconstructed catalytic sites would lead to a remarkable performance for photocatalytic CO_(2)reduction.At the initial 4-cycles testing,the in-situ formation of CoOx active sites on the Co(CoP)surface performed an increasing transient activity and selectivity toward CO evolution.The formation of reconstructive Co-O bond and the appearance of intermediate specie CO were simultaneously observed by the pre-operando Raman,revealing the dynamic relationship between catalytic site structure and the photocatalytic properties.Moreover,density functional theory calculations showed that the electronic structure of the reconstructive surface sites could modulate the ability of CO_(2)adsorption and CO desorption.The reduced barrier energy for the rate-determining step finally improved the activity and selectivity of CO_(2)reduction.
基金
the financial support from the National Natural Science Foundation of China(Nos.51776072,42007327,and 41731279)
the Fundamental Research Funds for the Central Universities(No.2021MS098)
the Natural Science Foundation of Hebei Province(No.B2022502005),and the Natural Science Foundation of Jiangsu Province(No.BK20220930)
The authors acknowledge that the XAS measurements were performed using[AS183/XAS/14123]beamline of Australian Synchrotron facility.