Operando reconstruction-induced CO2 reduction activity and selectivity for cobalt-based photocatalysis

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 CO2 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 CO2 adsorption and CO desorption. The reduced barrier energy for the rate-determining step finally improved the activity and selectivity of CO2 reduction.

Automated summary

The coordination of oxygen atoms induces the reconstruction of catalytic sites, which is crucial for understanding the mechanism in dynamic catalytic processes. We demonstrated that the reconstructed catalytic sites on Co (CoP) surface showed improved activity and selectivity for photocatalytic CO2 reduction. In-situ Raman spectroscopy revealed the formation of reconstructive Co-O bond and the appearance of intermediate CO, providing insights into the relationship between catalytic site structure and photocatalytic properties. Density functional theory calculations further showed that the electronic structure of reconstructive surface sites enhanced the ability of CO2 adsorption and CO desorption, leading to reduced barrier energy for the rate-determining step and improved CO2 reduction performance.