Insight into the mechanisms of CO2 reduction to CHO over Zr-doped Cu nanoparticle

Abstract Zr-doped icosahedral Cu nanoparticle (NP) with 54 Cu atoms and one Zr atom is studied in this work, where the Cu atom respectively being at the surface vertex (′v′) and edge (′e′) site, subsurface (′s′) and core (′c′) site of Cu NP is substituted by Zr atom. By using density functional theory (DFT), the adsorption energies of the reactants and intermediates and the energy barriers concerned are calculated. All the obtained results demonstrate that Zr doping on the surface of Cu NPs make them possess superior catalytic ability for CO2 reduction to methanol, even when Zr doping in bulk Cu surface. Moreover, if comparing Cu NPs with Zr respectively doping at ′v′ and ′e′ site, the latter shows it’s higher activity in the conversion from CO2 to CHO. In a word, Zr doping is a valid method to effectively enhance the activity of Cu-based catalysts for CO2 reduction.