Catalytic reduction of CO2 in the interface formed by monolayer graphene and metal atom (Pt, Ni, Pd, Co) doped Cu-nanoclusters: A theoretical design and investigation

In this study, pristine Cu-13 nanocluster and a series of metal atoms (Pt, Ni, Pd and Co) doped Cu12X were designed and placed on the top of a monolayer graphene to form novel catalysts for CO2 reduction. Based on the designed catalysts, we studied the reaction mechanisms of five catalysts for CO2 reduction leading to three different products: CH4, CH3OH and HCOOH. By comparing the activation energies of different reaction channels of different catalysts, we obtained the three different product rate-determining steps of CO2 reduction of CH4, CH3OH and HCOOH. The selectivity order of CO2 reduction products catalyzed by graphene-supported Cu-13/G and doped Cu12X/G catalysts is CH4>CH3OH>HCOOH. The order of catalyst activity is Cu12Co/G>Cu12Ni/G>Cu12Pd/G>Cu12Pt/G>Cu-13/G. The doping of the four metals Pt, Ni, Pd and Co are all beneficial for improving the catalytic activity of CO2 reduction, and the catalytic activity of metal Co doping is the optimal. These results agree well with the observed phenomena. Our study reveals a correlation between the CO2 reduction catalytic activity of graphene-supported Cu-13/Cu12X nanoclusters and their physical properties.