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

Abstract

In this study, pristine Cu13 nanocluster and a series metal atom (Pt, Ni, Pd and Co) doped Cu12X were designed and placed on the top of the monolayer graphene to form novel catalysts for CO2 reduction. Based on the designed catalysts, we have studied the reaction mechanism 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, three different product rate-determining steps of CO2 reduction of CH4, CH3OH and HCOOH were obtained. The selectivity order of CO2 reduction products catalyzed by graphene-supported Cu13/G and doped Cu12X/G catalysts is CH4>CH3OH>HCOOH. The order of catalyst activity is Cu12Co/G>Cu12Ni/G>Cu12Pd/G>Cu12Pt/G>Cu13/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 experimental phenomena. Our study reveals a correlation between CO2 reduction catalytic activity of graphene-supported Cu13/Cu12X nanoclusters and their physical properties.

Keywords: Research mechanism, DFT, Cu nanoclusters, CO2 reduction catalysts