Theoretical insights into CO2 reduction reaction on a CuPc/graphene single-atomic catalyst

Excessive CO2 emission has caused severe greenhouse problems. CO2 reduction reaction (CO2RR) is considered to be a promising strategy to effectively reduce CO2 emission, which not only captures CO2 in large quantity, but also produces high value-added chemicals. Herein, CO2RR on the CuPc/graphene single-atomic catalyst has been studied via density functional theory (DFT) calculations. It shows that CO2 is inclined to convert to CH3OH, followed by HCOOH and CH4. The most favored pathway to produce CH3OH is *CO2 -> *COOH -> *CO -> *CHO -> *OCH2 -> *OCH3 -> *OHCH3, for which the potential-limiting step is *CO2 -> *COOH (endothermic by 1.41 eV). Both density of states and differential charge further indicate the high reactivity of single atomic Cu, and uncover the effect of electrostatic interaction on the hydrogenation pathway. This study can provide an insight into the structure-reaction relationship for CO2RR on CuPc/graphene, and help guide the design of highly effective catalysts.