2-Electron Reduction of CO2 by Graphene Supported Ru Complexes - on the Role of Electron Donation

This work presents the theoretical activity of the graphene supported Ru-CNC pincer complexes, Ru-porphyrin in the electrocatalytic CO2 hydrogenation to FA, reduction to CO. The pathways with the formate, carboxyl intermediates are investigated to estimate the preferred pathway, the overpotential needed to overcome the thermodynamic limitations of the process. The effect of the electron donation from the supporting graphene sheet is discussed, based on the observed charge density difference. The results indicate the carboxyl intermediate as the more stable one the electron donation causes the additional stability of this intermediate, which in turn is likely to lead to the strongly bound carbonyl species.