Synthesis of Axially Coordinated Cobalt Porphyrin/graphene Oxide Nanocomposite for Enhanced Electrocatalytic CO2 Reduction to CO

The electrocatalysts containing cobalt-pyrrolic nitrogen-carbon (Co-N-C) moiety for COreduction reaction (CORR) have caught much attention.However,the effects of Co valence state and its synergy with graphene substrate are not clear yet.In this work,cobalt porphyrin (Co TPP) molecule with the intrinsic Co-N-C moiety is successfully combined with graphene oxide (GO) via three kinds of liquid-phase methods.The ratio of Co TPP to GO and the valence state of Co atom are studied to explore their catalysis for CORR to CO.It is found that axially-coordinated Co(III)TPPCl/GO nanocomposites synthesized via a chemical method exhibit better ability for CORR,as compared with Co(II)TPP+GO and/or Co(III)TPPCl+GO nanocomposites obtained via a physically mixing way.After optimizing the ratio of Co TPP to GO,the Faradaic efficiency (FE) is more than 90% for CORR to CO between-0.7 and-0.8 V vs.reversible hydrogen electrode (RHE) in Co(III)TPPCl/GO75.The synergy between Co TPP and GO and the effect of Co valence state are systematically investigated,indicating that their strong interaction plays the key role in electrocatalytic CORR.