Coordination chemistry of [Co(acac)2] with N-doped graphene: Implications for oxygen reduction reaction reactivity of organometallic Co-O4-N species

Abstract

Hybridization of organometallic complexes with graphene-based materials can give rise to enhanced catalytic performance. Understanding the chemical structures within hybrid materials is of primary importance. In this work, archetypical hybrid materials are synthesized by the reaction of an organometallic complex, [Co-II(acac)(2)] (acac=acetylacetonate), with N-doped graphene-based materials at room temperature. Experimental characterization of the hybrid materials and theoretical calculations reveal that the organometallic cobalt-containing species is coordinated to heterocyclic groups in N-doped graphene as well as to its parental acac ligands. The hybrid material shows high electrocatalytic activity for the oxygen reduction reaction (ORR) in alkaline media, and superior durability and methanol tolerance to a Pt/C catalyst. Based on the chemical structures and ORR experiments, the catalytically active species is identified as a Co-O-4-N structure.