Abstract

The efficient interconversion of electrical and chemical energy requires catalysts capable of accelerating complex multi-electron reactions at electrified interfaces. These reactions can be carried out at the metallic surface sites of heterogeneous electrocatalysts or via redox mediation at molecular electrocatalysts. Molecular catalysts yield readily to synthetic alteration of their redox properties and secondary coordination sphere, permitting systematic tuning of their activity and selectivity. Similar control is difficult to achieve with heterogeneous electrocatalysts because they typically exhibit a distribution of active site geometries and local electronic structures, which are recalcitrant to molecular-level synthetic modification. However, metallic heterogeneous electrocatalysts benefit from a continuum of electronic states which distribute the redox burden of a multi-electron transformation, enabling more efficient catalysis. We have developed a simple synthetic strategy for conjugating well-defined molecular catalyst active sites with the extended states of graphitic solids. Electrochemical and spectroscopic data indicate that these graphite-conjugated catalysts do not behave like their molecular analogues, but rather as metallic active sites with molecular definition, providing a unique bridge between the traditionally disparate fields of molecular and heterogeneous electrocatalysis.