Directing the reactivity of metal hydrides for selective CO₂ reduction.

Abstract

A critical challenge in electrocatalytic CO₂ reduction to renewable fuels is product selectivity. Desirable products of CO₂ reduction require proton equivalents, but key catalytic intermediates can also be competent for direct proton reduction to H₂ Understanding how to manage divergent reaction pathways at these shared intermediates is essential to achieving high selectivity. Both proton reduction to hydrogen and CO₂ reduction to formate generally proceed through a metal hydride intermediate. We apply thermodynamic relationships that describe the reactivity of metal hydrides with H⁺ and CO₂ to generate a thermodynamic product diagram, which outlines the free energy of product formation as a function of proton activity and hydricity (∆G_H-), or hydride donor strength. The diagram outlines a region of metal hydricity and proton activity in which CO₂ reduction is favorable and H⁺ reduction is suppressed. We apply our diagram to inform our selection of [Pt(dmpe)₂](PF₆)₂ as a potential catalyst, because the corresponding hydride [HPt(dmpe)₂]⁺ has the correct hydricity to access the region where selective CO₂ reduction is possible. We validate our choice experimentally; [Pt(dmpe)₂](PF₆)₂ is a highly selective electrocatalyst for CO₂ reduction to formate (>90% Faradaic efficiency) at an overpotential of less than 100 mV in acetonitrile with no evidence of catalyst degradation after electrolysis. Our report of a selective catalyst for CO₂ reduction illustrates how our thermodynamic diagrams can guide selective and efficient catalyst discovery.