An inverse design methodology suitable to assist the development and optimization of catalysts for CO2 reduction is introduced. We search for catalyst candidates that minimize free energy differences of rate limiting steps through continuous variation of the chemical nature of the molecular frameworks in the vicinity of a reference catalyst. The method is illustrated as applied to optimization of the catalytic activity of a Ni-II-iminothiolate complex in a CO2/CO conversion in aqueous solutions, a synthetic functional model of carbon monoxide dehydroxygenase (CODH). We propose a catalytic mechanism that is in-line with available experimental data and where the only endergonic step in the proposed cycle involves oxidation of a 4-coordinate [LNiII(COOH)]- intermediate leading to formation of a 5-coordinate [LNiIII(COOH)(H2O)]0 intermediate, followed by deprotonation and decarboxylation. The inverse design algorithm identifies catalysts that minimize the reaction energy of the oxidation step without causing qualitative changes to other steps in the catalytic cycle, demonstrating the capabilities of the methodology as a valuable tool for catalyst design. In addition, we review our recent progress on design and characterization of other electrocatalytic systems for CO2 reduction at metal/liquid interfaces, in joint computational and experimental efforts on structural and mechanistic characterization.

Inverse design and characterization of catalytic systems for CO2 reduction

249th National Meeting (2015)

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