A computational inverse design methodology is implemented for development and refinement of synthetic Ni(II) iminothiolate complexes, inspired by a Ni complex that is known to be an active catalysts for conversion of CO to CO2 in the presence of a low-potential redox mediator (methylviologen (mv+�/mv2+)) [Lu, Z.; Crabtree, R. H. J. Am. Chem. Soc. 1995  , 117, 3994-3998].  A plausible reaction mechanism is proposed and partially validated by calculations of free energy changes, during formation of reaction intermediates along the catalytic cycle, and direct comparisons with kinetics studies. The reported results suggest that by ligand design one could optimize the rate-limiting step, involving electron transfer from a 4-coordinate intermediate [LNiII(COOH)]- to mv2+. Such process leads to formation of the pentacoordinated intermediate [LNiIII(COOH)(H2O)]0 that forms CO2 by deprotonation and decarboxylation. The resulting insight is particularly valuable for optimization of catalytic activity in the experimental exploration of robust and efficient organometallic anode catalysts based on earth abundant metals.

Inverse design of catalysts for CO/CO<sub>2</sub> fuel cells

244th National Meeting (2012)

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Inverse design of catalysts for CO/CO2 fuel cells

Inverse design of catalysts for CO/CO₂ fuel cells