Designing electrocatalysts for the oxidation and production of H2 is important for the development of alternative energy sources. Our focus is on the [Ni(P2N2)2]2+ electrocatalysts, where P2N2 denotes 1,5-diaza-3,7-diphosphacyclooctane ligands with pendant amines.  We used theoretical methods to investigate the mechanism of the step in the catalytic cycle corresponding to [HNiII(P2N2)2]+ � e� ? [NiI(P2HN2)(P2N2)]2+ for H2 oxidation and the reverse for H2 production. This step involves electron transfer (ET) between the Ni complex and the electrode as well as proton transfer (PT) between the Ni and the N. We investigated the sequential mechanisms, PT�ET and ET�PT, for a series of molecular electrocatalysts with methyl, benzyl, and phenyl substituents on the phosphorous and nitrogen atoms. Density functional theory was used to calculate reduction potentials, pKa values, and PT reaction pathways, and the inner- and outer-sphere reorganization energies for electrochemical ET were calculated within the framework of Marcus theory.

Theoretical analysis of the sequential proton-coupled electron transfer mechanisms for H<sub>2</sub> oxidation and production pathways catalyzed by nickel molecular electrocatalysts

244th National Meeting (2012)

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Theoretical analysis of the sequential proton-coupled electron transfer mechanisms for H2 oxidation and production pathways catalyzed by nickel molecular electrocatalysts

Theoretical analysis of the sequential proton-coupled electron transfer mechanisms for H₂ oxidation and production pathways catalyzed by nickel molecular electrocatalysts