Predicting pH dependencies of electrode surface reactions in electrocatalysis

•Density functional theory calculation of electrode potential-dependent Gibbs Energy•Equilibrating electrode potential-dependent Gibbs energies of reactants and products•Predicting electrode-potential changes in structures at electrochemical interfaces•Predicting pH dependencies of interfacial reversible potentials and structures•Predicting non-linear dependencies of interfacial reversible potentials on pH

It is shown how to adopt the Nernst equation to electrode potential-dependent Gibbs energies, calculated for reactants and products from density functional theory, to make predictions of reversible potentials for redox reactions on electrode surfaces in electrolytes of any pH. The theory is general because any spectator species may be included in electrochemical interface. We demonstrate its application to H and OH deposition on Pt(111).

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