Theoretical studies of the possibility of forming ammonia electrochemically at ambient temperature and pressure are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy prole for the reduction of N 2 admolecules and N adatoms on several close-packed and stepped transition metal surfaces in contact with an acidic electrolyte. Trends in the catalytic activity were calculated for a range of transition metal surfaces and applied potentials under the assumption that the activation energy barrier scales with the free energy dierence in each elementary step. The most active surfaces, on top of the volcano diagrams, are Mo, Fe, Rh, and Ru, but hydrogen gas formation will be a competing reaction reducing the faradaic eciency for ammonia production. Since the early transition metal surfaces, such as Sc, Y, Ti, and Zr bind N-adatoms more strongly than H-adatoms, a signicant production of ammonia compared with hydrogen gas can be expected on those metal electrodes when a bias of -1 V to -1.5 V vs. SHE is applied. Defect-free surfaces of the early transition metals are catalytically more active than their stepped counterparts.

Density functional theory calculations have been performed for the three elementary steps-Tafel, Heyrovsky, and Volmer-involved in the hydrogen oxidation reaction (HOR) and its reverse, the hydrogen evolution reaction (HER). For the Pt(111) surface a detailed model consisting of a negatively charged Pt(111) slab and solvated protons in up to three water bilayers is considered and reaction energies and activation barriers are determined by using a newly developed computational scheme where the potential can be kept constant during a charge transfer reaction. We determine the rate limiting reaction on Pt(111) to be Tafel-Volmer for HOR and Volmer-Tafel for HER. Calculated rates agree well with experimental data. Both the H adsorption energy and the energy barrier for the Tafel reaction are then calculated for a range of metal electrodes, including Au, Ag, Cu, Pt, Pd, Ni, Ir, Rh, Co, Ru, Re, W, Mo, and Nb, different facets, and step of surfaces. We compare the results for different facets of the Pt electrode to experimental data. Our results suggest that the most important parameter for describing the HOR or the HER activity of an electrode is its binding free energy of H. We present a detailed kinetic model based entirely on the density functional theory calculations reactions and show that the exchange current follows a volcano curve when plotted against the H adsorption free energy in excellent agreement with experimental data.

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