Howalt, Jakob Geelmuyden4; Bligaard, Thomas3; Rossmeisl, Jan4; Vegge, Tejs1
1 Department of Energy Conversion and Storage, Technical University of Denmark2 Atomic scale modelling and materials, Department of Energy Conversion and Storage, Technical University of Denmark3 Department of Physics, Technical University of Denmark4 Center for Atomic-scale Materials Design, Center, Technical University of Denmark5 Theoretical Atomic-scale Physics, Department of Physics, Technical University of Denmark
Theoretical studies of the possibility of producing ammonia electrochemically at ambient temperature and pressure without direct N2 dissociation are presented. Density functional theory calculations were used in combination with the computational standard hydrogen electrode to calculate the free energy profile for the reduction of N2 admolecules and N adatoms on transition metal nanoclusters in contact with an acidic electrolyte. The work has established linear scaling relations for the dissociative reaction intermediates NH, NH2, and NH3. In addition, linear scaling relations for the associative reaction intermediates N2H, N2H2, and N2H3 have been determined. Furthermore, correlations between the adsorption energies of N, N2, and H have been established. These scaling relations and the free energy corrections are used to establish volcanoes describing the onset potential for electrochemical ammonia production. The competing hydrogen evolution reaction has also been analyzed for comparison.
Physical Chemistry Chemical Physics, 2013, Vol 15, p. 7785-7795