Electrocatalytic Reduction of Nitrogen to Ammonia: the Roles of Lattice O and N in Reduction at Vanadium Oxynitride Surfaces.

Vanadium oxynitride and other earth-abundant oxynitrides are of growing interest for the electrocatalytic reduction of nitrogen to NH3. A major unresolved issue, however, concerns the roles of lattice N and lattice O in this process. Electrochemistry and photoemission data reported here demonstrate that both lattice N and dissolved N2 are reduced to NH3 by cathodic polarization of vanadium oxynitride films at pH 7. These data also show that ammonia production from lattice N occurs in the presence or absence of N2 and involves the formation of V≡N: intermediates or similar unsaturated VN surface states on a thin vanadium oxide overlayer. In contrast, N2 reduction proceeds in the presence or absence of lattice N and without N incorporation into a vanadium oxide lattice. Thus, both lattice N and N2 reduction mechanisms involve oxide-supported V surface sites ([V]O) in preference to N-supported sites ([V]N). This result is supported by density functional theory-based calculations showing that the formation of V≡N:, V-N═N-H, and a few other plausible reaction intermediates is consistently energetically favored at [V]O rather than at [V]N surface sites. Similar effects are predicted for the oxynitrides of other oxophilic metals, such as Ti.