Firstly, the N2 evolution reaction was investigated via the mechanism outlined below (* denotes a surface site), which involves the adsorption of NO on the electrode surface, two sequential PCETs at the O atom, and the N-N coupling followed by N2 desorption. The computed Gibbs energy diagrams on the different electrocatalysts, depicted in Figure (left), revealed that the first PCET to form the intermediate *NOH (i.e. hydrogenated at the O, Eq. 2) is thermodynamically favorable on pure Zn (i.e. -0.95 eV), whereas this process is slightly endergonic both on pure Cu and Zn93Cu7 (i.e. +0.17 and +0.11 eV, respectively). These findings, and the highly exergonic formation of N2 predicted on Zn (i.e. -5.38 eV), are in line with the higher FE towards N2 observed in experiments on Zn compared to Cu and Zn93Cu7 (Figure ). Hence, theoretical calculations support hypothesis 4 that the formation of NH2OH (which eventually produces oxime) on pure Zn is disadvantaged by the competing NO3R pathway towards N2, which is marginally accessible on Cu and Zn93Cu7. These results could also explain the lower yields of oxime achieved on pure Zn relative to the Zn93Cu7 alloy (Figure ). The production of NH2OH and NH3 relies instead on the formation of the *NHO intermediate (i.e. hydrogenated at the N), which is thermodynamically more favorable than *NOH on all the electrocatalysts investigated in this work (Figure , right). Notably, while DFT calculations predict the generation of both *NOH and *NHO on Zn(101) to be essentially irreversible at room temperature due to their associated highly exergonic energies (i.e. -0.95 and -1.77 eV, respectively), for Cu and Zn93Cu7, only the formation of *NHO is thermodynamically driven (i.e. -0.28 and -0.70 eV, respectively). Hence, the relative stability between the *NHO vs *NOH intermediates and the binding strength of NH2OH can be used as descriptors to rationalize product selectivity, as we discuss in detail below.