The subsequent electroreduction of *NH2OH to NH3 was then examined according to the mechanism shown in Eqs. 7 Again, calculations predict the electroreduction of *NH2OH to NH3 to be thermodynamically downhill, in line with the experimental observation of NH3 with all the studied electrocatalysts (Figures and). However, we note that *NH2OH electroreduction is competing with *NH2OH desorption from the electrode surface, which is followed by a chemical reaction with the cyclohexanone in solution to produce oxime. Therefore, to shed light on the different NH3/oxime selectivities observed in experiments, we set out to compute both the thermodynamic driving force for *NH2OH desorption (ΔGdes) and the kinetic barrier for *NH2OH electroreduction (∆G ‡ ), the results of which are summarized in Figure . Notably, the *NH2OH desorption is almost thermoneutral on Cu (-0.03 eV), slightly endergonic on Zn (+0.19 eV), and exergonic on the Zn93Cu7 alloy (-0.14 and -0.44 eV from Zn and Cu sites, respectively). For the modelling of the *NH2OH electroreduction, we note that this step involves the hydrogenation of the O atom with the concomitant cleavage of the N-O bond, which can be promoted by either the aqueous electrolyte or the H surface coverage. However, given that the pKb of NH2OH in water is ca. 8.1, it is unlikely that NH2OH will be protonated by the aqueous electrolyte at the experimental pH 7. Hence, we focused on modelling the reaction kinetics of the *NH2OH electroreduction by sourcing a H atom from the electrode surface. Furthermore, because of the relatively large distance between the O lone pairs in *NH2OH and the nearest surface H (ca. 3.0 Å on Cu(111) and ca. 4.2 Å on both Zn93Cu7(101) and Zn(101)), we envisioned this process to be promoted by the aqueous electrolyte. To capture this in our kinetic studies, we introduced two H2O molecules to mediate the H transfer. This led to the following energy barriers for the different electrocatalysts: Cu (1.11 eV) ~ Zn93Cu7 (1.05 eV) < Zn (1.66 eV) (Figure ). With these values of ∆G ‡ and ΔGdes we can now rationalize the NH3/oxime selectivities on Cu, Zn93Cu7 and Zn as follows. On pure Cu, *NH2OH electroreduction (with moderate ∆G ‡ ) is favored over *NH2OH desorption, rendering NH3 as the major NO3R product. On the other hand, the high ∆G ‡ found for pure Zn hinders *NH2OH electroreduction, while the slightly endergonic ΔGdes allows *NH2OH desorption at room temperature, coherently with the product distribution observed experimentally (Figures and). Finally, on the Zn93Cu7 alloy, the moderate ∆G ‡ and exergonic ∆Gdes allow both the electroreduction and desorption of *NH2OH to occur at room temperature, in agreement with the formation of oxime and NH3 as major products (Figures 4b).