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Electrocatalytic nitrate reduction reaction (NO3–RR) opens opportunities for ammonia production. The sluggish kinetics of this multielectron and multiproton process has been regarded as the key issue. Herein, we report a Cu1Co5 alloy for electrocatalytic NO3–RR to NH3. It achieves a high current density (453 mA cm–2) and Faradaic efficiency (96.2%) for NH3 production at 0.075 V vs RHE, with a half-cell energy efficiency of 44.9%, higher than those of Cu, Co, and other Co-based alloys, and is among the highest value reported. We found that the interaction between Cu and Co reorganizes their electronic structure in alloys. The NO3– adsorption switches to a spontaneous process, and the *NO → *N and *NH → *NH2 processes are promoted. Importantly, the water dissociation process concerted with the transformation of N-species is proven to be rate-determining, which is facilitated on Co sites in the Cu1Co5 alloy and is essential for the enhanced NO3–RR. This inspires us a strategy for designing more efficient catalysts for NO3–RR under alkaline condition by promoting the H2O dissociation process.
Zhou et al. (Wed,) studied this question.