Cu-based catalysts have been widely
explored for the
electrochemical
nitrate reduction reaction (NO3RR), while the intrinsic
activity and selectivity of Cu metal for the NO3RR remain
ambiguous, preventing a genuine comparison of the NO3RR
performance. Here we use polycrystalline Cu foils for benchmarking
and elucidate the impact of often overlooked factors on the NO3RR, including Cu facet exposure, nitrate concentration, and
electrode surface area. An electropolished Cu foil exhibits a higher
activity and selectivity for the NO3RR to NH3 than a wet-etched Cu foil, benefiting from greater exposure of Cu(100)
facets that are more favorable for the NO3RR. While the
NH3 selectivity shows no apparent dependence on the nitrate
concentration, it increases monotonically with the Cu electrode area,
which is attributed to a promoted conversion of intermediately produced
NO2
– to NH3 on a larger electrode,
as validated by a 15N isotope labeling experiment. Our
work provides mechanistic insights toward the rational design of NO3RR electrocatalysts.