(Invited) Efficient Recycling of Dilute Nitrate to Ammonia Using Cu-Based Electrocatalyst

Abstract

The use of nitrogen fertilizers has contributed significantly to the growth of agricultural production, but the nitrogen use efficiency is typically lower than 40%, so most of the nitrogen readily leaches into ground water, rivers, and lakes, causing an increase of nitrate (NO3 −) concentration and severe environmental problems. Electrochemical reduction of nitrate has emerged as a promising route for the recycling of nitrate from wastewater and sustainable production of ammonia when powered by renewable electricity. Here I present our recent studies of the intrinsic activity and selectivity of Cu for nitrate electroreduction, as well as a rational design of Cu-based catalysts for single-pass conversion of nitrate to ammonia. Using polycrystalline Cu foils for benchmarking, we elucidated the impact of often overlooked factors on nitrate reduction, including Cu facet exposure, nitrate concentration, and electrode surface area. We find that an electropolished Cu foil exhibits a higher activity and selectivity for nitrate reduction to ammonia than a wet-etched Cu foil, benefiting from a greater exposure of Cu(100) facets that are more favorable for the reaction. The NH3 selectivity shows no apparent dependence on the nitrate concentration, but it increases monotonically with Cu electrode area, which is attributed to a promoted conversion of intermediately produced NO2 − to NH3 on a larger electrode. Based on the understandings, we further developed a Cu/Co-based tandem electrocatalyst, which achieved nearly 100% single-pass conversion of dilute nitrate (5−50 mM) to NH3 at a low overpotential using a flow cell.