AbstractElectrochemical nitrate reduction reaction (NO3RR) offers a route to balanced nitrogen cycle and sustainable ammonia production. However, unsatisfied performance in neutral media arising from competitive hydrogen evolution reaction and inefficient hydrogenation impede the further applications of NO3RR. Herein, the rational design of RuNi alloy nanostructures is reported. Benefited from the synergism effect between Ru and Ni, Ru20Ni80 alloy exhibits a high NH3 Faradaic efficiency of 98.02% at −0.35 V (vs reversible hydrogen electrode (RHE)) and a large NH3 yield rate of 27.88 mg mgcat−1 h−1 at −0.65 V (vs RHE). Importantly, the atomic scale cooperation between Ru and Ni active sites endows RuNi alloy a close‐to‐unity NH3 selectivity via HNO* pathway. Theoretical calculations have revealed that the interactions between Ru and Ni optimize the electronic structures of Ru20Ni80 alloy, where Ru sites with enhanced electroactivity improve the generation of active hydrogens and more electron‐rich Ni sites facilitate the reduction of nitrate. Accordingly, the adsorption strengths of key intermediates become stronger and the energy barriers of NO3RR are reduced to guarantee efficient NO3RR. Furthermore, a flow‐type reactor coupled with coprecipitation is established to achieve continuous NH3 generation and recovery as struvite.
Read full abstract