The electrocatalytic nitrate reduction reaction(NitRR)represents a promising approach toward achieving economically and environmentally sustainable ammonia.However,it remains a challenge to regulate the size effect of...The electrocatalytic nitrate reduction reaction(NitRR)represents a promising approach toward achieving economically and environmentally sustainable ammonia.However,it remains a challenge to regulate the size effect of electrocatalysts to optimize the catalytic activity and ammonia selectivity.Herein,the Cu-based catalysts were tailored at the atomic level to exhibit a size gradient ranging from single-atom catalysts(SACs,0.15–0.35 nm)to single-cluster catalysts(SCCs,1.0–2.8 nm)and nanoparticles(NPs,20–30 nm),with the aim of studying the size effect for the NO_(3)^(-)-to-NH_(3) reduction reaction.Especially,the Cu SCCs exhibit enhanced metal–substrate and metal–metal interactions by taking advantageous features of Cu SACs and Cu NPs.Thus,Cu SCCs achieve exceptional electrocatalytic performance for the NitRR with a maximum Faradaic efficiency of ca.96%NH_(3)and the largest yield rate of ca.1.99 mg·h^(-1)·cm^(-2) at-0.5 V vs.reversible hydrogen electrode(RHE).The theoretical calculation further reveals the size effect and coordination environment on the high catalytic activity and selectivity for the NitRR.This work provides a promising various size-controlled design strategy for aerogel-based catalysts effectively applied in various electrocatalytic reactions.展开更多
基金support from the National Nature Science Foundation of China(No.52202372)the Sichuan Science and Technology Program(Nos.2023NSFSC0436 and 2023NSFSC0089)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.YJ2021151 and 20826041G4185)T.T.G.acknowledges the Chengdu University new faculty start-up funding(No.2081920074).
文摘The electrocatalytic nitrate reduction reaction(NitRR)represents a promising approach toward achieving economically and environmentally sustainable ammonia.However,it remains a challenge to regulate the size effect of electrocatalysts to optimize the catalytic activity and ammonia selectivity.Herein,the Cu-based catalysts were tailored at the atomic level to exhibit a size gradient ranging from single-atom catalysts(SACs,0.15–0.35 nm)to single-cluster catalysts(SCCs,1.0–2.8 nm)and nanoparticles(NPs,20–30 nm),with the aim of studying the size effect for the NO_(3)^(-)-to-NH_(3) reduction reaction.Especially,the Cu SCCs exhibit enhanced metal–substrate and metal–metal interactions by taking advantageous features of Cu SACs and Cu NPs.Thus,Cu SCCs achieve exceptional electrocatalytic performance for the NitRR with a maximum Faradaic efficiency of ca.96%NH_(3)and the largest yield rate of ca.1.99 mg·h^(-1)·cm^(-2) at-0.5 V vs.reversible hydrogen electrode(RHE).The theoretical calculation further reveals the size effect and coordination environment on the high catalytic activity and selectivity for the NitRR.This work provides a promising various size-controlled design strategy for aerogel-based catalysts effectively applied in various electrocatalytic reactions.
