Electrochemical nitrate reduction reaction(NtrRR)has been emerging as an appealing route for both water treatment and NH_(3)synthesis.Herein,we report the structure analysis and electrocatalytic performance of a novel...Electrochemical nitrate reduction reaction(NtrRR)has been emerging as an appealing route for both water treatment and NH_(3)synthesis.Herein,we report the structure analysis and electrocatalytic performance of a novel homoleptic alkynyl-protected Ag_(20)Cu_(12)nanocluster(Ag_(20)Cu_(12)in short)with atomic precision,which has eight free electrons and displays characteristic absorbance feature.Single crystal X-ray diffraction(SC-XRD)discloses that,it adopts a Ag_(14)kernel capped by three Ag_(2)Cu_(4)(C≡CArF)_(8)metal–ligand binding motifs in the outer shell.Ag_(20)Cu_(12)exhibited excellent catalytic performance toward NtrRR,as manifested by the superior NH_(3)Faradaic efficiency(FE,84.6%)and yield rate(0.138 mmol·h^(−1)·mg−1)than the homoleptic alkynyl-protected Ag_(32)nanoclusters.Additionally,it demonstrates good catalytic recycling capability.Density functional theory(DFT)calculations revealed that,the de-ligated Ag_(20)Cu_(12)cluster can expose the available AgCu bimetallic sites as the efficient active sites for NH_(3)formation.In particular,the participation of Cu sites greatly facilitates the initial capture of NO_(3)−and simultaneously promotes the selectivity of the final product.This study discovers a novel homoleptic alkynyl-protected AgCu superatom,and offers a great example to elucidate the structure–performance relationship of bimetallic catalyst for NtrRR and other multiple protons/electrons coupled electrocatalytic reactions.展开更多
基金Z.H.T.acknowledges the financial support from the Guangdong Natural Science Funds(No.2022A1515011840)Q.T.thanks the grants from the National Natural Science Foundation of China(No.21903008)the Chongqing Science and Technology Commission(No.cstc2020jcyj-msxmX0382).
文摘Electrochemical nitrate reduction reaction(NtrRR)has been emerging as an appealing route for both water treatment and NH_(3)synthesis.Herein,we report the structure analysis and electrocatalytic performance of a novel homoleptic alkynyl-protected Ag_(20)Cu_(12)nanocluster(Ag_(20)Cu_(12)in short)with atomic precision,which has eight free electrons and displays characteristic absorbance feature.Single crystal X-ray diffraction(SC-XRD)discloses that,it adopts a Ag_(14)kernel capped by three Ag_(2)Cu_(4)(C≡CArF)_(8)metal–ligand binding motifs in the outer shell.Ag_(20)Cu_(12)exhibited excellent catalytic performance toward NtrRR,as manifested by the superior NH_(3)Faradaic efficiency(FE,84.6%)and yield rate(0.138 mmol·h^(−1)·mg−1)than the homoleptic alkynyl-protected Ag_(32)nanoclusters.Additionally,it demonstrates good catalytic recycling capability.Density functional theory(DFT)calculations revealed that,the de-ligated Ag_(20)Cu_(12)cluster can expose the available AgCu bimetallic sites as the efficient active sites for NH_(3)formation.In particular,the participation of Cu sites greatly facilitates the initial capture of NO_(3)−and simultaneously promotes the selectivity of the final product.This study discovers a novel homoleptic alkynyl-protected AgCu superatom,and offers a great example to elucidate the structure–performance relationship of bimetallic catalyst for NtrRR and other multiple protons/electrons coupled electrocatalytic reactions.
