Atomically precise alkynyl-protected Ag_(20)Cu_(12)nanocluster:Structure analysis and electrocatalytic performance toward nitrate reduction for NH_(3)synthesis  

作　　者：Guanyu Ma Fang Sun Liang Qiao Quanli Shen Lei Wang Qing Tang Zhenghua Tang 

机构地区：[1]New Energy Research Institute,School of Environment and Energy,South China University of Technology,Guangzhou Higher Education Mega Centre,Guangzhou 510006,China [2]School of Chemistry and Chemical Engineering,Chongqing Key Laboratory of Theoretical and Computational Chemistry,Chongqing University,Chongqing 401331,China [3]China Petrochemical Research Institute,PetroChina Company Limited,Beijing 102206,China

出　　处：《Nano Research》2023年第8期10867-10872,共6页纳米研究（英文版）

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).

摘　　要：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.

关 键 词：Ag_(20)Cu_(12)nanocluster alkynyl ligand nitrate reduction reaction(NtrRR) ammonia synthesis density functional theory(DFT)calculations 

分 类 号：O64[理学—物理化学]