Synergistic rare-earth yttrium single atoms and copper phosphide nanoparticles for high-selectivity ammonia electrosynthesis  

作　　者：Yi-Meng Cai Yang-Hua Li Yi Xiao Quentin Meyer Qian Sun Wan-Jing Lai Shu-Wen Zhao Jun Li Lin-Jie Zhang Han Wang Zhang Lin Jun Luo Li-Li Han 

机构地区：[1]School of Materials Science and Engineering,Institute for New Energy Materials and Low-Carbon Technologies,Tianjin University of Technology,Tianjin 300384,China [2]State Key Laboratory of Structural Chemistry,Fujian Institute of Research on the Structure of Matter,Chinese Academy of Sciences,Fuzhou 350002,China [3]School of Chemistry,The University of New South Wales,Sydney,NSW 2052,Australia [4]School of Metallurgy and Environment,Central South University,Changsha 410083,China [5]Chinese National Engineering Research Center for Control&Treatment of Heavy Metal Pollution,Changsha 410083,China [6]ShenSi Lab,Shenzhen Institute for Advanced Study,University of Electronic Science and Technology of China,Shenzhen 518110,China

出　　处：《Rare Metals》2024年第11期5792-5801,共10页稀有金属（英文版）

基　　金：financially supported by the National Key Research and Development Program of China(Nos.2022YFA1505700 and 2019YFA0210403);the National Natural Science Foundation of China(Nos.22205232 and 21601187);the Talent Plan of Shanghai Branch,Chinese Academy of Sciences(No.CASSHB-QNPD-2023-020);the Natural Science Foundation of Fujian Province(Nos.2023J06044 and 2023J01213);the Fund for Distinguished Young Scholars of FJIRSM(No.CXZX-2022-JQ06)。

摘　　要：Electrochemical nitrate reduction to NH_(3)holds a great promise for N-upcycling in nature,while its sluggish reaction kinetics involved in both the stepwise deoxygenation and hydrogenation processes necessitates the development of bespoke catalysts with multi-site engineering.Herein,we report a hybrid catalyst composed of rare-earth(RE)yttrium(Y)single atoms and copper phosphide(Cu_(3)P)nanoparticles loaded on N,P-doped carbon(Y_(SA)-Cu_(3)P/CNP)through a chelating and pyrolysis method.Owing to a synergistic contribution of Y single atoms and Cu_(3)P nanoparticles,Y_(SA)-Cu_(3)P/CNP achieves an impressive NH_(3)Faradaic efficiency(FE)of 92%at-0.5V(vs.RHE)and the highest NH_(3)yield rate of11.4 mg·h^(-1)·cm^(-2)at-0.6 V(vs.RHE)in an alkaline media,which surpass most of the reported electrocatalysts.The intricate reaction pathway has been explored by online differential electrochemical mass spectrometry(DEMS),and the synergistic effect between Y single atoms and Cu_(3)P nanoparticles has been studied by in situ synchrotron X-ray absorption spectroscopy.Moreover,density-functional theory(DFT)calculations unveil that the high-efficiency nitrate reduction on Y_(SA)-Cu_(3)P/CNP is attributed to a reduced energy barrier of the rate-determining deoxygenation step coupled with the enhanced stabilization of active hydrogen favorable for the hydrogenation steps,thereby boosting the overall reaction rates.In addition,a prototype Zn-nitrate battery utilizing Y_(SA)-Cu_(3)P/CNP as the cathode is unveiled.This work not only elucidates the mechanism behind the enhanced catalytic performance but also paves the way for the future development of highefficiency electrocatalysts through dual-site engineering.

关 键 词：Rare-earth single atom Cu_(3)P nanoparticle Synergistic electrocatalysis Nitrate reduction reaction Zn-nitrate battery 

分 类 号：TQ113.2[化学工程—无机化工] O643.36[理学—物理化学]