Thiol Ligand-Modified Au for Highly Efficient Electroreduction of Nitrate to Ammonia

作     者：Yuheng Wu Xiangdong Kong Yechao Su Jiankang Zhao Yiling Ma Tongzheng Ji Di Wu Junyang Meng Yan Liu Zhigang Geng Jie Zeng 

作者机构：Hefei National Research Center for Physical Sciences at the MicroscaleKey Laboratory of Strongly-Coupled Quantum Matter Physics of Chinese Academy of SciencesKey Laboratory of Surface and Interface Chemistry and Energy Catalysis of Anhui Higher Education InstitutesDepartment of Chemical PhysicsUniversity of Science and Technology of ChinaHefeiAnhui 230026P.R.China School of Chemistry&Chemical EngineeringAnhui University of TechnologyMa’anshanAnhui 243002P.R.China 

出 版 物：《Precision Chemistry》 (精准化学（英文）)

年 卷 期：2024年第2卷第3期

页      面：112-119页

学科分类：07[理学] 070304[理学-物理化学(含∶化学物理)] 0703[理学-化学] 

基　　金：This work was supported by Strategic Priority Research Program of the Chinese Academy of Sciences(XDB0450401) National Key Research and Development Program of China(2021YFA1500500 and 2019YFA0405600) NSFC(22209161,22209163,92061111,22322901,22221003,and 22250007) CAS Project for Young Scientists in Basic Research(YSBR-051 and YSBR-022) National Science Fund for Distinguished Young Scholars(21925204),China Postdoctoral Program for Innovative Talents(BX20200324) Fundamental Research Funds for the Central Universities.J.Z.acknowledges support from the Tencent Foundation through the XPLORER PRIZE.The authors acknowledge support from Prof.Chao Ma and Mr.Sunpei Hu in conducting the microscopic characterization,and Dr.Hong Wu in the DFT computations.This work was partially carried out at the Instruments Center for Physical Science,University of Science and Technology of China.This work was also partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication。 

主　　题：Ammonia synthesis NO_(3)-electroreduction Au nanoparticles thiol ligand modification electronic structure 

摘      要：Electroreduction of nitrate(NO_(3)-)to ammonia(NH_(3))is an environmentally friendly route for NH_(3)production,serving as an appealing alternative to the Haber-Bosch process.Recently,various noble metal-based electrocatalysts have been reported for electroreduction of NO_(3)-.However,the application of pure metal electrocatalysts is still limited by unsatisfactory performance,owing to the weak adsorption of nitrogen-containing intermediates on the surface of pure metal electrocatalysts.In this work,we report thiol ligand-modified Au nanoparticles as the effective electrocatalysts toward electroreduction of NO_(3)-.Specifically,three mercaptobenzoic acid(MBA)isomers,thiosalicylic acid(ortho-MBA),3-mercaptobenzoic acid(meta-MBA),and 4-mercaptobenzoic acid(para-MBA),were employed to modify the surface of the Au nanocatalyst.During the NO_(3)-electroreduction,para-MBA modified Au(denoted as para-Au/C)displayed the highest catalytic activity among these Au-based catalysts.At-1.0 V versus reversible hydrogen electrode(vs RHE),para-Au/C exhibited a partial current density for NH_(3)of 472.2 mA cm^(-2),which was 1.7 times that of the pristine Au catalyst.Meanwhile,the Faradaic efficiency(FE)for NH_(3)reached 98.7%at-1.0 V vs RHE for para-Au/C.The modification of para-MBA significantly improved the intrinsic activity of the Au/C catalyst,thus accelerating the kinetics of NO_(3)-reduction and giving rise to a high NH_(3)yield rate of para-Au/C.