铂–镍双原子分散在具有新型(NiPt)-N_(4)C_(2)构型的氮掺杂碳纳米结构上用于协同电催化析氢反应  

Dual Pt–Ni atoms dispersed on N-doped carbon nanostructure with novel(NiPt)-N_(4)C_(2)configurations for synergistic electrocatalytic hydrogen evolution reaction

作　　者：达毓敏 田章留 蒋睿 刘袁 连旭 席识博 施毅 王永平 鲁浩天 崔柏桦 张金凤 韩晓鹏 陈伟 胡文彬 Yumin Da;Zhangliu Tian;Rui Jiang;Yuan Liu;Xu Lian;Shibo Xi;Yi Shi;Yongping Wang;Haotian Lu;Baihua Cui;Jinfeng Zhang;Xiaopeng Han;Wei Chen;Wenbin Hu(Joint School of National University of Singapore and Tianjin University,International Campus of Tianjin University,Fuzhou 350207,China;Department of Chemistry,National University of Singapore,Singapore 117543,Singapore;School of Materials Science and Engineering,Tianjin Key Laboratory of Composite and Functional Materials,Key Laboratory of Advanced Ceramics and Machining Technology,Tianjin University,Tianjin 300071,China;Institute of Chemical and Engineering Sciences,A^(*)STAR,Singapore 627833,Singapore)

机构地区：[1]Joint School of National University of Singapore and Tianjin University,International Campus of Tianjin University,Fuzhou 350207,China [2]Department of Chemistry,National University of Singapore,Singapore 117543,Singapore [3]School of Materials Science and Engineering,Tianjin Key Laboratory of Composite and Functional Materials,Key Laboratory of Advanced Ceramics and Machining Technology,Tianjin University,Tianjin 300071,China [4]Institute of Chemical and Engineering Sciences,A^(*)STAR,Singapore 627833,Singapore

出　　处：《Science China Materials》2023年第4期1389-1397,共9页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(52122107 and 51972224);the National Research Foundation,Singapore;A*STAR under its LCER FI program Award(U2102d2002)。

摘　　要：单原子催化剂具有原子利用率高、活性中心明确、催化中心原子配位数低等优点,有望提高电催化性能.具有相邻杂原子的双原子催化剂(DAC)有望发挥两个原子的协同作用,从而进一步提高活性.在本文中,我们报道了一种PtNi-NC催化剂,该催化剂由固定在氮掺杂碳基底上的PtNi双原子构成,该基底采用原子层沉积技术合成.X射线吸收光谱证实了Pt–Ni双原子的存在.所制备的PtNi-NC催化剂具有优异的催化活性,在10 m A cm^(-2)的电流密度下,酸性介质中析氢反应(HER)的过电位为30 m V,与市售20 wt%Pt/C相当.特别值得注意的是,PtNi-NC具有比20 wt%Pt/C更高的质量活性,约为其21倍.密度泛函理论计算表明,Pt–Ni双原子通过调节局部电子结构和优化电荷分布产生协同效应,有助于优化吸附性能和增强电催化性能.这项工作为DAC的制备提供了新途径,揭示了它们在电催化HER等领域的应用潜力.Single-atom catalysts with high atomic utilization efficiency,well-defined active centers,and catalytic sites with low atomic coordination numbers are promising to boost electrocatalytic performance.Dual-atom catalysts(DACs)with neighboring heteroatoms are expected to exert the synergistic effect of the two atoms,further improving the activity.Herein,we report a PtNi-NC catalyst consisting of PtNi dual atoms anchored on a nitrogen-doped carbon substrate synthesized through atomic layer deposition.X-ray absorption spectroscopy confirms the existence of the PtNi dual atoms.The as-prepared PtNi-NC catalyst exhibits extraordinary catalytic activity,with an overpotential of 30 m V for hydrogen evolution reaction(HER)in acidic media at a current density of 10 m A cm^(-2),which is comparable to that of commercial 20 wt%Pt/C.Notably,PtNi-NC possesses a much higher mass activity,about 21 times,than 20 wt%Pt/C.Density functional theory calculations reveal that PtNi dual atoms generate a synergistic effect by modulating the local electronic structure and optimizing the charge distribution,contributing to optimized adsorption properties and enhanced electrocatalytic performance.This work provides a new avenue for the fabrication of DACs,revealing their potential applications in electrocatalytic HER and beyond.

关 键 词：双原子 单原子催化剂 电荷分布 析氢反应 活性中心 X射线吸收光谱 电催化 原子利用率 

分 类 号：TQ116.2[化学工程—无机化工] TQ426[一般工业技术—材料科学与工程] TB383.1