钒掺杂钨青铜内通道氨配位的钌单原子用于高效析氢反应  

Atomic Ru coordinated by channel ammonia in V‐doped tungsten bronze for highly efficient hydrogen‐evolution reaction

作　　者：韩策 梅丙宝 张庆华[4] 张慧敏 姚鹏飞 宋平[1] 宫雪 崔培昕 姜政[3] 谷林 徐维林[1,2] Ce Han;Bingbao Mei;Qinghua Zhang;Huimin Zhang;Pengfei Yao;Ping Song;Xue Gong;Peixin Cui;Zheng Jiang;Lin Gu;Weilin Xu(State Key Laboratory of Electroanalytical Chemistry,Jilin Province Key Laboratory of Low Carbon Chemical Power,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun 130022,Jilin,China;University of Science and Technology of China,Hefei 230026,Anhui,China;Shanghai Institute of Applied Physics,Chinese Academy of Sciences,Shanghai 201204,China;Beijing National Laboratory for Condensed Matter Physics,Institute of Physics,Chinese Academy of Sciences,Beijing 100190,China;Key Laboratory of Soil Environment and Pollution Remediation,Institute of Soil Science,Chinese Academy of Sciences,Nanjing 210008,Jiangsu,China;Beijing National Center for Electron Microscopy and Laboratory of Advanced Materials,Department of Materials Science and Engineering,Tsinghua University,Beijing 100084,China)

机构地区：[1]中国科学院长春应用化学研究所,吉林省低碳化工动力重点实验室,电分析化学国家重点实验室,吉林长春130022 [2]中国科学技术大学,安徽合肥230026 [3]中国科学院上海应用物理研究所,上海201204 [4]中国科学院物理研究所,北京凝聚态物理国家实验室,北京100190 [5]中国科学院土壤研究所,土壤环境与污染修复重点实验室,江苏南京210008 [6]清华大学材料科学与工程系,北京国家电子显微镜中心和先进材料实验室,北京100084

出　　处：《Chinese Journal of Catalysis》2023年第8期80-89,共10页催化学报（英文）

基　　金：国家自然科学基金(22102172,22072145,22005294,21925205,21721003);国家重点研发计划(2022YFA1203400).

摘　　要：通过电解水制备氢气是实现“碳中和”目标的理想途径之一.因此,可在全p H条件下使用的氢析出(HER)催化剂的研发是近年来电催化领域的研究热点.原子级分散的催化剂,能够在保留铂族金属(PGM)固有活性的同时,降低催化剂中PGM的用量.虽然可以通过X射线吸收光谱(XAS)来表征原子分散的PGM电催化剂的配位环境,但目前对原子空间分布的控制仍然具有挑战.本文制备了钒掺杂钨青铜内通道氨配位的钌单原子催化剂(Ru/V-NHWO),用于全p H范围内的HER反应.采用X射线衍射(XRD)、高角环形暗场扫描透射电镜(HAADF-STEM)、X射线光电子能谱(XPS)和原位X射线吸收光谱(XAS)等进行表征,研究了钌单原子与V-NHWO载体的结合方式以及构效关系,并采用密度泛函理论(DFT)计算探索了催化剂中诸多位点的活性贡献.在1 mol/LKOH, 0.5 mol/L H_(2)SO_(4)和1 mol/L磷酸盐缓冲溶液中,其在10 m Acm^(-2)下的过电位分别为28.0, 29.6和40.6 m V.同时,在过电位100 m V时,质量活性分别达到3930, 1941和602.8 m Amg^(-1)Ru,数倍于同等条件下的商业铂碳.XRD结果表明,钌的引入可以确保催化剂在氩气条件下热解后仍保持六方钨铵青铜晶相,证明钌与钨铵青铜六方晶体通道内氨物种,即“通道氨”的结合.HAADF-STEM结果表明,钌原子与NHWO间存在强烈相互作用,有助于提升HER性能.XPS和XAS结果表明, W5+信号出现在引入钌后,峰位置的结合能增加且峰面积降低,说明钌与通道氨之间存在相互作用.N的XPS结果表明,钌的引入导致了金属氨键的形成.XAS结果表明, Ru/V-NHWO/CC中钌单原子和钌团簇共存,钌单原子与通道氨配位,并且钒的引入会诱发V-NHWO中金属键长缩短,这表明催化剂的金属性得到了提升,有利于改善其导电性.采用DFT计算进一步研究了HER活性的来源.相比于V-NHWO载体和钌团簇修饰的V-NHWO,以单原子形式结合的钌具有更低的水解离能垒,该能垒在氨�Regulation of the atomic distribution is crucial for the development of atomically dispersed electrocatalysts.In this study,atomic Ru coordinated by channel ammonia in V-doped tungsten bronze(Ru/V-NHWO,Ru 0.44 wt%,V 0.45 wt%)was used as a high-performance catalyst for the hydrogen evolution reaction(HER),demonstrating remarkable mass activity in a wide pH range.Atomic Ru with a regulated spatial distribution and electronic structure was achieved owing to its unique coordination with the ammonia species in the hexagonal channels of V-NHWO.V doping in NHWO led to enhanced intrinsic activity and conductivity.Theoretical calculations revealed that the multichannel,vertically integrated Ru sites in the V-doped channels,as well as the coexisting Ru sites without multichannels or V-doping,improved the free energy of water dissociation and hydrogen sorption,which boosted the HER activity.Our study paves a new way for constructing atomically dispersed materials with a regulated spatial distribution for diverse applications.

关 键 词：单原子钌 通道氨 六方晶通道 钨青铜 析氢反应 

分 类 号：O64[理学—物理化学]