过渡金属原子替位掺杂SnO_(2)析氢反应的研究  

The research on the hydrogen evolution reaction of tin dioxide doped with single transition metal atoms

作　　者：肖文波[1,3] 孙雪琴 黄乐 廖海俊 李京波 XIAO Wenbo;SUN Xueqin;HUANG Le;LIAO Haijun;LI Jingbo(Jiangxi Provincial Key Laboratory of Nanchang Hangkong University Optoelectronic Information Sensing Technology and Instruments,Nanchang 330063,China;School of Materials and Energy,Guangdong University of Technology,Guangzhou 510006,China;College of Science and Technology,Nanchang Hang Kong University,Gongqing City 332020,China;School of Physics,Southeast University,Nanjing 211189,China;Nanchang Zhongke Semiconductor Co.,Ltd.,Nanchang 330013,China)

机构地区：[1]南昌航空大学光电信息感知技术与仪器江西省重点实验室,南昌330063 [2]广东工业大学材料与能源学院,广州510006 [3]南昌航空大学科技学院,共青城332020 [4]东南大学物理学院,南京211189 [5]南昌中科半导体有限公司,南昌330013

出　　处：《中国科学:物理学、力学、天文学》2025年第3期208-217,共10页Scientia Sinica Physica,Mechanica & Astronomica

基　　金：国家自然科学基金(编号:12064027,12464010);2022年江西省高层次高技能领军人才培养工程人选(编号:63);九江“浔城英才”(编号:JJXC2023032)项目;江西省创新创业高层次(编号:jxsq2018103003)项目资助。

摘　　要：在众多清洁能源中,氢能因其理想的环保特性,吸引了专家和学者广泛的关注.析氢反应裂解水,作为一种生产清洁氢气的有效技术,其应用受到了高过电位的限制.采用合适的催化剂能够有效降低反应势垒,从而促进析氢反应(HER)的进行.本文主要探索过渡金属单原子(TM=V,Cr,Mn,Fe,Co,Ni)替位掺杂SnO_(2)表面对其HER催化性能的影响.结果显示,特定的替位掺杂体系,如V_(Sn_5c)-SnO_(2),Cr_(Sn_6c)-SnO_(2),Mn_(Sn_6c)-SnO_(2)和Fe_(Sn_6c)-SnO_(2),展现了出色的HER活性,其吉布斯自由能分别为-0.13 eV,-0.02 eV,-0.13 eV和-0.17 eV.研究发现,过渡金属(TM)原子不是直接影响到HER的催化过程,而是通过改性电子结构间接影响HER的催化性能.费米能级处显著增加的态密度表明电导率的提升,这同时促进了HER催化性能的提升.本项研究证明了基于SnO_(2)的非贵金属HER催化剂作为高效替代品的巨大潜力,并为未来SnO_(2)基催化剂的开发与应用提供了理论基础.Among numerous clean energy sources,hydrogen energy has attracted extensive attention from experts and scholars because of its ideal environmental characteristics.The hydrogen evolution reaction(HER),a technique for producing clean hydrogen gas by splitting water,is limited by high overpotential.The use of appropriate catalysts can effectively reduce the reaction barrier,thus promoting HER.This paper mainly explores the effect of single transition metal atoms(TM=V,Cr,Mn,Fe,Co,Ni)doped on the surface of SnO_(2)on its HER catalytic performance.The results show that specific doped systems,such as V_(Sn_5c)-SnO_(2),Cr_(Sn_6c)-SnO_(2),Mn_(Sn_6c)-SnO_(2)and Fe_(Sn_6c)-SnO_(2),exhibit excellent HER activity with Gibbs free energies of-0.13 eV,-0.02 eV,-0.13 eV,and-0.17 eV,respectively.The results show that transition metal(TM)atoms do not directly affect the catalytic process of HER but indirectly influence the HER catalytic performance through modified electronic structures.The significant increase in the density of states at the Fermi level indicates an enhancement of conductivity,which simultaneously promotes the improvement of HER catalytic performance.This research demonstrates the huge potential of SnO_(2)-based non-noble metal HER catalysts as efficient alternatives and provides a solid theoretical basis for the future development and application of SnO_(2)-based catalysts.

关 键 词：析氢反应 吉布斯自由能 吸附能 交换电流密度 

分 类 号：O643.36[理学—物理化学] TQ116.2[理学—化学]