S vacancies in 2D SnS_(2) accelerating hydrogen evolution reaction  

富含S空位的二维SnS_(2)加速析氢反应

作　　者：Gonglei Shao Haiyan Xiang Mengjie Huang Yi Zong Jun Luo Yexin Feng Xiong-Xiong Xue Jie Xu Song Liu Zhen Zhou 邵功磊;向海燕;黄梦婕;宗怡;罗俊;冯页新;薛雄雄;许杰;刘松;周震(Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education,School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,China;Institute of Chemical Biology and Nanomedicine(ICBN),State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,China;School of Physics and Optoelectronics,Xiangtan University,Xiangtan 411105,China;Institute of Functional Nano and Soft Materials(FUNSOM),Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices,Soochow University,Suzhou 215123,China;School of Materials Science and Engineering,Tianjin University of Technology,Tianjin 300384,China;Hunan Provincial Key Laboratory of Low-Dimensional Structural Physics and Devices,School of Physics and Electronics,Hunan University,Changsha 410082,China)

机构地区：[1]Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education,School of Chemical Engineering,Zhengzhou University,Zhengzhou 450001,China [2]Institute of Chemical Biology and Nanomedicine(ICBN),State Key Laboratory of Chemo/Biosensing and Chemometrics,College of Chemistry and Chemical Engineering,Hunan University,Changsha 410082,China [3]School of Physics and Optoelectronics,Xiangtan University,Xiangtan 411105,China [4]Institute of Functional Nano and Soft Materials(FUNSOM),Jiangsu Key Laboratory for Carbon-Based Functional Materials&Devices,Soochow University,Suzhou 215123,China [5]School of Materials Science and Engineering,Tianjin University of Technology,Tianjin 300384,China [6]Hunan Provincial Key Laboratory of Low-Dimensional Structural Physics and Devices,School of Physics and Electronics,Hunan University,Changsha 410082,China

出　　处：《Science China Materials》2022年第7期1833-1841,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(22175060 and 21975067);the Natural Science Foundation of Hunan Province,China(2021JJ10014 and 2021JJ30092);support from the National Natural Science Foundation of China(11974105);the National Basic Research Program of China(2016YFA0300901);support from the Natural Science Foundation of Jiangsu Province,China(BK20210729);the Collaborative Innovation Center of Suzhou Nano Science and Technology;the 111 Project and the Joint International Research Laboratory of Carbon-Based Functional Materials and Devices。

摘　　要：Precise manipulation of atomic defects is essential for modulating the intrinsic properties of two-dimensional(2D)materials.In this study,sulfur(S)atoms are accurately knocked out in the 2D basal plane of pure tin disulfide(SnS_(2)).By varying the annealing temperatures(250–350℃),SnS_(2)with different S vacancy concentrations(Vs-SnS_(2))can be obtained.When SnS_(2)is annealed at 350℃ for 5 h,the S vacancies in the forms of single S atom and double S atoms could reach up to 30.5%.The Vs-SnS_(2)is tested in the microelectrocatalytic hydrogen evolution reaction(HER).Vs-SnS_(2)with S vacancies of 30.5%generates superior catalytic performance,with a Tafel slope of 74 mV dec^(-1) and onset potential of 141 mV.The mechanism has been proposed.First,computation confirms that the absence of S atoms prompts surface charge modulation and enhances electronic conductivity.In addition,the under-coordinated Sn atoms adjacent to S vacancy introduce the lattice distortion and charge density redistribution,which are beneficial to hydrogen binding in HER.In short,accurate knockout of specific atoms by controlling the annealing temperature is a promising strategy to explore structure-dependent properties of various 2D materials.精确调控二维平面内的原子缺陷可有效调节二维材料的各种基本性质.本研究通过改变退火温度(250-350℃),实现了二维二硫化锡(SnS_(2))基面上硫(S)原子的精确敲除,得到了具有不同S空位浓度的SnS_(2)(Vs-SnS_(2)).当SnS_(2)在350℃下退火5h时,大量出现单S原子和双S原子空位形态,S空位浓度可达30.5%.在自制微芯片中测试了Vs-SnS_(2)的电催化析氢性能.S空位浓度达到30.5%的Vs-SnS_(2)表现出优异的催化性能,Tafel斜率达到74 mV dec^(-1),起始电位低至141 mV.通过理论计算对反应机制进行研究,结果表明,S原子的缺失促进了表面电荷调制,提高了SnS_(2)的导电性.此外,S空位导致Sn原子的不饱和配位,从而引起晶格畸变和电荷密度重新分布,更加有利于析氢反应.简而言之,通过控制退火温度可精确敲除特定原子、制造缺陷,可成为探索各种2D材料结构相关特性的一种有效策略.

关 键 词：SnS_(2) ANNEALING S vacancy HAADF-STEM hydrogen evolution reaction 

分 类 号：TQ116.2[化学工程—无机化工] TQ426