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S vacancies in 2D SnS2 accelerating hydrogen evolution reaction

富含S空位的二维SnS2加速析氢反应

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Abstract

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 (SnS2). By varying the annealing temperatures (250–350°C), SnS2 with different S vacancy concentrations (Vs−SnS2) can be obtained. When SnS2 is annealed at 350°C 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−SnS2 is tested in the microelectrocatalytic hydrogen evolution reaction (HER). Vs−SnS2 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.

摘要

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°C), 实现了二维二硫化锡(SnS2)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SnS2(Vs−SnS2). 当SnS2 在350°C下退火5 h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Vs−SnS2的电催化析氢性能. S空位浓度达到30.5%的Vs−SnS2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SnS2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.

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Acknowledgements

This work was supported by the National Natural Science Foundation of China (22175060 and 21975067) and the Natural Science Foundation of Hunan Province, China (2021JJ10014 and 2021JJ30092). Feng Y acknowledges the support from the National Natural Science Foundation of China (11974105), the National Basic Research Program of China (2016YFA0300901). Xu J acknowledges the support from the Natural Science Foundation of Jiangsu Province, China (BK20210729), and 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. The computational resources were provided by the supercomputer TianHe in Changsha, China.

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Authors and Affiliations

  1. Engineering Research Center of Advanced Functional Material Manufacturing of Ministry of Education, School of Chemical Engineering, Zhengzhou University, Zhengzhou, 450001, China

    Gonglei Shao  (邵功磊) & Zhen Zhou  (周震)

  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

    Gonglei Shao  (邵功磊), Haiyan Xiang  (向海燕) & Song Liu  (刘松)

  3. School of Physics and Optoelectronics, Xiangtan University, Xiangtan, 411105, China

    Mengjie Huang  (黄梦婕) & Xiong-Xiong Xue  (薛雄雄)

  4. Institute of Functional Nano and Soft Materials (FUNSOM), Jiangsu Key Laboratory for Carbon-Based Functional Materials & Devices, Soochow University, Suzhou, 215123, China

    Yi Zong  (宗怡) & Jie Xu  (许杰)

  5. School of Materials Science and Engineering, Tianjin University of Technology, Tianjin, 300384, China

    Jun Luo  (罗俊) & Jie Xu  (许杰)

  6. Hunan Provincial Key Laboratory of Low-Dimensional Structural Physics and Devices, School of Physics and Electronics, Hunan University, Changsha, 410082, China

    Yexin Feng  (冯页新)

Authors
  1. Gonglei Shao  (邵功磊)
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  2. Haiyan Xiang  (向海燕)
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  3. Mengjie Huang  (黄梦婕)
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  4. Yi Zong  (宗怡)
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  6. Yexin Feng  (冯页新)
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  7. Xiong-Xiong Xue  (薛雄雄)
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  9. Song Liu  (刘松)
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  10. Zhen Zhou  (周震)
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Contributions

Author contributions Shao G and Xu J conceived the research. Shao G designed the experiments. Shao G and Xiang H performed the experiments and data analysis. Xue XX and Huang M contributed to the DFT simulation. Xu J, Zong Y, and Luo J performed STEM characterizations. Shao G, Xue XX, Feng Y, Zhou Z, Xu J and Liu S contributed to manuscript editing. Shao G, Liu S and Xue XX wrote the manuscript. All authors contributed to the general discussion.

Corresponding authors

Correspondence to Xiong-Xiong Xue  (薛雄雄), Jie Xu  (许杰) or Song Liu  (刘松).

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Conflict of interest The authors declare that they have no conflict of interest.

Additional information

Gonglei Shao received his PhD degree in chemistry from Hunan University in 2021. He joined the School of Chemical Engineering, Zhengzhou University as a researcher. At present, he is mainly engaged in the design and properties of novel 2D transition metal sulfide catalysts, the preparation of large-area 2D materials by chemical vapor deposition, and the preparation of ternary or multivariate 2D alloy materials.

Xiong-Xiong Xue received his PhD degree in physics from Hunan University in 2020. He is currently an associate professor at the School of Physics and Optoelectronics, Xiangtan University. His research concerns novel physical properties and applications of low-dimensional materials.

Jie Xu received his PhD degree from the School of Materials Science and Engineering, Tianjin University of Technology in 2020. Now he is a lecturer at the Institute of Functional Nano and Soft Materials (FUNSOM), Soochow University, China. His current interests include two-dimensional materials and electron microscopy research.

Song Liu received his PhD degree in 2011 from Peking University. He was a postdoctoral fellow working in Prof. Liming Dai’s group (2011–2013) in Case Western Reserve University. After three years research at the National University of Singapore (2013–2016), he is now a full professor at the Institute of Chemical Biology and Nanomedicine, Hunan University. His research interests focus on the controlled synthesis of low-dimensional materials, the application research of functional devices and Nano biological research.

Supplementary information Supporting data are available in the online version of the paper.

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Shao, G., Xiang, H., Huang, M. et al. S vacancies in 2D SnS2 accelerating hydrogen evolution reaction. Sci. China Mater. 65, 1833–1841 (2022). https://doi.org/10.1007/s40843-021-1991-6

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  • DOI: https://doi.org/10.1007/s40843-021-1991-6

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