Yang Mengya, Ren Xiaoyan, Li Shunfang, Zhang Yingjiu, Li Xinjian, Pang Rui, Shang Yuanyuan
International Laboratory for Quantum Functional Materials of Henan, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450001, P. R. China.
Key Laboratory of Material Physics, Ministry of Education, School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, 450052, P. R. China.
Phys Chem Chem Phys. 2022 Jul 27;24(29):17832-17840. doi: 10.1039/d2cp01095j.
Hydrogen energy is considered to be one of the most promising clean energy sources. The development of highly active, low-cost catalysts, and good stability is essential for hydrogen production. Herein, the catalytic activity of a two-dimensional β-Sb surface doped with main-group elements (N, P, As, O, S, Se, and Te) for the hydrogen evolution reaction (HER) was investigated by density functional theory, and the catalytic activity of the β-Sb monolayer can be improved by doping group VIA atoms. The catalytic activity of Se@Sb and O@Sb structures at the doping concentration of 2.78% and the S@Sb structure at the doping concentration of 5.56% may be as good as the Pt(111) surface, while keeping energetically stable. In addition, the catalytic performance could be optimized under biaxial strain. Further analysis suggests that the activity is caused by hole states in the lone pair electrons, which are created by the group VIA atom dopants. And our work also reveals that the density of states at the Fermi level could be an appropriate descriptor of the hydrogenation Gibbs free energy. This work not only proposes a novel non-platinum HER catalyst but also provides physical foundations for further application on antimonene-based catalysts.
氢能被认为是最有前途的清洁能源之一。开发高活性、低成本且稳定性良好的催化剂对于制氢至关重要。在此，通过密度泛函理论研究了掺杂主族元素（N、P、As、O、S、Se和Te）的二维β-Sb表面对析氢反应（HER）的催化活性，并且通过掺杂第VIA族原子可以提高β-Sb单层的催化活性。掺杂浓度为2.78%时Se@Sb和O@Sb结构以及掺杂浓度为5.56%时S@Sb结构的催化活性可能与Pt(111)表面相当，同时保持能量稳定。此外，在双轴应变下可以优化催化性能。进一步分析表明，活性是由第VIA族原子掺杂剂产生的孤对电子中的空穴态引起的。并且我们的工作还表明费米能级处的态密度可能是氢化吉布斯自由能的合适描述符。这项工作不仅提出了一种新型的非铂HER催化剂，还为基于锑烯的催化剂的进一步应用提供了物理基础。
