Liu Qing, Cheng Haixia, Wang Xiaoxu, Qian Ping
Beijing Advanced Innovation Center for Materials Genome Engineering, Beijing Key Laboratory for Magneto-Photoelectrical Composite and Interface Science, School of Mathematics and Physics, University of Science and Technology Beijing, Beijing, 100083, China.
Material Digital R&D Center, China Iron & Steel Research Institute Group, Beijing 100081, China.
Phys Chem Chem Phys. 2023 Feb 8;25(6):5056-5065. doi: 10.1039/d2cp05239c.
Non-metal doping engineering has shown great potential for designing high-performance MXene-based catalysts for electrocatalytic hydrogen evolution. We rationally design 14 kinds of nonmetal atom-doped MoCO catalysts and investigate the effects of nonmetal doping on the thermal stability and hydrogen evolution reaction (HER) catalytic activity of these structures through first-principles calculations. The results show that the addition of nonmetal dopants, such as Si, Cl, Br and I, on the MoCO surface can effectively improve the HER activity, making them promising candidates for effective HER catalysts. Besides, we studied the thermal stability of nonmetal doped MoCO by calculating the binding energy and explored the reason behind the variation in the binding energy. Furthermore, the origin of the HER activity difference regulated by various nonmetal dopants is explained based on the analysis of their electronic properties. We found that the number of valence electrons and Bader charge coupling of doped nonmetal atoms are effective electronic descriptors of the hydrogen adsorption strength and HER activity, which provide a clue for future prediction of highly efficient MXene-based HER catalysts.
非金属掺杂工程在设计用于电催化析氢的高性能MXene基催化剂方面显示出巨大潜力。我们合理设计了14种非金属原子掺杂的MoCO催化剂，并通过第一性原理计算研究了非金属掺杂对这些结构的热稳定性和析氢反应（HER）催化活性的影响。结果表明，在MoCO表面添加Si、Cl、Br和I等非金属掺杂剂可以有效提高HER活性，使其成为有效的HER催化剂的有希望的候选者。此外，我们通过计算结合能研究了非金属掺杂MoCO的热稳定性，并探讨了结合能变化背后的原因。此外，基于对各种非金属掺杂剂的电子性质分析，解释了由它们调节的HER活性差异的起源。我们发现，掺杂非金属原子的价电子数和巴德电荷耦合是氢吸附强度和HER活性的有效电子描述符，这为未来预测高效的MXene基HER催化剂提供了线索。
