College of Physical Science and Technology, Yangzhou University, Jiangsu, 225009, China.
School of Chemical Sciences, Meritorious Autonomous University of Puebla (BUAP), University City, 72570, Puebla, Mexico.
J Mol Model. 2023 Mar 1;29(3):80. doi: 10.1007/s00894-023-05486-8.
Previous theoretical studies have suggested that two-dimensional (2D) MBene materials might display adequate monatomic catalytic activity for the hydrogen evolution reaction (HER). Recently, a study reported the experimental synthesis of a 2D MBene (MoB), re-defined as boridene, albeit no effort has been devoted to explore the single-atom catalytic activity for HER of this experimentally synthesized 2D material. Therefore, we herein investigate the single-atom HER performance of the boridene. Interestingly, with Mo defects mixed with single Au and Zn atoms shows excellent hydrogen evolution performance, and the change in the Gibbs free energy ([Formula: see text]) value is close to 0 eV, which can even match the performance of Pt-based materials. Through analysis of the charge density difference and density of states, the mechanism affecting the HER performance is explained at the electronic level. This work provides a new direction for the use of the MoB monolayer two-dimensional materials in the field of single-atom catalysis for HER.
This study used the DFT calculations in Vienna ab initio simulation package. The GGA-Perdew-Burke-Ernzerhof functional with DFT-D2 correction is used to describe the exchange-correlation interactions. The projection augmented wave is used with the plane wave cutoff of 500 eV. The convergences of energy and force are 10 eV and 0.01 eV/Å, respectively. A vacuum layer with a height of 20 Å is set in the Z direction. For geometry optimization, self-consistent, and DOS calculations, the k-point grids sampled in Brillouin zones are 3 × 3 × 1, 9 × 9 × 1, and 9 × 9 × 1, respectively. The AIMD simulation is performed in the canonical ensemble (NVT), and the temperature was maintained at 300 K by Nosé-Hoover thermostats with a time step of 2.0 fs.
先前的理论研究表明，二维（2D）MBene 材料可能对析氢反应（HER）表现出足够的单原子催化活性。最近，有一项研究报道了二维 MBene（MoB）的实验合成，重新定义为硼烯，尽管尚未努力探索这种实验合成的二维材料的单原子催化 HER 活性。因此，我们在此研究了硼烯的单原子 HER 性能。有趣的是，Mo 缺陷与单个 Au 和 Zn 原子混合显示出优异的析氢性能，吉布斯自由能变化（[Formula: see text]）值接近 0 eV，甚至可以与基于 Pt 的材料相媲美。通过分析电荷密度差和态密度，从电子水平解释了影响 HER 性能的机制。这项工作为 MoB 单层二维材料在单原子催化 HER 领域的应用提供了新的方向。
本研究使用维也纳从头算模拟包中的 DFT 计算。使用 GGA-Perdew-Burke-Ernzerhof 函数与 DFT-D2 修正来描述交换相关相互作用。采用平面波截止值为 500 eV 的投影augmented wave。能量和力的收敛值分别为 10 eV 和 0.01 eV/Å。在 Z 方向设置了一个高度为 20 Å 的真空层。对于几何优化、自洽和 DOS 计算，布里渊区中的 k 点网格分别采样为 3 × 3 × 1、9 × 9 × 1 和 9 × 9 × 1。AIMD 模拟在正则系综（NVT）中进行，使用 Nosé-Hoover 热库将温度保持在 300 K，时间步长为 2.0 fs。
