PtSe₂, an emerging two-dimensional (2D) transition metal dichalcogenide (TMD), is a promising catalyst for the hydrogen evolution reaction (HER). Herein, we investigated the fundamental mechanism underlying the layer-dependent catalytic activity of PtSe₂ via first-principle calculations and demonstrated that interlayer interaction facilitates the catalytic activity by modifying the frontier orbitals of intact basal plane and anion (selenide, Se) vacancy of 2D-PtSe₂. The interlayer interaction promotes the catalytic activity by strengthening the bonding between atomic hydrogen and the surface of 2D-PtSe₂ through altering the electronic structure of the topmost PtSe₂ catalytic layer. We also conducted kinetic simulation to reveal the dominant reaction mechanism underlying the HER on both the basal plane and anion vacancy of different number of layer. The results manifested that the dominant reaction mechanism alters when the number of layer increases from one to two, which is in correlation with the enhancement of the bonding between the hydrogen adatom and PtSe₂ catalytic surface from interlayer interaction. Our study demonstrated the synergistic effect of interlayer interaction on HER on 2D-PtSe₂ catalyst.

中文翻译：

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层间相互作用诱导二维 PtSe2 析氢反应的层依赖性催化活性

PtSe ₂是一种新兴的二维 (2D) 过渡金属二硫属化物 (TMD)，是一种很有前途的析氢反应 (HER) 催化剂。在此，我们通过第一性原理计算研究了 PtSe ₂层依赖性催化活性的基本机制，并证明层间相互作用通过修改完整基面的前沿轨道和二维阴离子（硒化物，Se）空位来促进催化活性。 -PtSe ₂。层间相互作用通过改变最顶层 PtSe ₂的电子结构来加强原子氢与 2D-PtSe ₂表面之间的键合，从而促进催化活性催化层。我们还进行了动力学模拟，以揭示 HER 在基面和不同层数的阴离子空位上的主要反应机制。结果表明，当层数从1层增加到2层时，主要反应机制发生变化，这与氢吸附原子与PtSe ₂催化表面之间的键合通过层间相互作用增强有关。我们的研究证明了层间相互作用对 2D-PtSe ₂催化剂上的 HER 的协同作用。