The continuous quest of finding optimum catalysts for photo‐electrocatalytic (PEC) water splitting has been revolving around 2D ultrathin materials because of the fact of exploiting both the surface area. In this work, a threefold impact is envisaged route to enhance the activity both in terms of hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in the emerging Zirconium Tri‐sulfides (ZrS3) based pseudo‐monolayers. Due to the unique and distinct electronic properties of the tri‐chalcogenide systems as compared to the di‐chalcogenide counterpart of Zirconium, one could afford to explore the implications of not only single‐atom functionalization and vacancy defect, but also the external strain to expedite the bifunctional catalytic activity in this promising material. Rigorous electronic structure calculations have been performed for the mentioned threefold effect on not only the band‐edge alignment, but going beyond to it by further constructing the reaction coordinate mapping corresponding to HER and OER mechanism. The repercussion of external strain in addition to the single atom functionalization and vacancy defect on the adsorption free energies of the prime intermediates of HER and OER reaction has been further correlated with the work function variation in this pseudo‐monolayer system.

中文翻译：

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对锆基三硫属化物伪单层作为新兴的分解水超薄催化剂的反应坐标映射的三重影响


由于利用二维超薄材料的表面积，寻找光电催化 （PEC） 分解水最佳催化剂的不断追求一直围绕着 2D 超薄材料展开。在这项工作中，设想了三重影响途径，以增强新兴的基于三硫化锆 （ZrS3） 的伪单层中的析氢反应 （HER） 和析氧反应 （OER） 的活性。由于与锆的双硫属化物系统相比，三硫属化物系统具有独特而鲜明的电子性质，因此人们不仅可以探索单原子功能化和空位缺陷的影响，还可以探索加速这种有前途的材料中双功能催化活性的外部应变的影响。已经对上述三重效应进行了严格的电子结构计算，不仅对能带-边缘对齐，而且通过进一步构建对应于 HER 和 OER 机制的反应坐标映射来超越它。除了单原子官能化和空位缺陷外，外部应变对 HER 和 OER 反应的初级中间体的吸附自由能的影响进一步与该伪单层系统中的功函数变化相关。