Engineering material structures at the atomic level is a promising way to tune the physicochemical properties of materials and optimize their performance in various potential applications. Here, we show that the lithiation-induced amorphization of layered crystalline Pd₃P₂S₈ activates this otherwise electrochemically inert material as a highly efficient hydrogen evolution catalyst. Electrochemical lithiation of the layered Pd₃P₂S₈ crystal results in the formation of amorphous lithium-incorporated palladium phosphosulfide nanodots with abundant vacancies. The structure change during the lithiation-induced amorphization process is investigated in detail. The amorphous lithium-incorporated palladium phosphosulfide nanodots exhibit excellent electrocatalytic activity towards the hydrogen evolution reaction with an onset potential of −52 mV, a Tafel slope of 29 mV dec⁻¹ and outstanding long-term stability. Experimental and theoretical investigations reveal that the tuning of morphology and structure of Pd₃P₂S₈ (for example, dimension decrease, crystallinity loss, vacancy formation and lithium incorporation) contribute to the activation of its intrinsically inert electrocatalytic property. This work provides a unique way for structure tuning of a material to effectively manipulate its catalytic properties and functionalities.

在原子水平上工程材料结构是一种有前途的方法，可以调节材料的物理化学性质并优化其在各种潜在应用中的性能。在这里，我们显示了层状Pd ₃ P ₂ S ₈的锂化诱导非晶化将这种电化学惰性的材料激活为一种高效的析氢催化剂。层状Pd ₃ P ₂ S _8的电化学锂化晶体导致形成具有大量空位的无定形的掺锂锂磷硫化钯纳米点。详细研究了锂化引起的非晶化过程中的结构变化。非晶态结合锂的磷化钯钯纳米点对氢的释放反应具有出色的电催化活性，起始电势为-52 mV，Tafel斜率为29 mV dec ^-1，并且具有出色的长期稳定性。实验和理论研究表明，Pd ₃ P ₂ S ₈的形貌和结构的调整（例如，尺寸减小，结晶度损失，空位形成和锂掺入）有助于其固有惰性的电催化性能的活化。这项工作为材料的结构调整提供了一种独特的方法，可以有效地控制其催化性能和功能。