Understanding the dynamics changes of the water network at the electrode–solution interface during the hydrogen evolution reaction (HER) process, including how it is doubly regulated by the electrode material and electrolyte pH, and its subsequent effects on the reaction intermediates (H* and OH*), is crucial in electrochemistry. However, relevant studies are limited due to water's its dual role as both a reactant and a solvent. Thus, it is essential to construct an ideal model capable of decoupling the effects of interfacial water action from the surface catalytic HER process. In this study, M‐O atom pairs doped MoSe2 model catalyst is developed to achieve this goal and tailor the water network structure in a double‐layer microenvironment. Combined with molecular dynamics simulations and in situ spectroscopic characterization, correlations between water configuration, the water network, and water dissociation with HER activity are successfully established. This findings reveal that the pH‐dependent hydrogen‐bonding environment, modulated by oxophilic species, exerts a greater influence on acidic HER compared to alkaline media. The optimized Rh,O‐MoSe2‐x catalyst demonstrates exceptional performance in both acid and alkaline electrolytes and shows no activity decay during a PEMWE test at 1.5 A cm−2, making it promising for scalable water electrolyzers.

中文翻译：

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协同M-O双原子对诱导界面水氢键网络提高MoSe2电催化性能

了解析氢反应（HER）过程中电极-溶液界面水网络的动态变化，包括它如何受到电极材料和电解质pH值的双重调节，以及其对反应中间体（H*和 OH*），在电化学中至关重要。然而，由于水具有反应物和溶剂的双重作用，相关研究受到限制。因此，有必要构建一个能够将界面水作用与表面催化 HER 过程的影响分离的理想模型。本研究中，M-O原子对掺杂MoSe2模型催化剂的开发是为了实现这一目标，并在双层微环境中定制水网络结构。结合分子动力学模拟和原位光谱表征，成功建立了水构型、水网络和水解离与 HER 活性之间的相关性。这一发现表明，与碱性介质相比，由亲氧物质调节的 pH 依赖性氢键环境对酸性 HER 的影响更大。优化后的Rh,O-MoSe2-x催化剂在酸性和碱性电解质中均表现出优异的性能，并且在 1.5 A cm 的 PEMWE 测试中没有表现出活性衰减−2，使其成为可扩展的水电解槽的前景。