Currently, lack of ways to engineer specific and well‐defined active sites in zeolitic imidazolate frameworks (ZIFs) limits our fundamental knowledge with respect to the mechanistic details for (photo)electrocatalytic hydrogen evolution reaction (HER). Here, we introduce the open metal sites into ZIFs through the selective ligand removal (SeLiRe) strategy, comprehensively characterize the altered structural and electronic features, and evaluate their role in HER. In‐situ electrochemical analysis and X‐ray absorption spectroscopy reveal the formation of high‐valence HO−Zn−N2 sites through the binding of Zn−N2 with electrolyte hydroxide. The optimal OMS‐ZIF exhibits a low overpotential of 0.41 V to achieve an ampere‐level 1.0 A cm−2 with 120‐hour stability. Theoretical simulations indicate that these active sites accelerate the water molecules activation kinetics, consequently enhancing the efficiency of the Volmer step. This work demonstrates a versatile strategy to introduce highly active catalytic sites in ZIFs, providing new insights into the electrocatalytic mechanism in alkaline media.

中文翻译：

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沸石咪唑酸盐框架中 HO-Zn-N2 活性位点的工程设计，用于增强（光）电催化析氢


目前，缺乏在沸石咪唑酸盐框架 （ZIF） 中设计特定且定义明确的活性位点的方法限制了我们对（光）电催化析氢反应 （HER） 机理细节的基础知识。在这里，我们通过选择性配体去除 （SeLiRe） 策略将开放金属位点引入 ZIFs，全面表征改变的结构和电子特征，并评估它们在 HER 中的作用。原位电化学分析和 X 射线吸收光谱揭示了通过 Zn-N2 与氢氧化电解质结合形成高价 HO-Zn-N2 位点。最佳 OMS-ZIF 表现出 0.41 V 的低过电位，可实现安培级 1.0 A cm-2 和 120 小时的稳定性。理论模拟表明，这些活性位点加速了水分子活化动力学，从而提高了 Volmer 步骤的效率。这项工作展示了一种在 ZIF 中引入高活性催化位点的通用策略，为碱性介质中的电催化机制提供了新的见解。