Bearing triazine-centered linkers, three primitive metal–organic frameworks (MOFs) with a Zr₆O₄ cluster have been prepared as ZrL1 (without any branch), ZrL2 (with −F), and ZrL3 (with −SCH₃). The electrocatalytic hydrogen evolution reaction (HER) by their pristine and transition metal-loaded (TM-loaded) forms was studied. It was found that the loading of TM ions could enhance the electrocatalytic power of these TM-loaded MOFs in HER, as reflected by their lower overpotentials and smaller Tafel slopes when compared with primitive MOFs. More importantly, the best electrocatalytic HER performance of ZrL3-TM among all TM-loaded MOFs studied in this work highlights the effective housing of TM ions for unambiguous active sites through cooperative coordination by triazinic N and thioether pendants. This work proposes microenvironment regulation of MOFs as an effective strategy to enhance the electrocatalytic activity of MOF materials.

中文翻译：

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金属-有机骨架的微环境调控以锚定过渡金属离子用于电催化析氢反应

带有以三嗪为中心的连接子，具有 Zr ₆ O ₄簇的三种原始金属有机框架 (MOF) 已被制备为 Zr L1（无任何分支）、Zr L2（具有 -F）和 Zr L3（具有 -SCH ₃ ). 研究了其原始和负载过渡金属（TM 负载）形式的电催化析氢反应 (HER)。结果发现，与原始 MOF 相比，TM 离子的负载可以增强这些负载 TM 的 MOF 在 HER 中的电催化能力，这反映在它们较低的过电势和较小的 Tafel 斜率上。更重要的是，Zr L3的最佳电催化 HER 性能- 在这项工作中研究的所有负载 TM 的 MOF 中，TM 突出了通过三嗪 N 和硫醚悬垂物的协同协调，TM 离子有效容纳明确的活性位点。这项工作提出了 MOF 的微环境调节作为提高 MOF 材料电催化活性的有效策略。