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引用次数: 0
摘要
尽管沸石咪唑酸框架（ZIF-67）衍生的析氢反应（HER）催化剂普遍存在，但原始ZIF-67的催化潜力仍然被其固有的惰性所掩盖。在这项工作中，我们通过开发一种无退火策略将原子分散的贵金属（Ru， Rh和Pd）植入完整的ZIF-67框架来解决这一差距。值得注意的是，Ru单原子修饰将ZIF-67/CC在10 mA cm-2下的HER过电位降低了252 mV（从331 mV降至79 mV），并将Tafel斜率降低了70%，这代表了原始ZIF-67在HER中最显著的活化。Operando研究结合理论计算揭示了电化学重建途径：在操作过程中，ZIF-67骨架坍塌成Co(OH)2，而Ru原子聚集成纳米颗粒，导致相偏析。这种转变过度加强了氢的吸附，最终导致性能下降。我们的工作建立了单原子工程作为一种有效的方法来解锁原始mof的潜在活性，同时揭示它们在阴极条件下的重建行为。
Atomically dispersed Ru in ZIF-67 as a high-performance HER catalyst: in situ structural evolution and deactivation mechanism elucidation.
Despite the prevalence of zeolitic imidazolate framework (ZIF-67)-derived catalysts for the hydrogen evolution reaction (HER), the catalytic potential of pristine ZIF-67 remains obscured by its inherent inertness. In this work, we address this gap by developing an annealing-free strategy to implant atomically dispersed noble metals (Ru, Rh, and Pd) into the intact ZIF-67 framework. Remarkably, Ru single-atom modification reduces the HER overpotential of ZIF-67/CC by 252 mV at 10 mA cm-2 (from 331 mV to 79 mV) and slashes the Tafel slope by 70%, representing the most significant activation of pristine ZIF-67 reported for the HER. Operando studies combined with theoretical calculations uncover an electrochemical reconstruction pathway: during operation, the ZIF-67 skeleton collapses into Co(OH)2, while Ru atoms aggregate into nanoparticles, causing phase segregation. This transformation excessively strengthens hydrogen adsorption, ultimately degrading performance. Our work establishes single-atom engineering as an effective approach to unlock the latent activity of pristine MOFs while revealing their reconstruction behavior under cathodic conditions.
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