Atomically dispersed Ru in ZIF-67 as a high-performance HER catalyst: in situ structural evolution and deactivation mechanism elucidation.

IF 10.7 2区材料科学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Materials Horizons Pub Date : 2025-09-04 DOI:10.1039/d5mh01223f

Zhe Liu, Rui Jin, Gui Zhao, Qinshan Tang, Tianrui Kang, Maolin Wang, Jia Liu, Xiaoxiao Huang, Bingrong Guo, Xi Liu, Siwei Li

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Abstract

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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原子分散Ru在ZIF-67中作为高性能HER催化剂：原位结构演变和失活机理的阐明。

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。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

Materials Horizons CHEMISTRY, MULTIDISCIPLINARY-MATERIALS SCIENCE, MULTIDISCIPLINARY

CiteScore

18.90

自引率

2.30%

发文量

306

审稿时长

1.3 months

期刊介绍： Materials Horizons is a leading journal in materials science that focuses on publishing exceptionally high-quality and innovative research. The journal prioritizes original research that introduces new concepts or ways of thinking, rather than solely reporting technological advancements. However, groundbreaking articles featuring record-breaking material performance may also be published. To be considered for publication, the work must be of significant interest to our community-spanning readership. Starting from 2021, all articles published in Materials Horizons will be indexed in MEDLINE©. The journal publishes various types of articles, including Communications, Reviews, Opinion pieces, Focus articles, and Comments. It serves as a core journal for researchers from academia, government, and industry across all areas of materials research. Materials Horizons is a Transformative Journal and compliant with Plan S. It has an impact factor of 13.3 and is indexed in MEDLINE.