单原子ru触发晶格氧氧化还原机制增强酸性水氧化

IF 14.4 1区化学 Q1 CHEMISTRY, MULTIDISCIPLINARY

Journal of the American Chemical Society Pub Date : 2025-05-15 DOI:10.1021/jacs.5c05752

Menghui Qi, Xiangbowen Du, Xiaoyun Shi, Suwen Wang, Bing Lu, Jiadong Chen, Shanjun Mao, Hao Zhang, Yong Wang

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引用次数: 0

摘要

激活氧阴离子氧化还原是开发质子交换膜水电解槽（PEMWE）高活性析氧反应（OER）电催化剂的一条有前景的途径。在这里，我们设计了一个晶格限制的Ru单原子分散在层状氧化锰（MnO2）阳离子位点上。强的Ru-O键诱导o2p带向上移动，增强了金属-氧共价，使OER机制向晶格氧氧化途径转变，活性增加。原位光谱表征结合密度泛函理论（DFT）计算表明，从Mn到Ru的电子转移减轻了MnO6八面体结构内的Jahn-Teller效应，稳定了晶格。层状的Ru/MnO2结构也促进了氧气空位的快速补充，防止结构崩溃。结果，优化后的Ru/MnO2电催化剂在0.5 M H2SO4中，在10 mA cm-2条件下的OER过电位仅为179 mV，并且在100 mA cm-2条件下具有超过1000小时的耐久性。此外，基于Ru/ mno2的PEM器件只需要1.71 V就能达到1 A cm-2，并且在500 mA cm-2下显示出500小时的耐久性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Single-Atom Ru-Triggered Lattice Oxygen Redox Mechanism for Enhanced Acidic Water Oxidation

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Single-Atom Ru-Triggered Lattice Oxygen Redox Mechanism for Enhanced Acidic Water Oxidation

Activating the oxygen anionic redox presents a promising avenue for developing highly active oxygen evolution reaction (OER) electrocatalysts for proton-exchange membrane water electrolyzers (PEMWE). Here, we engineered a lattice-confined Ru single atom dispersed on a lamellar manganese oxide (MnO₂) cation site. The strong Ru–O bond induced an upward shift in the O 2p band, enhancing metal–oxygen covalency and reshaping the OER mechanism toward lattice oxygen oxidation pathway with increased activity. In situ spectral characterization combined with density functional theory (DFT) calculations revealed that electron transfer from Mn to Ru alleviates the Jahn–Teller effect within the MnO₆ octahedral structure, stabilizing the lattice. The layered Ru/MnO₂ architecture also promotes the rapid replenishment of oxygen vacancies, preventing structural collapse. As a result, the optimized Ru/MnO₂ electrocatalyst achieves an OER overpotential of only 179 mV at 10 mA cm^–2 in 0.5 M H₂SO₄, along with exceptional durability over 1000 h at 100 mA cm^–2. Moreover, the Ru/MnO₂-based PEM device requires only 1.71 V to reach 1 A cm^–2 and shows a durability of 500 h at 500 mA cm^–2.

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来源期刊

Journal of the American Chemical Society 化学-化学综合

CiteScore

24.40

自引率

6.00%

发文量

2398

审稿时长

1.6 months

期刊介绍： The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.