铬驱动的高熵氧化物晶格氧活化用于高效析氧反应

doi:10.1016/S1872-2067(26)65069-3

摘要/Abstract

摘要： 电解水制氢作为实现可再生能源高效转化与储存的关键技术, 其整体效率常受限于阳极析氧反应缓慢的动力学过程. 因此, 开发兼具高活性与长期稳定性的非贵金属催化剂仍是需要突破的核心挑战. 近年来, 高熵材料因多元素协同效应与熵稳定特性, 在电催化领域展现出显著优势. 然而, 在高熵体系中实现电子结构的精准调控, 并在反应过程中可控诱导表面重构以激活晶格氧仍存在难点. 研究表明, 引入高价金属(例如Mo, W, V, Cr)可通过调节金属-氧相互作用并诱导电荷再分配, 促进晶格氧参与反应. 然而高价组分也更易发生溶出并引发结构失稳, 进而影响催化剂的长期稳定性. 因此, 精确调节高价组分的引入是构建长寿命的电催化材料的重要设计思路.
本文采用水热-煅烧法在泡沫镍上原位构建出一种自支撑高熵尖晶石氧化物催化剂(FeNiMoMnCr)₃O₄/NF. 该催化剂呈现单相尖晶石结构, 并表现出显著的晶格畸变与结构缺陷, 从而提供了更大的电化学活性面积和快速的电子传输通道. 在碱性电解液中, (FeNiMoMnCr)₃O₄/NF展现出优异的催化活性与稳定性: 仅需248 mV过电位即可达到100 mA cm^-2的电流密度, 并在高电流密度下仍能维持长期稳定运行. 机理研究表明, 高价金属Cr对该高熵氧化物体系的催化行为具有双重调控作用: 一方面, Cr诱导的电子结构调控有效提高并稳定了Ni/Fe活性位点的高氧化态, 构建出更有利于反应中间体吸附与演化的表面氧化环境, 同时显著加速了界面电荷转移动力学; 另一方面, Cr诱导的电荷重分布促使Mo物种在近表面区域以可溶性MoO₄^2-形式选择性溶出; 该过程伴随大量氧空位的原位生成, 进而触发可控的表面重构, 形成热力学更稳定的金属羟基氧化物活性相. 多种表征结果表明, 反应过程中存在与晶格氧参与相关的动力学特征. 结合pH依赖性与探针实验, 发现(FeNiMoMnCr)₃O₄/NF相较于传统的AEM机制表现出更强的LOM路径倾向.密度泛函理论计算进一步从原子尺度上揭示, Cr的引入导致金属d带中心下移, 优化了M-O相互作用并削弱了晶格氧的束缚, 显著降低了晶格氧活化能垒, 使OER路径从热力学上更倾向于沿LOM路径进行.
综上, 本工作阐明了(FeNiMoMnCr)₃O₄/NF中Cr主导的电子结构调控与Mo诱导的可控表面重构之间的协同作用, 促进晶格氧参与反应, 从而实现了高催化活性与长期稳定性的统一. 本研究为利用高价金属协同调控电子结构与表面演化来设计高效OER电催化剂提供了新的设计思路.

关键词: 高价金属, 高熵氧化物, 析氧反应, 吸附质演化机制, 晶格氧氧化机制

Abstract: High-entropy oxides (HEOs) have emerged as promising electrocatalysts for the oxygen evolution reaction (OER) due to their unique tunable electronic structures and multi-site synergistic effects. Triggering the lattice oxygen oxidation mechanism (LOM) is considered an effective strategy to overcome the intrinsic limitations of the conventional adsorbate evolution mechanism (AEM). However, promoting the shift from AEM to LOM requires highly oxidized metal centers. Herein, we report on the rational design and synthesis of a (FeNiMoMnCr)₃O₄/NF HEO catalyst, wherein the introduction of high-valent Cr species serves as an electronic modulator to facilitate lattice-oxygen activity. The resulting catalyst exhibits a low overpotential of 248 mV at 100 mA cm^-2 in 1 mol L^-1 KOH and demonstrates excellent operational durability over 100 hours under high current densities. Comprehensive investigations, including pH-dependent electrochemical measurements, radical trapping experiments, and density functional theory calculations, reveal that the incorporation of Cr induces the in-situ formation of oxygen vacancies, thereby activating lattice-oxygen participation in the OER. This activation breaks the conventional linear scaling relationships associated with AEM, leading to enhanced reaction kinetics. This study provides mechanistic insights into how high-valent metals regulate electronic structure and lattice oxygen reactivity in HEOs, offering a feasible design strategy for advanced OER electrocatalysts based on the LOM pathway.

Key words: High-valent metals, High-entropy oxides, Oxygen evolution reaction, Adsorbate evolution mechanism, Lattice oxygen oxidation mechanism

王湫溶, Fozia Sultana, 李仁坤, 方燕, Selvi Mushina, 谭明务, 李彤彤, 李仁宏. 铬驱动的高熵氧化物晶格氧活化用于高效析氧反应[J]. 催化学报, DOI: 10.1016/S1872-2067(26)65069-3.

Qiurong Wang, Fozia Sultana, Renkun Li, Yan Fang, Selvi Mushina, Mingwu Tan, Tongtong Li, Renhong Li. Chromium-driven lattice oxygen activation in high-entropy oxide for efficient oxygen evolution reaction[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)65069-3.

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