钌氧化物表面阴离子介导的动态界面自由水富集微环境助力高效酸性氧析出反应

doi:10.1016/S1872-2067(26)64993-5

摘要/Abstract

摘要： 质子交换膜水电解(PEMWE)技术因其高电流密度、快速响应能力以及高纯度气体输出等优势, 被视为是制备绿氢以及推动可持续能源发展的重要途径. 然而, 其阳极析氧反应(OER)在酸性环境中面临动力学缓慢和催化剂稳定性差的双重挑战, 这限制了PEMWE的进一步应用. 近期研究表明, 酸性OER催化剂的动力学缓慢可能是源于催化反应物(表面自由水分子)补充迟缓, 因此调控动态界面水结构, 构建自由水富集的微环境是一种高效的改性策略. 但是受限于催化剂表面的相对惰性, 该策略的实现仍具挑战.
本文合成了由非金属元素磷(P)调控的Ru基催化剂(记为RuP_0.4O_x), 并系统研究了其在酸性OER反应中的性能与机理. 通过X射线光电子能谱与傅里叶变换红外光谱等测试对催化剂结构进行解析; 结果表明, 掺入的P元素以Ru-O-P的局部配位结构形式存在于催化剂晶格中, 同时在催化剂表面形成了PO₄^3‒阴离子修饰基团. 在0.5 mol L^‒1 H₂SO₄电解液中的电化学测试结果表明, 该催化剂在10 mA cm^‒2电流密度下仅需200 mV过电势, 比商业RuO₂催化剂降低了约103 mV, 塔菲尔斜率低至42.45 mV dec^-1, 并能在10 mA cm^-2电流密度下稳定运行超过500 h, 展现出优异的酸性OER电催化性能. 鉴于水分子解离是酸性OER的初始步骤, 本文利用原位衰减全反射表面增强红外吸收光谱对OER过程中催化剂界面水结构变化进行了分析; 结果表明, RuP_0.4O_x催化剂中的Ru-O-P局部结构与表面PO₄^3‒基团间的协同作用能够调控界面水分子的氢键网络, 形成自由水富集的界面微环境, 从而保障了反应物的充足与快速补充. 密度泛函理论计算从理论层面揭示了催化剂稳定性增强的本质原因, Ru-O-P局部结构与表面PO₄^3‒修饰之间的协同作用调控了O p带中心位置, 抑制OER过程中晶格氧的参与, 从而降低Ru-O-P共价性, 增强了催化剂在酸性环境中的结构稳定性. 同时, 理论计算以及动力学同位素效应实验进一步揭示了表面PO₄^3‒基团在反应机制中发挥的关键作用, 能够促进质子向其邻近氧位点的转移, 促使催化剂实现一种全新的PO₄^3‒协助的吸附质演化机制. 该机制加速了去质子化过程, 显著降低了反应能垒, 加快了反应动力学.
综上, 本文成功制备了具备高性能的RuO₂基催化剂, 证实了通过调控催化反应界面微环境提升电催化性能这一策略的有效性, 同时为开发兼具高活性和优异稳定性的酸性OER电催化剂提供了具体设计策略与理论指导.

关键词: 二氧化钌, 酸性析氧反应, 界面水结构, 表面阴离子改性

Abstract: Recent studies have revealed that the slow kinetics of active free water molecule replenishment on the surface of catalyst can be the potential cause responsible for the sluggish reaction kinetics of oxygen evolution reaction (OER) under acidic electrolyte. However, engineering the dynamic interfacial water structure to form the free water enriched microenvironment has rarely been implemented due to the relatively inherent inert catalyst surface. Herein, we demonstrate that surface modification of ruthenium dioxide (RuO₂) with PO₄^3- anions (RuP_0.4O_x) can effectively regulate the free water enriched microenvironment and significantly enhance the acidic OER performance. Experimental results including operando attenuated total reflectance surface-enhanced infrared absorption spectroscopy reveal that the introduction of PO₄^3- species can manipulate the interfacial water structure, resulting in a free-H₂O-enriched interfacial environment, which is conducive to the continuous supply of reactants. Moreover, theoretical studies indicate that the surface modified PO₄^3- could facilitate proton transfer to the oxygen sites of the PO₄^3- group, enabling a PO₄^3--assisted adsorption evolution mechanism with enhanced reaction kinetics. Consequently, the obtained RuP_0.4O_x catalyst, featuring a Ru-O-P local environment and modified by surface PO₄^3- anions, displays a low overpotential of 200 mV at 10 mA cm^-2 and operates stably for 500 h during the acidic OER process.

Key words: Ruthenium dioxide, Acidic oxygen evolution reaction, Interfacial water structure, Surface anion modification

吴立清, 黄文霞, 赵冰冰, 蔡苹, 罗威. 钌氧化物表面阴离子介导的动态界面自由水富集微环境助力高效酸性氧析出反应[J]. 催化学报, DOI: 10.1016/S1872-2067(26)64993-5.

Liqing Wu, Wenxia Huang, Bingbing Zhao, Ping Cai, Wei Luo. Surface anions-mediated dynamic interfacial free water enriched microenvironment on RuO₂ for efficient acidic oxygen evolution[J]. Chinese Journal of Catalysis, DOI: 10.1016/S1872-2067(26)64993-5.

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