Pt-Ru-Ir三元合金在40g/LNaF介质中HOR行为研究
首发时间:2026-11-10
摘要:针对电化学溶解氢传感器铂电极对氢的吸附仍然偏强、铍青铜基底上贵金属敏感膜结合力差且易受铜、铍溶出污染的问题,本文采用脉冲电沉积法在铍青铜基底上制备了不同Pt/Ru/Ir摩尔比的Pt-Ru-Ir三元合金敏感膜,并以纯Pt膜为对照,系统研究了其在40 g/L NaF介质(pH≈9.7)中的氢气氧化反应(HOR)性能。借助X射线衍射(XRD)、扫描电子显微镜与能谱(SEM/EDS)表征了膜的晶相结构、微观形貌与元素分布,并通过循环伏安(CV)、旋转圆盘电极线性扫描伏安(RDE-LSV)结合Koutecky-Levich(K-L)、微极化区Butler-Volmer拟合与Tafel分析,定量评价合金化对HOR动力学的提升。结果表明:Ir的引入可进一步细化晶粒并引起(111)衍射峰高角侧偏移,晶格畸变加剧;在所考察的六种配比中,Pt:Ru:Ir = 4:1:1敏感膜兼具细小均匀的颗粒、致密的膜层与适中的晶格畸变,HOR性能最优。机理上,HOR增强源于Ru、Ir诱导的Pt d带中心下移(电子效应)、Ru/Ir亲氧位点邻近供给OH*(双功能协同)以及晶粒细化与(111)择优取向(几何效应)的三重耦合。本研究为铍青铜基底上低成本、高性能三元合金敏感膜的设计及其在溶解氢传感器中的应用提供了实验依据。
关键词: 溶解氢传感器 氢气氧化反应 Pt-Ru-Ir 合金 铍青铜 脉冲电沉积
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Study on the HOR behavior of Pt-Ru-Ir ternary alloy in 40g/L NaF medium
Abstract:To address the issues of strong hydrogen adsorption on platinum electrodes in electrochemical dissolved hydrogen sensors, poor adhesion of noble metal sensing films on beryllium bronze substrates, and contamination from leaching copper and beryllium, this study employed pulse electrodeposition to fabricate ternary Pt-Ru-Ir alloy sensing films with various molar ratios of Pt/Ru/Ir on a beryllium bronze substrate. Pure Pt film was used as a control, and their performance in hydrogen oxidation reaction (HOR) was systematically investigated in a 40 g/L NaF medium (pH ≈ 9.7). The crystal structure, micro-morphology, and elemental distribution of the films were characterized using X-ray diffraction (XRD), scanning electron microscopy combined with energy-dispersive spectroscopy (SEM/EDS). Cyclic voltammetry (CV), rotating disk electrode linear sweep voltammetry (RDE-LSV), along with Koutecky-Levich (K-L) analysis, Butler-Volmer fitting in the low polarization region, and Tafel analysis were applied to quantitatively evaluate the enhancement of HOR kinetics by alloying. Results showed that introducing Ir further refined grain size and caused a high-angle shift of the (111) diffraction peak, increasing lattice distortion. Among the six compositions examined, the Pt:Ru:Ir = 4:1:1 film exhibited optimal HOR performance due to its fine and uniform particles, dense film structure, and moderate lattice distortion. Mechanistically, the enhanced HOR activity arises from a synergistic coupling of three effects: downshift of the Pt d-band center induced by Ru and Ir (electronic effect), supply of OH* via oxygen-affinity sites of Ru/Ir (bifunctional cooperation), and grain refinement with preferential (111) orientation (geometric effect). This work provides experimental guidance for designing low-cost, high-performance ternary alloy sensing films on beryllium bronze substrates and their application in dissolved hydrogen sensors.
Keywords: dissolved hydrogen sensor hydrogen oxidation reaction Pt-Ru-Ir alloy beryllium bronze pulsed electrodeposition
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Pt-Ru-Ir三元合金在40g/LNaF介质中HOR行为研究
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