碱水电解用NiPOH-RuO_(2)催化电极的析氢析氧反应研究  

Study on the HER and OER catalytic properties of NiPOH-RuO_(2) for alkaline water electrolysis

作　　者：李勇 朱思达 赵坤 邵艳群[2,3] Li Yong;Zhu Sida;Zhao Kun;Shao Yanqun(Fujian Inspection and Research Institute for Product Quality,Fuzhou 350002,China;College of Materials Science&Engineering,Fuzhou University,Fuzhou 350108,China;College of Electrical Engineering and Automation,Fuzhou University,Fuzhou 350108,China)

机构地区：[1]福建省产品质量检验研究院,福建福州350002 [2]福州大学材料科学与工程学院,福建福州350108 [3]福州大学至诚学院,福建福州350108

出　　处：《电镀与精饰》2024年第12期10-18,共9页Plating & Finishing

基　　金：福建省自然科学基金资助项目(2019J01230)。

摘　　要：电解水制氢用电极材料对析氢和析氧反应起着重要的作用。羟基亚磷酸镍(Ni_(11)(HPO_(3))_(8)(OH)_(6),缩写为Ni POH)具有多孔结构和丰富的活性中心备受关注,然而其低电导率以及相应的缓慢电子转移速率限制了其电催化性能。添加高导电性和活性物质提升电子传输效率和反应动力学,有望增强其在电解水过程中的催化活性与持久性。本文采用水热法在泡沫镍上原位生长Ni POH-x at.%RuO_(2)电极材料,采用X射线衍射仪(XRD)、X射线光电子能谱仪(XPS)、扫描电子显微镜(SEM)、线性扫描伏安法(LSV)和计时电位法(CP)等研究Ru O_(2)含量对电极微观形貌及其电化学性能的影响,辅以第一性原理计算探讨Ni POH-x at.%RuO_(2)在全解水过程中的性能。结果表明:添加Ru O_(2)可改变Ni POH微球的形貌,使其具有更大比表面积。Ni元素是由Ni2+和Ni3+组成,Ru由Ru^(3+)和Ru^(4+)组成。Ru掺杂使Ni POH的电子转移能垒降低,费米能级附近电子密度增大。当电流密度为10 m A/cm^(2)时,Ru O_(2)的加入明显降低了析氢过电位,NiPOH-3 at.%RuO_(2)的析氢过电位最低为93 mV,而Ni POH电极为161 mV,Ni POH-3 at.%RuO_(2)电极的析氧Tafel斜率同期达到最小。Ni POH-x at.%RuO_(2)电极的析氢过程是以Heyrovsky步骤为主的Volmer-Heyrovsky控制反应。Electrode materials for water electrolysis play an important role in hydrogen evolution and oxygen evolution.Nickel hydroxyphosphite(Ni_(11)(HPO_(3))_(8)(OH)_(6),abbreviated as NiPOH)has more porous structures and abundant active sites,however,its low conductivity with a corresponding slow electron transfer rate limits its electrocatalyticproperties.The addition of highly conductive and active substances can improve the electron transmission efficiency and reaction kinetics,which is expected to enhance its catalytic activity and stability during the process of water electrolysis.In this paper,the NiPOH-x at.% RuO_(2) electrodes was grown in situ on the nickel foam by a hydrothermal method.X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),scanning electron microscope(SEM),linear sweep voltammetry(LSV)and Chronopotentiometry(CP)wereused to study the influence of RuO_(2) content on the micromorphology and electrochemical properties of the prepared electrodes.The performance of NiPOH-x at.% RuO_(2) during the whole process of electrolyzing water was explored by the First-principles calculations.It’s shown that the RuO_(2) could change the morphology,and make the microspheres have a larger specific surface area.The Ni element was composed of Ni^(2+) and Ni^(3+),and Ru consisted of Ru^(3+) and Ru^(4+).The energy barriers for electron transfer were decreased after doping RuO_(2) to NiPOH,and the electron density near the Fermi level increased.When the current density was 10 mA/cm^(2),the hydrogen overpotential was significantly reduced with the addition of RuO_(2) and the hydrogen overpotential of NiPOH-3 at.% RuO_(2) could reach the minimum of 93 mV,while the hydrogen overpotential of the NiPOH electrode was 161 mV.The Tafel slope of the oxygen evolution of NiPOH-3 at.% RuO_(2) electrode could be the minimum at the same time.The hydrogen evolution process of the NiPOH-x at.% RuO_(2) electrode was a Volmer-Heyrovsky controlled reaction dominated by the Heyrovsky step.

关 键 词：Ru O_(2) Ni11(HPO_(3))_(8)(OH)_(6) 第一性原理计算 电解水 析氢反应 析氧反应 

分 类 号：TG172.3[金属学及工艺—金属表面处理]