硅酸盐学报2024，Vol.52Issue(6)：1861-1872,12.DOI:10.14062/j.issn.0454-5648.20240019
质子交换膜电解水制氢阳极析氧反应催化剂的研究进展
Research Progress on Anodic Oxygen Evolution Catalysts for Proton Exchange Membrane Water Electrolysis
摘要
Abstract
Hydrogen is considered as a clean energy carrier in the global energy transition and development due to its high energy density(142 kJ·g-1),cleanliness,and sustainability.At present,hydrogen is mainly produced through steam reforming of fossil fuels under harsh conditions,which are restrained by the complex operation and emission of carbon dioxide.Hydrogen production through water electrolysis is an effective and clean method for generating high-purity hydrogen using renewable energy sources without pollution.The electricity utilized in this process is obtained from renewable sources such as solar,hydropower,wind,and nuclear energy,enabling carbon-free and green hydrogen production.With the advancements in renewable energy generation technologies and electrolysis cell techniques over the past a few decades,the production of green hydrogen through water electrolysis is flourishing.Based on the type of electrolyte and operating conditions,water electrolysis technologies are primarily classified into four categories,i.e.,alkaline water electrolysis(AWE),proton exchange membrane(PEM)water electrolysis,anion exchange membrane(AEM)water electrolysis,and solid oxide electrolysis cell(SOEC)water electrolysis.PEM water electrolysis technology,distinguished by its prompt start-up and power modulation capabilities,is currently a sole technology capable of producing high-purity hydrogen coupled with renewable energy generation. This review firstly introduced several major hydrogen production technologies,emphasizing the advantages of PEM water electrolysis technology.Subsequently,we represented the latest developments in iridium(Ir)and ruthenium-based(Ru)oxygen evolution reaction(OER)electrocatalysts in acidic electrolyte,and summarized the strategies for developing acidic OER electrocatalysts with a high performance.Finally,this review highlighted the challenges associated with acidic OER electrocatalysts and outlined prospective avenues for future research. The electrolysis efficiency of PEM water electrolysis primarily depends on the overpotentials at the anode and cathode.Compared to the hydrogen evolution reaction involving a 2-electron transfer step at the cathode,the OER at the anode involving a 4-electron transfer step is considered as a rate-limiting step.The anodic overpotential is significantly higher than the cathodic overpotential,typically requiring an overpotential of 200-500 mV to drive a current density of 10 mA·cm-2.Unfortunately,the choice of anodic catalytic materials is greatly limited by the strong acid characteristics and the high anodic electrolysis voltage,which demands that the anodic catalysts can operate stably in a strong acid and oxidizing environment. According to the OER activity and stability of different metals,the precious metal iridium dioxide(IrO2)is commercially employed as a benchmark anodic catalyst of PEM electrolysis cells.However,Ir is one of the most expensive metals in the world.For Ir-based catalysts,researchers focus on reducing the Ir content in the catalyst,but the Ir content still generally exceeds 40%(in mass fraction).Therefore,developing efficient,stable,and low-cost non-Ir-based OER catalysts is also important in the development of PEM water electrolysis technology.Compared to Ir,metal Ru possesses a higher OER activity and is only one-tenth the price of Ir,that has a significant potential for application in PEM water electrolysis.In recent years,various types of Ru-based catalysts are developed in the acidic OER field,showing a promising potential as substitutes for Ir-based catalysts.Therefore,this review could provide a detailed overview of the research progress on Ir-and Ru-based catalysts in PEM water electrolysis for hydrogen production. Summary and Prospects The development of PEM water electrolysis for hydrogen production is currently flourishing,yet achieving a large-scale commercialization still requires overcoming several technical challenges.The extensive research on Ir-and Ru-based materials notably advances the development of highly active and stable OER catalysts,playing a crucial role in designing commercially viable PEM water electrolysis technology.Despite significant advancements in the research of such OER catalysts,there are still some issues that need to be addressed.The challenge of Ir-based catalysts remains in reducing the Ir content in catalysts and the Ir loading in membrane electrodes,while ensuring high activity and stability.Developing low-cost metal-supported catalysts with high stability and conductivity is an effective approach to reduce Ir usage.Metal oxides of specific elements(i.e.,Ti,Ta,Nb,W,and Mo)can stably exist under strong acidic and oxidizing conditions,demonstrating a good corrosion resistance,which is the potential candidates for substrates.Furthermore,enhancing the continuity of Ir-based catalysts and forming a dense conductive layer can improve the conductivity of these metal oxide supports.Enhancing the stability of Ru-based catalysts is a challenge to commercial application.Reducing the proportion of unstable Ru elements through supported or solid solution-type Ru-based catalysts can stabilize catalysts under acidic OER conditions.Suppressing the lattice oxygen participation in OER can prevent the structural collapse of Ru-based catalysts,and the mechanisms of Ru self-deposition phenomenon are required a further exploration.Finally,it is important to establish a unified and comprehensive testing standard system for assessing the activity of catalysts in the PEM water electrolysis,particularly under high current density conditions.关键词
质子交换膜电解水制氢/析氧反应/铱基电催化剂/钌基电催化剂Key words
proton exchange membrane water electrolysis/oxygen evolution reaction/iridium-based electrocatalysts/ruthenium-based electrocatalysts分类
化学化工引用本文复制引用
曹雪洁,杨磊,徐光宇,焦丽芳..质子交换膜电解水制氢阳极析氧反应催化剂的研究进展[J].硅酸盐学报,2024,52(6):1861-1872,12.基金项目
国家重点研发计划(2021YFB4000200)中国博士后科学基金(2023M741810) （2021YFB4000200）
