金属-掺杂氧化铈体系H_(2)/CO电化学反应机理研究进展  

Research progress of H_(2)and CO electrochemical oxidation mechanisms in metal and doped ceria system

作　　者：林梅洁 米烁东 包成 LIN Meijie;MI Shuodong;BAO Cheng(School of Energy and Environmental Engineering,University of Science and Technology Beijing,Beijing 100083,China;Beijing Huairou Laboratory,Beijing 101400,China)

机构地区：[1]北京科技大学能源与环境工程学院,北京100083 [2]北京怀柔实验室,北京101400

出　　处：《化工进展》2024年第S01期209-224,共16页Chemical Industry and Engineering Progress

基　　金：国家重点研发计划(2021YFB2500401);国家自然科学基金面上项目(51976009)。

摘　　要：应用金属-稀土元素掺杂氧化铈阳极是固体氧化物燃料电池(SOFC)中低温化的重要策略之一。掺杂氧化铈自身的混合离子电子导体(MIEC)特性拓展了反应界面,也使得反应机理更为复杂。本文综述了金属-掺杂氧化铈体系H_(2)和CO的电化学氧化反应机理,指出在H_(2)电化学反应中类Ni/YSZ型H溢出机理占主导地位;对于CO电化学反应,结合在CO催化反应中主要的Marse-van Krevelen(MvK)机制和CO_(2)电化学还原反应逆过程,预测其电荷转移步骤主要发生在氧空位形成和CO_(2)形成反应。在MIEC型反应机理中,H_(2)氧化反应路径的主要区别在于H_(2)解离吸附位点的不同;而CO氧化反应路径根据吸附位点可分为与CeO_(2)晶格氧反应直接生成CO_(2)或者生成碳酸盐中间体,电荷转移步骤为碳酸盐形成和CO_(2)形成反应。综上,H_(2)电化学氧化以H溢出为主,CO电化学氧化的主导反应机理尚不明确,亟待深入研究。本文工作对明晰H_(2)和CO乃至H_(2)/CO混合燃料体系类Ni/YSZ型和MIEC型反应机理具有一定的指导意义。The application of metal-rare earth doped ceria anode is one of the most important strategies for the moderate and low temperature solid oxide fuel cells(SOFC).The mixed ionic and electronic conductor(MIEC)characteristic of doped ceria expands the reaction interface and complicates the reaction mechanism.This article reviewed the electrochemical oxidation mechanism of H_(2)and CO in metal and doped ceria system.It was pointed out that the Ni/YSZ-like H spillover mechanism was dominant in the H_(2)electrochemistry.For the CO electrochemistry,combined with the predominant Marsevan Krevelen(MvK)type mechanism in the CO catalytic reaction and the reverse process of the CO_(2)electrochemical reduction reaction,it was predicted that the charge transfer step mainly occurred in the oxygen vacancy formation and the CO_(2)formation reactions.In the MIEC type reaction mechanism,the main difference in the H_(2)oxidation reaction pathways was the difference of H_(2)dissociation adsorption site.The CO oxidation reaction pathway can be categorized into two modes based on the adsorption site:directly reacting with CeO_(2)lattice oxygen to generate CO_(2)or generating carbonate intermediates,and the charge transfer step involved carbonate formation and CO_(2)formation reactions.In summary,H_(2)electrochemical oxidation was dominated by H spillover,while the dominant reaction mechanism of CO electrochemical oxidation was still unclear and required further study.This article was instructive for clarifying the reaction mechanisms of Ni/YSZ and MIEC types in H_(2)and CO,as well as H_(2)/CO hybrid fuel systems.

关 键 词：固体氧化物燃料电池 电化学 氧化 反应机理 混合离子电子导体 Ce基氧化物 催化 

分 类 号：TK91[动力工程及工程热物理]