Pt基和Pd基催化剂催化甲酸电化学氧化机制的理论研究

项目名称： Pt基和Pd基催化剂催化甲酸电化学氧化机制的理论研究

项目编号： No.21273131

项目类型： 面上项目

立项/批准年度： 2013

项目学科： 数理科学和化学

项目作者： 张冬菊

作者单位： 山东大学

项目金额： 78万元

中文摘要： 直接甲酸燃料电池（DFAFCs）被认为是最有应用前景的新型能源系统,甲酸的电化学氧化效率是决定该类电池性能的关键因素.寻找对甲酸氧化催化活性好、抗中毒能力强的催化剂是DFAFCs研究中迫切需要解决的关键科学问题. 铂基和钯基催化剂被发现是甲酸电化学氧化最有效的阳极催化剂，但有关的分子机理尚不十分清楚,一些实验现象尚不能得以合理解释.本项目着眼于在原子分子水平上理解铂基和钯基催化剂催化甲酸电化学氧化的微观机理，用量子化学方法开展系统的理论研究,探讨甲酸电化学氧化的各种反应路径，分析反应的热力学和动力学性质,识别甲酸氧化过程中各种活性中间体和过渡态结构的相对稳定性,研究外加电位对反应性能的影响，弄清铂基和钯基双金属催化剂催化增效机制的微观本质,掌握控制催化活性的关键因素, 完善甲酸电化学氧化的理论模型，从而为DFAFCs新型阳极催化剂的开发和设计奠定一定的理论基础、提供一定的理论指导.

中文关键词： 甲酸氧化；贵金属催化剂；均相催化；异相催化；量子化学计算

英文摘要： Among various types of fuel cells, direct formic acid fuel cells (DFAFCs) are considered as the most promising power source that can offer the most extensive application in the near future. The electro-oxidation efficiency of formic acid is a key factor in determining the proerty of this class of fuel cells. Searching for the catalysts that are of excellent catalytic activity and improved tolerance towards CO-poisoning is becoming a challenging issue in the study of DFAFCs. Pt and Pd mono-mental catalysts as well as Pt- and Pd-based bimetal catalysts are found to be the most effective catalysts towards the electro-oxidation activity of formic acid. However, the relevant mechanism behind the phenomenon remains unclear, and some experimental observations are still not well understood. This proposal aims to elucidate the molecular mechanism of formic acid electro-oxidation promoted by a series of Pt- and Pd-based catalysts based on the results of quantum chemistry calculations. Our studies will pay substantial attentions on the following several aspects: (i) the mechanism details of formic acid oxidation along various possible pathways, (ii) the thermodynamic and dynamical properties of the formic acid oxidation, (iii) the relative stability of various activate intermediates and transition states involved along eac

英文关键词： formic oxidation；nobel metal catalysts；homogeneous catalysis；heterogeneous catalysis；quantum chemistry calculations