Fundamental studies of ethanol oxidation reaction in direct ethanol fuel cells using density functional theory (DFT) calculations

In this thesis, first-principles calculations within the density functional theory (DFT) framework were utilized to investigate heterogeneous catalytic reactions in direct ethanol fuel cell. The ethanol electrooxidation on Pd and binary Pd systems are studied, concerning mainly on the activity and selectivity, respectively. Meanwhile, due to the high cost of Pt and Pd and the CO poisoning effect, we aim to reduce the loading of Pd and Pt in catalysts. In this thesis, three ways of improving electrocatalytic performance of catalysts have been studied: (i) using some additives to promote the catalyst; (ii) tuning the catalytic surface thickness to get higher active surface area; (iii) controlling the structure or shape of particles to form some extremely active sites. From our theoretical studies, some basic principle has been obtained for rational design of high performance ethanol oxidation reaction catalysts: (i) active surface sites for C–C bond breaking; (ii) a suitable surface composition to increase selectivity for CO2 formation; (iii) the ability to facilitate the adsorption and activation of water (OH*) for the initiation of reaction. [Continues.]