Use of ethanol in fuel cells: electrocatalysis of its direct oxidation reaction and of the hydrogen oxidation reaction containing CO obtained by its steam reform

Author(s)

Pietro Papa Lopes

• Document type: Doctoral Thesis
• Press: São Carlos.
• Institution: Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT)
• Defense date: 2013-04-30

Examining board members

Edson Antonio Ticianelli; Hamilton Brandão Varela de Albuquerque; Eduardo Gonçalves Ciapina; Paulo Olivi; Ernesto Chaves Pereira de Souza

• Advisor: Edson Antonio Ticianelli

Abstract

This work comprises studies of the hydrogen oxidation reaction in the presence of CO in a Proton Exchange Membrane single-cells and the alcohol oxidation reaction in alkaline media on single crystal surfaces. These two themes are based on the use of ethanol as a renewable energy vector in electrochemical energy conversion devices, like fuel cells. The study of the effect of temperature over the CO tolerance during the hydrogen oxidation reaction was tackled with the perspective of the distinct tolerance processes that take place in Pt/C, PtRu/C and PtMo/C materials. Therefore, techniques such as Transmission Electron Microscopy, Energy Dispersive X-ray Spectroscopy, X-ray Diffraction and in situ X-ray Absorption Spectroscopy were employed to characterize the catalysts chemical composition, crystalline structure and electronic occupancy, highlighting the development of a spectro-electrochemical cell with the purpose of obtaining the XAS information under a real operando fuel cell environment, thus allowing evaluations of the effects of temperature and distinct chemical environments. These results were analyzed along with anode polarization profiles, so to emphasize the distinct way that the temperature affects each CO tolerance process. A reaction mechanism analysis allowed estimating the H, CO and OH surface coverages, which are paramount to best understand the processes that take place in PEMFC anodes fed with H2/CO. On the other hand, the ethanol oxidation studies in alkaline media allowed obtaining fundamental information to understand the ethanol oxidation reaction mechanism. These studies comprised the evaluation of the alkali cation effect over the alcohol oxidation reaction kinetics, bringing to light the role of alcohol acidity together with Li to enhance the catalytic effect. Besides observing the acidity role of both alcohol and solvent towards the catalytic promotion resulting from non-covalent interactions, this study allowed a broader analysis based on the molecular properties of distinct alcohols, as calculated by Density Functional Theory. In this way, it was possible to establish a correlation between frontier orbital properties with the portion of the alcohol molecule reacting first, along with the identification of the Highest Occupied Molecular Orbital - Lowest Unoccupied Molecular Orbital energy difference serving as a reactivity descriptor over a given surface. The role of the metal surface oxophilicity was identified, and this evidenced a close relation between OH and alcohol adsorption properties. At last, results obtained from Infrared Spectroscopy so to identify the oxidation products were combined with the information gained from the other studies allowed to elaborate a mechanism for the alcohol oxidation reaction applicable to several distinct alcohols. (AU)

• FAPESP's process: 08/10529-0 - Development and characterization of nanoparticulated electrocatalysts of PtMo/C and PtW/C for the hydrogen oxidation reaction on the presence of CO in PEM fuel cells
• Grantee: Pietro Papa Lopes
• Support Opportunities: Scholarships in Brazil - Doctorate