Full text
| |
| Author(s): |
Luis Gustavo da Silva Pereira
Total Authors: 1
|
| Document type: | Doctoral Thesis |
| Press: | São Carlos. |
| Institution: | Universidade de São Paulo (USP). Instituto de Química de São Carlos (IQSC/BT) |
| Defense date: | 2009-12-07 |
| Examining board members: |
Edson Antonio Ticianelli;
Ernesto Rafael Gonzalez;
Marcelo Linardi
|
| Advisor: | Edson Antonio Ticianelli |
| Abstract | |
The search for alternative sources of energy is a global trend, and in this context, the fuel cell supplied with hydrogen obtained by biofuels reforming is one of the most promising alternative. However, the performance of proton exchange membrane fuel cells (PEMFC) with Pt-based anode is drastically lowered when using CO-contain hydrogen, as that produced by reform. In this work, the electrocatalysis of CO tolerance and the stability of Pt/C, PtRu/C, PtFe/C, PtMo/C, and PtW/C electrocatalysts at a PEM fuel cell anode has been investigated using single cell polarization and on line electrochemical mass spectrometry (EMS) measurements, and cyclic voltammetry, X-ray diffraction (XRD), and X-ray absorption near edge structure (XANES) analyses of the electrocatalysts. For all bimetallic electrocatalysts, which presented higher CO tolerance, EMS results have shown that the production of CO2 starts at lower hydrogen electrode overpotentials as compared to Pt/C, confirming the occurrence of the so-called bifunctional mechanism. On the other hand, XANES results indicate an increase in the Pt 5d-band vacancies for the bimetallic catalysts, particularly for PtFe/C, this leading to a weakening of the Pt-CO bond, helping to increase the CO tolerance (the so-called electronic effect). For PtMo/C and PtRu/C supplied with H2/CO, the formation of CO2 is observed even when the cell is at open circuit, confirming some elimination of CO by a chemical process, most probably the water gas shift reaction. A decay of the fuel cell performance was observed as a function of the operation time. The causes of degradation during long-term operation were found to be a complex process that involves several parallel mechanisms, including: electrocatalyst loss or redistribution, carbon corrosion, and electrolyte (Nafion®) degradation. (AU) | |