Faculty Advisor

Ravindra Datta

Faculty Advisor

Ilie Fishtik

Faculty Advisor

Aaron Deskins

Faculty Advisor

Erkan Tuzel

Faculty Advisor

David DiBiasio

Abstract

A fundamental understanding of the kinetics and mechanisms of the catalytic reaction steps involved in the process of converting a fuel into hydrogen rich stream suitable for a fuel cell, as well as the electro-catalytic reactions within a fuel cell, is not only conceptually appealing, but could provide a sound basis for the design and development of efficient fuel processor/fuel cell systems. With the quantum chemical calculations on kinetics of elementary catalytic reaction steps becoming rather commonplace, and with increasing information now available in terms of electronic structures, vibration spectra, and kinetic data (activation energy and pre-exponential factors), the stage is set for development of a comprehensive approach. Toward this end, we have developed a framework that can utilize this basic information to develop a comprehensive understanding of catalytic and electrocatalytic reaction networks. The approach is based on the development of Reaction Route (RR) Graphs, which not only represent the reaction pathways pictorially, but are quantitative networks consistent with the Kirchhoff's laws of flow networks, allowing a detailed quantitative analysis by exploiting the analogy with electrical circuits. The result is an unambiguous portrayal of the reaction scheme that lays bare the dominant pathways. Further, the rate-limiting steps are identified rationally with ease, based on comparison of step resistances, as are the dominant pathways via flux analysis. In fact, explicit steady-state overall reaction (OR) rate expression can also be derived in an Ohm's law form, i.e. OR rate = OR motive force/OR resistance of an equivalent electric circuit, which derives directly from the RR graph of its mechanism. This approach is utilized for a detailed analysis of the catalytic and electro-catalytic reaction systems involved in reformer/fuel cell systems. The catalytic reaction systems considered include methanol decomposition, water gas shift, ammonia decomposition, and methane steam reforming, which have been studied mechanistically and kinetically. A detailed analysis of the electro-catalytic reactions in connection to the anode and cathode of fuel cells, i.e. hydrogen electrode reaction and the oxygen reduction reaction, has also been accomplished. These reaction systems have not so far been investigated at this level of detail. The basic underlying principles of the RR graphs and the topological analysis for these reaction systems are discussed.

Publisher

Worcester Polytechnic Institute

Degree Name

PhD

Department

Chemical Engineering

Project Type

Dissertation

Date Accepted

2010-04-19

Accessibility

Unrestricted

Subjects

methane steam reforming, water gas shit, ammonia decomposition, hydrogen oxidation, methanol decomposition, electro-catalysis, fuel cells, reaction route graph theory, oxygen reduction, fuel cell model, catalysis

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