Date of Award

Fall 2013

Degree Type


Degree Name

Doctor of Philosophy (PhD)


Materials Engineering

First Advisor

Eric Kvam

Committee Chair

Eric Kvam

Committee Member 1

Eabio Ribeiro

Committee Member 2

Eric Stach

Committee Member 3

Alejandro Strachan


Water-gas shift (WGS), CO + H2 O [Special characters omitted.] CO2 + H2 (ΔH° = -41 kJ mol -1 ), is an industrially important reaction for the production of high purity hydrogen. Commercial Cu/ZnO/Al2 O3 catalystsare employed to accelerate this reaction, yet these catalysts suffer from certain drawbacks, including costly regeneration processes and sulfur poisoning. Extensive research is focused on developing new catalysts to replace the current technology. Supported noble metals stand out as promising candidates, yet comprise intricate nanostructures complicating the understanding of their working mechanism.

In this study, the structure of the supported Pt catalysts is explored by transmission electron microscopy andX-ray spectroscopy. The effect of the supporting phase and the use of secondary metals on the reaction kinetics is investigated. Structural heterogeneities are quantified and correlated with the kinetic descriptors ofthe catalysts to develop a fundamental understanding of the catalytic mechanism. The effect of the reaction environment on catalyst structure is examined by in-situ techniques. This study benefitted greatly from the use of model catalysts that provide a convenient medium for the atomic level characterization ofnanostructures.

Based on these studies, Pt supported on iron oxide nano islands deposited on inert spherical alumina exhibited 48 times higher WGS turnover rate (normalized by the total Pt surface area) than Pt supported on bulk iron oxide. The rate of aqueous phase glycerol reforming reaction of Pt supported on multiwall carbon nanotubes (MWCNT) is promoted by co-impregnating with cobalt. The synthesis resulted in a variety ofnanostructures among which Pt-Co bimetallic nanoparticles are found to be responsible for the observed promotion. The unprecedented WGS rate of Pt supported on Mo 2 C is explored by forming Mo 2 C patches on top of MWCNTs and the rate promotion is found to be caused by the Pt-Mo bimetallic entities.