Graduation Year


Document Type




Degree Granting Department

Chemical Engineering

Major Professor

Babu Joseph

Co-Major Professor

Venkat R. Bhethanabotla


deactivation, Density Functional Theory, Fischer Tropsch Synthesis, promoted catalyst, reaction mechanisms


CO hydrogenation and CO oxidation are two important processes addressing the energy and environmental issues of great interest. Both processes are carried out using metallic catalysts. The objective of this dissertation is to study the catalytic processes that govern these two reactions from a molecular perspective using quantum mechanical calculations. Density Functional Theory (DFT) has proven to be a valuable tool to study adsorption, dissociation, chain growth, reaction pathways etc., on well-defined surfaces. DFT was used to study the CO reduction reactions on promoted cobalt catalyst surfaces and CO oxidation mechanisms on cobalt surfaces.

CO hydrogenation via Fischer-Tropsch Synthesis (FTS) is a process used to produce liquid fuels from synthesis gas. The economics of the Fischer-Tropsch process strongly depends on the performance of the catalyst used. The desired properties of a catalyst include selectivity towards middle distillate products such as diesel and jet fuel, higher activity and longer catalyst life. Catalysts are often modified by adding promoters to obtain these desirable properties. Promoters can influence the reaction pathways, reducibility, dispersion, activity and selectivity. In FTS, understanding the effect of promoters in the molecular scale would help in tailoring catalysts with higher activity and desired selectivity. Preventing deactivation of catalyst is important in FTS to increase the catalyst life. Deactivation of Co catalyst can occur by reoxidation, C deposition, sintering, formation of cobalt-support compounds etc. Designing catalyst with resistance to deactivation by the use of promoters is explored in this dissertation. The influence of promoters on the initiation pathways of CO hydrogenation is also explored as a first step towards determining the selectivity of promoted catalyst.

The influence of Pt promoter on O removal from the surface of Co catalyst showed that Pt promoter reduced the activation barrier for the removal of O on both flat and stepped Co surfaces. An approximate kinetic model was developed and a volcano plot was established. The turn-over frequency (TOF) calculated based on the activation barriers showed that Pt promoted Co surface had a higher rate than unpromoted Co surface. The effect of Pt and Ru promoters on various pathways of C deposition on Co catalyst was studied to gain a mechanistic understanding. The promoters did not affect the subsurface C formation but they increased the barriers for C-C and C-C-C formation and also decreased the barriers for C-H formation. The promoters also influence the stabilities of C compounds on the Co surface suggesting that Pt and Ru promoters would decrease C deposition on Co catalysts. The effect of Pt promoter on unassisted and H-assisted CO activation pathways on Co catalyst was studied. Pt promoted Co surface followed H-assisted CO activation. Pt promoter decreased the activation barriers for CO activation pathways on Co catalyst thereby increasing the activity of Co catalyst.

CO oxidation is a process used to prevent poisoning of fuel cell catalysts and reduce pollution of the atmosphere through exhaust gases containing CO. Expensive catalysts like Pt are widely used for CO oxidation which significantly increases the cost of the process and hence it is necessary to search for alternative lower cost catalysts. Understanding the mechanism of a reaction is the first step towards designing better and efficient catalyst. DFT is helpful in determining the basic mechanism and intermediates of reactions.

The mechanism of CO oxidation on CoO catalyst was explored. Four possible mechanisms for CO oxidation on CoO catalyst were studied to determine the most likely mechanism. The mechanism was found to be a two-step process with activation barrier for formation of CO2 larger than the barrier for formation of the intermediate species.