Date of Award

May 2019

Document Type


Degree Name

Doctor of Philosophy (PhD)


Chemical and Biomolecular Engineering

Committee Member

Rachel B Getman

Committee Member

David Bruce

Committee Member

Sapna Sarupria

Committee Member

Stephen Creager


Aqueous-phase heterogeneous catalysis is an important chemical process in applications such as water remediation, fuel cells, and the production of fuels and chemicals, including from biomass sources. However, designing alternative, improved catalyst materials for these applications is difficult due to fluctuations in the solvation environment surrounding the catalytic species. In order to elucidate the thermodynamics and kinetics of the relevant reactions, it is imperative to gain a better understanding of the roles of liquid water molecules in these reactions. In this work, a method combining both classical and quantum simulations was developed to generate configurations of liquid water molecules over catalytic species adsorbed on a catalyst surface, which can provide valuable insight into the roles of the liquid water reaction environment on aqueous-phase heterogeneous catalysis.

The method developed in this work entails combining force field molecular dynamics (FFMD) and density functional theory (DFT) simulations. This method leverages the strengths of each type of simulation to enable the calculation of catalytic energies under “realistic” liquid water configurations. FFMD simulations are used to generate trajectories of liquid water configurations that include thermal fluctuations, while DFT simulations are used to capture the energies associated with bond breaking and forming that are required for microkinetic modeling and catalyst design studies.

This FFMD-DFT method was used to calculate the interaction energies between the liquid water environment and the reaction intermediate or transition state species. The trend in the calculated interaction energies was shown to correlate with the trend in hydrogen-bond formation between liquid water molecules and the catalytic species. This work also demonstrated that entropic effects due to the thermal fluctuations in the solvation environment are a significant contribution to the free energies calculated for aqueous-phase, heterogeneously-catalyzed systems.

The FFMD-DFT method was also used to calculate reaction energies, activation barriers, and pre-exponential factors to study the kinetics of example O—H and C—H cleavage reactions on a platinum catalyst surface under an aqueous reaction environment. Using this method, it was found that O—H cleavage reactions prefer H2O-mediated pathways, while C—H cleavage reactions prefer non-H2O-mediated pathways.

In summary, the FFMD-DFT method developed in this work has been shown to be a robust technique for generating realistic liquid water configurations over catalytic species on a platinum catalyst surface. Those liquid water configurations can be used to calculate catalytic properties that can provide insight into the roles of water molecules in these reactions and facilitate microkinetic modeling and catalyst design studies.



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