Date of Award
Fall 2025
Document Type
Open Access Dissertation
Department
Chemical Engineering
First Advisor
Andreas Heyden
Abstract
First-principles modeling has become central to heterogeneous catalysis research, offering mechanistic insight and guiding catalyst design, yet conventional approaches often struggle to accurately describe complex catalytic systems due to methodological uncertainties, simplified assumptions, and the structural diversity of nanoparticle catalysts. This dissertation addresses these challenges using ethane dehydrogenation (EDH) and hydrogenolysis (EH) over platinum catalysts as model systems. The first study benchmarks density functional theory (DFT) functionals against the random phase approximation (RPA) for the EDH network on Pt(111), identifying cost-effective functionals and demonstrating the efficiency of BEEF-vdW ensembles for capturing functional uncertainty. The second study (addressed in prior work) applies Bayesian uncertainty quantification to propagate and calibrate enthalpic and entropic errors, providing a statistically rigorous framework for active-site identification across Pt facets. The third study introduces a particle-based microkinetic modeling (PB-MKM) framework that integrates terrace and edge facets into a nanoparticle-level description, enabling the study of cross-facet communication and particle-size effects. The fourth study evaluates alternative microkinetic treatments of the Pt(211) facet, showing how assumptions about site occupancy and facet interactions can substantially affect predicted kinetics. Together, these studies advance first-principles catalysis by addressing inaccuracies in energetics, uncertainty propagation, and microkinetic assumptions, leading to experimentally consistent predictions for Pt-catalyzed hydrocarbon conversion and offering transferable tools for other catalytic systems where particle size, active-site identification, uncertainty quantification, and accurate description of kinetic trends are critical.
Rights
© 2025, Mubarak Ayo Bello
Recommended Citation
Bello, M. A.(2025). Towards Accurate First-Principles Modeling in Heterogenous Catalysis: Ethane Dehydrogenation and Hydrogenolysis Over PT Catalysts. (Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/8674