Date of Award
Summer 2025
Document Type
Open Access Dissertation
Department
Chemistry and Biochemistry
First Advisor
Aaron K. Vannucci
Abstract
Transition metal catalysis has revolutionized chemical synthesis, enabling efficient and selective transformations critical to the pharmaceutical, agricultural, and materials industries. However, traditional methods often rely on expensive, non-sustainable metals and harsh reaction conditions that generate significant waste. This dissertation explores a series of innovations aimed at bridging the gap between homogeneous and heterogeneous catalysis through the development of hybrid catalysts. These systems combine the molecular precision of homogeneous catalysts with the stability and practicality of heterogeneous supports, offering a pathway to more sustainable and scalable catalytic processes.
The first area of focus investigates nickel-based hybrid catalysts as a cost-effective and sustainable alternative to palladium. While palladium remains a cornerstone of cross-coupling chemistry, its rarity and high cost necessitate alternatives. Nickel, with its redox versatility and abundance, shows promise but suffers from challenges such as dimerization and selectivity issues. Immobilizing nickel catalysts on metal oxide (MOx) supports through novel binding motifs, including the MOx-ester linkage, mitigates these limitations by preventing bimolecular deactivation and variability in speciation.
The MOx-ester binding motif, developed as part of this work, establishes a covalent attachment between molecular catalysts and oxide supports, enabling hybrid systems with tunable reactivity. This anchoring approach boasts several distincedistinct advantages over traditional anchoring moieties, namely high catalyst loading to the support and enhanced tunability.
This dissertation further examines the role of Atomic Layer Deposition (ALD) in stabilizing hybrid catalysts. ALD techniques provide molecular-level control over catalyst encapsulation, improving resistance to leaching and maintaining activity under harsh conditions. By integrating ALD with MOx-ester catalysts or acid anchoring groups, the catalyst can achieve enhanced longevity and reusability.
Finally, the current limitations of surface modifications, such as scalability, uniformity, and understanding of catalyst-support interactions, are critically evaluated. This comprehensive study underscores the potential of hybrid catalysts to address the pressing need for sustainable catalysis and highlights avenues for future research, including broader applications in industrial and green chemistry.
This dissertation represents a contribution to the field of catalysis, providing new tools and methodologies for achieving efficient, sustainable, and scalable chemical transformations.
Rights
© 2025, Joseph John Kuchta
Recommended Citation
Kuchta, J. J.(2025). Determination of Structure-Function Relationships in Hybrid Catalysts on Metal Oxide Supports. (Doctoral dissertation). Retrieved from https://scholarcommons.sc.edu/etd/8408