Computational modelling in bio-based heterogeneous catalysis

Quayle, Max 2025. Computational modelling in bio-based heterogeneous catalysis. PhD Thesis, Cardiff University. Item availability restricted.

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Abstract

Since the advent of the Industrial Revolution, the cost of society’s dependence on fossil fuels has only continued to grow. For humanity to have any hope of outgrowing its reliance on non-renewable feedstocks, it is critical that the mechanistic chemistry behind heterogeneous catalysis is properly understood so that sustainable catalytic processes may be developed. In the hope of contributing towards this goal, this thesis is a comprehensive computational study of the catalytic conversion of bio-based platform molecules. Particular emphasis has been devoted to the hydrogenation, reductive amination, and pyrolysis of biomass derivatives over platinum group metal and metal oxide catalysts. By constructing density functional theory (DFT) models of key intermediates and their associated transition states, accessible pathways for the hydrogenation of both the chain C=C bond and furanic ring system of the furfural derivative ALD-1 were identified over Pd(111). In agreement with experiment, chain hydrogenation was shown to be facile over Pt(111) and Ru(0001), but not ring hydrogenation. Partial charge analysis revealed that the distribution of electron density across the adsorbate played a critical role in the selectivity of these catalysts. This work was then extended to the reductive amination of furfural derivatives over Pd(111) and Ru(0001), where accessible mechanisms were identified for the formation and hydrogenation of imine intermediates. A final DFT study on the ceria-catalysed pyrolysis of sinapic acid (SA) confirmed that the disappearance of С=О and O–H vibrational modes in experimental infrared spectra was caused by SA’s decarboxylation to 4-vinylsyringol. By complementing all calculations with experimental data, it is the hope of the author that this thesis will help inform the development of sustainable syntheses and deepen our collective understanding of bio-based heterogeneous catalysis.

Item Type:	Thesis (PhD)
Date Type:	Completion
Status:	Unpublished
Schools:	Schools > Chemistry
Date of First Compliant Deposit:	23 February 2026
Last Modified:	23 Feb 2026 16:25
URI:	https://orca.cardiff.ac.uk/id/eprint/185103

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