Zeolites are remarkable materials with adjustable confinement and Brønsted acid strength that catalyze reactions for preparation of valuable chemicals and fuels. Understanding these characteristics, such as acid strength and structural confinement, will be important for rational design and synthesis of zeolites for targeted reactions. Here we use a prototype C-C coupling reaction to reveal several structural and electronic effects on the reaction mechanism. In particular, we will focus on the acylation reaction between biomass-derived aromatic compounds, such as furanics and phenolics, and acetic acids and esters that are also generated during biomass conversion. Insight into the transition state obtained from density functional theory calculations demonstrates that the ability of aromatic substances to stabilize the charge of the acylium ion is important for lowering the activation barrier for the C-C coupling reaction. In addition, by comparing different zeolites, we find that the structural confinement also plays an important role in determining the rate-limiting step. Finally, we will show that the interaction between water and the zeolite framework further complicates the reaction mechanism. These insights obtained from atomic simulations provide the foundation for “ab initio” design and synthesis of the zeolite for targeting reactions.

Zeolite-catalyzed C-C coupling reactions between biomass-derived compounds: Insights from first-principles calculations

254th National Meeting (2017)

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