Spatial Scale Matters: Hydrolysis of Aryl Methyl Ethers over Zeolites

The local environment of the active site, such as the confinement of hydronium ions within zeolite pores, significantly influences catalytic turnover, similar to enzyme functionality. This study explores these effects in the hydrolysis of guaiacols─lignin-derived compounds─over zeolites in water. In addition to the interesting catechol products, this reaction is advantageous for study due to its bimolecular hydrolysis pathway, which involves a single energy barrier and no intermediates, simplifying kinetic studies and result interpretation. As in alcohol dehydration, hydronium ions show enhanced activity in ether hydrolysis due to undercoordination and increased electrophilicity when confined within zeolite pores, compared to bulk water. In addition, a volcano-shaped relationship between hydronium ion activity and Brønsted acid density was observed. However, unlike alcohol dehydration, this activity distribution cannot be attributed to variations in ionic strength within the pores, as the rate-determining step in the hydrolysis of guaiacols involves the attack of a neutral water molecule, unaffected by ionic strength. Instead, a detailed transition state analysis revealed a significant thermodynamic energy compensation effect, driven by the spatial organization of the transition state. This organization is influenced by the available reaction space, the interaction between the reacting species and the zeolite environment, leading to the volcano-shaped dependence. This phenomenon also explains the unusual reactivity order of the 4-R-guaiacol derivatives (R = H, Me, Et, Pr) with zeolite catalysis, extending beyond the traditional steric and electronic effects to provide a deeper understanding of reactant reactivity. The work concludes that the critical spatial parameters for fast ether hydrolysis─resulting in the highest hydronium activity─are determined by a combination of zeolite properties (topology and acid density) and reactant size.