Revealing the Mechanism of Ketonization of Acetic Acid on HBEA Zeolite via Metadynamics Simulations

Abstract Ketonization of biomass‐derived carboxylic acids offers a promising approach to remove oxygen and upgrade into valuable chemicals. However, the mechanism on Brønsted acid site (BAS) confined in micropores of zeolite remains elusive, due to the difficulty to observe the reaction intermediates experimentally and to locate the transition state via static density functional theory (DFT) calculations. Herein, ketonization of acetic acid on HBEA at 673 K was studied by metadynamics simulations based on DFT. The first reaction step was the concerted protonation and dehydroxylation of acetic acid, resulting in an electrophilic acylium cation and H 2 O (Δ G ‡ = 1.53 eV). The subsequent likely steps, including C─C coupling through the nucleophilic attack of acetic acid (path I), ketene (path II), and 1,1‐dihydroxyethene (path III) toward acylium cation were tracked and compared. The high barriers for formation of more nucleophilic intermediates of ketene and 1,1‐dihydroxyethene made the overall path II and III less favorable than the direct coupling between acetic acid and acylium cation (path I, Δ G ‡ = 2.15 eV). These results indicate that acylium cation is a key intermediate, and the C─C coupling between acetic acid and acylium cation via nucleophilic attack is the most favorable path on BAS confined in zeolite.