Intermolecular Interaction‐Facilitated Unimolecular Dehydration of Cyclohexanol on Rutile TiO 2 (110) Surface

Abstract

ABSTRACT Alcohol dehydration reactions on oxide catalysts serve one of the foundational reactions in biomass valorization and fine chemical synthesis. The dehydration mechanism has been established as the unimolecular pathway (E1 and E1cb) or bimolecular cooperation pathway (E2). Herein, via a combined experimental and theoretical study of cyclohexanol dehydration reaction on the rutile TiO 2 (110) surface, we unravel an interesting intermolecular interaction‐facilitated unimolecular dehydration mechanism (termed as E1d), in which one cyclohexanol molecule of a molecularly‐adsorbed dimer at the five‐coordinated Ti sites undergoes dehydration to produce cyclohexene while the other cyclohexanol molecule molecularly desorbs simultaneously. Such an E1d dehydration mechanism of complex alcohol molecules on oxide catalysts highlights the critical role of intermolecular interactions in modulating the configuration and consequently dehydration activity of adsorbed alcohol molecules.