Effects of Phosphonic Acid Monolayers on the Dehydration Mechanism of Aliphatic Alcohols on TiO₂

The kinetics for surface-catalyzed alcohol dehydration reactions often depend on the structure of the alcohol. Studies of structure–activity relations across primary, secondary, and tertiary alcohols can provide fundamental information on the nature of active sites on the surface. Here, we investigated the dehydration of 1-butanol, 2-butanol, and tert-butanol over TiO₂ anatase catalysts modified with various phosphonic acid (PA) self-assembled monolayers (SAMs). As a response to the presence of PAs, the three C4 alcohol isomers showed different dehydration rates, with 1-butanol dehydration being enhanced to the greatest extent by PA modification. Furthermore, the fluorinated, more polar 4-fluorobenzyl­phosphonic acid outperformed alkyl PAs across all alcohols. Steady-state kinetic measurements and temperature-programmed desorption studies indicated that PA SAMs significantly lowered the dehydration activation barrier; the extent of reduction in the barrier was sensitive to both the substitution of the alcohol and the charge distribution on the PA in a way that was consistent with stabilization of a carbenium-like transition state. Overall, the effect of PA modifiers on alcohol dehydration rates was found to be determined from a balance between transition state stabilization and active site blocking effects, with the potential to tune activity and selectivity based on the structure and coverage of the SAM.