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

Ballesteros-Soberanas, Jordi; Ellis, Lucas D.; Medlin, J. Will

doi:10.1021/acscatal.9b02082

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

Journal Article · Wed Jul 17 00:00:00 EDT 2019 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.9b02082· OSTI ID:1658625

Ballesteros-Soberanas, Jordi ^[1]; Ellis, Lucas D. ^[2]; ^[2]

Univ. of Colorado, Boulder, CO (United States); University of Colorado Boulder
Univ. of Colorado, Boulder, CO (United States)

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 in this paper, 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.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Colorado, Boulder, CO (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0005239

OSTI ID:: 1658625

Alternate ID(s):: OSTI ID: 1610819

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 9 Vol. 9; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Role of tungsten modifiers in bimetallic catalysts for enhanced hydrodeoxygenation activity and selectivity Rasmussen, Mathew J.; Medlin, J. Will Catalysis Science & Technology, Vol. 10, Issue 2 https://doi.org/10.1039/c9cy02240f	journal	January 2020

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Related Subjects

09 BIOMASS FUELS
36 MATERIALS SCIENCE
TiO₂
alcohol
dehydration
metal oxide
phosphonic acid
self-assembled monolayer