Organic Modifiers Promote Furfuryl Alcohol Ring Hydrogenation via Surface Hydrogen-Bonding Interactions

Interactions between surface adsorbed species can affect catalyst reactivity, and thus, the ability to tune these interactions is of considerable importance. Deposition of organic modifiers provides one method of intentionally introducing controllable surface interactions onto catalyst surfaces. In...

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Bibliographic Details
Published in:ACS catalysis 2021-03, Vol.11 (6), p.3730-3739
Main Authors: Coan, Patrick D, Farberow, Carrie A, Griffin, Michael B, Medlin, J. Will
Format: Article
Language:English
Subjects:
09 BIOMASS FUELS
catalyst modification
furfuryl alcohol
heterogeneous catalysis
INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
phosphonic acids
ring hydrogenation
self-assembled monolayers
thiols
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Summary:Interactions between surface adsorbed species can affect catalyst reactivity, and thus, the ability to tune these interactions is of considerable importance. Deposition of organic modifiers provides one method of intentionally introducing controllable surface interactions onto catalyst surfaces. In this study, Pd/Al2O3 catalysts were modified with either thiol or phosphonic acid (PA) ligands and tested in the hydrogenation of furanic species. The thiol modifiers were found to inhibit ring hydrogenation (RH) activity, with the degree of inhibition trending with the thiol surface coverage. This suggests that thiols do not strongly interact with the reactants and simply serve to block active sites on the Pd surface. PAs, on the other hand, were found to enhance RH when furfuryl alcohol (FA) was used as the reactant. Density functional theory calculations suggested that this enhancement was due to hydrogen-bonding interactions between FA-derived surface intermediates and PA modifiers. Here, installation of hydrogen-bonding groups on the Pd surface served to preferentially stabilize RH product states. Furthermore, the promotional effect on the RH of FA was observed to be greater when a higher-coverage PA was used, providing a rate more than twice that of the unmodified Pd/Al2O3. The results of this work suggest that organic ligands can be designed to impart tunable surface interactions on heterogeneous catalysts, providing an additional method of controlling catalytic performance.
ISSN:2155-5435
2155-5435
DOI:10.1021/acscatal.0c04138