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

Coan, Patrick D.; Farberow, Carrie A.; Griffin, Michael B.; Medlin, J. Will

doi:10.1021/acscatal.0c04138

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

Journal Article · Tue Mar 09 00:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.0c04138· OSTI ID:1778707

Coan, Patrick D. ^[1]; Farberow, Carrie A. ^[2]; Griffin, Michael B. ^[2]; ^[1]

Univ. of Colorado, Boulder, CO (United States)
National Renewable Energy Lab. (NREL), Golden, CO (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States); Univ. of Colorado, Boulder, CO (United States)

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

Grant/Contract Number:: AC36-08GO28308; SC0005239

OSTI ID:: 1778707

Alternate ID(s):: OSTI ID: 1785252

Report Number(s):: NREL/JA--5100-78029; MainId:31938; UUID:4dcd458b-805f-465f-a19e-8f2a778525b4; MainAdminID:21279

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 6 Vol. 11; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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

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