Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

Hensley, Alyssa R.; Wang, Yong; Mei, Donghai; McEwen, Jean-Sabin

doi:10.1021/acscatal.7b02576

Title: Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

Journal Article · Wed Jan 10 00:00:00 EST 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b02576· OSTI ID:1772335

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Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions because water is ubiquitous in such reaction systems. Here we present a study for phenol HDO on Fe catalysts using density functional theory which examines the effect of water on three elementary pathways for phenol HDO using an explicit solvation model. The presence of water is found to significantly decrease activation barriers required by hydrogenation reactions via two pathways. First, proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotes the direct tautomerization of phenol. Second, due to the high degree of oxophilicity on Fe, liquid water molecules are found to be easily dissociated into surface hydroxyl groups that can act as Brønsted acid sites. Furthermore, these sites dramatically promote hydrogenation reactions on the Fe surface. As a result, hydrogen-assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides fundamental insights into aqueous phase HDO of biomass-derived oxygenates over Fe-based catalysts; e.g., the activity of Fe-based catalysts can be optimized by tuning the surface coverage of Brønsted acid sites via surface doping.

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Research Organization:: Washington State Univ., Pullman, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0014560; AC05-06OR23100; FG02-05ER15712

OSTI ID:: 1772335

Journal Information:: ACS Catalysis, Vol. 8, Issue 3; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 35 works

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hydrodeoxygenation
mechanistic effect of liquid water
phenol
Fe catalyst
density functional theory
reaction pathways
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Title: Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites

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Cited By (3)

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