Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites
Abstract
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.
- Authors:
-
[1];
[1];
[2];
[1]
- 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)
- Publication Date:
- Research Org.:
- Washington State Univ., Pullman, WA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1772335
- Grant/Contract Number:
- SC0014560; AC05-06OR23100; FG02-05ER15712
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 3; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 97 MATHEMATICS AND COMPUTING; hydrodeoxygenation; mechanistic effect of liquid water; phenol; Fe catalyst; density functional theory; reaction pathways; Brønsted acid sites; redox reactions; chemical reactions; aromatic compounds; hydrogenation
Citation Formats
Hensley, Alyssa R., Wang, Yong, Mei, Donghai, and McEwen, Jean-Sabin. Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites. United States: N. p., 2018.
Web. doi:10.1021/acscatal.7b02576.
Hensley, Alyssa R., Wang, Yong, Mei, Donghai, & McEwen, Jean-Sabin. Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites. United States. https://doi.org/10.1021/acscatal.7b02576
Hensley, Alyssa R., Wang, Yong, Mei, Donghai, and McEwen, Jean-Sabin. Wed .
"Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites". United States. https://doi.org/10.1021/acscatal.7b02576. https://www.osti.gov/servlets/purl/1772335.
@article{osti_1772335,
title = {Mechanistic Effects of Water on the Fe-Catalyzed Hydrodeoxygenation of Phenol. The Role of Brønsted Acid Sites},
author = {Hensley, Alyssa R. and Wang, Yong and Mei, Donghai and McEwen, Jean-Sabin},
abstractNote = {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.},
doi = {10.1021/acscatal.7b02576},
journal = {ACS Catalysis},
number = 3,
volume = 8,
place = {United States},
year = {Wed Jan 10 00:00:00 EST 2018},
month = {Wed Jan 10 00:00:00 EST 2018}
}
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