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

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

Journal Article · Tue Jan 09 23:00:00 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); Washington State University
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.

View Accepted Manuscript (DOE)

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

Alternate ID(s):: OSTI ID: 1427904

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

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (50)

Mechanistic Role of Water on the Rate and Selectivity of Fischer-Tropsch Synthesis on Ruthenium Catalysts Hibbitts, David D.; Loveless, Brett T.; Neurock, Matthew Angewandte Chemie International Edition, Vol. 52, Issue 47 https://doi.org/10.1002/anie.201304610	journal	October 2013
Role of Oxide Reducibility in the Deoxygenation of Phenol on Ruthenium Clusters Supported on the Anatase Titania (1 0 1) Surface Chen, Hsin-Yi Tiffany; Pacchioni, Gianfranco ChemCatChem, Vol. 8, Issue 15 https://doi.org/10.1002/cctc.201600457	journal	June 2016
Guaiacol Hydrodeoxygenation Mechanism on Pt(111): Insights from Density Functional Theory and Linear Free Energy Relations Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A. ChemSusChem, Vol. 8, Issue 2 https://doi.org/10.1002/cssc.201402940	journal	December 2014
Elucidation of reaction mechanism for m-cresol hydrodeoxygenation over Fe based catalysts: A kinetic study Hong, Yongchun; Wang, Yong Catalysis Communications, Vol. 100 https://doi.org/10.1016/j.catcom.2017.06.028	journal	September 2017
Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol Sun, Junming; Karim, Ayman M.; Zhang, He Journal of Catalysis, Vol. 306 https://doi.org/10.1016/j.jcat.2013.05.020	journal	October 2013
Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts He, Jiayue; Zhao, Chen; Lercher, Johannes A. Journal of Catalysis, Vol. 309 https://doi.org/10.1016/j.jcat.2013.09.009	journal	January 2014
Acid strength and bifunctional catalytic behavior of alloys comprised of noble metals and oxophilic metal promoters Hibbitts, David; Tan, Qiaohua; Neurock, Matthew Journal of Catalysis, Vol. 315 https://doi.org/10.1016/j.jcat.2014.03.016	journal	June 2014
Kinetics and mechanism of m-cresol hydrodeoxygenation on a Pt/SiO2 catalyst Nie, Lei; Resasco, Daniel E. Journal of Catalysis, Vol. 317 https://doi.org/10.1016/j.jcat.2014.05.024	journal	August 2014
Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface Lu, Jianmin; Heyden, Andreas Journal of Catalysis, Vol. 321 https://doi.org/10.1016/j.jcat.2014.11.003	journal	January 2015
Catalytic water dehydrogenation and formation on nickel: Dual path mechanism in high electric fields Che, Fanglin; Gray, Jake T.; Ha, Su Journal of Catalysis, Vol. 332 https://doi.org/10.1016/j.jcat.2015.09.010	journal	December 2015
Mechanistic analysis of the role of metal oxophilicity in the hydrodeoxygenation of anisole Tan, Qiaohua; Wang, Gonghua; Long, Alex Journal of Catalysis, Vol. 347 https://doi.org/10.1016/j.jcat.2017.01.008	journal	March 2017
Theoretical study of oxygen adsorption at the Fe(110) and (100) surfaces Błoński, P.; Kiejna, A.; Hafner, J. Surface Science, Vol. 590, Issue 1 https://doi.org/10.1016/j.susc.2005.06.011	journal	September 2005
Adsorption of phenol on Fe (110) and Pd (111) from first principles Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin Surface Science, Vol. 630 https://doi.org/10.1016/j.susc.2014.08.003	journal	December 2014
Oxygen adsorption on Fe(110) surface revisited Ossowski, Tomasz; Kiejna, Adam Surface Science, Vol. 637-638 https://doi.org/10.1016/j.susc.2015.03.001	journal	July 2015
Adsorption of guaiacol on Fe (110) and Pd (111) from first principles Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin Surface Science, Vol. 648 https://doi.org/10.1016/j.susc.2015.10.030	journal	June 2016
Molecular-Level Details about Liquid H ₂ O Interactions with CO and Sugar Alcohol Adsorbates on Pt(111) Calculated Using Density Functional Theory and Molecular Dynamics Bodenschatz, Cameron J.; Sarupria, Sapna; Getman, Rachel B. The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b02333	journal	June 2015
Role of Carbon Monoxide in Catalyst Reconstruction for CO Hydrogenation: First-Principles Study of the Composition, Structure, and Stability of Cu/Co(101̅2) as a Function of CO Pressure Collinge, Greg; Kruse, Norbert; McEwen, Jean-Sabin The Journal of Physical Chemistry C, Vol. 121, Issue 4 https://doi.org/10.1021/acs.jpcc.6b09527	journal	January 2017
Adsorption and Decomposition of a Lignin β-O-4 Linkage Model, 2-Phenoxyethanol, on Pt(111): Combination of Experiments and First-Principles Calculations Ould Hamou, Cherif A.; Réocreux, Romain; Sautet, Philippe The Journal of Physical Chemistry C, Vol. 121, Issue 18 https://doi.org/10.1021/acs.jpcc.7b01099	journal	May 2017
Different Product Distributions and Mechanistic Aspects of the Hydrodeoxygenation of m-Cresol over Platinum and Ruthenium Catalysts Tan, Qiaohua; Wang, Gonghua; Nie, Lei ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b00765	journal	September 2015
Experimental and Theoretical Insights into the Hydrogen-Efficient Direct Hydrodeoxygenation Mechanism of Phenol over Ru/TiO ₂ Nelson, Ryan C.; Baek, Byeongjin; Ruiz, Pamela ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01554	journal	October 2015
Mechanism of Dehydration of Phenols on Noble Metals via First-Principles Microkinetic Modeling Gu, Geun Ho; Mullen, Charles A.; Boateng, Akwasi A. ACS Catalysis, Vol. 6, Issue 5 https://doi.org/10.1021/acscatal.6b00776	journal	April 2016
Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations Réocreux, Romain; Ould Hamou, Cherif A.; Michel, Carine ACS Catalysis, Vol. 6, Issue 12 https://doi.org/10.1021/acscatal.6b02253	journal	November 2016
Stabilization of Iron-Based Catalysts against Oxidation: An In Situ Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS) Study Hong, Yongchun; Zhang, Shiran; Tao, Franklin Feng ACS Catalysis, Vol. 7, Issue 5 https://doi.org/10.1021/acscatal.7b00636	journal	April 2017
Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds Wang, Huamin; Male, Jonathan; Wang, Yong ACS Catalysis, Vol. 3, Issue 5 https://doi.org/10.1021/cs400069z	journal	April 2013
Enhanced Fe ₂ O ₃ Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions Hensley, Alyssa J. R.; Hong, Yongchun; Zhang, Renqin ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500565e	journal	September 2014
Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of m -Cresol Hong, Yongchun; Zhang, He; Sun, Junming ACS Catalysis, Vol. 4, Issue 10 https://doi.org/10.1021/cs500578g	journal	August 2014
Hydrodeoxygenation of Guaiacol over Ru(0001): A DFT Study Chiu, Cheng-chau; Genest, Alexander; Borgna, Armando ACS Catalysis, Vol. 4, Issue 11 https://doi.org/10.1021/cs500911j	journal	October 2014
Phenol Deoxygenation Mechanisms on Fe(110) and Pd(111) Hensley, Alyssa J. R.; Wang, Yong; McEwen, Jean-Sabin ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs501403w	journal	December 2014
Theoretical Investigation of the Reaction Mechanism of the Guaiacol Hydrogenation over a Pt(111) Catalyst Lu, Jianmin; Behtash, Sina; Mamun, Osman ACS Catalysis, Vol. 5, Issue 4 https://doi.org/10.1021/cs5016244	journal	March 2015
Role of Dissociation of Phenol in Its Selective Hydrogenation on Pt(111) and Pd(111) Li, Gaofeng; Han, Jinyu; Wang, Hua ACS Catalysis, Vol. 5, Issue 3 https://doi.org/10.1021/cs501805y	journal	February 2015
First-Principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase Yoon, Yeohoon; Rousseau, Roger; Weber, Robert S. Journal of the American Chemical Society, Vol. 136, Issue 29 https://doi.org/10.1021/ja501592y	journal	July 2014
Coverage dependent water dissociative adsorption on Fe(110) from DFT computation Liu, Shaoli; Tian, Xinxin; Wang, Tao Physical Chemistry Chemical Physics, Vol. 17, Issue 14 https://doi.org/10.1039/C5CP00044K	journal	January 2015
C–O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites Chiu, Cheng-chau; Genest, Alexander; Borgna, Armando Physical Chemistry Chemical Physics, Vol. 17, Issue 23 https://doi.org/10.1039/C5CP01027F	journal	January 2015
Composition-directed Fe _X Mo _2−X P bimetallic catalysts for hydrodeoxygenation reactions Rensel, Dallas J.; Kim, Jongsik; Jain, Varsha Catalysis Science & Technology, Vol. 7, Issue 9 https://doi.org/10.1039/C7CY00324B	journal	January 2017
Accelerated, energy-conserving Born–Oppenheimer molecular dynamics via Fock matrix extrapolation Herbert, John M.; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 7, Issue 18 https://doi.org/10.1039/b509494a	journal	January 2005
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra The Journal of Chemical Physics, Vol. 140, Issue 8 https://doi.org/10.1063/1.4865107	journal	February 2014
Surface Science and Catalysis—Studies on the Mechanism of Ammonia Synthesis: The P. H. Emmett Award Address Ertl, G. Catalysis Reviews, Vol. 21, Issue 2 https://doi.org/10.1080/03602458008067533	journal	January 1980
Chemical accuracy for the van der Waals density functional Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Journal of Physics: Condensed Matter, Vol. 22, Issue 2 https://doi.org/10.1088/0953-8984/22/2/022201	journal	December 2009
New design paradigm for heterogeneous catalysts Vojvodic, Aleksandra; Nørskov, Jens K. National Science Review, Vol. 2, Issue 2 https://doi.org/10.1093/nsr/nwv023	journal	April 2015
Special points for Brillouin-zone integrations Monkhorst, Hendrik J.; Pack, James D. Physical Review B, Vol. 13, Issue 12, p. 5188-5192 https://doi.org/10.1103/PhysRevB.13.5188	journal	June 1976
High-precision sampling for Brillouin-zone integration in metals Methfessel, M.; Paxton, A. T. Physical Review B, Vol. 40, Issue 6 https://doi.org/10.1103/PhysRevB.40.3616	journal	August 1989
Ab initiomolecular dynamics for liquid metals Kresse, G.; Hafner, J. Physical Review B, Vol. 47, Issue 1, p. 558-561 https://doi.org/10.1103/PhysRevB.47.558	journal	January 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Van der Waals density functionals applied to solids Klimeš, Jiří; Bowler, David R.; Michaelides, Angelos Physical Review B, Vol. 83, Issue 19 https://doi.org/10.1103/PhysRevB.83.195131	journal	May 2011
Accuracy of exchange-correlation functionals and effect of solvation on the surface energy of copper Fishman, Matthew; Zhuang, Houlong L.; Mathew, Kiran Physical Review B, Vol. 87, Issue 24 https://doi.org/10.1103/PhysRevB.87.245402	journal	June 2013
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data Momma, Koichi; Izumi, Fujio Journal of Applied Crystallography, Vol. 44, Issue 6 https://doi.org/10.1107/S0021889811038970	journal	October 2011
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis Zope, B. N.; Hibbitts, D. D.; Neurock, M. Science, Vol. 330, Issue 6000 https://doi.org/10.1126/science.1195055	journal	September 2010
The critical role of water at the gold-titania interface in catalytic CO oxidation Saavedra, J.; Doan, H. A.; Pursell, C. J. Science, Vol. 345, Issue 6204 https://doi.org/10.1126/science.1256018	journal	September 2014

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

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References (50)

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