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

Hensley, Alyssa J.  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 · 30 January 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b02576· OSTI ID:1427904

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The Gene &, Linda Voiland School of Chemical Engineering and Bioengineering, ∥Department of Physics and Astronomy, and ⊥Department of Chemistry, Washington State University, Pullman, Washington 99164, United States; Institute for Integrated Catalysis and §Fundamental and Computational Sciences Directorate, Pacific Northwest National Laboratory, Richland, Washington 99352, United States

A mechanistic understanding of the roles of water is essential for developing highly active and selective catalysts for hydrodeoxygenation (HDO) reactions since 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, the proton transfer in the hydrogen bonding network of the liquid water phase is nearly barrierless, which significantly promotes the direct through space 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. These sites dramatically promote hydrogenation reactions on the Fe surface. As a result, the hydrogen assisted dehydroxylation becomes the dominant phenol HDO pathway. This work provides new 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.

Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

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

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1427904

Report Number(s):: PNNL-SA-130676; 49339; KC0302010

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

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

References (50)

Mechanism of Dehydration of Phenols on Noble Metals via First-Principles Microkinetic Modeling No authors listed ACS Catalysis https://doi.org/10.1021/acscatal.6b00776		April 2016
Guaiacol Hydrodeoxygenation Mechanism on Pt(111): Insights from Density Functional Theory and Linear Free Energy Relations No authors listed ChemSusChem https://doi.org/10.1002/cssc.201402940		December 2014
Different Product Distributions and Mechanistic Aspects of the Hydrodeoxygenation of m-Cresol over Platinum and Ruthenium Catalysts No authors listed ACS Catalysis https://doi.org/10.1021/acscatal.5b00765		September 2015
Theoretical Investigation of the Reaction Mechanism of the Guaiacol Hydrogenation over a Pt(111) Catalyst No authors listed ACS Catalysis https://doi.org/10.1021/cs5016244		March 2015
Mechanistic analysis of the role of metal oxophilicity in the hydrodeoxygenation of anisole No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2017.01.008		March 2017
Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations No authors listed ACS Catalysis https://doi.org/10.1021/acscatal.6b02253		November 2016
Adsorption and Decomposition of a Lignin β-O-4 Linkage Model, 2-Phenoxyethanol, on Pt(111): Combination of Experiments and First-Principles Calculations No authors listed The Journal of Physical Chemistry C https://doi.org/10.1021/acs.jpcc.7b01099		May 2017
Theoretical investigation of the reaction mechanism of the hydrodeoxygenation of guaiacol over a Ru(0 0 0 1) model surface No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2014.11.003		January 2015
Experimental and Theoretical Insights into the Hydrogen-Efficient Direct Hydrodeoxygenation Mechanism of Phenol over Ru/TiO ₂ No authors listed ACS Catalysis https://doi.org/10.1021/acscatal.5b01554		October 2015
Role of Oxide Reducibility in the Deoxygenation of Phenol on Ruthenium Clusters Supported on the Anatase Titania (1 0 1) Surface No authors listed ChemCatChem https://doi.org/10.1002/cctc.201600457		June 2016
Hydrodeoxygenation of Guaiacol over Ru(0001): A DFT Study No authors listed ACS Catalysis https://doi.org/10.1021/cs500911j		October 2014
C–O cleavage of aromatic oxygenates over ruthenium catalysts. A computational study of reactions at step sites No authors listed Physical Chemistry Chemical Physics https://doi.org/10.1039/C5CP01027F		January 2015
Phenol Deoxygenation Mechanisms on Fe(110) and Pd(111) No authors listed ACS Catalysis https://doi.org/10.1021/cs501403w		December 2014
Composition-directed Fe _X Mo _2−X P bimetallic catalysts for hydrodeoxygenation reactions No authors listed Catalysis Science & Technology https://doi.org/10.1039/C7CY00324B		January 2017
Kinetics and mechanism of m-cresol hydrodeoxygenation on a Pt/SiO2 catalyst No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2014.05.024		August 2014
Synergistic Catalysis between Pd and Fe in Gas Phase Hydrodeoxygenation of m -Cresol No authors listed ACS Catalysis https://doi.org/10.1021/cs500578g		August 2014
Impact of solvent for individual steps of phenol hydrodeoxygenation with Pd/C and HZSM-5 as catalysts No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2013.09.009		January 2014
First-Principles Study of Phenol Hydrogenation on Pt and Ni Catalysts in Aqueous Phase No authors listed Journal of the American Chemical Society https://doi.org/10.1021/ja501592y		July 2014
Recent Advances in Hydrotreating of Pyrolysis Bio-Oil and Its Oxygen-Containing Model Compounds No authors listed ACS Catalysis https://doi.org/10.1021/cs400069z		April 2013
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis No authors listed Science https://doi.org/10.1126/science.1195055		September 2010
The critical role of water at the gold-titania interface in catalytic CO oxidation No authors listed Science https://doi.org/10.1126/science.1256018		September 2014
Acid strength and bifunctional catalytic behavior of alloys comprised of noble metals and oxophilic metal promoters No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2014.03.016		June 2014
Adsorption of guaiacol on Fe (110) and Pd (111) from first principles No authors listed Surface Science https://doi.org/10.1016/j.susc.2015.10.030		June 2016
Adsorption of phenol on Fe (110) and Pd (111) from first principles No authors listed Surface Science https://doi.org/10.1016/j.susc.2014.08.003		December 2014
Carbon-supported bimetallic Pd–Fe catalysts for vapor-phase hydrodeoxygenation of guaiacol No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2013.05.020		October 2013
Ab initiomolecular dynamics for liquid metals No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.47.558		January 1993
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.54.11169		October 1996
From ultrasoft pseudopotentials to the projector augmented-wave method No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.59.1758		January 1999
Van der Waals density functionals applied to solids No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.83.195131		May 2011
Chemical accuracy for the van der Waals density functional No authors listed Journal of Physics: Condensed Matter https://doi.org/10.1088/0953-8984/22/2/022201		December 2009
High-precision sampling for Brillouin-zone integration in metals No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.40.3616		August 1989
Accelerated, energy-conserving Born–Oppenheimer molecular dynamics via Fock matrix extrapolation No authors listed Physical Chemistry Chemical Physics https://doi.org/10.1039/b509494a		January 2005
Special points for Brillouin-zone integrations No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.13.5188		June 1976
A climbing image nudged elastic band method for finding saddle points and minimum energy paths No authors listed The Journal of Chemical Physics https://doi.org/10.1063/1.1329672		December 2000
Accuracy of exchange-correlation functionals and effect of solvation on the surface energy of copper No authors listed Physical Review B https://doi.org/10.1103/PhysRevB.87.245402		June 2013
Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways No authors listed The Journal of Chemical Physics https://doi.org/10.1063/1.4865107		February 2014
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 No authors listed The Journal of Physical Chemistry C https://doi.org/10.1021/acs.jpcc.6b09527		January 2017
Elucidation of reaction mechanism for m-cresol hydrodeoxygenation over Fe based catalysts: A kinetic study No authors listed Catalysis Communications https://doi.org/10.1016/j.catcom.2017.06.028		September 2017
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data No authors listed Journal of Applied Crystallography https://doi.org/10.1107/S0021889811038970		October 2011
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 No authors listed The Journal of Physical Chemistry C https://doi.org/10.1021/acs.jpcc.5b02333		June 2015
Coverage dependent water dissociative adsorption on Fe(110) from DFT computation No authors listed Physical Chemistry Chemical Physics https://doi.org/10.1039/C5CP00044K		January 2015
Theoretical study of oxygen adsorption at the Fe(110) and (100) surfaces No authors listed Surface Science https://doi.org/10.1016/j.susc.2005.06.011		September 2005
Oxygen adsorption on Fe(110) surface revisited No authors listed Surface Science https://doi.org/10.1016/j.susc.2015.03.001		July 2015
Mechanistic Role of Water on the Rate and Selectivity of Fischer-Tropsch Synthesis on Ruthenium Catalysts No authors listed Angewandte Chemie International Edition https://doi.org/10.1002/anie.201304610		October 2013
Role of Dissociation of Phenol in Its Selective Hydrogenation on Pt(111) and Pd(111) No authors listed ACS Catalysis https://doi.org/10.1021/cs501805y		February 2015
Stabilization of Iron-Based Catalysts against Oxidation: An In Situ Ambient-Pressure X-ray Photoelectron Spectroscopy (AP-XPS) Study No authors listed ACS Catalysis https://doi.org/10.1021/acscatal.7b00636		April 2017
Enhanced Fe ₂ O ₃ Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions No authors listed ACS Catalysis https://doi.org/10.1021/cs500565e		September 2014
Catalytic water dehydrogenation and formation on nickel: Dual path mechanism in high electric fields No authors listed Journal of Catalysis https://doi.org/10.1016/j.jcat.2015.09.010		December 2015
Surface Science and Catalysis—Studies on the Mechanism of Ammonia Synthesis: The P. H. Emmett Award Address No authors listed Catalysis Reviews https://doi.org/10.1080/03602458008067533		January 1980
New design paradigm for heterogeneous catalysts No authors listed National Science Review https://doi.org/10.1093/nsr/nwv023		April 2015

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Mechanistic insights into hydrodeoxygenation of phenol on bimetallic phosphide catalysts No authors listed Catalysis Science & Technology https://doi.org/10.1039/c8cy00977e		January 2018
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