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Title: Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model

Abstract

The effect of two solvents, liquid water and 1,4-dioxane, has been studied from first-principles on the hydrodeoxygenation of propionic acid over a Ni(111) catalyst surface model. A mean-field microkinetic model was developed to investigate these effects at a temperature of 473 K. Under all reaction conditions, a decarbonylation mechanism is favored significantly over a decarboxylation pathway. Although no significant solvent effects were observed on the decarbonylation rate, a substantial solvent stabilization of two key surface intermediates in the decarboxylation mechanism, CH3CCOO and CH3CHCOO, leads to a notable increase of the decarboxylation rate by 2 orders of magnitude in liquid water and by 1 order of magnitude in liquid 1,4- dioxane. Furthermore, a significant solvent stabilization of the transition state of C–H bond cleavage of the α-carbon of CH3CHCO, relative to the stabilization of the C–C bond cleavage of the α-carbon of CH3CHCO, leads to a change in dominant pathway in the liquid phase environments. Finally, a sensitivity analysis shows that the C–OH bond cleavage of propionic acid and C–C bond cleavage of the α-carbon of CH3CHCO are the most rate controlling states in the gas phase. In contrast, in solvents the dehydrogenation of CH3CHCO becomes the most influential step. Thismore » shift in rate controlling state is attributed to the solvent effect on the dehydrogenation of CH3CHCO, which is facilitated in the aqueous phase. Altogether, it is likely that the investigated (111) facet of Ni is not active for the hydrodeoxygenation of propionic acid in either the gas or the liquid phase and other Ni facets or phases must be responsible for the experimentally observed kinetics.« less

Authors:
 [1]; ORCiD logo [1];  [1];  [1]; ORCiD logo [1]
  1. University of South Carolina, Columbia, SC (United States)
Publication Date:
Research Org.:
Univ. of South Carolina, Columbia, SC (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1656888
Grant/Contract Number:  
SC0007167
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 124; Journal Issue: 30; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Redox reactions; Free energy; Adsorption; Surface reactions; Solvents

Citation Formats

Zare, Mehdi, Solomon, Rajadurai Vijay, Yang, Wenqiang, Yonge, Adam, and Heyden, Andreas. Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model. United States: N. p., 2020. Web. https://doi.org/10.1021/acs.jpcc.0c04437.
Zare, Mehdi, Solomon, Rajadurai Vijay, Yang, Wenqiang, Yonge, Adam, & Heyden, Andreas. Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model. United States. https://doi.org/10.1021/acs.jpcc.0c04437
Zare, Mehdi, Solomon, Rajadurai Vijay, Yang, Wenqiang, Yonge, Adam, and Heyden, Andreas. Tue . "Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model". United States. https://doi.org/10.1021/acs.jpcc.0c04437. https://www.osti.gov/servlets/purl/1656888.
@article{osti_1656888,
title = {Theoretical Investigation of Solvent Effects on the Hydrodeoxygenation of Propionic Acid over a Ni(111) Catalyst Model},
author = {Zare, Mehdi and Solomon, Rajadurai Vijay and Yang, Wenqiang and Yonge, Adam and Heyden, Andreas},
abstractNote = {The effect of two solvents, liquid water and 1,4-dioxane, has been studied from first-principles on the hydrodeoxygenation of propionic acid over a Ni(111) catalyst surface model. A mean-field microkinetic model was developed to investigate these effects at a temperature of 473 K. Under all reaction conditions, a decarbonylation mechanism is favored significantly over a decarboxylation pathway. Although no significant solvent effects were observed on the decarbonylation rate, a substantial solvent stabilization of two key surface intermediates in the decarboxylation mechanism, CH3CCOO and CH3CHCOO, leads to a notable increase of the decarboxylation rate by 2 orders of magnitude in liquid water and by 1 order of magnitude in liquid 1,4- dioxane. Furthermore, a significant solvent stabilization of the transition state of C–H bond cleavage of the α-carbon of CH3CHCO, relative to the stabilization of the C–C bond cleavage of the α-carbon of CH3CHCO, leads to a change in dominant pathway in the liquid phase environments. Finally, a sensitivity analysis shows that the C–OH bond cleavage of propionic acid and C–C bond cleavage of the α-carbon of CH3CHCO are the most rate controlling states in the gas phase. In contrast, in solvents the dehydrogenation of CH3CHCO becomes the most influential step. This shift in rate controlling state is attributed to the solvent effect on the dehydrogenation of CH3CHCO, which is facilitated in the aqueous phase. Altogether, it is likely that the investigated (111) facet of Ni is not active for the hydrodeoxygenation of propionic acid in either the gas or the liquid phase and other Ni facets or phases must be responsible for the experimentally observed kinetics.},
doi = {10.1021/acs.jpcc.0c04437},
journal = {Journal of Physical Chemistry. C},
number = 30,
volume = 124,
place = {United States},
year = {2020},
month = {7}
}

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Works referenced in this record:

Catalytic Production of Liquid Fuels from Biomass‐Derived Oxygenated Hydrocarbons: Catalytic Coupling at Multiple Length Scales
journal, September 2009


Hydrodeoxygenation of model compounds and catalytic systems for pyrolysis bio-oils upgrading
journal, January 2012


Ni-based sol–gel catalysts as promising systems for crude bio-oil upgrading: Guaiacol hydrodeoxygenation study
journal, February 2012


Ni-Based Catalysts for the Hydrotreatment of Fast Pyrolysis Oil
journal, December 2015


Catalytic hydrotreatment of fast pyrolysis liquids in batch and continuous set-ups using a bimetallic Ni–Cu catalyst with a high metal content
journal, January 2016

  • Yin, Wang; Kloekhorst, Arjan; Venderbosch, Robertus H.
  • Catalysis Science & Technology, Vol. 6, Issue 15
  • DOI: 10.1039/C6CY00503A

Catalytic hydrotreatment of fast-pyrolysis oil using non-sulfided bimetallic Ni-Cu catalysts on a δ-Al2O3 support
journal, May 2012


Catalytic deoxygenation of oleic acid in continuous gas flow for the production of diesel-like hydrocarbons
journal, May 2011

  • Arend, Matthias; Nonnen, Thomas; Hoelderich, Wolfgang F.
  • Applied Catalysis A: General, Vol. 399, Issue 1-2
  • DOI: 10.1016/j.apcata.2011.04.004

Aqueous Phase Hydrogenation of Acetic Acid and Its Promotional Effect on p -Cresol Hydrodeoxygenation
journal, November 2012

  • Wan, Haijun; Chaudhari, Raghunath V.; Subramaniam, Bala
  • Energy & Fuels, Vol. 27, Issue 1
  • DOI: 10.1021/ef301400c

Investigation of solvent effects on the hydrodeoxygenation of guaiacol over Ru catalysts
journal, January 2019

  • Saleheen, Mohammad; Verma, Anand Mohan; Mamun, Osman
  • Catalysis Science & Technology, Vol. 9, Issue 22
  • DOI: 10.1039/C9CY01763A

Computational Investigation of Aqueous Phase Effects on the Dehydrogenation and Dehydroxylation of Polyols over Pt(111)
journal, July 2019

  • Saleheen, Mohammad; Zare, Mehdi; Faheem, Muhammad
  • The Journal of Physical Chemistry C, Vol. 123, Issue 31
  • DOI: 10.1021/acs.jpcc.9b04994

Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985


The Role and Perspective of Ab Initio Molecular Dynamics in the Study of Biological Systems
journal, June 2002

  • Carloni, Paolo; Rothlisberger, Ursula; Parrinello, Michele
  • Accounts of Chemical Research, Vol. 35, Issue 6
  • DOI: 10.1021/ar010018u

New Implicit Solvation Scheme for Solid Surfaces
journal, October 2012

  • Faheem, Muhammad; Suthirakun, Suwit; Heyden, Andreas
  • The Journal of Physical Chemistry C, Vol. 116, Issue 42
  • DOI: 10.1021/jp308212h

Theoretical Investigation of the Reaction Mechanism of the Decarboxylation and Decarbonylation of Propanoic Acid on Pd(111) Model Surfaces
journal, June 2012

  • Lu, Jianmin; Behtash, Sina; Heyden, Andreas
  • The Journal of Physical Chemistry C, Vol. 116, Issue 27
  • DOI: 10.1021/jp301926t

Solvent effects on the hydrodeoxygenation of propanoic acid over Pd(111) model surfaces
journal, January 2014

  • Behtash, Sina; Lu, Jianmin; Faheem, Muhammad
  • Green Chem., Vol. 16, Issue 2
  • DOI: 10.1039/C3GC41368C

Theoretical investigation of the decarboxylation and decarbonylation mechanism of propanoic acid over a Ru(0 0 0 1) model surface
journal, April 2015


Unraveling the mechanism of the hydrodeoxygenation of propionic acid over a Pt (1 1 1) surface in vapor and liquid phases
journal, January 2020


Solvation Effects in the Hydrodeoxygenation of Propanoic Acid over a Model Pd(211) Catalyst
journal, February 2016

  • Behtash, Sina; Lu, Jianmin; Mamun, Osman
  • The Journal of Physical Chemistry C, Vol. 120, Issue 5
  • DOI: 10.1021/acs.jpcc.5b10419

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Accurate and simple density functional for the electronic exchange energy: Generalized gradient approximation
journal, June 1986


A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives
journal, October 1999

  • Henkelman, Graeme; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 111, Issue 15
  • DOI: 10.1063/1.480097

Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method
journal, December 2005

  • Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J.
  • The Journal of Chemical Physics, Vol. 123, Issue 22
  • DOI: 10.1063/1.2104507

Electronic structure calculations on workstation computers: The program system turbomole
journal, October 1989


Efficient molecular numerical integration schemes
journal, January 1995

  • Treutler, Oliver; Ahlrichs, Reinhart
  • The Journal of Chemical Physics, Vol. 102, Issue 1
  • DOI: 10.1063/1.469408

Accurate Coulomb-fitting basis sets for H to Rn
journal, January 2006

  • Weigend, Florian
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 9
  • DOI: 10.1039/b515623h

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005

  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

RI-MP2: optimized auxiliary basis sets and demonstration of efficiency
journal, September 1998


Auxiliary basis sets to approximate Coulomb potentials
journal, June 1995


Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials
journal, October 1997

  • Eichkorn, Karin; Weigend, Florian; Treutler, Oliver
  • Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4
  • DOI: 10.1007/s002140050244

Performance of parallel TURBOMOLE for density functional calculations
journal, November 1998


Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena
journal, February 1995


Refinement and Parametrization of COSMO-RS
journal, June 1998

  • Klamt, Andreas; Jonas, Volker; Bürger, Thorsten
  • The Journal of Physical Chemistry A, Vol. 102, Issue 26
  • DOI: 10.1021/jp980017s

Implicit solvation model for density-functional study of nanocrystal surfaces and reaction pathways
journal, February 2014

  • Mathew, Kiran; Sundararaman, Ravishankar; Letchworth-Weaver, Kendra
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4865107

Accuracy of exchange-correlation functionals and effect of solvation on the surface energy of copper
journal, June 2013


A Formulation for the Static Permittivity of Water and Steam at Temperatures from 238 K to 873 K at Pressures up to 1200 MPa, Including Derivatives and Debye–Hückel Coefficients
journal, July 1997

  • Fernández, D. P.; Goodwin, A. R. H.; Lemmon, Eric W.
  • Journal of Physical and Chemical Reference Data, Vol. 26, Issue 4
  • DOI: 10.1063/1.555997

Hydrodeoxygenation of propanoic acid over silica-supported palladium: effect of metal particle size
journal, January 2014

  • Lugo-José, Yuliana K.; Monnier, John R.; Heyden, Andreas
  • Catal. Sci. Technol., Vol. 4, Issue 11
  • DOI: 10.1039/C4CY00605D

Unraveling the mechanism of propanoic acid hydrodeoxygenation on palladium using deuterium kinetic isotope effects
journal, September 2015

  • Lugo-José, Yuliana K.; Behtash, Sina; Nicholson, Marjorie
  • Journal of Molecular Catalysis A: Chemical, Vol. 406
  • DOI: 10.1016/j.molcata.2015.05.019

A Method for Obtaining Liquid–Solid Adsorption Rates from Molecular Dynamics Simulations: Applied to Methanol on Pt(111) in H 2 O
journal, March 2020

  • Zhang, Xiaohong; Savara, Aditya; Getman, Rachel B.
  • Journal of Chemical Theory and Computation, Vol. 16, Issue 4
  • DOI: 10.1021/acs.jctc.9b01249

A self-adjusting platinum surface for acetone hydrogenation
journal, January 2020

  • Demir, Benginur; Kropp, Thomas; Rivera-Dones, Keishla R.
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 7
  • DOI: 10.1073/pnas.1917110117

Catalysis by Doped Oxides
journal, December 2012

  • McFarland, Eric W.; Metiu, Horia
  • Chemical Reviews, Vol. 113, Issue 6
  • DOI: 10.1021/cr300418s

First-principles study of the role of solvent in the dissociation of water over a Pt-Ru alloy
journal, August 2003


Mechanistic Role of Water on the Rate and Selectivity of Fischer-Tropsch Synthesis on Ruthenium Catalysts
journal, October 2013

  • Hibbitts, David D.; Loveless, Brett T.; Neurock, Matthew
  • Angewandte Chemie International Edition, Vol. 52, Issue 47
  • DOI: 10.1002/anie.201304610

On the water structure at hydrophobic interfaces and the roles of water on transition-metal catalyzed reactions: A short review
journal, May 2017


Electrochemical Hydrogen Oxidation on Pt(110): A Combined Direct Molecular Dynamics/Density Functional Theory Study
journal, March 2010

  • Santana, Juan A.; Mateo, Juan J.; Ishikawa, Yasuyuki
  • The Journal of Physical Chemistry C, Vol. 114, Issue 11
  • DOI: 10.1021/jp909834q

Combined First-Principles Molecular Dynamics/Density Functional Theory Study of Ammonia Electrooxidation on Pt(100) Electrode
journal, November 2013

  • Skachkov, Dmitry; Venkateswara Rao, Chitturi; Ishikawa, Yasuyuki
  • The Journal of Physical Chemistry C, Vol. 117, Issue 48
  • DOI: 10.1021/jp4048874

Reaction mechanisms of CO2 electrochemical reduction on Cu(111) determined with density functional theory
journal, April 2014


A theoretical study on the catalytic role of water in methanol steam reforming on PdZn(111)
journal, January 2015

  • Huang, Zheng-Qing; Long, Bo; Chang, Chun-Ran
  • Catalysis Science & Technology, Vol. 5, Issue 5
  • DOI: 10.1039/C5CY00016E

Gas-phase, catalytic hydrodeoxygenation of propanoic acid, over supported group VIII noble metals: Metal and support effects
journal, January 2014

  • Lugo-José, Yuliana K.; Monnier, John R.; Williams, Christopher T.
  • Applied Catalysis A: General, Vol. 469
  • DOI: 10.1016/j.apcata.2013.10.025

Future Directions and Industrial Perspectives Micro- and macro-kinetics: Their relationship in heterogeneous catalysis
journal, September 1994


Finding the Rate-Determining Step in a Mechanism
journal, December 2001


Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates
journal, June 2009

  • Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T.
  • Journal of the American Chemical Society, Vol. 131, Issue 23
  • DOI: 10.1021/ja9000097

Kinetic-Quantum Chemical Model for Catalytic Cycles: The Haber−Bosch Process and the Effect of Reagent Concentration
journal, July 2008

  • Kozuch, Sebastian; Shaik, Sason
  • The Journal of Physical Chemistry A, Vol. 112, Issue 26
  • DOI: 10.1021/jp8004772

A Combined Kinetic−Quantum Mechanical Model for Assessment of Catalytic Cycles:  Application to Cross-Coupling and Heck Reactions
journal, March 2006

  • Kozuch, Sebastian; Shaik, Sason
  • Journal of the American Chemical Society, Vol. 128, Issue 10
  • DOI: 10.1021/ja0559146