skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Solvation Effects in the Hydrodeoxygenation of Propanoic Acid over a Model Pd(211) Catalyst

Abstract

The effects of liquid water and 1,4-dioxane on the hydrodeoxygenation of propionic acid over Pd(211) model surfaces have been studied from first principles. Here, a microkinetic model with parameters obtained from density functional theory and implicit solvation models was developed to study the effects of these solvents on the reaction mechanism and kinetic parameters. In the presence of water, dehydrogenated derivatives of propionic acid and propionate are stabilized, and a new decarboxylation mechanism involving CH3CCOOH surface species is facilitated, leading to a higher decarboxylation rate. However, stronger adsorption of CO in the presence of liquid water resulted in fewer free sites and an overall lower turnover frequency. By contrast, in the presence of 1,4-dioxane, the most dominant decarboxylation pathway does not involve a dehydrogenated propionate species, but propionate goes through decarboxylation to form CO2 and C2 fragments very similar to the mechanism in the gas phase. Again, in the presence of 1,4-dioxane, CO adsorbs more strongly, and fewer free sites are available for catalysis, leading to a slightly smaller turnover frequency. In all reaction environments, we observed that the decarbonylation mechanism is slightly preferred over the decarboxylation mechanism and that C–OH bond cleavage is the most rate-controlling step followed bymore » α-carbon dehydrogenation steps and (in liquid water) decarboxylation of dehydrogenated derivatives. Comparing solvent effects over Pd(211) with those over Pd(111), we observe that the free site coverage is reduced in the presence of solvents on all Pd surfaces, which reduces the activity of Pd(211). In addition, elementary steps that involve a carboxyl/carboxylate group changing its orientation from the surface to the liquid phase, such as the dehydrogenation of propionate, are significantly facilitated such that liquid water increased the activity of Pd(111).« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [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:
1656910
Grant/Contract Number:  
SC0007167
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 120; Journal Issue: 5; 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; Organic reactions; Chemical reactions; Solvents; Water

Citation Formats

Behtash, Sina, Lu, Jianmin, Mamun, Osman, Williams, Christopher T., Monnier, John R., and Heyden, Andreas. Solvation Effects in the Hydrodeoxygenation of Propanoic Acid over a Model Pd(211) Catalyst. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.jpcc.5b10419.
Behtash, Sina, Lu, Jianmin, Mamun, Osman, Williams, Christopher T., Monnier, John R., & Heyden, Andreas. Solvation Effects in the Hydrodeoxygenation of Propanoic Acid over a Model Pd(211) Catalyst. United States. https://doi.org/10.1021/acs.jpcc.5b10419
Behtash, Sina, Lu, Jianmin, Mamun, Osman, Williams, Christopher T., Monnier, John R., and Heyden, Andreas. Tue . "Solvation Effects in the Hydrodeoxygenation of Propanoic Acid over a Model Pd(211) Catalyst". United States. https://doi.org/10.1021/acs.jpcc.5b10419. https://www.osti.gov/servlets/purl/1656910.
@article{osti_1656910,
title = {Solvation Effects in the Hydrodeoxygenation of Propanoic Acid over a Model Pd(211) Catalyst},
author = {Behtash, Sina and Lu, Jianmin and Mamun, Osman and Williams, Christopher T. and Monnier, John R. and Heyden, Andreas},
abstractNote = {The effects of liquid water and 1,4-dioxane on the hydrodeoxygenation of propionic acid over Pd(211) model surfaces have been studied from first principles. Here, a microkinetic model with parameters obtained from density functional theory and implicit solvation models was developed to study the effects of these solvents on the reaction mechanism and kinetic parameters. In the presence of water, dehydrogenated derivatives of propionic acid and propionate are stabilized, and a new decarboxylation mechanism involving CH3CCOOH surface species is facilitated, leading to a higher decarboxylation rate. However, stronger adsorption of CO in the presence of liquid water resulted in fewer free sites and an overall lower turnover frequency. By contrast, in the presence of 1,4-dioxane, the most dominant decarboxylation pathway does not involve a dehydrogenated propionate species, but propionate goes through decarboxylation to form CO2 and C2 fragments very similar to the mechanism in the gas phase. Again, in the presence of 1,4-dioxane, CO adsorbs more strongly, and fewer free sites are available for catalysis, leading to a slightly smaller turnover frequency. In all reaction environments, we observed that the decarbonylation mechanism is slightly preferred over the decarboxylation mechanism and that C–OH bond cleavage is the most rate-controlling step followed by α-carbon dehydrogenation steps and (in liquid water) decarboxylation of dehydrogenated derivatives. Comparing solvent effects over Pd(211) with those over Pd(111), we observe that the free site coverage is reduced in the presence of solvents on all Pd surfaces, which reduces the activity of Pd(211). In addition, elementary steps that involve a carboxyl/carboxylate group changing its orientation from the surface to the liquid phase, such as the dehydrogenation of propionate, are significantly facilitated such that liquid water increased the activity of Pd(111).},
doi = {10.1021/acs.jpcc.5b10419},
journal = {Journal of Physical Chemistry. C},
number = 5,
volume = 120,
place = {United States},
year = {2016},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 26 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels
journal, January 2011

  • Serrano-Ruiz, Juan Carlos; Dumesic, James A.
  • Energy Environ. Sci., Vol. 4, Issue 1
  • DOI: 10.1039/C0EE00436G

First-principles calculations of the initial incorporation of carbon into flat and stepped Pd surfaces
journal, February 2010


Dependence of biodiesel fuel properties on the structure of fatty acid alkyl esters
journal, June 2005


Influence of fatty acid composition of raw materials on biodiesel properties
journal, January 2009


Hydroprocessing of Bio-Oils and Oxygenates to Hydrocarbons. Understanding the Reaction Routes
journal, January 2009

  • Donnis, Bjørn; Egeberg, Rasmus Gottschalck; Blom, Peder
  • Topics in Catalysis, Vol. 52, Issue 3
  • DOI: 10.1007/s11244-008-9159-z

Processing biomass in conventional oil refineries: Production of high quality diesel by hydrotreating vegetable oils in heavy vacuum oil mixtures
journal, October 2007


Transformation of Vegetable Oils into Hydrocarbons over Mesoporous-Alumina-Supported CoMo Catalysts
journal, December 2008

  • Kubička, David; Šimáček, Pavel; Žilková, Naděžda
  • Topics in Catalysis, Vol. 52, Issue 1-2
  • DOI: 10.1007/s11244-008-9145-5

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

Theoretical investigation of the hydrodeoxygenation of methyl propionate over Pd (111) model surfaces
journal, January 2014

  • Behtash, Sina; Lu, Jianmin; Heyden, Andreas
  • Catal. Sci. Technol., Vol. 4, Issue 11
  • DOI: 10.1039/C4CY00511B

Catalytic Deoxygenation of Fatty Acids and Their Derivatives
journal, January 2007

  • Mäki-Arvela, Päivi; Kubickova, Iva; Snåre, Mathias
  • Energy & Fuels, Vol. 21, Issue 1, p. 30-41
  • DOI: 10.1021/ef060455v

Catalytic Deoxygenation of Stearic Acid and Palmitic Acid in Semibatch Mode
journal, February 2009

  • Lestari, Siswati; Mäki-Arvela, Päivi; Simakova, Irina
  • Catalysis Letters, Vol. 130, Issue 1-2
  • DOI: 10.1007/s10562-009-9889-y

Decarboxylation of fatty acids over Pd supported on mesoporous carbon
journal, February 2010


Catalytic Deoxygenation of C18 Fatty Acids Over Mesoporous Pd/C Catalyst for Synthesis of Biofuels
journal, January 2011

  • Simakova, Irina; Rozmysłowicz, Bartosz; Simakova, Olga
  • Topics in Catalysis, Vol. 54, Issue 8-9
  • DOI: 10.1007/s11244-011-9608-y

Catalytic reaction pathways in liquid-phase deoxygenation of C18 free fatty acids
journal, February 2010


Diesel-like Hydrocarbons from Catalytic Deoxygenation of Stearic Acid over Supported Pd Nanoparticles on SBA-15 Catalysts
journal, December 2009


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

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

Influence of Hydrogen in Catalytic Deoxygenation of Fatty Acids and Their Derivatives over Pd/C
journal, December 2011

  • Rozmysłowicz, Bartosz; Mäki-Arvela, Päivi; Tokarev, Anton
  • Industrial & Engineering Chemistry Research, Vol. 51, Issue 26
  • DOI: 10.1021/ie202421x

Palladium Catalysts for Fatty Acid Deoxygenation: Influence of the Support and Fatty Acid Chain Length on Decarboxylation Kinetics
journal, March 2012


Catalytic hydroconversion of tricaprylin and caprylic acid as model reaction for biofuel production from triglycerides
journal, February 2010


Effect of Palladium Surface Structure on the Hydrodeoxygenation of Propanoic Acid: Identification of Active Sites
journal, January 2015

  • Behtash, Sina; Lu, Jianmin; Williams, Christopher T.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 4
  • DOI: 10.1021/jp511618u

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

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

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988


Density-functional approximation for the correlation energy of the inhomogeneous electron gas
journal, June 1986


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

Influence of Electron Correlation Effects on the Solvation of Cu 2+
journal, October 2004

  • Schwenk, Christian F.; Rode, Bernd M.
  • Journal of the American Chemical Society, Vol. 126, Issue 40
  • DOI: 10.1021/ja046784o

Ab initiomolecular dynamics for liquid metals
journal, January 1993


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


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


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

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

Auxiliary basis sets to approximate Coulomb potentials (Chem. Phys. Letters 240 (1995) 283-290)
journal, September 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


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

Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals
journal, February 2010


Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation
journal, February 2011

  • Grabow, L. C.; Mavrikakis, M.
  • ACS Catalysis, Vol. 1, Issue 4
  • DOI: 10.1021/cs200055d

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

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

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

    Works referencing / citing this record:

    Advances and challenges in modeling solvated reaction mechanisms for renewable fuels and chemicals
    journal, August 2019

    • Basdogan, Yasemin; Maldonado, Alex M.; Keith, John A.
    • WIREs Computational Molecular Science, Vol. 10, Issue 2
    • DOI: 10.1002/wcms.1446

    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

    Solvation effect on binding modes of model lignin dimer compounds on MWW 2D-zeolite
    journal, September 2019

    • Jain, Varsha; Wilson, Woodrow N.; Rai, Neeraj
    • The Journal of Chemical Physics, Vol. 151, Issue 11
    • DOI: 10.1063/1.5112101

    Mechanistic study of the ceria supported, re-catalyzed deoxydehydration of vicinal OH groups
    journal, January 2018

    • Xi, Yongjie; Yang, Wenqiang; Ammal, Salai Cheettu
    • Catalysis Science & Technology, Vol. 8, Issue 22
    • DOI: 10.1039/c8cy01782d

    Origins of complex solvent effects on chemical reactivity and computational tools to investigate them: a review
    journal, January 2019

    • Varghese, Jithin John; Mushrif, Samir H.
    • Reaction Chemistry & Engineering, Vol. 4, Issue 2
    • DOI: 10.1039/c8re00226f

    Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling
    journal, February 2019

    • Sharapa, Dmitry I.; Doronkin, Dmitry E.; Studt, Felix
    • Advanced Materials, Vol. 31, Issue 26
    • DOI: 10.1002/adma.201807381

    Can microsolvation effects be estimated from vacuum computations? A case-study of alcohol decomposition at the H 2 O/Pt(111) interface
    journal, January 2019

    • Schweitzer, Benjamin; Steinmann, Stephan N.; Michel, Carine
    • Physical Chemistry Chemical Physics, Vol. 21, Issue 10
    • DOI: 10.1039/c8cp06331a

    Moving Frontiers in Transition Metal Catalysis: Synthesis, Characterization and Modeling
    text, January 2019