Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases

Faheem, Muhammad; Saleheen, Mohammad; Lu, Jianmin; Heyden, Andreas

doi:10.1039/c6cy02111e

Title: Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases

Journal Article · Fri Oct 28 00:00:00 EDT 2016 · Catalysis Science and Technology

DOI:https://doi.org/10.1039/c6cy02111e· OSTI ID:1656907

Faheem, Muhammad ^[1]; Saleheen, Mohammad ^[2]; Lu, Jianmin ^[3]; Heyden, Andreas ^[2]

University of South Carolina, Columbia, SC (United States); University of Engineering & Technology, Lahore (Pakistan)
University of South Carolina, Columbia, SC (United States)
University of South Carolina, Columbia, SC (United States); Chinese Academy of Sciences, Liaoning (China)

First-principles, periodic density functional theory (DFT) calculations and mean-field microkinetic modeling have been used to investigate the decomposition of ethylene glycol for hydrogen production on Pt(111) in vapor and aqueous phases. All dehydrogenated species derived from ethylene glycol (C₂H_xO₂, x = 0–6) and methanol (CH_yO, y = 0–4), and all elementary C–C, C–H, and O–H bond breaking steps are included in the microkinetic model. Reaction path analysis in vapor phase indicates that both initial C–H and O–H dehydrogenation steps are kinetically relevant at all temperatures (470–530 K). Initial O–H bond cleavage is reversible at low temperatures but accounts for an increasingly dominant fraction of the total reaction flux at higher temperatures. C–C bond scission is observed only after significant dehydrogenation (x ≤ 3) and is more likely to happen in surface intermediates where one of the cleavage products is CO. Here, the process is highly selective to the production of H2 compared to methanol. For aqueous-phase model development, free energies of solvation were computed for all surface intermediates and transition states using a continuum solvation approach. Our aqueous-phase microkinetic model predicts a 0.4 eV lower apparent activation energy and an order of magnitude larger turnover frequencies. Initial C–H bond cleavage becomes more important but the general trends are similar to the vapor phase, suggesting that the reaction chemistry is similar in both vapor and aqueous phases.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Univ. of South Carolina, Columbia, SC (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0007167

OSTI ID:: 1656907

Journal Information:: Catalysis Science and Technology, Vol. 6, Issue 23; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 31 works

Citation information provided by
Web of Science

References (61)

A review of catalytic hydrogen production processes from biomass Tanksale, Akshat; Beltramini, Jorge Norberto; Lu, GaoQing Max Renewable and Sustainable Energy Reviews, Vol. 14, Issue 1 https://doi.org/10.1016/j.rser.2009.08.010	journal	January 2010
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Aqueous-Phase Reforming of Ethylene Glycol Over Supported Platinum Catalysts Shabaker, J. W.; Huber, G. W.; Davda, R. R. Catalysis Letters, Vol. 88, Issue 1/2, p. 1-8 https://doi.org/10.1023/A:1023538917186	journal	May 2003
Density-functional exchange-energy approximation with correct asymptotic behavior Becke, A. D. Physical Review A, Vol. 38, Issue 6 https://doi.org/10.1103/PhysRevA.38.3098	journal	September 1988
Universality in Heterogeneous Catalysis Nørskov, J. K.; Bligaard, T.; Logadottir, A. Journal of Catalysis, Vol. 209, Issue 2 https://doi.org/10.1006/jcat.2002.3615	journal	July 2002
Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering Huber, George W.; Iborra, Sara; Corma, Avelino Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098 https://doi.org/10.1021/cr068360d	journal	September 2006
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
Periodic boundary conditions in ab initio calculations Makov, G.; Payne, M. C. Physical Review B, Vol. 51, Issue 7 https://doi.org/10.1103/PhysRevB.51.4014	journal	February 1995
Aqueous-phase reforming of ethylene glycol on silica-supported metal catalysts Davda, R. R.; Shabaker, J. W.; Huber, G. W. Applied Catalysis B: Environmental, Vol. 43, Issue 1, p. 13-26 https://doi.org/10.1016/S0926-3373(02)00277-1	journal	June 2003
Electronic structure calculations on workstation computers: The program system turbomole Ahlrichs, Reinhart; Bär, Michael; Häser, Marco Chemical Physics Letters, Vol. 162, Issue 3 https://doi.org/10.1016/0009-2614(89)85118-8	journal	October 1989
Competitive Paths for Methanol Decomposition on Pt(111) Greeley, Jeff; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 126, Issue 12 https://doi.org/10.1021/ja037700z	journal	March 2004
Auxiliary basis sets for main row atoms and transition metals and their use to approximate Coulomb potentials Eichkorn, Karin; Weigend, Florian; Treutler, Oliver Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 97, Issue 1-4 https://doi.org/10.1007/s002140050244	journal	October 1997
A dimer method for finding saddle points on high dimensional potential surfaces using only first derivatives Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 111, Issue 15 https://doi.org/10.1063/1.480097	journal	October 1999
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
Advanced solution methods for microkinetic models of catalytic reactions: A methanol synthesis case study Rubert-Nason, Patricia; Mavrikakis, Manos; Maravelias, Christos T. AIChE Journal, Vol. 60, Issue 4 https://doi.org/10.1002/aic.14322	journal	December 2013
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
A review of catalytic issues and process conditions for renewable hydrogen and alkanes by aqueous-phase reforming of oxygenated hydrocarbons over supported metal catalysts Davda, R. R.; Shabaker, J. W.; Huber, G. W. Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 171-186 https://doi.org/10.1016/j.apcatb.2004.04.027	journal	March 2005
Accurate Coulomb-fitting basis sets for H to Rn Weigend, Florian Physical Chemistry Chemical Physics, Vol. 8, Issue 9 https://doi.org/10.1039/b515623h	journal	January 2006
Hydrogen from catalytic reforming of biomass-derived hydrocarbons in liquid water Cortright, R. D.; Davda, R. R.; Dumesic, J. A. Nature, Vol. 418, Issue 6901 https://doi.org/10.1038/nature01009	journal	August 2002
Reaction Kinetics of Ethylene Glycol Reforming over Platinum in the Vapor versus Aqueous Phases Kandoi, Shampa; Greeley, Jeff; Simonetti, Dante The Journal of Physical Chemistry C, Vol. 115, Issue 4 https://doi.org/10.1021/jp104136s	journal	August 2010
Efficient methods for finding transition states in chemical reactions: Comparison of improved dimer method and partitioned rational function optimization method Heyden, Andreas; Bell, Alexis T.; Keil, Frerich J. The Journal of Chemical Physics, Vol. 123, Issue 22 https://doi.org/10.1063/1.2104507	journal	December 2005
Towards a first principles prediction of p K _a : COSMO-RS and the cluster-continuum approach Eckert, Frank; Diedenhofen, Michael; Klamt, Andreas Molecular Physics, Vol. 108, Issue 3-4 https://doi.org/10.1080/00268970903313667	journal	February 2010
A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu Grimme, Stefan; Antony, Jens; Ehrlich, Stephan The Journal of Chemical Physics, Vol. 132, Issue 15 https://doi.org/10.1063/1.3382344	journal	April 2010
Catalytic Reforming of Oxygenated Hydrocarbons for Hydrogen with Low Levels of Carbon Monoxide Davda, Rupali R.; Dumesic, James A. Angewandte Chemie International Edition, Vol. 42, Issue 34 https://doi.org/10.1002/anie.200351664	journal	September 2003
Differentiation of O–H and C–H Bond Scission Mechanisms of Ethylene Glycol on Pt and Ni/Pt Using Theory and Isotopic Labeling Experiments Salciccioli, Michael; Yu, Weiting; Barteau, Mark A. Journal of the American Chemical Society, Vol. 133, Issue 20 https://doi.org/10.1021/ja201801t	journal	May 2011
Aqueous-phase reforming of methanol and ethylene glycol over alumina-supported platinum catalysts Shabaker, J. Journal of Catalysis, Vol. 215, Issue 2 https://doi.org/10.1016/S0021-9517(03)00032-0	journal	April 2003
Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy Weigend, Florian; Ahlrichs, Reinhart Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305 https://doi.org/10.1039/b508541a	journal	January 2005
Use of Solution-Phase Vibrational Frequencies in Continuum Models for the Free Energy of Solvation Ribeiro, Raphael F.; Marenich, Aleksandr V.; Cramer, Christopher J. The Journal of Physical Chemistry B, Vol. 115, Issue 49 https://doi.org/10.1021/jp205508z	journal	December 2011
Finding the Rate-Determining Step in a Mechanism Campbell, Charles T. Journal of Catalysis, Vol. 204, Issue 2 https://doi.org/10.1006/jcat.2001.3396	journal	December 2001
Aqueous phase reforming of xylitol and sorbitol: Comparison and influence of substrate structure Kirilin, Alexey V.; Tokarev, Anton V.; Kustov, Leonid M. Applied Catalysis A: General, Vol. 435-436 https://doi.org/10.1016/j.apcata.2012.05.050	journal	September 2012
Correction to Kinetic Modeling of Pt Catalyzed and Computation-Driven Catalyst Discovery for Ethylene Glycol Decomposition Salciccioli, M.; Vlachos, D. G. ACS Catalysis, Vol. 2, Issue 2 https://doi.org/10.1021/cs300016f	journal	January 2012
Transition State Theory Pechukas, P. Annual Review of Physical Chemistry, Vol. 32, Issue 1 https://doi.org/10.1146/annurev.pc.32.100181.001111	journal	October 1981
Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 78, Issue 7 https://doi.org/10.1103/PhysRevLett.78.1396	journal	February 1997
Understanding Trends in Catalytic Activity: The Effect of Adsorbate–Adsorbate Interactions for CO Oxidation Over Transition Metals Grabow, Lars C.; Hvolbæk, Britt; Nørskov, Jens K. Topics in Catalysis, Vol. 53, Issue 5-6 https://doi.org/10.1007/s11244-010-9455-2	journal	February 2010
Comment on the Correct Use of Continuum Solvent Models Ho, Junming; Klamt, Andreas; Coote, Michelle L. The Journal of Physical Chemistry A, Vol. 114, Issue 51 https://doi.org/10.1021/jp107136j	journal	December 2010
Is the water–gas shift reaction on Pt simple? Mhadeshwar, A. B.; Vlachos, D. G. Catalysis Today, Vol. 105, Issue 1 https://doi.org/10.1016/j.cattod.2005.04.003	journal	July 2005
Solvent effects on the hydrodeoxygenation of propanoic acid over Pd(111) model surfaces Behtash, Sina; Lu, Jianmin; Faheem, Muhammad Green Chem., Vol. 16, Issue 2 https://doi.org/10.1039/C3GC41368C	journal	January 2014
Conductor-like Screening Model for Real Solvents: A New Approach to the Quantitative Calculation of Solvation Phenomena Klamt, Andreas The Journal of Physical Chemistry, Vol. 99, Issue 7 https://doi.org/10.1021/j100007a062	journal	February 1995
A First-Principles Study of Methanol Decomposition on Pt(111) Greeley, Jeff; Mavrikakis, Manos Journal of the American Chemical Society, Vol. 124, Issue 24 https://doi.org/10.1021/ja017818k	journal	June 2002
Theoretical insights into the structure and reactivity of the aqueous/metal interface Taylor, Christopher D.; Neurock, Matthew Current Opinion in Solid State and Materials Science, Vol. 9, Issue 1-2 https://doi.org/10.1016/j.cossms.2006.03.007	journal	February 2005
COSMO Implementation in TURBOMOLE: Extension of an efficient quantum chemical code towards liquid systems Schäfer, Ansgar; Klamt, Andreas; Sattel, Diana Physical Chemistry Chemical Physics, Vol. 2, Issue 10 https://doi.org/10.1039/b000184h	journal	January 2000
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
Kinetic Modeling of Pt Catalyzed and Computation-Driven Catalyst Discovery for Ethylene Glycol Decomposition Salciccioli, M.; Vlachos, D. G. ACS Catalysis, Vol. 1, Issue 10 https://doi.org/10.1021/cs2003593	journal	August 2011
Microkinetic modeling of Pt-catalyzed ethylene glycol steam reforming Christiansen, Matthew A.; Vlachos, Dionisios G. Applied Catalysis A: General, Vol. 431-432 https://doi.org/10.1016/j.apcata.2012.04.010	journal	July 2012
New Implicit Solvation Scheme for Solid Surfaces Faheem, Muhammad; Suthirakun, Suwit; Heyden, Andreas The Journal of Physical Chemistry C, Vol. 116, Issue 42 https://doi.org/10.1021/jp308212h	journal	October 2012
Density-functional approximation for the correlation energy of the inhomogeneous electron gas Perdew, John P. Physical Review B, Vol. 33, Issue 12 https://doi.org/10.1103/PhysRevB.33.8822	journal	June 1986
Renewable hydrogen by aqueous-phase reforming of glucoseElectronic Supplementary Information (ESI) available: catalyst preparation and characterization; reaction kinetics studies; acknowledgements. See http://www.rsc.org/suppdata/cc/b3/b310152e/ Davda, Rupali R.; Dumesic, James A. Chemical Communications, Issue 1 https://doi.org/10.1039/b310152e	journal	January 2004
Jaguar: A high-performance quantum chemistry software program with strengths in life and materials sciences Bochevarov, Art D.; Harder, Edward; Hughes, Thomas F. International Journal of Quantum Chemistry, Vol. 113, Issue 18 https://doi.org/10.1002/qua.24481	journal	July 2013
Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory Klimeš, Jiří; Michaelides, Angelos The Journal of Chemical Physics, Vol. 137, Issue 12 https://doi.org/10.1063/1.4754130	journal	September 2012
Aqueous-phase reforming of ethylene glycol over supported Pt and Pd bimetallic catalysts Huber, George W.; Shabaker, John W.; Evans, Steven T. Applied Catalysis B: Environmental, Vol. 62, Issue 3-4 https://doi.org/10.1016/j.apcatb.2005.07.010	journal	February 2006
Fully optimized contracted Gaussian basis sets of triple zeta valence quality for atoms Li to Kr Schäfer, Ansgar; Huber, Christian; Ahlrichs, Reinhart The Journal of Chemical Physics, Vol. 100, Issue 8 https://doi.org/10.1063/1.467146	journal	April 1994
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T. Journal of the American Chemical Society, Vol. 131, Issue 37 https://doi.org/10.1021/ja9065199	journal	September 2009
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
Materials simulations using VASP—a quantum perspective to materials science Hafner, J. Computer Physics Communications, Vol. 177, Issue 1-2 https://doi.org/10.1016/j.cpc.2007.02.045	journal	July 2007
Prediction of Experimental Methanol Decomposition Rates on Platinum from First Principles Kandoi, Shampa; Greeley, Jeff; Sanchez-Castillo, Marco A. Topics in Catalysis, Vol. 37, Issue 1 https://doi.org/10.1007/s11244-006-0001-1	journal	March 2006
Self-Consistent Reaction Field Model for Aqueous and Nonaqueous Solutions Based on Accurate Polarized Partial Charges Marenich, Aleksandr V.; Olson, Ryan M.; Kelly, Casey P. Journal of Chemical Theory and Computation, Vol. 3, Issue 6 https://doi.org/10.1021/ct7001418	journal	October 2007
Density Functional Theory-Derived Group Additivity and Linear Scaling Methods for Prediction of Oxygenate Stability on Metal Catalysts: Adsorption of Open-Ring Alcohol and Polyol Dehydrogenation Intermediates on Pt-Based Metals Salciccioli, M.; Chen, Y.; Vlachos, D. G. The Journal of Physical Chemistry C, Vol. 114, Issue 47 https://doi.org/10.1021/jp107836a	journal	November 2010
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
DFT studies for cleavage of C$z.sbnd;C and C$z.sbnd;O bonds in surface species derived from ethanol on Pt(111) Alcala, R. Journal of Catalysis, Vol. 218, Issue 1 https://doi.org/10.1016/S0021-9517(03)00090-3	journal	August 2003
An overview of aqueous-phase catalytic processes for production of hydrogen and alkanes in a biorefinery Huber, George W.; Dumesic, James A. Catalysis Today, Vol. 111, Issue 1-2 https://doi.org/10.1016/j.cattod.2005.10.010	journal	January 2006
Degree of Rate Control: How Much the Energies of Intermediates and Transition States Control Rates Stegelmann, Carsten; Andreasen, Anders; Campbell, Charles T. Journal of the American Chemical Society, Vol. 131, Issue 23 https://doi.org/10.1021/ja9000097	journal	June 2009

Cited By (2)

Can microsolvation effects be estimated from vacuum computations? A case-study of alcohol decomposition at the H ₂ O/Pt(111) interface Schweitzer, Benjamin; Steinmann, Stephan N.; Michel, Carine Physical Chemistry Chemical Physics, Vol. 21, Issue 10 https://doi.org/10.1039/c8cp06331a	journal	January 2019
Insights into the roles of water on the aqueous phase reforming of glycerol Xie, Tianjun; Bodenschatz, Cameron J.; Getman, Rachel B. Reaction Chemistry & Engineering, Vol. 4, Issue 2 https://doi.org/10.1039/c8re00267c	journal	January 2019

Similar Records

Reaction kinetics of ethylene glycol reforming over platinum in the vapor versus aqueous phases

Journal Article · Sat Jan 01 00:00:00 EST 2011 · Journal of Physical Chemistry. C · OSTI ID:1656907

Kandoi, S; Greeley, J; Simonetti, D; +3 more

Reaction kinetics of ethylene glycol reforming over platinum in the vapor versus aqueous phases

Journal Article · Thu Aug 12 00:00:00 EDT 2010 · Journal of Physical Chemistry. C · OSTI ID:1656907

Kandoi, Shampa; Greeley, Jeff; Simonetti, Dante; +3 more

Reaction Kinetics of Ethylene Glycol Reforming over Platinum in the Vapor versus Aqueous Phases

Journal Article · Thu Aug 12 00:00:00 EDT 2010 · Journal of Physical Chemistry C, 115(4):961–971 · OSTI ID:1656907

Kandoi, Shampa; Greeley, Jeffrey P.; Simonetti, Dante A.; +3 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
DFT
Ethylene glycol
Microkinetic modeling
Aqueous-phase reforming
Implicit solvation
Solvent effects

Title: Ethylene glycol reforming on Pt(111): first-principles microkinetic modeling in vapor and aqueous phases

Citation Formats

References (61)

Cited By (2)

Similar Records

Related Subjects