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Title: Benchmarking the accuracy of coverage-dependent models: adsorption and desorption of benzene on Pt (111) and Pt3Sn (111) from first principles

Abstract

Bimetallic catalysts have demonstrated properties favorable for upgrading biofuel through catalytic hydrodeoxygenation. However, the design and optimization of such bimetallic catalysts requires the ability to construct accurate, predictive models of these systems. To generate a model that predicts the kinetic behavior of benzene adsorbed on Pt (111) and a Pt3Sn (111) surface alloy (Pt3Sn (111)), the adsorption of benzene was studied for a wide range of benzene coverages on both surfaces using density functional theory (DFT) calculations. The adsorption energy of benzene was found to correlate linearly with benzene coverage on Pt (111) and Pt3Sn (111); both surfaces exhibited net repulsive lateral interactions. Through an analysis of the d-band properties of the metal surface, it was determined that the coverage dependence is a consequence of the electronic interactions between benzene and the surface. The linear coverage dependence of the adsorption energy allowed us to quantify the influence of the lateral interactions on the heat of adsorption and temperature programmed desorption (TPD) spectra using a mean-field model. A comparison of our simulated TPD to experiment showed that this mean-field model adequately reproduces the desorption behavior of benzene on Pt (111) and Pt3Sn (111). In particular, the TPD correctly exhibits a broadeningmore » desorption peak as the initial coverage of benzene increases on Pt (111) as well as and a low temperature desorption peak on Pt3Sn (111). Furthermore, due to the sensitivity of the TPD peak temperature to the desorption energy, precise alignment of experimental and theoretical TPD spectra demands an accurate calculation of the adsorption energy. Therefore, an analysis of the effect of the exchange-correlation functional on TPD modeling is presented. Through this work, we show the necessity of incorporating lateral interactions into theoretical models in order to correctly predict experimental behavior.« less

Authors:
 [1];  [1];  [1];  [2];  [2]
+ Show Author Affiliations
  1. Washington State Univ., Pullman, WA (United States)
  2. Washington State Univ., Pullman, WA (United States); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1755213
Alternate Identifier(s):
OSTI ID: 1543038
Grant/Contract Number:  
SC0014560; 1347973
Resource Type:
Accepted Manuscript
Journal Name:
Progress in Surface Science
Additional Journal Information:
Journal Volume: 94; Journal Issue: 2; Journal ID: ISSN 0079-6816
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 74 ATOMIC AND MOLECULAR PHYSICS; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 77 NANOSCIENCE AND NANOTECHNOLOGY; 42 ENGINEERING; Lateral interactions; coverage effects; temperature programmed desorption (TPD); multi-scale modeling; mean-field model

Citation Formats

Wong, Breanna M., Collinge, Greg, Hensley, Alyssa J. R., Wang, Yong, and McEwen, Jean-Sabin. Benchmarking the accuracy of coverage-dependent models: adsorption and desorption of benzene on Pt (111) and Pt3Sn (111) from first principles. United States: N. p., 2019. Web. doi:10.1016/j.progsurf.2019.04.001.
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Wong, Breanna M., Collinge, Greg, Hensley, Alyssa J. R., Wang, Yong, & McEwen, Jean-Sabin. Benchmarking the accuracy of coverage-dependent models: adsorption and desorption of benzene on Pt (111) and Pt3Sn (111) from first principles. United States. https://doi.org/10.1016/j.progsurf.2019.04.001
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Wong, Breanna M., Collinge, Greg, Hensley, Alyssa J. R., Wang, Yong, and McEwen, Jean-Sabin. Tue . "Benchmarking the accuracy of coverage-dependent models: adsorption and desorption of benzene on Pt (111) and Pt3Sn (111) from first principles". United States. https://doi.org/10.1016/j.progsurf.2019.04.001. https://www.osti.gov/servlets/purl/1755213.
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@article{osti_1755213,
title = {Benchmarking the accuracy of coverage-dependent models: adsorption and desorption of benzene on Pt (111) and Pt3Sn (111) from first principles},
author = {Wong, Breanna M. and Collinge, Greg and Hensley, Alyssa J. R. and Wang, Yong and McEwen, Jean-Sabin},
abstractNote = {Bimetallic catalysts have demonstrated properties favorable for upgrading biofuel through catalytic hydrodeoxygenation. However, the design and optimization of such bimetallic catalysts requires the ability to construct accurate, predictive models of these systems. To generate a model that predicts the kinetic behavior of benzene adsorbed on Pt (111) and a Pt3Sn (111) surface alloy (Pt3Sn (111)), the adsorption of benzene was studied for a wide range of benzene coverages on both surfaces using density functional theory (DFT) calculations. The adsorption energy of benzene was found to correlate linearly with benzene coverage on Pt (111) and Pt3Sn (111); both surfaces exhibited net repulsive lateral interactions. Through an analysis of the d-band properties of the metal surface, it was determined that the coverage dependence is a consequence of the electronic interactions between benzene and the surface. The linear coverage dependence of the adsorption energy allowed us to quantify the influence of the lateral interactions on the heat of adsorption and temperature programmed desorption (TPD) spectra using a mean-field model. A comparison of our simulated TPD to experiment showed that this mean-field model adequately reproduces the desorption behavior of benzene on Pt (111) and Pt3Sn (111). In particular, the TPD correctly exhibits a broadening desorption peak as the initial coverage of benzene increases on Pt (111) as well as and a low temperature desorption peak on Pt3Sn (111). Furthermore, due to the sensitivity of the TPD peak temperature to the desorption energy, precise alignment of experimental and theoretical TPD spectra demands an accurate calculation of the adsorption energy. Therefore, an analysis of the effect of the exchange-correlation functional on TPD modeling is presented. Through this work, we show the necessity of incorporating lateral interactions into theoretical models in order to correctly predict experimental behavior.},
doi = {10.1016/j.progsurf.2019.04.001},
journal = {Progress in Surface Science},
number = 2,
volume = 94,
place = {United States},
year = {Tue May 28 00:00:00 EDT 2019},
month = {Tue May 28 00:00:00 EDT 2019}
}
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Works referenced in this record:

Adsorption and desorption of CO on Ru(0001): A comprehensive analysis
journal, December 2005

Adsorption and desorption of CO on Pt(111): a comprehensive analysis
journal, November 2003

A review of theoretical models of adsorption, diffusion, desorption, and reaction of gases on metal surfaces
journal, July 1991

Isosteric heat of adsorption for repulsive interactions
journal, December 1991

Rare-gas thermal desorption from flat and stepped platinum surfaces: Lateral interactions and the influence of dimensionality
journal, February 1998

Multilayer adsorption and desorption: Au and Cu on Mo(110)
journal, January 1996

First-principles reaction site model for coverage-sensitive surface reactions: Pt(111)–O temperature programmed desorption
journal, April 2014

Electric field induced oscillations in the catalytic water production on rhodium: A theoretical analysis
journal, August 2010

Anisole and Guaiacol Hydrodeoxygenation over Monolithic Pt–Sn Catalysts
journal, September 2011

  • González-Borja, Miguel Ángel; Resasco, Daniel E.
  • Energy & Fuels, Vol. 25, Issue 9
  • DOI: 10.1021/ef200728r

Adsorption of cyclohexane and benzene on ordered tin/platinum (111) surface alloys
journal, January 1994

  • Xu, Chen; Tsai, Yi Li; Koel, Bruce E.
  • The Journal of Physical Chemistry, Vol. 98, Issue 2
  • DOI: 10.1021/j100053a038

A BPTDS and HREELS study of the interaction of cyclohexane with the platinum (111) surface
journal, July 1992

  • Bussell, Mark E.; Henn, Frederic C.; Campbell, Charles T.
  • The Journal of Physical Chemistry, Vol. 96, Issue 14
  • DOI: 10.1021/j100193a061

Effect of potassium addition on bimetallic PtSn supported θ-Al2O3 catalyst for n-butane dehydrogenation to olefins
journal, September 2014

Effect of tin and potassium addition on the nature of platinum supported on silica
journal, March 2005

Production of ethanol by gas phase hydrogenation of acetic acid over carbon nanotube-supported Pt–Sn nanoparticles
journal, October 2013

Effect of Sn Addition in Gas Phase Hydrogenation of Acetic Acid on Alumina Supported PtSn Catalysts
journal, February 2014

On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces
journal, November 2013

Coverage-Induced Conformational Effects on Activity and Selectivity: Hydrogenation and Decarbonylation of Furfural on Pd(111)
journal, November 2014

  • Wang, Shengguang; Vorotnikov, Vassili; Vlachos, Dionisios G.
  • ACS Catalysis, Vol. 5, Issue 1
  • DOI: 10.1021/cs5015145

DFT-Based Coverage-Dependent Model of Pt-Catalyzed NO Oxidation
journal, August 2010

DFT-Based Characterization of the Multiple Adsorption Modes of Nitrogen Oxides on Pt(111)
journal, January 2007

  • Getman, Rachel B.; Schneider, William F.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 1
  • DOI: 10.1021/jp064841p

Steps or Terraces? Dynamics of Aromatic Hydrocarbons Adsorbed at Vicinal Metal Surfaces
journal, August 2015

The Brønsted–Evans–Polanyi Relation and the Volcano Plot for Ammonia Synthesis over Transition Metal Catalysts
journal, January 2001

  • Logadottir, A.; Rod, T. H.; Nørskov, J. K.
  • Journal of Catalysis, Vol. 197, Issue 2
  • DOI: 10.1006/jcat.2000.3087

Ab initiomolecular dynamics for liquid metals
journal, January 1993

Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Projector augmented-wave method
journal, December 1994

Insight into the description of van der Waals forces for benzene adsorption on transition metal (111) surfaces
journal, February 2014

  • Carrasco, Javier; Liu, Wei; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 140, Issue 8
  • DOI: 10.1063/1.4866175

Trends in Adsorption Characteristics of Benzene on Transition Metal Surfaces: Role of Surface Chemistry and van der Waals Interactions
journal, September 2013

  • Yildirim, Handan; Greber, Thomas; Kara, Abdelkader
  • The Journal of Physical Chemistry C, Vol. 117, Issue 40
  • DOI: 10.1021/jp404487z

DFT-Based Method for More Accurate Adsorption Energies: An Adaptive Sum of Energies from RPBE and vdW Density Functionals
journal, February 2017

  • Hensley, Alyssa J. R.; Ghale, Kushal; Rieg, Carolin
  • The Journal of Physical Chemistry C, Vol. 121, Issue 9
  • DOI: 10.1021/acs.jpcc.6b10187

Perspective: Advances and challenges in treating van der Waals dispersion forces in density functional theory
journal, September 2012

  • Klimeš, Jiří; Michaelides, Angelos
  • The Journal of Chemical Physics, Vol. 137, Issue 12
  • DOI: 10.1063/1.4754130

How low can you go? Minimum energy pathways for O2 dissociation on Pt(111)
journal, January 2012

  • McEwen, J. -S.; Bray, J. M.; Wu, C.
  • Physical Chemistry Chemical Physics, Vol. 14, Issue 48
  • DOI: 10.1039/c2cp42225e

Integrated X-ray photoelectron spectroscopy and DFT characterization of benzene adsorption on Pt(111), Pt(355) and Pt(322) surfaces
journal, January 2013

  • Zhang, Renqin; Hensley, Alyssa J.; McEwen, Jean-Sabin
  • Physical Chemistry Chemical Physics, Vol. 15, Issue 47
  • DOI: 10.1039/c3cp53127a

Tailoring the Adsorption of Benzene on PdFe Surfaces: A Density Functional Theory Study
journal, November 2013

  • Hensley, Alyssa J. R.; Zhang, Renqin; Wang, Yong
  • The Journal of Physical Chemistry C, Vol. 117, Issue 46
  • DOI: 10.1021/jp406425q

Adsorption of benzene on ordered Sn/Pt(111) surface alloys
journal, June 2002

Probing ensemble effects in surface reactions. 2. Benzene adsorption on clean and bismuth-covered platinum(111)
journal, January 1989

  • Campbell, J. M.; Seimanides, S.; Campbell, C. T.
  • The Journal of Physical Chemistry, Vol. 93, Issue 2
  • DOI: 10.1021/j100339a057

High-precision sampling for Brillouin-zone integration in metals
journal, August 1989

Phenol near Ni(111), Ni(110), and Ni(221) surfaces in a vertical ring geometry: A density functional study of the oxygen-surface bonding and O-H cleavage
journal, March 2007

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011

Theory of dissociative and nondissociative adsorption and desorption
journal, April 1999

  • Kreuzer, H. J.; Payne, S. H.; Drozdowski, A.
  • The Journal of Chemical Physics, Vol. 110, Issue 14
  • DOI: 10.1063/1.478604

Adsorption, mobility, and dimerization of benzaldehyde on Pt(111)
journal, May 2012

  • Rasmussen, Anton M. H.; Hammer, Bjørk
  • The Journal of Chemical Physics, Vol. 136, Issue 17
  • DOI: 10.1063/1.4707952

Calorimetric Measurement of the Heat of Adsorption of Benzene on Pt(111) †
journal, September 2004

  • Ihm, Hyeran; Ajo, Henry M.; Gottfried, J. M.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 38
  • DOI: 10.1021/jp040159o

Thermodynamics and kinetics of CO and benzene adsorption on Pt(111) studied with pulsed molecular beams and microcalorimetry
journal, November 2010

CO oxidation on electrically charged gold nanotips
journal, December 2006

  • McEwen, J. -S.; Gaspard, P.
  • The Journal of Chemical Physics, Vol. 125, Issue 21
  • DOI: 10.1063/1.2400035

Hindered Translator and Hindered Rotor Models for Adsorbates: Partition Functions and Entropies
journal, April 2016

  • Sprowl, Lynza H.; Campbell, Charles T.; Árnadóttir, Líney
  • The Journal of Physical Chemistry C, Vol. 120, Issue 18
  • DOI: 10.1021/acs.jpcc.5b11616

Femtomole Adsorption Calorimetry on Single-Crystal Surfaces
journal, April 1998

  • Brown, W. A.; Kose, R.; King, D. A.
  • Chemical Reviews, Vol. 98, Issue 2
  • DOI: 10.1021/cr9700890

Density Functional Study of Benzene Adsorption on Pt(111)
journal, August 2002

  • Saeys, Mark; Reyniers, Marie-Françoise; Marin, Guy B.
  • The Journal of Physical Chemistry B, Vol. 106, Issue 30
  • DOI: 10.1021/jp0201231

A diffuse LEED study of the adsorption structure of disordered benzene on Pt(111)
journal, June 1991

Site dependence of the apparent shape of a molecule in scanning tunneling micoscope images: Benzene on Pt{111}
journal, November 1993

Influence of Dipole–Dipole Interactions on Coverage-Dependent Adsorption: CO and NO on Pt(111)
journal, May 2012

  • Deshlahra, Prashant; Conway, Jonathan; Wolf, Eduardo E.
  • Langmuir, Vol. 28, Issue 22
  • DOI: 10.1021/la300975s

Adsorption of aromatics on the (111) surface of PtM and PtM 3 (M = Fe, Ni) alloys
journal, January 2015

  • Hensley, Alyssa J. R.; Schneider, Sebastian; Wang, Yong
  • RSC Advances, Vol. 5, Issue 104
  • DOI: 10.1039/C5RA13578H

Chemisorption of Benzene on Pt(111), Pd(111), and Rh(111) Metal Surfaces:  A Structural and Vibrational Comparison from First Principles
journal, May 2004

  • Morin, C.; Simon, D.; Sautet, P.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 18
  • DOI: 10.1021/jp0373503

Intermediates in the hydrogenation of benzene to cyclohexene on Pt(111) and Pd(111): A comparison from DFT calculations
journal, March 2006

Electronic factors determining the reactivity of metal surfaces
journal, December 1995

Correlations in coverage-dependent atomic adsorption energies on Pd(111)
journal, May 2009

Density functional theory in surface chemistry and catalysis
journal, January 2011

  • Norskov, J. K.; Abild-Pedersen, F.; Studt, F.
  • Proceedings of the National Academy of Sciences, Vol. 108, Issue 3
  • DOI: 10.1073/pnas.1006652108

Thermal desorption kinetics
journal, March 1992

The analysis of temperature programmed desorption experiments of systems with lateral interactions; implications of the compensation effect
journal, December 2003

  • Nieskens, D. L. S.; van Bavel, A. P.; Niemantsverdriet, J. W.
  • Surface Science, Vol. 546, Issue 2-3
  • DOI: 10.1016/j.susc.2003.09.035

Interaction between Coronene and Graphite from Temperature-Programmed Desorption and DFT-vdW Calculations: Importance of Entropic Effects and Insights into Graphite Interlayer Binding
journal, June 2013

  • Thrower, John D.; Friis, Emil E.; Skov, Anders L.
  • The Journal of Physical Chemistry C, Vol. 117, Issue 26
  • DOI: 10.1021/jp404240h

Thermal Desorption of Large Molecules from Solid Surfaces
journal, October 2002

Desorption energies of linear and cyclic alkanes on surfaces: anomalous scaling with length
journal, April 2004

Decomposition Mechanism of Anisole on Pt(111): Combining Single-Crystal Experiments and First-Principles Calculations
journal, November 2016

  • Réocreux, Romain; Ould Hamou, Cherif A.; Michel, Carine
  • ACS Catalysis, Vol. 6, Issue 12
  • DOI: 10.1021/acscatal.6b02253

Identifying the Thermal Decomposition Mechanism of Guaiacol on Pt(111): An Integrated X-ray Photoelectron Spectroscopy and Density Functional Theory Study
journal, January 2018

  • Hensley, Alyssa J. R.; Wöckel, Claudia; Gleichweit, Christoph
  • The Journal of Physical Chemistry C, Vol. 122, Issue 8
  • DOI: 10.1021/acs.jpcc.7b10006

Probing ensemble effects in surface reactions. 1. Site-size requirements for the dehydrogenation of cyclic hydrocarbons on platinum(111) revealed by bismuth site blocking
journal, January 1989

  • Campbell, Charles T.; Campbell, J. M.; Dalton, P. J.
  • The Journal of Physical Chemistry, Vol. 93, Issue 2
  • DOI: 10.1021/j100339a056

Density Functional Theory Analysis of Benzene (De)hydrogenation on Pt(111):  Addition and Removal of the First Two H-Atoms
journal, April 2003

  • Saeys, Mark; Reyniers, Marie-Françoise; Neurock, Matthew
  • The Journal of Physical Chemistry B, Vol. 107, Issue 16
  • DOI: 10.1021/jp022166n

A benchmark database for adsorption bond energies to transition metal surfaces and comparison to selected DFT functionals
journal, October 2015

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