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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

Journal Article · · Progress in Surface Science
 [1];  [1];  [1];  [2];  [2]
  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)
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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.

Research Organization:
Washington State Univ., Pullman, WA (United States)
Sponsoring Organization:
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)
Grant/Contract Number:
SC0014560; 1347973
OSTI ID:
1755213
Alternate ID(s):
OSTI ID: 1543038
Journal Information:
Progress in Surface Science, Vol. 94, Issue 2; ISSN 0079-6816
Publisher:
ElsevierCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

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Related Subjects

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