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Chemisorption of Organics on Platinum. 2. Chemisorption of C_2H_x and CH_x on Pt(111)

Kua, Jeremy and Goddard, William A., III (1998) Chemisorption of Organics on Platinum. 2. Chemisorption of C_2H_x and CH_x on Pt(111). Journal of Physical Chemistry B, 102 (47). pp. 9492-9500. ISSN 1520-6106. http://resolver.caltech.edu/CaltechAUTHORS:20180522-151358898

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Abstract

Using the interstitial electron surface model (IESM) developed in the accompanying part, we examined the structures and energetics of a number of organic fragments on Pt surfaces. Using nonlocal density functional methods (B3LYP) we find that organics covalently bond to the Pt(111) surface with localized σ bonds to the surface Pt atoms, leading to tetrahedral hybridization of each carbon bonded to the surface. Thus, (i) CH_3 prefers an on-top site (a bond energy of ∼54 kcal/mol), (ii) CH_2 prefers a 2-fold bridge site (a bond energy of ∼104 kcal/mol), and (iii) CH prefers the fcc 3-fold bridge site (a bond energy of ∼167 kcal/mol). Similarly, C_2H_4 forms a strong (36 kcal/mol) di-σ bond (the π bond is BE = 8.5 kcal/mol), while CHCH_2 forms a tri-σ bond. The results for C_2H_x/Pt_8 are in good agreement with available experimental results on Pt(111) (π- and di-σ-bonded ethylene and ethylidyne). These results are used to obtain heats of formation (ΔH_f) for chemisorbed intermediates useful in estimating the energetics of various hydrocarbon intermediates on Pt surfaces. The application of these ΔH_f values is illustrated by considering ethylene hydrogenation and the decomposition of C_2H_4 on Pt(111).


Item Type:Article
Related URLs:
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https://doi.org/10.1021/jp982527sDOIArticle
ORCID:
AuthorORCID
Goddard, William A., III0000-0003-0097-5716
Alternate Title:Chemisorption of Organics on Platinum. 2. Chemisorption of C2Hx and CHx on Pt(111)
Additional Information:© 1998 American Chemical Society. Received: June 8, 1998; In Final Form: August 18, 1998. Publication Date (Web): November 3, 1998. The research was funded by the NSF (CHE 95−22179). The facilities of the MSC are also supported by grants from DOE-ASCI, BP Chemical, Beckman Institute, Seiko-Epson, Exxon, Owens-Corning, Asahi Chemical, Chevron Petroleum Technology Co., Chevron Chemical Co., Chevron Research and Technology Corp., and Avery-Dennison. Some calculations were carried out at NCSA, University of Illinois.
Funders:
Funding AgencyGrant Number
NSFCHE 95-22179
Department of Energy (DOE)UNSPECIFIED
BP ChemicalUNSPECIFIED
Caltech Beckman InstituteUNSPECIFIED
Seiko-EpsonUNSPECIFIED
ExxonUNSPECIFIED
Owens-CorningUNSPECIFIED
Asahi ChemicalUNSPECIFIED
Chevron Petroleum Technology Co.UNSPECIFIED
Chevron Chemical Co.UNSPECIFIED
Chevron Research and Technology Corp.UNSPECIFIED
Avery-DennisonUNSPECIFIED
Record Number:CaltechAUTHORS:20180522-151358898
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20180522-151358898
Official Citation:Chemisorption of Organics on Platinum. 2. Chemisorption of C2Hx and CHx on Pt(111). Jeremy Kua and and William A. Goddard III. The Journal of Physical Chemistry B 1998 102 (47), 9492-9500 DOI: 10.1021/jp982527s
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:86558
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:24 May 2018 16:40
Last Modified:24 May 2018 16:40

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