The heat of adsorption and sticking probability of cyclohexene on Pt(111) were measured as a function of coverage using single-crystal adsorption calorimetry in the temperature range from 100 to 300 K. At 100 K, cyclohexene adsorbs as intact di-sigma bonded cyclohexene on Pt(111), and the heat of adsorption is well described by a second-order polynomial (130 - 47 theta - 1250 theta(2)) kJ/mol, yielding a standard enthalpy of formation of di-sigma bonded cyclohexene on Pt(111) at low coverages of -135 kJ/mol and a C-Pt sigma bond strength of 205 kJ/mol. At 281 K, cyclohexene dehydrogenates upon adsorption, forming adsorbed 2-cyclohexenyl (c-C6H(9,a)) and adsorbed hydrogen, and the heat of adsorption is well described by another second-order polynomial (174 - 700 theta + 761 theta(2)) kJ/mol. This yields a standard enthalpy of formation of adsorbed 2-cyclohexenyl on Pt(111) at a low coverage of -143 kJ/mol. At coverages below 0.10 ML, the sticking probability of cyclohexene on Pt(111) is close to unity (>0.95), independent of temperature.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/ja801856s | DOI Listing |
Phys Chem Chem Phys
November 2015
University of Lyon, CNRS, Laboratoire de Chimie, ENS de Lyon, 46 Allée d'Italie, 69364 Lyon, France.
Molecular chemisorption at a metal surface is a key step for many processes, such as catalysis, electrochemistry, surface treatment, tribology and friction. Modeling with density functional theory is largely used on these systems. From a detailed comparison with accurate micro-calorimetric data on ten systems (involving ethylene, cyclohexene, benzene, naphthalene, CO, O2, H2, methane, ethane), we study the accuracy, for chemisorption on Pt(111), of five exchange-correlation functionals including one generalized gradient approximation functional (PBE) and four functionals that take into account van der Waals interactions (optPBE-vdW, optB86b-vdW, BEEF-vdW, PBE-dDsC).
View Article and Find Full Text PDFJ Am Chem Soc
August 2008
Department of Chemistry, University of Washington, Box 351700, Seattle, Washington 98195-1700, USA.
The heat of adsorption and sticking probability of cyclohexene on Pt(111) were measured as a function of coverage using single-crystal adsorption calorimetry in the temperature range from 100 to 300 K. At 100 K, cyclohexene adsorbs as intact di-sigma bonded cyclohexene on Pt(111), and the heat of adsorption is well described by a second-order polynomial (130 - 47 theta - 1250 theta(2)) kJ/mol, yielding a standard enthalpy of formation of di-sigma bonded cyclohexene on Pt(111) at low coverages of -135 kJ/mol and a C-Pt sigma bond strength of 205 kJ/mol. At 281 K, cyclohexene dehydrogenates upon adsorption, forming adsorbed 2-cyclohexenyl (c-C6H(9,a)) and adsorbed hydrogen, and the heat of adsorption is well described by another second-order polynomial (174 - 700 theta + 761 theta(2)) kJ/mol.
View Article and Find Full Text PDFNano Lett
October 2007
Department of Chemistry, University of California, Berkeley, California 94720, USA.
Benzene hydrogenation was investigated in the presence of a surface monolayer consisting of Pt nanoparticles of different shapes (cubic and cuboctahedral) and tetradecyltrimethylammonium bromide (TTAB). Infrared spectroscopy indicated that TTAB binds to the Pt surface through a weak C-H..
View Article and Find Full Text PDFJ Phys Chem B
November 2006
Department of Chemistry, Joseph Black Building, University of Glasgow, Glasgow G12 8QQ, UK.
We have shown using a combination of temperature-programmed desorption and UV photoelectron spectroscopy that the presence of preadsorbed atomic sulfur promotes the bonding of cyclic unsaturated hydrocarbons (benzene and cyclohexene) to Cu(111). This promoting behavior of sulfur can be rationalized in terms of the ability of adsorbed sulfur to influence the balance between charge donation from the adsorbate to metal, and back-donation from the metal to adsorbate. The effects of sulfur on Cu(111) are dramatically different from those observed in previous studies on Pt(111), which found that it caused a downward shift in the desorption temperature of adsorbed benzene, through purely steric effects.
View Article and Find Full Text PDFJ Phys Chem B
October 2006
Department of Chemistry, University of California, Berkeley, California 94720, USA.
The mechanism that controls bond breaking at transition metal surfaces has been studied with sum frequency generation (SFG), scanning tunneling microscopy (STM), and catalytic nanodiodes operating under the high-pressure conditions. The combination of these techniques permits us to understand the role of surface defects, surface diffusion, and hot electrons in dynamics of surface catalyzed reactions. Sum frequency generation vibrational spectroscopy and kinetic measurements were performed under 1.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!