Adsorption structure, energetics, and thermal reactions of vinyl chloride on Ag()

Pursell, David P.; Bocquet, Marie‐Laure; Vohs, John M.; Dai, Hai‐Lung

doi:10.1016/s0039-6028(02)02333-6

Cited by 15 publications

(28 citation statements)

References 41 publications

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“…For both ViBr and AllBr, calculations show small changes in geometry during adsorption, with the CC bond length increasing from 1.33 Å to ∼1.40 Å for all adsorption geometries of both molecules, significantly less than a typical CC bond length of 1.52 Å . We therefore interpret these molecules as physisorbed, in agreement with previous studies of vinyl halides and allyl halides on related copper and silver surfaces. − …”

Section: Resultssupporting

confidence: 90%

Direct and Delayed Dynamics in Electron-Induced Surface Reaction

et al. 2017

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The electron-induced reaction of physisorbed vinyl bromide (ViBr) and allyl bromide (AllBr) on Cu(110) at 4.6 K was studied experimentally by scanning tunneling microscopy and theoretically by molecular dynamics. ViBr and AllBr were found to react by two pathways: "Direct", in which the molecule reacted under the tip, and "Delayed", in which reaction occurred spontaneously after the molecule had diffused across the surface away from the tip. The novel pathway of Delayed reaction constituted a major route for both vinyl bromide (68%) and allyl bromide (53%). The observed reaction dynamics for ViBr and AllBr gave evidence of a long-lived vibrationally excited intermediate for both Direct and Delayed reactions. Molecular dynamics simulations with reagent excitation by way of selected vibrational normal modes resulted in either Direct or Delayed reaction, depending on the vibrational mode.

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Section: Resultssupporting

confidence: 90%

Direct and Delayed Dynamics in Electron-Induced Surface Reaction

et al. 2017

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“…Second-order desorption has been reported mainly in associative desorption of O 2 , 50,51 H 2 , 52,53 and other molecules. [54][55][56] However, Wang and Koel 57 reported fascinating observations concerning NO 2 adsorption and desorption over ice surfaces on an Au(111) substrate under ultrahigh vacuum conditions: NO + NO 3 À was formed on the amorphous ice surface via NO 2 dimerization and disproportionation at 200-260 K. Upon heating to 275-400 K, adsorbed NO + NO 3 À decomposed to evolve gas-phase NO 2 . 57 Likewise, Givan and Loewenschuss 58 observed that NO + NO 3 À decomposed into NO 2 monomers via a molecular NONO 3 intermediate at an extremely low temperature.…”

Section: Desorption Ordersmentioning

confidence: 99%

Analysis of the adsorption state and desorption kinetics of NO2 over Fe–zeolite catalyst by FT-IR and temperature-programmed desorption

Iwasaki

Shinjoh

2010

Phys. Chem. Chem. Phys.

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States of NO(2) adsorption and kinetics of NO(2) desorption over a Fe-loaded ZSM-5 type zeolite were investigated using Fourier transform infrared (FT-IR) spectroscopy and temperature-programmed desorption (TPD). The FT-IR spectra in NO(2)/N(2) flows showed that several adsorption species (NO(2), nitrite, nitrate, and NO(+)) existed; except for NO(2), these were considered to be formed via NO(2) dimerization and disproportionation reactions. The TPD spectra showed two distinct peaks, a low-temperature (LT) peak that can be assigned to weakly adsorbed NO(x) in the zeolite channel and a high-temperature (HT) peak that can be assigned to chemisorbed NO(x) bonded to ion-exchanged Fe sites. By varying flow rates and heating rates in TPD measurements, the peak maximum temperatures in the both peaks were found to be constant with the former, but shifted to higher temperatures with the latter; this suggests that desorption is not controlled by an adsorption/desorption equilibrium, i.e., in the no-readsorption limit. Furthermore, it was found that desorption at both LT and HT peaks proceeds at second order; this implies that the reverse reaction of NO(2) dimerization and disproportionation and/or some sort of lateral interaction between NO(2) molecules might be occurring. The desorption energies and the pre-exponential factors were estimated to be 67 +/- 1 kJ mol(-1) and 10(5.5+/-0.2) s(-1) for the LT peak and 138 +/- 4 kJ mol(-1) and 10(9.8+/-0.3) s(-1) for the HT peak. These values show that interaction strengths between adsorbed NO(x) and Fe sites are relatively large.

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“…For the synchrotron-based photoemission study, the sample was cooled to 130 K, well above the multilayer desorption temperature of 92 K [35], and exposed to a 20 L dose of vinyl chloride at 130 K. Following the 20 L dose, photoemission spectra were collected at 130 K then the sample was heated to consecutively higher temperatures. Following each heating treatment, the sample was cooled again to near 130 K and photoemission spectra were collected in an attempt to isolate any surface intermediates formed during the thermally-induced surface reaction of vinyl chloride.…”

Section: X-ray Photoelectron Spectroscopymentioning

confidence: 99%