Abstract
The reaction of iron atoms with carbon tetrachloride (CCl 4) in gas phase was studied using density functional theory. A recent experimental study (Parkinson, G. S.; Dohna'lek, Z.; Smith, R. S.; Kay, B. D. J. Phys. Chem. C 2009, 113, 1818) of this reaction, performed by dropping Fe atoms into CCl4 deposited on a cold FeO(111) surface, demonstrates rich chemistry with several products (C 2Cl 4, C 2Cl 6, OCCl 2, CO, FeCl 2, and FeCl 3) observed. The reactions of Fe with CCl 4 was studied under three stoichiometries, one Fe with one CCl 4, one Fe with two CCl 4 molecules, and two Fe with one CCl 4, modeling the stoichiometric, CCl 4-rich, and Fe-rich environments of the experimental work. The electronic structure calculations give insight into the reactions leading to the experimentally observed products, in particular with regard to the formation of FeCl 3 and other oxygen containing compounds that are not predicted from the simplest reactive model of successive Cl atom abstractions. They rather suggest that novel Fe-C-Cl containing species are important intermediates in these reactions. The intermediate complexes are formed in highly exothermic reactions, in agreement with the experimentally observed reactivity on the surface at low temperature (30 K). This initial survey of the reactivity of Fe with CCl 4 identifies some potential reaction pathways that are important in the effort to use Fe nanoparticles to differentiate harmful pathways that lead to the formation of contaminants like chloroform (CHCl 3) from harmless pathways that lead to products such as formate (HCO 2 -) or carbon oxides in water and soil.
| Original language | English |
|---|---|
| Pages (from-to) | 1830-1836 |
| Number of pages | 7 |
| Journal | Journal of Physical Chemistry C |
| Volume | 113 |
| Issue number | 5 |
| DOIs | |
| Publication status | Published - Feb 5 2009 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Electronic, Optical and Magnetic Materials
- Surfaces, Coatings and Films
- Energy(all)
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Modeling the reaction of Fe Atoms with CCl4. / Camaioni, Donald M.; Ginovska, Bojana; Dupuis, Michel.
In: Journal of Physical Chemistry C, Vol. 113, No. 5, 05.02.2009, p. 1830-1836.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Modeling the reaction of Fe Atoms with CCl4
AU - Camaioni, Donald M.
AU - Ginovska, Bojana
AU - Dupuis, Michel
PY - 2009/2/5
Y1 - 2009/2/5
N2 - The reaction of iron atoms with carbon tetrachloride (CCl 4) in gas phase was studied using density functional theory. A recent experimental study (Parkinson, G. S.; Dohna'lek, Z.; Smith, R. S.; Kay, B. D. J. Phys. Chem. C 2009, 113, 1818) of this reaction, performed by dropping Fe atoms into CCl4 deposited on a cold FeO(111) surface, demonstrates rich chemistry with several products (C 2Cl 4, C 2Cl 6, OCCl 2, CO, FeCl 2, and FeCl 3) observed. The reactions of Fe with CCl 4 was studied under three stoichiometries, one Fe with one CCl 4, one Fe with two CCl 4 molecules, and two Fe with one CCl 4, modeling the stoichiometric, CCl 4-rich, and Fe-rich environments of the experimental work. The electronic structure calculations give insight into the reactions leading to the experimentally observed products, in particular with regard to the formation of FeCl 3 and other oxygen containing compounds that are not predicted from the simplest reactive model of successive Cl atom abstractions. They rather suggest that novel Fe-C-Cl containing species are important intermediates in these reactions. The intermediate complexes are formed in highly exothermic reactions, in agreement with the experimentally observed reactivity on the surface at low temperature (30 K). This initial survey of the reactivity of Fe with CCl 4 identifies some potential reaction pathways that are important in the effort to use Fe nanoparticles to differentiate harmful pathways that lead to the formation of contaminants like chloroform (CHCl 3) from harmless pathways that lead to products such as formate (HCO 2 -) or carbon oxides in water and soil.
AB - The reaction of iron atoms with carbon tetrachloride (CCl 4) in gas phase was studied using density functional theory. A recent experimental study (Parkinson, G. S.; Dohna'lek, Z.; Smith, R. S.; Kay, B. D. J. Phys. Chem. C 2009, 113, 1818) of this reaction, performed by dropping Fe atoms into CCl4 deposited on a cold FeO(111) surface, demonstrates rich chemistry with several products (C 2Cl 4, C 2Cl 6, OCCl 2, CO, FeCl 2, and FeCl 3) observed. The reactions of Fe with CCl 4 was studied under three stoichiometries, one Fe with one CCl 4, one Fe with two CCl 4 molecules, and two Fe with one CCl 4, modeling the stoichiometric, CCl 4-rich, and Fe-rich environments of the experimental work. The electronic structure calculations give insight into the reactions leading to the experimentally observed products, in particular with regard to the formation of FeCl 3 and other oxygen containing compounds that are not predicted from the simplest reactive model of successive Cl atom abstractions. They rather suggest that novel Fe-C-Cl containing species are important intermediates in these reactions. The intermediate complexes are formed in highly exothermic reactions, in agreement with the experimentally observed reactivity on the surface at low temperature (30 K). This initial survey of the reactivity of Fe with CCl 4 identifies some potential reaction pathways that are important in the effort to use Fe nanoparticles to differentiate harmful pathways that lead to the formation of contaminants like chloroform (CHCl 3) from harmless pathways that lead to products such as formate (HCO 2 -) or carbon oxides in water and soil.
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U2 - 10.1021/jp807604f
DO - 10.1021/jp807604f
M3 - Article
VL - 113
SP - 1830
EP - 1836
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7447
IS - 5
ER -