Transient kinetics investigations of reaction intermediates involved in CF2Cl2 hydrodechlorination

Deshmukh, Subodh; d’Itri, Julie L.

doi:10.1016/s0920-5861(98)00066-2

Cited by 59 publications

(29 citation statements)

References 20 publications

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“…It is also very unlikely that both configurations are suffering the effects of steric hindrance. The small reduction of the DE may be an indication that this species is weakly bound to the surface, as proposed by experimental studies [20,37,38].…”

Section: Effect Of Total Coveragementioning

confidence: 65%

“…This could be the percursor of the completely dechlorinated molecules and methane, which are usually found in experimental studies [20,21,24,30,31,[35][36][37][38][39]52]. …”

Section: Resultsmentioning

confidence: 89%

“…Chlorine was chosen because it is the most likely species to be present during the hydrodechlorination reaction, as shown in several experimental studies [20,21,24,30,31,[35][36][37][38][39]52], it is strongly bound to Pd surface at low/medium coverages [58][59][60] and it can be found at coverages up to 0.6 [58,59].…”

Section: Effect Of Total Coveragementioning

confidence: 99%

“…Regarding the selectivity of the hydrodechlorination reaction on Pd it is higher for the formation of fully or partially dechlorinated products in the case of C2 fluorochlorocarbons [20,21,31,35,36] and for fully dehalogenated in the case C1 fluorochlorocarbons [20,24,30,[37][38][39]. Fully dehalogenated or partially dechlorinated molecules are not desirable, because the target is to substitute chlorine atoms of the CFC's molecules by hydrogen atoms.…”

Section: Introductionmentioning

confidence: 99%

“…The CF 2 carbene is considered the most important intermediary of the hydrodechlorination of CF 2 Cl 2 on Pd catalysts [20,24,32,[37][38][39]. It seems to be the key for this reaction selectivity.…”

Section: Introductionmentioning

confidence: 99%

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Theoretical Study of the Stability of Carbene Intermediates Formed During the Hydrodechlorination Reaction of the CF x Cl4−x Family on the Pd(110) Surface

2009

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In the present work the stability of the species CCl 2 , CFCl, CF 2 and CHF, which are produced during the hydrodechlorination reaction of the CF x Cl 4-x family, have been investigated on the Pd(110) surface by applying ab initio periodic Density Functional Theory. The most stable configuration for these carbenes on this surface is the short-bridge. Hollow positions have not been found as stationary points in most of the cases. For the chlorinated fragments, the optimisation of these hollow positions resulted in partial or full dechlorinated fragments. The most stable configuration for the carbenes (short-bridge) was compared to the least stable one (top) within different surface conditions in order to verify any change in this stability trend. Both geometries are equally affected by the surface modifications for most of the carbenes. The shortbridge is, however, more sensitive to the coverage increase in the CHF case. CHF has the strongest binding energy to the Pd(110) surface, whilst CF 2 has the least one. The stability trend of CHF, CFCl and CF 2 helped to better understand the selectivity of the hydrodechlorination reaction of the mono carbon CFC's, for example, the suggestion that CF 2 is the most important intermediate on the hydrodechlorination of CF 2 Cl 2 was confirmed by the calculations.

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Section: Effect Of Total Coveragementioning

confidence: 65%

“…This could be the percursor of the completely dechlorinated molecules and methane, which are usually found in experimental studies [20,21,24,30,31,[35][36][37][38][39]52]. …”

Section: Resultsmentioning

confidence: 89%

Section: Effect Of Total Coveragementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Theoretical Study of the Stability of Carbene Intermediates Formed During the Hydrodechlorination Reaction of the CF x Cl4−x Family on the Pd(110) Surface

2009

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Catalytic Dehalogenation

Howe

2008

Handbook of Heterogeneous Catalysis

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The sections in this article are Introduction Organohalogen Compounds Reaction Types Decomposition Hydrodehalogenation Oxidation Hydrolysis Supported Metal Catalysts Zeolite Catalysts

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Supported Transition Metal Catalysts for Hydrodechlorination Reactions

2011

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As halogenated waste is xenobiotic with no analogous compounds in nature, there is no natural means of ameliorating the negative environmental impact caused by halo‐organic emissions. The presence of organo‐halogens in effluent discharges is of increasing concern, owing to the mounting evidence of adverse stratospheric ozone, ecological effects, and the impact on public health. There is a pressing need, driven by legislative and financial imperatives, to develop robust and efficient treatment technologies. This Review considers the application of catalytic hydrodechlorination (HDC) as a progressive approach to the conversion and recycling of toxic chloro‐compounds. An overview of the existing treatment technologies is provided with an assessment of the benefits of catalytic HDC over separation/oxidation methodologies. Taking the transformation of chloro‐aromatics, the catalytic HDC of liquid and gas phase reactants is considered in turn with a critical analysis of the pertinent literature. Two “case studies” are considered in detail: i) the liquid phase HDC of chlorophenols over alumina supported palladium, focusing on the critical process and catalyst structural characteristics that influence HDC performance; ii) the gas phase conversion of a range of halogenated (Cl and Br) aromatics over silica supported nickel with an examination of the dehalogenation activity/selectivity response as a function of the nature of the aromatic reactant.

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Transient kinetics investigations of reaction intermediates involved in CF2Cl2 hydrodechlorination

Cited by 59 publications

References 20 publications

Theoretical Study of the Stability of Carbene Intermediates Formed During the Hydrodechlorination Reaction of the CF x Cl4−x Family on the Pd(110) Surface

Theoretical Study of the Stability of Carbene Intermediates Formed During the Hydrodechlorination Reaction of the CF x Cl4−x Family on the Pd(110) Surface

Catalytic Dehalogenation

Supported Transition Metal Catalysts for Hydrodechlorination Reactions

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