Mechanistic investigation of the hydrodechlorination of 1,1,1,2-tetrafluorodichloroethane on metal fluoride-supported Pt and Pd

Irmina Kris Murwani; Erhard Kemnitz; Tomaž Skapin; Mahmood Nickkho-Amiry; John M. Winfield

doi:10.1016/j.cattod.2003.11.011

Mechanistic investigation of the hydrodechlorination of 1,1,1,2-tetrafluorodichloroethane on metal fluoride-supported Pt and Pd

Irmina Kris Murwani, Erhard Kemnitz^*, Tomaž Skapin, Mahmood Nickkho-Amiry, John M. Winfield

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

17 Citations (Scopus)

Abstract

The hydrodechlorination of CF₃CCl₂F over Pd and Pt supported on β-AlF₃ and MgF₂ with D₂ gas has been investigated employing temperature programmed isotope exchange (TPIE) under static conditions. The isotope exchange observed between the H-loaded metal catalyst and the D₂ gas phase demonstrates the significantly higher hydrogen uptake capability of Pd-based catalysts. Both Pd and Pt on β-AlF₃, show significantly higher hydrogen/deuterium uptake and isotope exchange activity as compared with the MgF₂ support, probably due to the presence of hexagonal channels in β-AlF₃ and its higher Lewis acidity. The combination of these properties make Pd/β-AlF₃ a superior catalyst for selective hydrodechlorination of CF₃CCl₂F. Based on the results of the hydrodechlorination of CF₃CCl₂F with D₂, a competitive rather than a consecutive mechanism is proposed. The data from H/D-TPIE are best interpreted by the formation of surface carbene species as intermediates.

Original language	English
Pages (from-to)	153-168
Number of pages	16
Journal	Catalysis Today
Volume	88
Issue number	3-4
DOIs	https://doi.org/10.1016/j.cattod.2003.11.011
Publication status	Published - 15 Feb 2004
Externally published	Yes

Keywords

Deuterium
Hydrodechlorination of CFCClF
Mechanism
Pd and Pt supported on β-AlF and MgF
Surface carbene
Temperature programmed H/D-isotope exchange

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10.1016/j.cattod.2003.11.011

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title = "Mechanistic investigation of the hydrodechlorination of 1,1,1,2-tetrafluorodichloroethane on metal fluoride-supported Pt and Pd",

abstract = "The hydrodechlorination of CF3CCl2F over Pd and Pt supported on β-AlF3 and MgF2 with D2 gas has been investigated employing temperature programmed isotope exchange (TPIE) under static conditions. The isotope exchange observed between the H-loaded metal catalyst and the D2 gas phase demonstrates the significantly higher hydrogen uptake capability of Pd-based catalysts. Both Pd and Pt on β-AlF3, show significantly higher hydrogen/deuterium uptake and isotope exchange activity as compared with the MgF2 support, probably due to the presence of hexagonal channels in β-AlF3 and its higher Lewis acidity. The combination of these properties make Pd/β-AlF3 a superior catalyst for selective hydrodechlorination of CF3CCl2F. Based on the results of the hydrodechlorination of CF3CCl2F with D2, a competitive rather than a consecutive mechanism is proposed. The data from H/D-TPIE are best interpreted by the formation of surface carbene species as intermediates.",

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author = "Murwani, {Irmina Kris} and Erhard Kemnitz and Toma{\v z} Skapin and Mahmood Nickkho-Amiry and Winfield, {John M.}",

year = "2004",

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AU - Murwani, Irmina Kris

AU - Kemnitz, Erhard

AU - Skapin, Tomaž

AU - Nickkho-Amiry, Mahmood

AU - Winfield, John M.

PY - 2004/2/15

Y1 - 2004/2/15

N2 - The hydrodechlorination of CF3CCl2F over Pd and Pt supported on β-AlF3 and MgF2 with D2 gas has been investigated employing temperature programmed isotope exchange (TPIE) under static conditions. The isotope exchange observed between the H-loaded metal catalyst and the D2 gas phase demonstrates the significantly higher hydrogen uptake capability of Pd-based catalysts. Both Pd and Pt on β-AlF3, show significantly higher hydrogen/deuterium uptake and isotope exchange activity as compared with the MgF2 support, probably due to the presence of hexagonal channels in β-AlF3 and its higher Lewis acidity. The combination of these properties make Pd/β-AlF3 a superior catalyst for selective hydrodechlorination of CF3CCl2F. Based on the results of the hydrodechlorination of CF3CCl2F with D2, a competitive rather than a consecutive mechanism is proposed. The data from H/D-TPIE are best interpreted by the formation of surface carbene species as intermediates.

AB - The hydrodechlorination of CF3CCl2F over Pd and Pt supported on β-AlF3 and MgF2 with D2 gas has been investigated employing temperature programmed isotope exchange (TPIE) under static conditions. The isotope exchange observed between the H-loaded metal catalyst and the D2 gas phase demonstrates the significantly higher hydrogen uptake capability of Pd-based catalysts. Both Pd and Pt on β-AlF3, show significantly higher hydrogen/deuterium uptake and isotope exchange activity as compared with the MgF2 support, probably due to the presence of hexagonal channels in β-AlF3 and its higher Lewis acidity. The combination of these properties make Pd/β-AlF3 a superior catalyst for selective hydrodechlorination of CF3CCl2F. Based on the results of the hydrodechlorination of CF3CCl2F with D2, a competitive rather than a consecutive mechanism is proposed. The data from H/D-TPIE are best interpreted by the formation of surface carbene species as intermediates.

KW - Deuterium

KW - Hydrodechlorination of CFCClF

KW - Mechanism

KW - Pd and Pt supported on β-AlF and MgF

KW - Surface carbene

KW - Temperature programmed H/D-isotope exchange

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DO - 10.1016/j.cattod.2003.11.011

M3 - Article

AN - SCOPUS:0742267139

SN - 0920-5861

VL - 88

SP - 153

EP - 168

JO - Catalysis Today

JF - Catalysis Today

IS - 3-4

ER -

Mechanistic investigation of the hydrodechlorination of 1,1,1,2-tetrafluorodichloroethane on metal fluoride-supported Pt and Pd

Abstract

Keywords

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