Gas-phase photocatalytic oxidation of dichlorobutenes

Noel A. Hamill; Christopher Hardacre; Johannes A C Barth; Robert M. Kalin; Joseph F. Cunningham

doi:10.1021/es001939n

Gas-phase photocatalytic oxidation of dichlorobutenes

Noel A. Hamill, Christopher Hardacre^*, Johannes A C Barth, Robert M. Kalin, Joseph F. Cunningham

^*Corresponding author for this work

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

Abstract

Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO₂ and 3%WO₃/TiO₂ supported on SiO₂. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO₂ formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O₂ concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.

Original language	English
Pages (from-to)	2823-2827
Number of pages	5
Journal	Environmental Science and Technology
Volume	35
Issue number	13
DOIs	https://doi.org/10.1021/es001939n
Publication status	Published - 1 Jul 2001

Access to Document

10.1021/es001939n

Cite this

@article{94100433a42b4b91816a7f5eec535e4b,

title = "Gas-phase photocatalytic oxidation of dichlorobutenes",

abstract = "Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO2 and 3%WO3/TiO2 supported on SiO2. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO2 formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O2 concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.",

author = "Hamill, {Noel A.} and Christopher Hardacre and Barth, {Johannes A C} and Kalin, {Robert M.} and Cunningham, {Joseph F.}",

year = "2001",

month = jul,

day = "1",

doi = "10.1021/es001939n",

language = "English",

volume = "35",

pages = "2823--2827",

journal = "Environmental Science and Technology",

issn = "0013-936X",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Gas-phase photocatalytic oxidation of dichlorobutenes

AU - Hamill, Noel A.

AU - Hardacre, Christopher

AU - Barth, Johannes A C

AU - Kalin, Robert M.

AU - Cunningham, Joseph F.

PY - 2001/7/1

Y1 - 2001/7/1

N2 - Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO2 and 3%WO3/TiO2 supported on SiO2. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO2 formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O2 concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.

AB - Gas-phase photocatalysis of 1,4-dichlorobut-2-enes and 3,4-dichlorobut-1-ene (DCB) has been studied using TiO2 and 3%WO3/TiO2 supported on SiO2. DCB was found to oxidize efficiently over these catalysts; however, only low rates of CO2 formation were observed. With these chlorinated hydrocarbons, the catalysts were found to deactivate over time, probably via the formation of aldol condensation products of chloroacetaldehyde, which is the predominant intermediate observed. The variation in rate and selectivity of the oxidation reactions with O2 concentration is reported and a mechanism is proposed. Using isotope ratio mass spectrometry, the initial step for the DCB removal has been shown not to be a carbon bond cleavage but is likely to be hydroxyl radical addition to the carbon-carbon double bond.

UR - http://www.scopus.com/inward/record.url?scp=0035387986&partnerID=8YFLogxK

U2 - 10.1021/es001939n

DO - 10.1021/es001939n

M3 - Article

C2 - 11452616

AN - SCOPUS:0035387986

SN - 0013-936X

VL - 35

SP - 2823

EP - 2827

JO - Environmental Science and Technology

JF - Environmental Science and Technology

IS - 13

ER -

Gas-phase photocatalytic oxidation of dichlorobutenes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this