title: X-ray spectroscopic studies of the high temperature reduction of Cu(II)O by 2-chlorophenol on a simulated fly ash surface.
abstract: The reaction of 2-chlorophenol on Cu(II)O at 375 degrees C is studied using X-ray absorption near edge structure (XANES) spectroscopy. A mixture of copper(II) oxide and silica is prepared to serve as a surrogate for fly ash in combustion systems. 2-Chlorophenol is utilized as a model precursor for formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/F). The Cu K-edge spectra shiftto lower binding energy, reflecting the reduction of the copper. The substrate is found to form a mixture of Cu(II), Cu(I), and Cu(O), with the dominant species being Cu(I). The data are fitted well with a first-order reaction scheme, with a time constant at 375 degrees C of 76 s. This is the first application of XANES spectroscopy for studying the kinetics and mechanism of heterogeneous reactions relevant to combustion processes, and the results demonstrate the utility and desirability of such X-ray spectroscopic studies.
authors.affiliation: Department of Chemistry, Louisiana State University, Baton Rouge, Louisiana 70803, USA.
authors.forename: George R
authors.initials: GR
authors.lastname: Farquar
authors.forename: S L
authors.initials: SL
authors.lastname: Alderman
authors.forename: E D
authors.initials: ED
authors.lastname: Poliakoff
authors.forename: B
authors.initials: B
authors.lastname: Dellinger
mesh_terms: D000393:Air Pollutants / Q000032:analysis; D001572:Benzofurans / Q000737:chemistry*; D002733:Chlorophenols / Q000737:chemistry*; D003300:Copper / Q000737:chemistry*; D000072338:Dibenzofurans, Polychlorinated; D007700:Kinetics; D010084:Oxidation-Reduction; D000072317:Polychlorinated Dibenzodioxins / Q000031:analogs & derivatives* / Q000737:chemistry*; D012989:Soil Pollutants / Q000032:analysis*; D013057:Spectrum Analysis; D013696:Temperature
chemical_list: D000393:Air Pollutants; D001572:Benzofurans; D002733:Chlorophenols; D000072338:Dibenzofurans, Polychlorinated; D000072317:Polychlorinated Dibenzodioxins; D012989:Soil Pollutants; D003300:Copper; C030683:2-chlorophenol; C030973:cupric oxide