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Preparation and characterization of copper-thorium oxide catalysts. 2. ESR study of copper(II) ion pairs and correlation with the selective hydrogenation of isoprene

Journal Article · · Chemistry of Materials; (United States)
DOI:https://doi.org/10.1021/cm00011a011· OSTI ID:5470331
; ; ; ;  [1];  [2]
  1. Universite des Sciences et Techniques de Lille Flandres-Artois, Villeneuve d'Ascq (France)
  2. Universite Libanaise (France)

CuThO oxides prepared with an atomic ratio Cu/Th > 0.01 were extensively studied by electron spin resonance (ESR) and X-ray photoelectron spectroscopies (XPS). The XPS analysis of these solids showed that the thoria surface is enriched with copper. The X-ray diffraction patterns for Cu/Th > 0.25 revealed two distinct phase systems, ThO{sub 2} and CuO. ESR studies evidenced two signals of monomeric Cu{sup 2+} species (M{sub 1} and M{sub 2}) and a well-resolved D signal ({Delta}m{sub 2} = 1) of Cu{sup 2+} ion pairs, accompanied by a weak signal at half magnetic field intensity ({Delta}m{sub s} = 2). From the {Delta}m{sub 2} = 2/{Delta}m{sub s} = 1 intensities ratio and from the fine splitting observed for the D signal, the distance between the Cu{sup 2+} ions in the pair have been calculated. These copper-thorium oxide catalysts are active for selective hydrogenation of isoprene at 373 K after reduction of the oxide phase at 523 K. A correlation between this activity and the relative intensities of M{sub 1}, M{sub 2} and D signals was established.

OSTI ID:
5470331
Journal Information:
Chemistry of Materials; (United States), Journal Name: Chemistry of Materials; (United States) Vol. 2:5; ISSN CMATE; ISSN 0897-4756
Country of Publication:
United States
Language:
English