TY - JOUR
T1 - Selective side-chain oxidation of alkyl aromatic compounds catalyzed by cerium modified silver catalysts
AU - Beier, Matthias J.
AU - Schimmoeller, Bjoern
AU - Hansen, Thomas W.
AU - Andersen, Jens E.T.
AU - Pratsinis, Sotiris E.
AU - Grunwaldt, Jan Dierk
PY - 2010/10/1
Y1 - 2010/10/1
N2 - Silver supported on silica effectively catalyzes the aerobic side-chain oxidation of alkyl aromatic compounds under solvent-free conditions. Toluene, p-xylene, ethylbenzene and cumene were investigated as model substrates. Typically, the reaction was performed at ambient pressure; only for toluene an elevated pressure was required. Carboxylic acids, such as benzoic acid or p-toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation and flame spray pyrolysis. Addition of a Ce precursor to the FSP catalyst resulted in significantly smaller silver particles. Ce-doped FSP catalysts in general exhibited a superior catalytic performance with TONs up to 2000 except for cumene oxidation that appeared to proceed mainly by homogeneous catalysis. In addition, flame-made catalysts were more stable against silver leaching compared to the impregnated catalysts. The structure of the silver catalysts was studied in detail both by X-ray absorption spectroscopy and transmission electron microscopy suggesting metallic silver to be required for catalytic activity. Catalytic studies point to a radical mechanism which differs depending on the type of substrate.
AB - Silver supported on silica effectively catalyzes the aerobic side-chain oxidation of alkyl aromatic compounds under solvent-free conditions. Toluene, p-xylene, ethylbenzene and cumene were investigated as model substrates. Typically, the reaction was performed at ambient pressure; only for toluene an elevated pressure was required. Carboxylic acids, such as benzoic acid or p-toluic acid, additionally increased the reaction rate while CeO2 could act both as a promoter and an inhibitor depending on the substrate and the reaction conditions. Silver catalysts were prepared both by standard impregnation and flame spray pyrolysis. Addition of a Ce precursor to the FSP catalyst resulted in significantly smaller silver particles. Ce-doped FSP catalysts in general exhibited a superior catalytic performance with TONs up to 2000 except for cumene oxidation that appeared to proceed mainly by homogeneous catalysis. In addition, flame-made catalysts were more stable against silver leaching compared to the impregnated catalysts. The structure of the silver catalysts was studied in detail both by X-ray absorption spectroscopy and transmission electron microscopy suggesting metallic silver to be required for catalytic activity. Catalytic studies point to a radical mechanism which differs depending on the type of substrate.
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U2 - 10.1016/j.molcata.2010.08.001
DO - 10.1016/j.molcata.2010.08.001
M3 - Article
AN - SCOPUS:77957323436
SN - 1381-1169
VL - 331
SP - 40
EP - 49
JO - Journal of Molecular Catalysis A: Chemical
JF - Journal of Molecular Catalysis A: Chemical
IS - 1-2
ER -