Structural and Compositional Effect of Heteropolyoxoanions [NiMo6-x WxO24H6]4- on the Catalytic Activity of Clean Selective Oxidation of Diphenylsulfide

Author(s): Mercedes Munoza, Maria G. Egusquiza, Irma L. Botto, Carmen I. Cabello

Journal Name: Current Catalysis

Volume 3 , Issue 2 , 2014

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Graphical Abstract:


Diphenyilsulfide oxidation by H2O2 as oxidant was studied through the structural effect of the isomorphous W-Mo systems, Anderson type, with [Ni(II)Mo(VI)6-xW(VI)xO24H6]4- composition. These phases were proved as alternative catalysts instead of W and Mo conventional systems. The characterization of the substituted phases was carried out by different physico-chemical techniques (AAS, DRS, micro-Raman, XRD, TPR). The catalytic evaluation for the phase NiW6 revealed that the process was selective to the sulfone formation (selectivity ~ 81-88 %) while the Ni-Mo bi-metallic system (NiMo6) was only selective to the sulfoxide production (selectivity 98 %). The activity was 90 % at 60 and 180 min for the NiMo6 and NiW6 respectively, whereas the substituted phases presented intermediate values. The observed differences can be related to the strength of the bridge bonds (Mo-O…Ni and W-O…Ni) associated to the higher electronegativity and ionic potential of Mo with respect to W. Hence, the W-O bond is more reactive by the inductive effect of Ni, which produces a higher oxidation of diphenyilsulfide to give sulfone, considering the electronic mobility in the redox processes.

Keywords: Clean oxidation, Diphenylsulfone, Diphenylsulfoxide, Hydrogen peroxide, Selective oxidation, W and Mo heteropolymetalates.

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Article Details

Year: 2014
Published on: 24 December, 2013
Page: [139 - 146]
Pages: 8
DOI: 10.2174/2211544702666131224232754

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