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Vanadium phosphorus oxide (VPO) was immobilized on SBA-15 via a facile impregnation process. The structure and VPO species on SBA-15 were characterized by XRD, TEM, BET, FTIR and XPS techniques. It was found the VPO/SBA-15 catalysts maintained the two-dimensional hexagonal structure of SBA-15, and the supported VPO species existed in a highly dispersed amorphous state. VPO/SBA-15 catalyst was tested for the ammoxidation of dichlorotoluenes (DCTs) to corresponding dichlorobenzonitriles (DCNs) in a lab-scale tube reactor. Compared with VPO/SiO2 (large-pore silica-supported VPO), VPO/SBA-15 exhibited appreciable enhancement in the catalytic performance due to the unique channel structure of SBA-15. The yield and selectivity toward 2,4-DCN increased by 7% and 6%, while toward the sterically hindered 2,6-DCN increased by 7% and 13%, respectively. [ABSTRACT FROM AUTHOR]

Preparation of 2-Chlorobenzonitrile, and benzonitrile are reported here from the corresponding 2-Chlorobenzaldehyde and benzaldehyde by the reaction of ammonium hydroxide/VPO titania, VPO bulk (ammonium metavanadate) CuCr catalyst/air system in methanol. All these catalysts showed better conversions with reasonable selectivity to aromatic. The results prove that BET surface area results show VPO is present on the catalysts surface which has high surface area, attributed to increase in activity of the catalysts.

The structural properties and oxidation state of vanadium in alumina-supported vanadium-phosphorous oxides at nearly monolayer coverage influence its catalytic performances. The population distribution VVO and VIVO species in the amorphous VPO phase strongly depends on the sample history. By using alumina-supported VPO instead of conventional bulk catalysts, we facilitate enhanced discrimination between active phase and bulk phase signals in the vanadium-phosphorous oxygen system. This brings light on the speciation of VPO catalysts in general. Our observations were achieved by using mainly in situ EPR operando Raman–GC spectroscopic techniques at relevant temperatures and gas conditions, showing that the (VivO)2P2O7 phase is formed during propane ammoxidation at 753K. Such transformation is less intense in inert atmosphere at 753K. Ammonia adsorption on the VPO catalyst surface leads to the formation of VO2+ sites, probably bearing Brønsted and/or Lewis acidity. Propane ammoxidation appears to promote the formation of mixed valence compounds. [ABSTRACT FROM AUTHOR]

In unsupported V-containing catalysts, V4+ sites are frequently present in amorphous oxidic clusters and/or crystalline paramagnetic bulk phases in which they are coupled by effective spin–spin exchange interactions. This work presents two EPR procedures for evaluating these interactions and relating their strength to the degree of disorder and catalytic performance, namely (1) evaluating permanent structural disorder by calculating exchange energies and integrals and (2) monitoring transient electronic disorder caused by catalyst–reactant interaction in working catalysts using the ratio of the fourth and the square of the second moment of the EPR signal. Selected application examples comprise VPO catalysts such as (i) (VO)2P2O7, in which a certain degree of structural disorder revealed to be essential for high catalytic performance in the selective oxidation of n-butane to maleic anhydride, (ii) (NH4)2(VO)3(P2O7)2 in which transient perturbation of spin–spin exchange sensitively reflects the strength of reactant adsorption during ammoxidation of toluene and (iii) (NH4)2VOP2O7 in which an amorphous VO2+-containing phase could be identified as active component besides inactive crystalline phases. Based on operando-EPR measurements, reasons for activity differences in MoVTeNb oxide catalysts could be suggested. [ABSTRACT FROM AUTHOR]