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Vanadium oxide supported on mesoporous zirconium phosphate catalysts has been synthesized, characterized and tested in the selective oxidation of H2S to sulfur. The nature of the vanadium species depends on the V-loading of catalyst. Catalysts with a V-content lower than 4wt% present both isolated vanadium species and V2O5 crystallites. However, V2O5 crystallites have been mainly observed in catalysts with higher V-content, although the presence of isolated V-species on the surface of the metal oxide support cannot be completely ruled out. The catalytic behaviour also depends on V-loading of catalysts. Thus, while the catalytic activity of catalysts can be related to the number of V-sites, the catalyst decay is clearly observed in samples with low V-loading. The characterization of catalysts after the catalytic tests indicates the presence of sulfur on the catalyst, which is favoured on catalysts with low V-loading. However, a clear transformation of V2O5 to V4O9 can be proposed according to XRD and Raman results of used catalysts with high V-loading. The importance of V5+-O-V4+ pairs in activity and selectivity is also discussed. (C) 2009 Elsevier B.V. All rights reserved., The authors gratefully acknowledge financial support from CICYT, Spain (NAN2004-09267-C03-01 and NAN2004-09267-C03-02). MDS thanks a fellowship from the Universidad Politecnica of Valencia.

Vanadium oxide supported on porous clay heterostructures (PCH) catalysts have been synthesized, characterized and evaluated in the selective oxidation of H2S to elemental sulfur. The catalysts were characterized by XRD, adsorption-desorption of N-2 at -196 degrees C, diffuse reflectance UV-vis, H-2-TPR, Raman spectroscopy and XPS. The catalysts with higher vanadium content are more active and selective, exhibiting a H2S conversion close to 70% after 360h on stream with a high selectivity toward elemental sulfur and a low formation of undesired SO2. The catalysts with V2O5 crystallites have shown a higher activity and resistance to the deactivation. The analysis of the spent catalyst has revealed the formation of V4O9 crystals during the catalytic test, which has been reported as the active phase in the selective oxidation of the H2S. (C) 2015 Elsevier B.V. All rights reserved., The authors would like to thank the DGICYT in Spain (Projects CTQ2012-37925-C03-01, CTQ2012-37925-C03-03 and FEDER funds, and MAT2010-19837-C06-05) and project of Excellence of Junta de Andalucia (project P12-RNM-1565) for financial support. A. Natoli thanks to SECAT (Spain) for a grant.

[EN] Na-containing V2O5 materials have been prepared hydrothermally from gels with Na/V ratios of 0.02-0.26, and calcined at 500 degrees C. The calcined samples have been characterized and tested as catalysts in the partial oxidation of H2S to elemental sulfur. At low Na-contents, V2O5 and NaV6O15 bronze are formed, with the NaV6O15/V2O5 ratio increasing with the Na-content. Pure NaV6O15 bronze is mainly formed from gels containing a Na/V ratio of 0.18. However, NaV6O15 and Na1.164V3O8 are formed from gels with Na/V ratio higher than 0.35. NaV6O15 based catalyst shows high conversion for the oxidation of H2S with a high selectivity into elemental sulfur. These catalysts are more active and stable than pure or Na-doped V2O5 catalysts. V4O9 is observed after reaction in both pure Na-doped V2O5 catalysts but also in NaV6O15/V2O5 mixed catalysts. However, no changes in the NaV6O15 crystalline structure are observed in the Na-promoted catalysts. Accordingly, NaV6O15 crystalline phase is stable for several hours of catalysisat a difference with V2O5. The active sites in V-containing vanadium catalysts are probably V5+-O-V4+ pairs as previously proposed for V4O9 crystalline phase. The best catalytic performances were achieved on V2O5-NaV6O15 mixtures which are transformed into V4O9-NaV6O15 mixtures during the catalytic tests. These catalytic results could be due to the intrinsic physical properties of both phases but also because of the optimal dispersion obtained in the synthesis procedure. (C) 2014 Elsevier B.V. All rights reserved., The authors would like to thank the DGICYT in Spain (Projects CTQ2012-37925-C03-01, CTQ2012-37925-C03-03 and MAT2010-19837-C06-05) for financial support.