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A catalyst comprising vanadium phosphorus oxide combined with a thermally conductive material is particularly useful for the selective hydrocarbon oxidations (e.g., butane to maleic anhydride) and can be prepared by forming a suspension comprising a vanadium (IV) phosphate compound in a liquid medium (via hydrochloric acid digestion of V2O5 and H3PO4 in an aqueous solvent or via heating vanadium pentoxide with at least one substantially anhydrous unsubstituted alcohol having 1-10 carbon atoms, 1-3 hydroxyl groups and free from olefinic double bonds to form a feed of vanadium pentoxide reduced to a valence between 4 and 4.6, and then contacting the feed with a solution of orthophosphoric acid and at least one unsubstituted alcohol), adding a thermally conductive material to the suspension under agitation at moderated temperature between 40 DEG C and 120 DEG C, followed by drying, optionally but preferably washing and calcining (either in situ or ex situ) the material thus formed.