Upon modification of V 2 O 5 with SnO 2 or ZrO 2 , increase in the activity and selectivity of the vanadium-oxide catalyst in the vapor-phase oxidation of 3-methylpyridine into nicotinic acid were observed. It was shown that the promoting effects of SnO 2 and ZrO 2 were the result of increases under their influence of the proton affinity of the vanadyl oxygen and decreases in the enthalpy of deprotonation of the methyl group of the substrate, connected by a nitrogen atom with the Lewis acidic center (vanadium ion). The given characteristics were calculated by the density functional theory quantum-chemical method. Modification of binary V 2 O 5-SnO 2 and V 2 O 5-ZrO 2-catalysts by TiO 2 addition resulted in a further increase in the nucleophility of the vanadyl oxygen and, as a consequence, an increase in the catalytic activity and selectivity for nicotinic acid formation.

Catalysts based on vanadium pentoxide modified by Ti, Sn, Zr and W oxides were tested in the oxidative ammonolysis of 4-methylpyridine. The role of the main process parameters such as temperature, the ratio of the initial components in the conversion of the methyl group to the nitrile one, and the optimal conditions for the oxidative ammonolysis of 4-methylpyridine were determined. It is determined that the V-Ti-Zr-O-catalyst and the sample containing 9% of tungsten oxide are superior in catalytic activity to the V-Ti-Zr-Sn-O contact. Conditions that ensure a high selectivity for the formation of 4-cyanopyridine were found. The highest yield of the target product (85-86%) was obtained on V-Ti-Zr-W-O at 270 °C, and the yield of 4-cyanopyridine was 87.5% at 310° C on the V-Ti-Zr-Sn-O catalyst. The phase composition and structural changes occurring in modified vanadium oxide catalysts have been studied. It is determined that mixed V-Ti-Zr-Sn-O and V-Ti-Zr-W-O catalysts contain ZrV2O7, the monoclinic modification of ZrO2 (baddeleyite), TiO2 (anatase), SnO2, WO3, and V2O5. In catalysts, it can exist in small amounts as a separate VO2 phase. The V-Ti-Zr-W-O catalyst showed the best catalytic properties. It has highactivity and selectivity towards 4-cyanopyridine.