Oxidation of sulfur dioxide over supported solid V_2O_5/SiO_2 and supported molten salt V_2O_5-Cs_2SO_4/SiO_2 catalysts:molecular structure and reactivity

摘要

The molecular structure and reactivity of supported solid V2O5/SiO2 catalysts with 6.5 wt% V content and surface densities in the range 0.97-2.04 V atomsm have been studied by in situ Raman spectroscopy and activity measurements for the oxidation of SO_2-Different sol-gel routes,resulting in variations of surface area and pore volume,were used for preparing the catalysts.These catalysts were found to be practically inactive for the oxidation of SO_2 while their molecular structure evolves from isolated distorted tetrahedral O=V-(O-Si)_3 units exhibiting the characteristic Raman band due to V=O terminal stretch at 1032-1035 cm~(-1)to bulk V_2O_5 crystals when vanadia loading exceeds the maximum coverage of surface vanadium oxide species on silica.Promotion of the catalysts with cesium(by impregnation with Cs_2SO_4 at Cs:V = 3)results in thorough structural transformation of the studied materials which is followed by dramatic improvements in their reactivity for SO_2 oxidation.Amorphous and crystalline vanadia is extracted during calcination and dissolved in a sulfate molten salt,which remains distributed at the surface of the silica support.In situ Raman spectroscopy shows that vanadium occurs in the sulfate molten salt predominantly in the form of the mononuclear V~VO_2(SO_4)_2~(3-)molten oxosulfato complex(with characteristic bands at 1034 cm~(-1)due to v(V=O)and 942 cm~(-1)due to sulfate).A fairly good correlation between the surface areas of V_2O_5/SiO_2 precursors and TOF(turnover frequency)values was found for the V_2O_5-Cs_2SO_4/SiO_2 molten salt catalysts.Activation of these catalysts,following exposure to a SO_2/O_2/N_2 mixture,results in uptake of 803 and formation of a pyrosulfate molten salt,in which-as shown by the in situ Raman spectra-vanadium occurs predominantly in the form of the binuclear(V~VO)_2O(SO_4)_4~(4-)molten oxosulfato complex(with characteristic bands at 1046 cm~(-1)due to v(V=O),830 cm~(-1)due to v(S-O-V)and 770 cm"1 due to V-O-V).Exposure of the catalysts to reducing atmosphere,i.e.,SO_2/N_2,results in formation of V~IV species,which are catalytically inactive for the oxidation of SO_2-The results should be very useful for an understanding of the structure/activity relationships in V_2O_5-Cs_2SO_4/SiO_2 molten salt catalysts.