Surface and Bulk Aspects of Mixed Oxide Catalytic Nanoparticles: Oxidation and Dehydration of CH3OH by Polyoxometallates

The molecular structures and surface chemistry of mixed metal oxide heteropolyoxo vanadium tungstate (H(3+x)PW(12-x)V(x)O(40) with x = 0, 1, 2, and 3) Keggin nanoparticles (NPs), where vanadium is incorporated into the primary Keggin structure, and supported VO(x) on tungstophosphoric acid (TPA, H(3)PW(12)O(40)), where vanadium is present on the surface of the Keggin unit, were investigated with solid-state magic angle spinning (51)V NMR, FT-IR, in situ Raman, in situ UV-vis, CH(3)OH temperature-programmed surface reaction (TPSR), and steady-state methanol oxidation. The incorporated VO(x) unit possesses one terminal V horizontal lineO bond, four bridging V-O-W/V bonds, and one long V-O-P bond in the primary Keggin structure, and the supported VO(x) unit possesses a similar coordination in the secondary structure under ambient conditions. The specific redox reaction rate for VO(x) in the Keggin primary structure is comparable to that of bulk V(2)O(5) and the more active supported vanadium oxide catalysts. The specific acidic reaction rate for the WO(x) in the TPA Keggin, however, is orders of magnitude greater than found for bulk WO(3), supported tungsten oxide catalysts, and even the highly acidic WO(3)-ZrO(2) catalyst synthesized by coprecipitation of ammonium metatungstate and ZrO(OH)(2). From CH(3)OH-TPSR and in situ Raman spectroscopy it was found that incorporation of vanadium oxide into the primary Keggin structure is also accompanied by the formation of surface VO(x) species at secondary sites on the Keggin outer surface. Both CH(3)OH-TPSR and steady-state methanol oxidation studies demonstrated that the surface VO(x) species on the Keggin outer surface are significantly less active than the VO(x) species incorporated into the primary Keggin structure. The presence of the less active surface VO(x) sites in the Keggins, thus, decreases the specific reaction rates for both methanol oxidation and methanol dehydration. During methanol oxidation/dehydration (O(2)/CH(3)OH = 2.17, T = 225 degrees C), in situ UV-vis diffuse reflectance spectroscopy revealed that vanadium oxide is primarily present as the V(+5) cation, which reflects the Mars-van Krevelen redox mechanism and rapid reoxidation by molecular O(2). The bulk TPA Keggin structure becomes more disordered and less thermally stable as the vanadium content increases. Although surface polyaromatic carbon forms during methanol oxidation on the Keggin surfaces, its influence on the reaction kinetics seems minimal as the carbon content diminishes as the vanadium oxide content increases and the reaction temperature is raised. No relationships were found between the electronic structure (UV-vis E(g) values) and TOF(redox) and TOF(acid) (TOF = turnover frequency) kinetics, which reflect the complexity of H(3+x)PW(12-x)V(x)O(40) Keggins. The overall catalytic performance of the H(3+x)PW(12-x)V(x)O(40) Keggin materials results from a complex interplay among the presence of redox vanadium (as secondary surface VO(x) species and substituted VO(x) sites in the primary Keggin NP structure), structural disorder of the Keggin NPs, exposed surface acid and redox sites, and coke deposition. These new insights reveal that the Keggin heteropolyoxometallates are much more complex than originally thought and that care must be taken in using Keggins as model mixed metal oxide NPs in catalytic kinetic and theoretical studies because their surface and bulk structures are dynamic under the reaction conditions.