Effect of TiO₂ on Acidity and Dispersion of H₃PW₁₂O₄₀ in Bifunctional Cu-ZnO(Al)-H₃PW₁₂O₄₀/TiO₂ Catalysts for Direct Dimethyl Ether Synthesis

The performance of bifunctional hybrid catalysts based on phosphotungstic acid (H3PW12O40, HPW) supported on TiO2 combined with a Cu-ZnO(Al) catalyst in the direct synthesis of dimethyl ether (DME) from syngas has been investigated. In this work, different types of TiO2 were used as a support to study the effect of changes in the structure of the TiO2 support on the acidity and dispersion of HPW. Various TiO2 supports with different structural and surface characteristics have been studied and the results indicate that: (i) the crystallinity and crystallite size of the primary particles of the HPW units depend on the TiO2 support; (ii) the pore size distribution of the TiO2 support affects the surface segregation of the heteropolyacids; and (iii) changes in the supported HPW acid catalysts do not significantly alter the crystal structure of the CuO and ZnO phases after contact with CZA in bifunctional catalysts. The activity results indicate that the variation in the intrinsic activity of the Cu-ZnOx centers in the bifunctional catalysts for direct DME synthesis is minimal due to the limited alteration of the crystal structure of the centers.