Direct synthesis and structural characteristics of ordered SBA-15 mesoporous silica containing tungsten oxides and tungsten carbides

A series Of WO3-SBA-15 materials with different Si/W ratios have been hydrothermally synthesized using tetraethyl orthosilicate (TEOS) as silica precursor, ammonium paratungstate as tungsten precursor, and EO20PO70EO20 (P] 23) as structure-directing reagent. After temperature-programmed carburization (TPC) in flowing CH4/H-2 (20/80 v/v mixture), the materials were converted to the corresponding WxC-SBA- 15 materials. The structure of the oxide and carbide materials has been characterized using X-ray diffraction (XRD), X-ray fluorescence (XRF), nitrogen adsorption -desorption measurements, Si-29 magic-angle spinning (MAS) NMR spectroscopy, Fourier transform infrared (FTIR) spectroscopy, transmission electron microscopy (TEM), and thermogravimetric and differential scanning calorimetric analysis (TG-DSC) measurements. The results show that after hydrothermal synthesis using different amounts of tungsten and subsequent carburization, the materials retain the mesopore structure of SBA- 15. When Si/W = 30-15, the majority of the tungsten is dispersed in the channels of SBA-15 with the remainder being incorporated into the framework of SBA-15 with the formation of Si-O-W bonds. The tungsten carbide exists as a single W2C phase after carburization. At higher tungsten content (Si/W = 7.5), the amount of tungsten in the framework of SBA-15 increases with the formation of both Si-O-W bonds and W-O-W bonds. The tungsten carbide formed after carburization exists as a mixture Of W2C and WC phases. A model for the distribution of tungsten in SBA-15 is proposed involving three different tungsten species: alpha-W inside SBA-15 channels, beta-W embedded in the internal surfaces of the SBA- 15 channels, and gamma-W inside the framework of SBA- 15. After temperature-programmed carburization, alpha-W sites are transformed into W2C, whereas beta-W sites afford WC; in contrast, gamma-W sites show little change after carburization.