Ultrasound-Assisted Hydrothermal Synthesis of V2O5/Zr-SBA-15 Catalysts for Production of Ultralow Sulfur Fuel

This work reports the results of the ultrasound-assisted hydrothermal synthesis of two sets of V2O5 dispersed on SBA-15 and Zr doped SBA-15 catalysts used for the oxidation of dibenzothiophene (DBT) in a model diesel via the combination of oxidation, catalysis, and extraction technical route. These catalysts contained Lewis acidity as major and Brønsted acidity as minor. The amount of acidity varied with the content of vanadia and zirconium doping. It was found that DBT conversion is very sensitive to the Lewis acidity. DBT conversion increased by increasing the vanadium content and correlated well with the amount of surface Lewis acidity. Under the optimal experimental condition (Reaction temperature: 60 °C, reaction time 40 min, catalyst concentration: 1 g/L oil; H2O2/DBT mole ratio = 10), the 30% V2O5/SBA-15 and 30% V2O5/Zr-SBA-15 catalysts could convert more than 99% of DBT. Two reaction pathways of DBT oxidation involving vanadia surface structure, Lewis acidity, and peroxometallic complexes were proposed. When the vanadia loading V2O5 ≤ 10 wt%, the oxidative desulfurization (ODS) went through the Pathway I; in the catalysts with moderate vanadia content (V2O5 = 20–30 wt%), ODS proceeded via the Pathways II or/and the Pathway I.

In-Operando Diffraction and Spectroscopic Evaluation of Pure, Zr-, and Ce-Doped Vanadium Dioxide Thermochromic Films Derived via Glycolate Synthesis

Pure and doped vanadia (VO2, V0.98Zr0.02O2, V0.98Ce0.02O2) samples were prepared by wet chemistry synthesis from vanadyl glycolate intermediate phase and tape casted into films. Combining in-operando grazing incidence synchrotron X-ray diffraction and Raman spectroscopy, we studied the structural evolution of the films under isothermal conditions. The setup allowed assessment of the thermochromic functionality with continuous monitoring of the monoclinic to tetragonal transition in pure and doped vanadia phases, responsible for the transmission and reflection of light in the infrared part of the solar spectrum. The materials characterisation by X-ray diffraction beamline (MCX) goniometer demonstrated ideal performance, combining flexible geometry, high resolution, and the potential to accommodate the multi-channel equipment for in-operando characterisation. This method proved viable for evaluating the relevant structural and physical, and thereof functional properties of these systems. We revealed that dopants reduce the transition temperature by 5 °C on average. The synthetic route of the films was held responsible for the observed phase separation. The more favourable behaviour of cerium-doped sample was attributed to cerium alkoxide behaviour. In addition, structural, microstructural, thermal, and spectroscopic characterisation on powder samples was performed to gain more insight into the development of the phases that are responsible for thermochromic features in a broader range of doping ratios. The influence of the dopants on the extent of the thermochromic transition (transmission to reflection hysteresis) was also evaluated using (micro) structural, thermal and spectroscopic methods of powder samples. Characterisations showed that zirconium doping in 2, 4, and 6 mol% significantly influenced the phase composition and morphology of the precursor. Vanadium oxides other than VO2 can easily crystallise; however, a thermal treatment regime that allowed crystallisation of VO2 as a single phase was established.