Preparation and characterization of metals supported on nanostructured TiO2 hollow spheres for production of hydrogen via photocatalytic reforming of glycerol

- Nanostructured titania hollow spheres have been used.
- High activity for the photoconversion of glycerol in water is found.
- Hydrogen is the major product.
- Cu-modified systems exhibit the highest activity.

Nanostructured TiO2 hollow spheres (THS) were prepared via a simple hydrothermal method with titanium butoxide, ethanol, urea, and ammonium sulphate. The effects of Ti/ethanol, and reflux temperature on the morphological properties of the nanostructured THS were investigated. An impregnation method was subsequently employed to load metals such as Cu, Co, Cr, Ag, and Ni on the optimized THS, followed by calcination in H2/N2 at 450 °C for 4 h. The morphological properties of the prepared samples were characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and ultraviolet-visible spectroscopy (UV/vis). The SEM and TEM pictures showed that the Ti/ethanol ratio of 1:10 resulted in the formation of uniform hollow spheres. The XRD spectre revealed that phase transformation took place as the reflux temperature was increased, with pure anatase TiO2 hollow spheres being formed at 200 °C. The BET surface areas of the calcined photocatalysts were in the range of 80.6-116 m2/g−1. The UV/vis spectra of the photocatalysts showed that loading of transition metals reduced the band gap of the THS. The activities of the prepared catalysts were tested for hydrogen production via photocatalytic reforming of glycerol under solar irradiation. The improved hydrogen evolution from photocatalytic reforming of glycerol was attributed to: the high surface area which enhanced the adsorption of glycerol onto the surface of photocatalysts; high crystallinity and the reduced band gap which improved the solar light harvesting; the hollow chamber within the TiO2 spheres which produced multiple reflection of the light harvested, thus producing efficient electron/hole pair formation; and the detailed composition of the solids retarded the electron/hole recombination by trapping the electrons generated during the photo excitation of the photocatalysts, and thereby promoted their activity.

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