A set of polycrystalline TiO 2 photocatalysts loaded with various ions of transition metals (Co, Cr, Cu, Fe, Mo, V, and W) were prepared by using the wet impregnation method. The samples were characterized by using some bulk and surface techniques, namely X-ray diffraction, BET specific surface area determination, scanning electron microscopy, point of zero charge determination, and femtosecond pump-probe diffuse reflectance spectroscopy (PP-DRS). The samples were employed as catalysts for 4-nitrophenol photodegradation in aqueous suspension, used as a probe reaction. The characterization results have confirmed the difficulty to find a straightforward correlation between photoactivity and single specific properties of the powders. Diffuse reflectance measurements showed a slight shift in the band gap transition to longer wavelengths and an extension of the absorption in the visible region for almost all the doped samples. SEM observation and EDX measurements indicated a similar morphology for all the particles, and a not homogeneous distribution of the metal species onto the surface of catalyst particles. The impregnated samples revealed recombination rates always higher than that of bare TiO 2 . The photoactivity of TiO 2 was reduced by the presence of transition metal ions with the exception of W, which instead played a beneficial role. The results of femtosecond pumpprobe diffuse reflectance spectroscopy appear quite in accord with the observed photocatalytic activity only for the lowest values of electron-hole recombination rate of the samples.
Boron nitride (BN), which is an insulator with a wide band gap, supported on Au is theoretically suggested and experimentally proved to act as an electrocatalyst for oxygen reduction reaction (ORR). Density-functional theory calculations show that the band gap of a free h-BN monolayer is 4.6 eV but a slight protrusion of the unoccupied BN states toward the Fermi level is observed if BN is supported on Au(111) due to the BN-Au interaction. A theoretically predicted metastable configuration of O2 on h-BN/Au(111), which can serve as precursors for ORR, and free energy diagrams for ORR on h-BN/Au(111) via two- and four-electron pathways show that ORR to H2O2 is possible at this electrode. It is experimentally proved that overpotential for ORR at the gold electrode is significantly reduced by depositing BN nanosheets. No such effect is observed at the glassy carbon electrode, demonstrating the importance of BN-substrate interaction for h-BN to act as the ORR electrocatalyst. A possible role of the edge of the BN islands for ORR is also discussed.
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