Yu Niu,Fuying Li,Kai Yang,Ting Qiu,Renzhang Wang,Cheng Lin
A unique Rh/TiO 2 solid acid catalyst modified with H 2 SO 4 was synthesized and evaluated in the esterification reaction of propylene glycol methyl ether and decomposition of methyl orange (MO) in aqueous phase under halogen lamp irradiation. For this purpose, rhodium (Rh) nanoparticles were loaded on SO 4 2 − /TiO 2 via the photo-deposition method. It was found that SO 4 2 − /Rh–TiO 2 exhibited stronger catalytic activity than SO 4 2 − /TiO 2 . The new catalysts were characterized by X-ray powder diffraction (XRD), Brunauer–Emmett–Teller (BET), Transmission electron microscopy (TEM) and high-resolution (HRTEM), X-ray photoelectron spectroscopy (XPS) and Fourier Transform infrared spectroscopy (FTIR). Results from XRD and BET show that SO 4 2 − /Rh–TiO 2 has higher specific surface area and smaller pore size than SO 4 2 − /TiO 2 . The distribution of loaded Rh was found to be uniform with a particle size of 2–4 nm. Data from XPS reveal that Rh primarily exists as Rh 0 and Rh 3 + in Rh–TiO 2 and SO 4 2 − /Rh–TiO 2 . These valence forms of Rh likely contribute to the enhanced catalytic activity. Furthermore, FT-IR spectra of the catalysts show an abundance of surface hydroxyl groups, which help the formation of hydroxyl radicals and the enhancement of surface acid density. The results show that more acid sites are formed on the sulfated Rh–TiO 2 , and these acidic sites are largely responsible for improving the catalytic performance. This superior SO 4 2 − /Rh–TiO 2 catalyst has potential applications in reactions requiring efficient acid catalysts, including esterification reactions and waste water treatment.
Photocatalytic hydrogen production from water is a promising method to obtain clean energy in the future. In this work, the sulfated TiO2 photocatalyst is successfully constructed in situ via a soft-templated method for photocatalytic water splitting to produce hydrogen. The content of sulfate species in TiO2 can be tuned by changing the amount of the surfactant. The photocatalyst with the appropriate content of sulfate ions exhibits an apparent quantum efficiency (AQE) of 3.9% at 365 nm and a high hydrogen production rate of 24.32 mmol h−1 g−1, which is 1.65 times that of commercial TiO2 (P25). The optimized photocatalyst has excellent photocatalytic activity for hydrogen evolution benefitting from the presence of sulfate ions on the surface of TiO2, large surface area and oxygen vacancies, which facilitates the rapid migration of photo-generated electrons to its surface and the improvement of the separation efficiency of photo-generated carriers. This work may inspire the rational design and the development of high-efficiency photocatalysts.