Hierarchical spheres assembled from large ultrathin anatase TiO2 nanosheets for photocatalytic hydrogen evolution from water splitting

We report the synthesis of TiO₂ hierarchical spheres (THS) with large specific surface area via a facile one-pot solvothermal method. The as-prepared THS are self-assembled by ultrathin TiO₂ nanosheets with thickness of several nanometers and they show a uniform spherical morphology with an average size of 500–700 nm. However, the as-prepared light yellow THS exhibit inferior photocatalytic activity for hydrogen evolution from water splitting due to the poor crystallization of TiO₂ and the existence of oxygen vacancies. Significantly, a subsequent thermal treatment improves the crystallinity of THS, reduces the oxygen vacancies, and thereby enhances the photocatalytic performance. It demonstrates that the sample annealed at 550 °C (THS550) exhibits the highest photocatalytic activity, about 5 times higher than that of commercial TiO₂ nanoparticles (CTiO₂). Moreover, the THS550 sample loaded with 1 wt% Pt exhibits an hydrogen evolution rate as high as 17.9 mmol h^?1g^?1, and the corresponding apparent quantum efficiency has been determined to be 28.46% under 350 nm light irradiation.     

Hybridizing MoS2 and C60 via a van der Waals heterostructure toward synergistically enhanced visible light photocatalytic hydrogen production activity

Molybdenum disulfide (MoS₂) as a representative transition-metal dichalcogenide (TMD) has been extensively used as a noble-metal-free cocatalyst for photocatalytic hydrogen (H₂) production, but suffers from poor photocatalytic activity due to the catalytic inactivity of its basal plane. Herein, by bounding another metal-free cocatalyst, C₆₀, with MoS₂, we report the first MoS₂-C₆₀ hybrid featuring a van der Waals heterostructure prepared via a facile and eco-friendly solid-state mechanochemical route. C₆₀ bounding onto the edge of MoS₂ nanosheets leads to the decreases of both the number of layers and the size of MoS₂ nanosheets, as well as a negative shift of the conduction band minimum along with a positive shift of valance band maximum relative to the bulk MoS₂ and MoS₂ ball-milled without C₆₀ (MoS₂-BM). Under the optimized weight ratio of MoS₂:C₆₀ (1:1) in the raw mixture subject to ball-milling, MoS₂-C₆₀ hybrid containing 2.8 wt% C₆₀ shows an exceptional visible light photocatalytic H₂ production rate of 6.89 mmol h^?1 g^?1 in the presence of a photosensitizer Eosin Y (EY), which is significantly enhanced relative to the bulk MoS₂ and pristine C₆₀, both of which show almost no photocatalytic H₂ activity. Thus, the synergistic enhancement of photocatalytic activities of both MoS₂ and C₆₀ is revealed.     

g-C3N4 coated SrTiO3 as an efficient photocatalyst for H2 production in aqueous solution under visible light irradiation

A highly active photocatalyst based on g-C₃N₄ coated SrTiO₃ has been synthesized simply by decomposing urea in the presence of SrTiO₃ at 400 °C. The catalyst demonstrates a high H₂ production rate ∼440 μmol h⁻¹/g catalyst in aqueous solution under visible light irradiation, which is much higher than conventional anion doped SrTiO₃ or physical mixtures of g-C₃N₄ and SrTiO₃. The improved photocatalytic activity can be ascribed to the close interfacial connections between g-C₃N₄ and SrTiO₃ where photo-generated electron and holes are effectively separated. The newly synthesized catalyst also exhibited a stable performance in the repeated experiments.     

Poly(vinyl alcohol)/poly(acrylic acid)/TiO2/graphene oxide nanocomposite hydrogels for pH-sensitive photocatalytic degradation of organic pollutants

Poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were prepared using radical polymerization and condensation reaction for the photocatalytic treatment of waste water. Graphene oxide was used as an additive to improve the photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂ nanocomposite hydrogels. Both TiO₂ and graphene oxide were immobilized in poly(vinyl alcohol)/poly(acrylic acid) hydrogel matrix for an easier recovery after the waste water treatment. The photocatalytic activity of poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels was evaluated on the base of the degradation of pollutants by using UV spectrometer. The improved removal of pollutants was due to the two-step mechanism based on the adsorption of pollutants by nanocomposite hydrogel and the effective decomposition of pollutants by TiO₂ and graphene oxide. The highest swelling of nanocomposite hydrogel was observed at pH 10 indicating that poly(vinyl alcohol)/poly(acrylic acid)/TiO₂/graphene oxide nanocomposite hydrogels were suitable as a promising system for the treatment of basic waste water.     

Recent progress in mesoporous titania materials: adjusting morphology for innovative applications

Abstract

This review article summarizes recent developments in mesoporous titania materials, particularly in the fields of morphology control and applications. We first briefly introduce the history of mesoporous titania materials and then review several synthesis approaches. Currently, mesoporous titania nanoparticles (MTNs) have attracted much attention in various fields, such as medicine, catalysis, separation and optics. Compared with bulk mesoporous titania materials, which are above a micrometer in size, nanometer-sized MTNs have additional properties, such as fast mass transport, strong adhesion to substrates and good dispersion in solution. However, it has generally been known that the successful synthesis of MTNs is very difficult owing to the rapid hydrolysis of titanium-containing precursors and the crystallization of titania upon thermal treatment. Finally, we review four emerging fields including photocatalysis, photovoltaic devices, sensing and biomedical applications of mesoporous titania materials. Because of its high surface area, controlled porous structure, suitable morphology and semiconducting behavior, mesoporous titania is expected to be used in innovative applications.     

Nitrogen-doped titanium dioxide photocatalysts for visible response prepared by using organic compounds

In order to utilize visible light in photocatalytic reactions, nitrogen atoms were doped in commercially available photocatalytic TiO₂ powders by using an organic compound such as urea and guanidine. Analysis by X-ray photoelectron spectroscopy (XPS) indicated that N atoms were incorporated into two different sites of the bulk phase of TiO₂. A significant shift of the absorption edge to a lower energy and a higher absorption in the visible light region were observed. These N-doped TiO₂ powders exhibited photocatalytic activity for the decomposition of 2-propanol in aqueous solution under visible light irradiation. The photocatalytic activity increased with the decrease of doped N atoms in O site, while decreased with decrease of the other sites. Degradation of photocatalytic activity based on the release of nitrogen atoms was observed for the reaction in the aqueous suspension system.     

Preparations and photocatalytic degradation of methyl orange in water on magnetically separable Bi12TiO20 supported on nickel ferrite

A magnetically separable photocatalyst Bi₁₂TiO₂₀/SiO₂/NiFe₂O₄ (BSN) with a typical ferromagnetic hysteresis was prepared by a simple process: the magnetic 200 wt% SiO₂/NiFe₂O₄ (SN) dispersion prepared by a liquid catalytic phase transformation method and the visible-light-active photocatalyst Bi₁₂TiO₂₀ prepared by a simple coprecipitation processing were mixed, sonificated, dried, and calcined at 550°C. The prepared photocatalyst showed high photocatalytic activity for the degradation of methyl orange in water under UV irradiation and visible-light irradiation (λ>400 nm), and it was easy to be separated from a slurry-type photoreactor under the application of an external magnetic field, being one of promising photocatalysts for wastewater treatment. Transmission electron microscope (TEM) and X-ray diffractometer (XRD) were used to characterize the structure of the photocatalyst, indicating that the magnetic SN particles adhered to the surface of the Bi₁₂TiO₂₀ congeries. SiO₂ layer round the surface of NiFe₂O₄ nanoparticles prevented effectively the injection of charges from TiO₂ particles to NiFe₂O₄, which gave rise to the increase in photocatalytic activity.     

Fabrication of noble-metal-free Cd0.5Zn0.5S/NiS hybrid photocatalyst for efficient solar hydrogen evolution

Up to now, most of the semiconductor photocatalysts can only achieve their high photocatalytic activity for hydrogen production with the loading of noble metals, such as Pt or Ru, as cocatalysts, which drastically increases the total cost of the designed photocatalyst. Herein, we report the design and fabrication of a highly efficient Cd_0.5Zn_0.5S photocatalyst decorated with nanosized NiS surface heterojunctions. The hydrogen evolution rate over this photocatalyst reached 1.4 mmol/h, with a remarkable quantum yield of 33.9%. This efficiency is even much higher than many noble metal loaded photocatalysts. In this hybrid photocatalyst, the nanosized NiS on the surface can serve as electron trapping sites, by which, photogenerated electrons were extracted from Cd_0.5Zn_0.5S substrate, leading to spatially separated photoreduction and oxidation reactions. More interestingly, it was found that NiS played a similar role as noble metal, providing active sites for proton reduction, and hence efficiently enhancing the overall hydrogen production rate. Our work demonstrates the possibility of substitution of noble metal cocatalyst by a properly engineered surface hetero-junction to achieve efficient and low cost photocatalytic hydrogen production.     

Effects of the preparation order of the ternary P25/GO/Pt hybrid photocatalysts on hydrogen production

In this study, ternary P25/GO/Pt hybrid photocatalysts are prepared in different orders, using Degussa's TiO₂ (P25), graphene oxide (GO), chloroplatinic acid as precursor. The prepared catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). This work is first time to compare the hydrogen production of the ternary P25/GO/Pt hybrid photocatalysts prepared in different orders. We focus on studying the introduction of GO and find that the quantity of introduced GO and electronic transfer path play an important role in photocatalytic activity on ternary P25/GO/Pt hybrid catalysts. When the proper Pt particle loaded on the flat surface of GO which was 0.5wt% of P25, the highest H₂ evolution was obtained.     

Photocatalytic hydrogen production over CuO and TiO2 nanoparticles mixture

Cheap and efficient photocatalysts were fabricated by simply mixing TiO₂ nanoparticles (NPs) and CuO NPs. The two NPs combined with each other to form TiO₂/CuO mixture in an aqueous solution due to the opposite surface charge. The TiO₂/CuO mixture exhibited photocatalytic hydrogen production rate of up to 8.23 mmol h⁻¹ g⁻¹ under Xe lamp irradiation when the weight ratio of P25 to CuO was optimized to 10. Although the conduction band edge position of CuO NPs is more positive than normal hydrogen electrode, the TiO₂/CuO mixture exhibited good photocatalytic hydrogen production performance because of the inter-particle charge transfer between the two NPs. The detailed mechanism of the photocatalytic hydrogen production is discussed. This mixing method does not require a complicated chemical process and allows mass production of the photocatalysts.