g-C3N4 modified Bi2O3 composites with enhanced visible-light photocatalytic activity

Novel g-C₃N₄ modified Bi₂O₃ (g-C₃N₄/Bi₂O₃) composites were synthesized by a mixing-calcination method. The samples were characterized by thermogravimetry (TG), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), transmission electron microscopy (TEM), UV–vis diffuse reflection spectroscopy (DRS), photoluminescence (PL) and photocurrent-time measurement (PT). The photocatalytic activity of the composites was evaluated by degradation of Rhodamine B (RHB) and 4-chlorophenol (4-CP) under visible light irradiation (>400 nm). The results indicated that the g-C₃N₄/Bi₂O₃ composites showed higher photocatalytic activity than that of Bi₂O₃ and g-C₃N₄. The enhanced photocatalytic activity of the g-C₃N₄/Bi₂O₃ composites could be attributed to the suitable band positions between g-C₃N₄ and Bi₂O₃. This leads to a low recombination between the photogenerated electron–hole pairs. The proposed mechanism for the enhanced visible-light photocatalytic activity of g-C₃N₄/Bi₂O₃ composites was proven by PL and PT analysis.     

石墨相氮化碳的制备条件优化用以提高其在可见光下的光催化活性

通过染料的光降解实验和敏感性数学分析探讨了石墨相氮化碳(g-C₃N₄)的制备条件与其稳定性和光催化活性之间的联系. 结果表明,相比于焙烧时间,焙烧温度的改变更为显著地影响了g-C₃N₄ 的光催化活性. 制备条件优化之后的g-C₃N₄在可见光照射下催化降解罗丹明B(RhB)的活性比未优化时提高了约100倍,归因于材料比表面积的增大和表面光生电子-空穴迁移速度的增强.     

A facile in situ solvothermal method for two-dimensional layered g-C<Subscript>3</Subscript>N<Subscript>4</Subscript>/SnS<Subscript>2</Subscript> p-n heterojunction composites with efficient visible-light photocatalytic activity

To overcome the fast recombination rate of electron-hole pairs of individual SnS₂, p-n heterojunction g-C₃N₄/SnS₂ composites were fabricated as high-efficiency visible-light photocatalyst to photodegradate the organic dye MB. The morphologies, structures, compositions, and photocatalytic properties were characterized. The SnS₂ shows two-dimensional layer structure with an average thickness of 20 nm and diameter size of about 2 μm, and the g-C₃N₄ nanoflakes were uniformly deposited on the surface of SnS₂ nanosheets. In comparison with the bare g-C₃N₄ and SnS₂, the composites show improved photocatalytic activity under visible light, which is sensitive to the content of g-C₃N₄. In particular, the 15% g-C₃N₄/SnS₂ composites exhibit the highest photocatalytic activity and outstanding reusability, which can degrade 88.01% MB after only 1 h in the visible light (λ?>?420 nm) range. The g-C₃N₄/SnS₂ heterojunction composites show outstanding reusability after four times cycling experiments. The improved photocatalytic activities of composites are attributed to abundant active species, increased charge separation, and decreased electron-hole pair recombination, which originated from the large specific surface area and efficient interfacial transport of photo-induced charge carriers between SnS₂ and g-C₃N₄. These results suggest that the two-dimensional layered g-C₃N₄/SnS₂ p-n heterojunction composites are promised to be a high-efficiency visible-light photocatalyst.     

g-C3N4/SnS2异质结构:一类有潜力的光解水催化剂

采用第一性原理方法研究了层间耦合作用对g-C₃N₄/SnS₂异质结构的电子结构和吸光性质的影响.发现g-C₃N₄/SnS₂是一类典型的范德瓦异质结构,能有效吸收可见光,其价带顶和导带底与水的氧化还原势匹配,且由于电荷转移而导致的界面处极化场有利于光生载流子的分离.这些理论研究结果表明g-C₃N₄/SnS₂异质结构是一类非常有潜力的光解水催化材料.     

Hydrothermal synthesis of graphitic carbon nitride–BiVO4 composites with enhanced visible light photocatalytic activities and the mechanism study

Novel graphitic carbon nitride (C₃N₄) and bismuth vanadate (BiVO₄) composite photocatalysts were successfully synthesized by a facile hydrothermal method. The scanning electron microscopy (SEM) revealed that an intimate interface between C₃N₄ and BiVO₄ formed in the composites. Compared with the pure C₃N₄ and BiVO₄, the C₃N₄–BiVO₄ photocatalysts showed remarkably the higher photocatalytic activities in degrading rhodamine B (Rh B). The best active heterojunction proportion was 0.5C₃N₄–0.5BiVO₄. Over this catalyst, the 100% degradation of Rh B (0.002 mmol L⁻¹) was obtained under visible light irradiation (λ>420 nm) for 40 min. The active species in Rh B degradation were examined by adding a series of scavengers. The study on photocatalytic mechanism revealed that the electrons injected directly from the conduction band of C₃N₄ to that of BiVO₄, resulting in the production of superoxide radical (O₂^•−) and hydroxyl radical (OH^•) in the conduction band of BiVO₄. Simultaneously, the rich holes in the valence band of g-C₃N₄ oxidized Rh B directly to promote the photocatalytic degradation reaction.     

Carbon quantum dots supported ZnO sphere based photocatalyst for dye degradation application

A Carbon quantum dots supported ZnO hollow Sphere (ZnO/C-dots) were synthesized through a solvothermal method using polyethylene glycol 400 (PEG 400) as a solvent. The phase and crystal structure of as-prepared ZnO/C-dots photocatalyst were characterized by powder X-ray diffraction (XRD). The surface morphology and size of the composite were analyzed using field emission scanning microscopy (FE-SEM). The optical properties of the as-prepared nanocomposites were examined using UV–visible (UV–Vis) spectrometer. The photocatalytic activity of pure ZnO and ZnO/C-dots nanocomposites were evaluated by the degradation of methylene blue (MB) under UV–Visible light irradiation. The ZnO/C-dots nanocomposites exhibited maximum photocatalytic MB dye degradation efficiency of 96% which is much higher that the pure ZnO (63%). The enhanced photocatalytic activity of ZnO/C-dots is due to the extended light absorption in the visible region and suppressed photoexcited electron-hole pair recombination rate. Moreover, the activity of photocatalyst after five cycles exhibits high stability, which is vital for the sustainable photocatalytic procedures. It is concluded that the prepared ZnO/C-dots composite have low cost, good stability and has a great potential application for Photocatalytic dye degradation.     

Photophysical and enhanced daylight photocatalytic properties of N-doped TiO2/g-C3N4 composites

N-doped TiO₂/C₃N₄ composite samples were synthesized by heating the mixture of the hydrolysis product of TiCl₄ and C₃N₄ at different weight ratios. The samples were characterized by X-ray diffraction (XRD), Raman spectrum, UV–vis absorption spectrum, photoluminescence spectrum, X-ray photon electron spectrum (XPS) and surface photovoltage spectrum (SPS). The XRD and Raman results indicate that the introduction of C₃N₄ could inhibit the formation of rutile TiO₂. The composite samples show slight visible light absorption due to the introduction of C₃N₄. The XPS result reveals that some amount of nitrogen is doped into TiO₂, and C₃N₄ exists in the composite sample. The intensities of the SPS signal in the composite samples decrease with the rise in the amount of C₃N₄ in the samples. The photocatalytic activity was evaluated from the Rhodamine B (RhB) degradation under fluorescence light irradiation. The composite samples show significantly enhanced photocatalytic activities and the RhB self-sensitized photodegradation in this system was observed by measuring the photocurrent in the dye sensitized solar cell using the composite as the working electrode.     

Preparation and photocatalytic properties of hybrid core–shell reusable CoFe2O4–ZnO nanospheres

Magnetically separable and reusable core–shell CoFe₂O₄–ZnO photocatalyst nanospheres were prepared by the hydrothermal synthesis technique using glucose derived carbon nanospheres as the template. The morphology and the phase of core–shell hybrid structure of CoFe₂O₄–ZnO were assessed via TEM, SEM and XRD. The magnetic composite showed high UV photocatalytic activity for the degradation of methylene blue in water. The photocatalytic activity was found to be ZnO shell thickness dependent. Thicker ZnO shells lead to higher rate of photocatalytic activity. Hybrid nanospheres recovered using an external magnetic field demonstrated good repeatability of photocatalytic activity. These results promise the reusability of the hybrid nanospheres for photocatalytic activity.     

高比表面积TiO2与g-C3N4复合材料的光催化性能及机理研究

本文通过简单的溶剂热法制备了g-C₃N₄与高比表面积的TiO₂复合材料,该方法操作简单且能耗低. 甲基橙降解实验结果表明,高比表面积的TiO₂有效提高了光催化活性. 光电化学测试结果表明,与g-C₃N₄复合后,TiO₂的电荷载流子迁移速率得到明显改善. g-C₃N₄/高比表面积-TiO₂的光催化活性很强,在100分钟内,6%-g-C₃N₄/高比表面积-TiO₂对甲基橙的降解程度可达92.44%. 6%-g-C₃N₄/高比表面积-TiO₂不仅具有良好的光催化降解性能,还具有较高的稳定性. 本文对6%-g-C₃N₄/高比表面积-TiO₂的光催化机理也进行了系统的研究.     

Characteristics and heterostructure of metal-doped TiO2/ZnO nanocatalysts

In this study, Ag or Al-doped TiO₂/ZnO heterostructure nanocatalysts were prepared using a sol-gel method for photocatalysis to evaluate the degradability. The photocatalytic behavior was evaluated by the degradation of methylene blue (MB) under ultraviolet (UV) light irradiation. Photocatalytic studies suggested that 1 mol% Ag-doped TiO₂/ZnO (TiO₂/ZnO = 0.75/0.25) heterostructure nanocatalysts showed higher photocatalytic activity, and that the degradation efficiency can reach 83% in 4 h, 14% higher than that for pure TiO₂. Finally, the photocatalysis mechanism for the Ag-doped TiO₂/ZnO heterostructure nanocatalysts is discussed.     

Sol-gel derived S,I-codoped mesoporous TiO2 photocatalyst with high visible-light photocatalytic activity

A mesoporous S,I-codoped TiO₂ photocatalyst with high visible light photocatalytic activity was synthesized through the hydrolysis and condensation of titanium isopropoxide with thiourea and iodic acid as the precursors. The as-prepared catalysts were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), UV-vis diffuse reflectance (DRS), X-ray photoelectron spectroscopy (XPS), Fourier translation infrared spectroscopy (FT-IR), and N₂ adsorption. The results showed that the cations of S⁶⁺ and I⁵⁺ could substitute for some of the lattice titanium (Ti⁴⁺). The S,I-codoping forms the new bands above the valence band and narrows the band-gap of the TiO₂, then shifts the absorption edge from UV light region to visible light range. The activity of the catalyst was examined by photodegradation of methylene blue in an aqueous solution under visible light irradiation. The activity of the S,I-codoped catalyst is far superior to that of single S or I-doped TiO₂ counterpart. The high visible light photocatalytic activity could be attributed to the strong absorption of light, well-crystalline anatase phase, and mesoporous microstructure.     

Hydrothermal synthesis of well-dispersed ultrafine N-doped TiO2 nanoparticles with enhanced photocatalytic activity under visible light

Ultrafine nitrogen-doped TiO₂ nanoparticles with narrow particle size distribution, good dispersion, and high surface area were synthesized in the presence of urea and PEG-4000 via a hydrothermal procedure. TEM observation, N₂ adsorption, XRD, UV-vis spectroscopy, the Raman spectroscopy and XPS analysis were conducted to characterize the synthesized TiO₂ particles. The synthesized TiO₂ particles were a mixture of 49.5% anatase and 50.5% rutile with a size of around 5 nm. The photocatalytic activities were tested in the degradation of an aqueous solution of a reactive Brilliant Blue KN-R under both UV and visible light. The synthesized TiO₂ particles showed much higher photocatalytic activity than a commercial P25 TiO₂ powder under both UV and visible light irradiations. The high performance is associated to N doping, the reduced particle size, good dispersion, high surface area, and a quantum size effect.     

Characterization and photocatalytic activity of Zn–TiO2/AC composite photocatalyst

Activated carbon (AC) supported Zn²⁺–TiO₂ photocatalyst was prepared by sol–gel method. The prepared samples were characterized by X-ray diffraction, scanning electron micrograph, nitrogen absorption, diffuse reflectance UV/VIS and X-ray photoelectron spectroscopy. Using toluene as a pollution target, the photocatalytic activity of photocatalyst was evaluated. The results showed that prepared photocatalyst was obviously helpful for the removal of toluene in air. The photocatalytic degradation of toluene by Zn²⁺–TiO₂/AC reached 100% for 40 min and remained 75% after 160 min, while degradation by TiO₂ was only 30%. It indicated that the photocatalytic activity of prepared photocatalyst was enhanced. It is due to Zn²⁺-doping increased the oxidation and reduction of hole–electron pairs, which was the important factor in heterogeneous photocatalysis.     

Effects of microwave drying on the microstructure and photocatalytic activity of bimodal mesoporous TiO2 powders

Bimodal nanocrystalline mesoporous TiO₂ powders with highly photocatalytic activity were prepared by a hydrothermal method using tetrabutylorthotitanate as precursor, and then dried in microwave oven. The prepared samples were characterized by XRD, SEM, TEM, HRTEM and N₂ adsorption-desorption measurement. The photocatalytic activity was evaluated by the photocatalytic degradation of acetone in air under UV light irradiation at room temperature. The effects of microwave drying on the microstructures and photocatalytic activity of the TiO₂ powders were investigated and discussed. The results show that microwave drying not only promotes the growth of the pores but also greatly reduces the state of agglomeration within the powders. All the microwave-dried TiO₂ powders show higher photocatalytic activity than Degussa P-25 (P25) and the TiO₂ powders dried by conventional method.     

The synthesis of graphene-TiO<Subscript>2</Subscript>/g-C<Subscript>3</Subscript>N<Subscript>4</Subscript> super-thin heterojunctions with enhanced visible-light photocatalytic activities

In this paper, an efficient strategy for the synthesis of graphene nanobelt-titanium dioxide/graphitic carbon nitride (graphene-TiO₂/g-C₃N₄) heterostructure photocatalyst was applied to fabricate a kind of visible-light-driven photocatalyst. The heterostructure shows higher absorption edge towards harvesting more solar energy compared with pure TiO₂ and pure g-C₃N₄ respectively. Furthermore, the as-prepared graphene-TiO₂/g-C₃N₄ heterostructure can show enhanced photocatalytic activity under visible-light irradiation. These outstanding performances of photocatalytic activities for graphene-TiO₂/g-C₃N₄ composites can be attributed to the heterojunction interfaces which can separate the electron-hole pairs and impede the recombination of electrons and holes more efficiently. This study conclusively demonstrates a facile and environmentally friendly new strategy to design highly efficient graphene-TiO₂/g-C₃N₄ heterostructure photocatalytic materials for potential applications under visible-light irradiation.

Open image in new window

Graphical abstract ?

     

Characterization and optimization of Ce0.6Zr0.4−x Mn x O2 (x ≤ 0.4)

In situ synthesis method is used to synthesize g-C₃N₄-P25 composite photocatalysts with different mass rations. The experiment result shows that P25 particles with diameter at range of 20–30 nm were embedded homogenously in the sheets of g-C₃N₄. Coupling g-C₃N₄ with P25 can not only improve the visible light absorption, but also improve the visible light photocatalytic activity of P25. The g-C₃N₄-P25 nanocomposite has the higher photocatalytic activity than g-C₃N₄ under visible light. The optimal g-C₃N₄ content with the highest photocatalytic activity is determined to be 84 %, which is almost 3.3 times higher than that of individual g-C₃N₄ under the visible light. The enhanced visible light photocatalytic activity could be ascribed to the formation of g-C₃N₄ and TiO₂ heteojunction, which results in an efficient separation and transfer of photo-induced charge carriers. The electron spin resonance results show that the ^·O₂ ^? radicals are main active species for g-C₃N₄ and the g-C₃N₄-P25 nanocomposites.     

Preparation and characterization of visible light responsive Fe2O3-TiO2 composites

In this study we present the effects of iron oxide (Fe₂O₃) on titanium dioxide (TiO₂) in synthesising visible-light reactive photocatalysts. A Fe₂O₃-TiO₂ composite photocatalyst was synthesized from Fe₂(SO₄)₃ and Ti(SO₄)₂ by a ethanol-assisted hydrothermal method. The preparation conditions were optimized through the investigation of the effects of hydrothermal temperature and time as well as molar ratio of Ti to Fe on the photocatalytic activity. The visual, physical and chemical properties of the Fe₂O₃-TiO₂ composites were investigated. The results showed that α-Fe₂O₃ and anatase TiO₂ were present in the composites. The Fe₂O₃-TiO₂ synthesized under optimum condition consisted of mesoporous structure with an average pore size of 4 nm and a surface area of 43 m²/g. Under visible and solar light irradiation, the photocatalytic activity of optimized sample was significantly higher than that of pure TiO₂. This sample led to a photodegradation efficiency of 90% and 40% of auramine under visible light and solar light, respectively.     

Ag3PO4/rectorite nanocomposites: Ultrasound-assisted preparation,characterization and enhancement of stability and visible-light photocatalytic activity

To overcome the drawback of low stable brought by the transformation of Ag⁺ into Ag, a highly efficient and stable photocatalyst Ag₃PO₄/rectorite composite was successfully synthesized by ultrasound-assisted precipitation method. The as-prepared samples were characterized by field-emission scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, N₂ adsorption-desorption, room-temperature photoluminescence spectra, Fourier transform infrared spectrum measurements and UV–vis diffuse reflectance spectra. The absorption edges of the Ag₃PO₄/rectorite display a noticeable shift to the visible light region as compared to that of the Ag₃PO₄. Compared with bare Ag₃PO₄, the Ag₃PO₄/rectorite composite by ultrasound-assisted precipitation process exhibits significantly enhanced photocatalytic activity and stable for methyl orange (MO) degradation under visible light irradiation. The improved activity of the Ag₃PO₄/rectorite photocatalyst could be attributed to the expanded visible light absorption, the enhanced interfacial charge transfer and the inhibited recombination of electron-hole pairs. Therefore, the facile ultrasound-assisted preparation process provides some insight into the application of Ag₃PO₄/rectorite nanocomposites in photocatalytic degradation of organic pollutants.     

Ag/TiO2 sol prepared by a sol–gel method and its photocatalytic activity

Ag/TiO₂ sol with narrow particle size distribution was synthesized using TiCl₄ as the starting material. TiCl₄ was converted to Ti(OH)₄ gel. The Ag/TiO₂ sol was prepared by a process where H₂O₂ was added and then heated at 90–97 °C. After condensation reaction and crystallization, a transparent sol with suspended Ag/TiO₂ was formed. Ag/TiO₂ was characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, contact angle analysis, and X-ray photoelectron spectroscopy. The photocatalytic properties of Ag/TiO₂ film were evaluated by degradation of methylene blue in aqueous solution under UV light irradiation. The suspended Ag/TiO₂ particles were rhombus primary particles with the major axis ca. 40 nm and the minor axis ca. 10 nm. Ag nanoparticles were well dispersed on TiO₂ and the particle size was only 1–2 nm. Ag could restrain the recombination of photo-generated electrons and holes effectively. Transparent thin films could be obtained through dip-coating glass substrate in the sol. The thin film had strong hydrophilicity after being illuminated by UV light. Ag/TiO₂ film showed a significant increase in photocatalytic activity compared to the TiO₂ film. The high amount of surface hydroxyls on Ag/TiO₂ film also played an important role in its photocatalytic activity.     

Band structure and photocatalytic properties of perovskite-type compound Ca2NiWO6 for water splitting

An oxide semiconductor Ca₂NiWO₆, with double-perovskite crystal structure, was synthesized by solid-state reaction method. The compound Ca₂NiWO₆ was characterized by X-ray diffraction, UV-visible diffuse reflectance, and photoluminescence. The photocatalytic properties of the compound for water splitting were investigated under UV and visible light irradiation. The results showed H₂ evolution was not observed over the compound under visible light irradiation (λ>420 nm) with a 300 W xenon arc lamp when using methanol (CH₃OH) as electron donor, although the compound was responsive to visible light region. Based on the experimental results, a possible band structure was proposed through theoretical calculation of the electronic structure by using the full potential-linearized augmented plane wave (F-LAPW). The band structure and photocatalytic properties were attributed to the special crystal and electronic structures. Due to the oxygen vacancies in the compound, which worked as electron-hole recombination centers, the photocatalytic activity of the compound was low.