Synergistic effect of efficient adsorption g-C3N4/ZnO composite for photocatalytic property

Novel g-C₃N₄/ZnO composite photocatalyst was synthesized from an oxygen-containing precursor by direct thermal decomposition urea in air without any other templates assistance. Different percentages of g-C₃N₄ were hybridized with ZnO via the monolayer-dispersed method. The prepared g-C₃N₄/ZnO composites were characterized by XRD, SEM, UV–vis diffuse reflectance spectra (DRS), FT-IR, TEM and XPS. The composites showed much higher efficiency for degradation of Rhodamine B (RhB) than ZnO under UV and visible light irradiation. Especially, the photocatalytic efficiency was the highest under UV light irradiation when the percentage of g-C₃N₄ was 6%. The improved photocatalytic activity may be due to synergistic effect of photon acquisition and direct contact between organic dyestuff and photocatalyst. Then, effective separation of photogenerated electron–hole pairs at the interface of g-C₃N₄ is an important factor for improvement of photocatalytic activity. This work indicates that g-C₃N₄ hybrid semiconductors photocatalyst is a promising material in pollutants degradation.     

rGO supported self-assembly of 2D nano sheet of (g-C3N4) into rod-like nano structure and its application in sonophotocatalytic degradation of an antibiotic

Graphitic carbon nitride (g-C₃N₄) is an analog of graphite due to its unique electronic structure. g-C₃N₄ based materials have been used in photocatalytic applications. However, pure g-C₃N₄ suffers from major shortcomings which include poor disparity, low surface area and a high recombination rate of photo generated electron-hole pairs that significantly reduce its photocatalytic activity. In this work, self-assembly of g-C₃N₄ sheet into rod shaped g-C₃N₄ was developed via a simple polymerisation method. A composite made of g-C₃N₄ nanorods and rGO (rGO-RCN) was also prepared. The band gap g-C₃N₄ was shifted from 2.77 to 2.6 eV evidented by UV-DRS data. As a result, rGO-RCN showed a relatively high absorption in the visible region. Moreover, a fast electron transfer rate was observed with rGO-RCN composite as conformed from PL analysis and photocurrent measurement. The formation of nanorod and sheet morphologies was confirmed via TEM analysis. The photocatalytic activities of prepared sheet-g-C₃N₄ (SCN)_, Rod g-C₃N₄ (RCN), reduced graphene oxide supported sheet-g-C₃N₄ (rGO-SCN) and reduced graphene oxide supported Rod-g-C₃N₄ (rGO-RCN) were evaluated using a commonly used antibiotic (tetracycline). Among these catalysts, rGO-RCN nanocomposite showed sonophotocatalytic activity 3 times higher compared to pure g-C₃N₄. This superior sonophotocatalytic activity could be due to enhanced visible light absorption of the material, active sites generated by ultrasound, and the high electron transport property of rGO.     

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.     

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.     

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.     

Mechanistic investigations on emission characteristics from g-C3N4, g-C3N4@Pt and g-C3N4@Ag nanostructures using X-ray absorption spectroscopy

An improved method for the preparation of g-C₃N₄ is described. Currently, heating (>400 C°) of urea is the common method used for preparing the g-C₃N₄. We have found that sonication of melamine in HNO₃ solution, followed by washing with anhydrous ethanol, not only reduce the crystallite size of g-C₃N₄ but also facilitate intriguing electronic structure and photoluminescence (PL) properties. Moreover, loading of metal (Pt and Ag) nanoparticles, by applying the borohydride reduction method, has resulted in multicolor-emission from g-C₃N₄. With the help of PL spectra and local electronic structure study, at C K-edge, N K-edge, Pt L-edge and Ag K-edge by X-ray absorption spectroscopy (XAS), a precise mechanism of tunable luminescence is established. The PL mechanism ascribes the amendments in the transitions, via defect and/or metal states assimilation, between the π* states of tris-triazine ring of g-C₃N₄ and lone pair states of nitride. It is evidenced that interaction between the C/N 2p and metal 4d/5d orbitals of Ag/Pt has manifested a net detraction in the δ*→LP transitions and enhancement in the π*→LP and π*→ π transitions, leading to broad PL spectra from g-C₃N₄ organic semiconductor compound.     

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.     

Fabrication and efficient visible light-induced photocatalytic activity of Bi2MoO6/BiPO4 composite

Novel Bi₂MoO₆/BiPO₄ composites with heterojunction structure were fabricated by a one-step hydrothermal method. The photocatalytic properties of Bi₂MoO₆/BiPO₄ composites were evaluated by photocatalytic degradation of rhodamine B (Rh B) under visible light irradiation (λ>420 nm). The results showed that Bi₂MoO₆/BiPO₄ photocatalysts showed much higher photocatalytic activity for the Rh B degradation than the pure BiPO₄ and Bi₂MoO₆ under visible light. The best photocatalytic performance of Bi₂MoO₆/BiPO₄ with about 98.0% Rh B degradation located at molar ratio of 2:1 under visible light illumination for 30 min. The enhanced photocatalytic activity could be mainly ascribed to the formation of heterojunction interface in Bi₂MoO₆/BiPO₄ composites, which is beneficial to the transfer and separation of photogenerated electron–hole pairs, as well as the strong visible light absorption resulting from the sensitization role of Bi₂MoO₆ to BiPO₄. It was also observed that the photodegradation of Rh B is chiefly attributed to the oxidation action of the generated O₂⁻ radicals and the action of h_vb⁺ through direct hole oxidation process.     

The effects of Gd3+ doping on the physical structure and photocatalytic performance of Bi2MoO6 nanoplate crystals

Gd³⁺ doped Bi₂MoO₆ nanoplate crystals were fabricated by solvothermal combined calcination method. The effects of Gd³⁺ doping with different concentrations on the texture, crystal and optical properties of Bi₂MoO₆ were investigated by N₂ physical adsorption, X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscope (TEM), Fourier transform infrared spectroscopy (FT-IR) and ultraviolet–visible diffuse reflection spectrum (UV–vis DRS), photoluminescence (PL) spectroscopy, and X-ray photoelectron spectroscopy (XPS). Under simulated solar light irradiation, the influences of Gd³⁺doping on photocatalytic activity of Bi₂MoO₆ were evaluated by photocatalytic degradation of Rhodamine B. The characterization results showed that with Gd³⁺ doping, a contraction of lattice and a decrease in crystallite size occurred. Meanwhile, an increase in surface area over Gd³⁺ doped Bi₂MoO₆ was observed. Moreover, Gd³⁺ doping could obviously enhance the visible light harvesting of Bi₂MoO₆ and promoted the separation of photogenerated electrons and holes. With optimum Gd³⁺(6 wt%) doping, Gd/Bi₂MoO₆ exhibited the best activity and stability in degradation of Rhodamine B.     

Preparation and characterization of graphitic carbon nitride through pyrolysis of melamine

Graphitic carbon nitride (g-C₃N₄) has been synthesized via a two-step pyrolysis of melamine (C₃H₆N₆) at 800°C for 2 h under vacuum conditions. X-ray diffraction (XRD) patterns strongly indicate that the synthesized sample is g-C₃N₄. Transmission electron microscopy (TEM) and scanning electron microscopy (SEM) morphologies indicate that the product is mainly composed of graphitic carbon nitride. The stoichiometric ratio of C:N is determined to be 0.72 by elemental analysis (EA). Chemical bonding of the sample has been investigated by X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). Electron energy loss spectroscopy (EELS) verifies the bonding state between carbon and nitrogen atoms. Optical properties of the g-C₃N₄ were investigated by PL (photoluminescence) measurements and UV–Vis (ultraviolet–visible) absorption spectra. We suppose its luminescent properties may have potential application as component of optical nanoscale devices. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) were also performed.     

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.     

Preparation, characterization and photocatalytic activity of polycrystalline Bi2O3/SrTiO3 composite powders

Bi₂O₃/SrTiO₃ composite powders have been prepared and their photocatalytic activities were investigated by photooxidation of methanol. These powders were characterized by UV-Visible diffuse reflectance spectra, SEM and X-ray diffraction (XRD). The results revealed that all the Bi₂O₃/SrTiO₃ composite powders exhibited higher photocatalytic activity than pure SrTiO₃, Bi₂O₃ and TiO₂ (P25) under visible light irradiation (λ>440 nm). The effects of the Bi₂O₃ contents on the photocatalytic activities of the composite powders were examined, the photocatalytic activities increased with the content of Bi₂O₃ increasing to a maximum of 83% and then decreased under visible light irradiation. The effects of the calcination temperatures on the photocatalytic activities of the composite powders were also investigated.     

Graphene-based hollow TiO2 composites with enhanced photocatalytic activity for removal of pollutants

Catalytically active graphene-based hollow TiO₂ composites(TiO₂/RGO) were successfully synthesized via the solvothermal method. Hollow TiO₂ microspheres are uniformly dispersed on RGO. X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS) and photoluminescence (PL) were used for the characterization of prepared photocatalysts. The mass of GO was optimized in the photocatalytic removal of rhodamine B (RhB) as a model dye pollutants. The results showed that graphene-based hollow TiO₂ composites exhibit a significantly enhanced photocatalytic activity in degradation of RhB under either UV or visible light irradiation. The formation of the graphene-based hollow TiO₂ composites and the photocatalytic mechanisms under UV and visible light were also discussed.     

Hierarchical ZnO/Bi2O3 nanostructures: synthesis, characterization, and electron-beam modification

Two types of ZnO/Bi₂O₃ nanonecklace heterostructures were fabricated using the vapor-phase transport (VPT) method for the first time. These hierarchical structures were well characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) with energy dispersive spectroscopy (EDS) attached. The growth mechanism of the novel structures were proposed based on these characterizations. Electron-beam irradiation was found to be a powerful and controllable tool in further tailoring such ZnO/Bi₂O₃ nanonecklace heterostructures. In addition, photoluminescence (PL) emission from the hierarchical nanostructures showed enhancement comparing to the pure Bi₂O₃ powder.     

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.     

Studies on nanocrystalline (Sr,Pb)TiO3 solid solutions prepared via a facile self-propagating combustion method

Macroporous nanocrystalline (Sr,Pb)TiO₃ solid solutions were prepared by a facile self-propagating combustion method. The samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), energy dispersive X-ray spectrum (EDS) and X-ray photoelectron spectroscopy (XPS). (Sr,Pb)TiO₃ solid solutions showed enhanced photocatalytic activity for the degradation of methyl orange (MO) than pure SrTiO₃ and an optimum performance was observed for Sr_29/32Pb_3/32TiO₃. The possible mechanism for the enhanced photocatalytic activity on (Sr,Pb)TiO₃ solid solutions was proposed.     

Aqueous synthesis and enhanced photocatalytic activity of ZnO/Fe2O3 heterostructures

We report a facile synthesis of ZnO/Fe₂O₃ heterostructures based on the hydrolysis of FeCl₃ in the presence of ZnO nanoparticles. The material structure, composition, and its optical properties have been examined by means of transmission electron microscopy, scanning electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy and diffuse reflectance UV–visible spectroscopy. Results obtained show that 2.9 nm-sized Fe₂O₃ nanoparticles produced assemble with ZnO to form ZnO/Fe₂O₃ heterostructures. We have evaluated the photodegradation performances of ZnO/Fe₂O₃ materials using salicylic acid under UV-light. ZnO/Fe₂O₃ heterostructures exhibited enhanced photocatalytic capabilities than commercial ZnO due to the effective electron/hole separation at the interfaces of ZnO/Fe₂O₃ allowing the enhanced hydroxyl and superoxide radicals production from the heterostructure.     

Remarkable catalytic activity of Bi<Subscript>2</Subscript>O<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanocomposites prepared by hydrothermal method for the degradation of methyl orange

Visible light Bi₂O₃/TiO₂ nanocomposites are successfully prepared with different dosages of Bi₂O₃ by hydrothermal process. All the as-prepared samples are characterized by X-ray diffraction (XRD), scanning and transmission electron microscopes (SEM and TEM), Brunauer-Emmett-Teller analysis (BET), N₂ adsorption-desorption measurement, and UV-Vis diffuse reflectance spectra (DRS). XRD and Raman spectra reveal the anatase phase of both TiO₂ and Bi₂O₃/TiO₂ nanocomposites. X-ray diffraction patterns demonstrate that the bismuth ions did not enter into the lattice of TiO₂, and Bi₂O₃ is extremely dispersive on the surface of TiO₂ nanoparticles. The incorporation of Bi₂O₃ in TiO₂ leads to the spectral response of TiO₂ in the visible light region and efficient separation of charge carriers. The enhanced visible light activity is tested by the photocatalytic degradation of methyl orange under light illumination, and the performance of Bi₂O₃/TiO₂ nanocomposites are superior than that of pure TiO₂ which is ascribed to the efficient charge separation and transfer across the Bi₂O₃/TiO₂ junction. Bi₂O₃/TiO₂ nanocomposite (20 mg) loaded with 0.25 of Bi₂O₃ dispersed in 50 ml of 5 ppm methyl orange solution exhibited the highest photocatalytic activity of 98.86% within 240 min of irradiation, which is attributed to the low band gap, high surface area, and the strong interaction between Bi₂O₃ and TiO₂.     

Solid-state synthesis of Bi2O3/BaTiO3 heterostructure: preparation and photocatalytic degradation of methyl orange

In this work, Bi₂O₃/BaTiO₃ heterostructure were prepared through a solid milling and annealing process. It was found that Bi³⁺ dissolved in the BaTiO₃ lattice and the chemical bond was constructed between the interface of Bi₂O₃ and BaTiO₃ after annealing process. Powder X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and UV-visible absorption spectra were used to characterize the Bi₂O₃/BaTiO₃ heterostructure. Furthermore, UV-induced catalytic activities of the Bi₂O₃/BaTiO₃ heterostructure was studied by a degradation reaction of methyl orange (MO) dye. The band gap of the Bi₂O₃/BaTiO₃ heterostructure was estimated to be 3.0 eV. Compared with pure Bi₂O₃ powders, the Bi₂O₃/BaTiO₃ heterostructure had a much higher catalytic activity. An excellent performance of the photocatalytic property of the Bi₂O₃/BaTiO₃ heterostructure is ascribed to high mobility of species and effective separation of photogenerated carriers driven by the photoinduced potential difference generated at the Bi₂O₃/BaTiO₃ junction interface, demonstrating that the Bi₂O₃/BaTiO₃ heterostructure is a promising candidate as a photocatalyst.     

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.

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