Fabrication of Bi2WO6/In2O3 photocatalysts with efficient photocatalytic performance for the degradation of organic pollutants: Insight into the role of oxygen vacancy and heterojunction

Photocatalysis is an attractive and green strategy for organic pollutant removal. The development of alternative and effective photocatalysts has attracted great attention. Herein, we rationally engineer an alternative rich-oxygen vacancies (OVs) Bi₂WO₆/In₂O₃ composite photocatalyst via integrating the calcination and hydrothermal method for removing organic dyes (rhodamine B). Thanks to the synergistic effect of OVs and heterojunction structure, the 80 wt% Bi₂WO₆/In₂O₃ (BiIn80) displays enhanced photocatalytic degradation effect. The degradation rate of BiIn80 is up to 97.3% under light irradiation within 120 min and the reaction rate constant k value (0.03221 min⁻¹) is about 15-fold and 4.17-fold as high as those of In₂O₃ (0.00203 min⁻¹) and Bi₂WO₆ (0.00772 min⁻¹), respectively. The heterostructure of Bi₂WO₆/In₂O₃ can extend the lifespan of the photogenerated charge carriers. Moreover, the density functional theory (DFT) calculations reveal that the OVs in Bi₂WO₆/In₂O₃ can boost visible light absorbability by decreasing band gap value and serve as the extra electron transfer channels to enhance the separation efficiency of photogenerated electron-hole pairs. This study not only provides an alternative route for fabricating highly efficient heterojunction photocatalysts, but also obtains better understanding of the synergistic effect of OVs and heterojunction on enhancing the photocatalytic performance.     

A facile decoration of anatase Fe3O4/TiO2 nanocomposite with graphene quantum dots: Synthesis,characterization, and photocatalytic activity

A combination of electron-rich graphene quantum dots (GQDs) with Fe₃O₄/TiO₂ nanocomposites may develop an efficient electron transfer for enhanced photocatalytic activity. In this report, a facile decoration of GQDs with maltose precursor was synthesized and loaded onto magnetic anatase TiO₂ nanocomposites under hydrothermal methods. The as-synthetized magnetic TiO₂/GQDs nanocomposite resulted in a specific surface area of 38.00 m²/g and a total pore volume of 0.186 cm³/g. The HRTEM images showed a lattice plane distance of 0.350 nm related to the interplanar spacing of the anatase TiO₂ (1 0 1) plane and that of 0.299 nm observed for the in-plane lattice part of GQDs. The effects of magnetic loading ratio and GQDs loading onto TiO₂, pH, photocatalyst dosage, and methylene blue (MB) concentration were thoroughly evaluated to find the optimum conditions of mineralization MB for getting the highest photocatalytic efficiency. The removal efficiency of around 86.08 ± 3.62% was obtained at pH11, photocatalytic dose 400 mg/100 mL, and MB concentration 10 mg/L. Moreover, the photogenerated electron transfers and MB degradation mechanism by the resulting Fe₃O₄/TiO₂/GQD_S under irradiation of UVA light are proposed. The as-synthesized material improved meaningfully greater photocatalytic efficiency for degrading MB under UVA light irradiation than merely pure anatase TiO₂. Also, the predominant mechanism of MB degradation was direct oxidative decomposition through the photogenerated holes. The photocatalytic destruction of MB complied with the apparent first-order models under UVA light irradiation.     

Synthesis of Bi2Fe4O9/reduced graphene oxide composite by one-step hydrothermal method and its high photocatalytic performance

Visible-light-driven degraded organic pollutant with high efficiency is crucial in the current photocatalysis research. A new kind composite photocatalyst with high visible-light photocatalytic activity which consists of Bi₂Fe₄O₉ and reduced graphene oxide (RGO) has been synthesized through one-step hydrothermal method at low temperature. Pure Bi₂Fe₄O₉ was formed with the addition of graphene oxide (GO) when the concentration of NaOH is 12 mol/L (M) at 180 °C for 72 h hydrothermal reaction. At the same time, the GO was reduced to RGO and adsorbed on the surface of Bi₂Fe₄O₉. The resultant composite photocatalyst showed higher absorption not only in the UV range but also in the visible light than pure Bi₂Fe₄O₉ indicating more electron–hole pairs generated. The band gap of photocatalysis was reduced from 1.91 to 1.69 eV and recombination of photo-generated electron–hole pairs in composites were decreased through marrying RGO with Bi₂Fe₄O₉. As a result, the Bi₂Fe₄O₉/RGO composite photocatalyst displayed higher catalytic activity for the degradation of methyl violet under visible light irradiation than rare Bi₂Fe₄O₉, promising the use of the Bi₂Fe₄O₉/RGO composite in visible-light photocatalysis.     

Ternary novel TiO2/MgBi2O6/Bi2O3 nanocomposites with n-n-p heterojunctions: Impressive visible-light-triggered photocatalytic degradation of tetracycline

A series of novel ternary TiO₂/MgBi₂O₆/Bi₂O₃ nanocomposites were synthesized by a facile hydrothermal method. The ternary nanocomposites were characterized by XRD, FESEM, HRTEM, EDX, PL, EIS, Photocurrent, UV–vis DRS, BET, XPS, Raman, and FT-IR analyses. The photocatalytic performance of TiO₂ for the degradation of tetracycline antibiotic after combining with MgBi₂O₆/Bi₂O₃ was significantly improved, which is 46.1 and 18.5 times higher than pristine TiO₂ and MgBi₂O₆/Bi₂O₃ photocatalysts, respectively. Furthermore, the ternary photocatalyst efficiently degraded MO, RhB, and MB dye pollutants, which is 22.5, 30.4, and 30.0 as high as TiO₂ and 11.2, 14.4, and 17.8 folds larger than MgBi₂O₆/Bi₂O₃ photocatalysts, respectively. The photoluminescence and electrochemical analyses confirmed promoted separation and facile transfer of the charges thanks to construction of n-n-p heterojunctions among n-TiO₂, n-MgBi₂O₆, and p-Bi₂O₃ components and more production of charge carriers due to integration of small band gap MgBi₂O₆ and Bi₂O₃ components with wide band gap TiO₂.     

Enhanced photocatalytic degradation of industrial dye by g-C3N4/TiO2 nanocomposite: Role of shape of TiO2

The photocatalytic degradation of toxic dyes has brought a new revolution to reduce water pollution. To degrade industrial dyes, TiO₂ is an important photocatalyst but the role of morphology is also important in degradation. We have synthesized g-C₃N₄/TiO₂ nanocomposite (1:1) having different shapes of TiO₂ (nanorods (NR), nanospheres (NS), and nanotubes (NT)), to show the effect of morphology on its photocatalytic activity. To improve the photocatalytic efficiency of TiO₂ in visible light, we have incorporated g-C₃N₄, a visible light active photocatalyst. The HRTEM, FESEM and Electron Diffraction studies with color mapping indicate successful synthesis of g-C₃N₄/TiO₂ nanocomposites. The increased photocatalytic efficiency of the nanocomposites regarding the degradation of Rhodamine B (RhB) dye under visible light irradiation is due to the incorporation of g-C₃N₄ with different shapes of TiO₂. The studies show that, the shape of TiO₂ has a remarkable effect in photodegradation. The best degradation performance (～97%) was obtained from g-C₃N₄/TiO₂ -nanotubes composite with a rate constant of 0.0403?min^?1 within 80?min, whereas degradation efficiency of other shapes of TiO₂ like NS (92%) and NR (94.5%) were also found to be greater than that of commercial TiO₂ (P25) composite (74%). Results from UV–Vis absorption study, X-ray Diffraction studies, X-ray photoelectron spectroscopy and BET analysis suggest that the improvement in photocatalytic activity of composite is due to increased light absorption in visible region and increase in surface area (137.1?m²/g). Results from different scavengers study (DMSO, ascorbic acid and methanol) indicate that electron and superoxide ions act as main reactive species in photodegradation of RhB dye. The reusability efficiency of the catalyst shows 86% degradation after 5 consecutive cycles. The effect of pH and catalyst concentration was also determined which shows that maximum degradation occurs at pH?～?7 (98%) and degradation efficiency is increased with increase of catalyst dose from 0.1?mg/ml to 0.6?mg/ml and after that saturation occur due to increase in opacity and scattering of light. A comparative study was done with literature which suggests that this nanocomposites act as one of the best photocatalysts for degradation of toxic dyes.     

两步水热法制备还原氧化石墨烯/纳米TiO_2复合材料及其光催化性能

为研究由还原氧化石墨烯(RGO)和具有高活性晶面的TiO_2组成的复合材料的制备方法及其光催化性能,首先采用两步水热法制备了RGO/纳米TiO_2复合材料:第1步为合成暴露高活性晶面的纳米TiO_2;第2步为将合成的纳米TiO_2与氧化石墨烯(GO)复合,形成RGO/纳米TiO_2复合材料。然后,利用XRD、SEM、X射线光电子能谱仪和紫外-可见漫反射光谱等手段对制备的暴露不同晶面的纳米TiO_2和RGO/纳米TiO_2复合材料进行了表征,评价了其光催化性能。结果表明:在水热法的第1步中,通过调节HF的浓度能可控制备出具有高活性的(001)和(101)晶面的纳米TiO_2,氟原子在纳米TiO_2中以物理吸附态和化学结合态这2种形态存在;在第2步后,GO与纳米TiO_2复合形成RGO/纳米TiO_2复合材料,同时在此过程中GO被转化成RGO。在紫外光照射下,两步水热法合成的RGO/纳米TiO_2复合材料具有很好的光催化性能,明显优于商用TiO_2(P25)和纳米TiO_2的。RGO/纳米TiO_2复合材料的光催化性能有明显的提高,RGO和TiO_2暴露的晶面对光催化活性有影响。     

Enhanced performance of TiO2/reduced graphene oxide doped by rare-earth ions for degrading phenol in seawater excited by weak visible light

La³⁺- or Yb³⁺-doped TiO₂ supported on the surface of reduced graphene oxide were fabricated by adsorbed-layer nanoreactor synthesis (ANS) coupling with a solvothermal treatment to extend photocatalysis application in the advanced treatment of simulated wastewater with high salt concentration. Results showed that La³⁺ or Yb³⁺ could distribute in the TiO₂ lattice, only in ANS preparation with graphene oxide as the carrier, to replace Ti⁴⁺ during the solvothermal treatment, thus introducing TiO₂ mixed-crystal and heterojunction structures in the catalysts. La³⁺ or Yb³⁺ caused lattice distortion structures and anionic vacancies in the TiO₂ lattice. The anionic vacancies (oxygen vacancies) might generate Ti³⁺ in catalysts, thus enhancing visible-light response, due to impurity levels introduced by La³⁺ or Yb³⁺. As the strong adsorption capability of the catalyst for phenol was not interfered by salt ions in the simulated wastewater, the catalysts could efficiently degrade phenol. The highest removal rate of phenol was approximately 90%.     

Bi2WO6/NH2-MIL-88B(Fe) heterostructure: An efficient sunlight driven photocatalyst for the degradation of antibiotic tetracycline in aqueous medium

The development of highly efficient sunlight assisted photocatalysts has been acknowledged as a promising strategy for the enhanced degradation of antibiotics. In this work, effectual fabrication of a novel Bi₂WO₆/NH₂-MIL-88B(Fe) heterostructure was carried through solvothermal route. The structural, morphological and compositional analysis was done by employing number of analytical techniques, namely XRD, FTIR, HRTEM, FESEM, XPS, PL and BET surface area. The prepared Bi₂WO₆/NH₂-MIL-88B(Fe) heterostructure was utilized as an efficient photocatalyst towards decomposition of a typical antibiotic tetracycline (TC) in aqueous medium. It was found that Bi₂WO₆/NH₂-MIL-88B(Fe) heterostructure exhibited improved degradation efficiency of about 89.4% within 130 min of solar illumination than pristine NH₂-MIL-88B(Fe) under optimized parameters i.e. initial drug solution of 10 mg/L concentration at pH 4 with 0.35 g/L dose of catalyst. Moreover, adsorption studies, kinetics and isotherms of adsorption on TC were also investigated. Results revealed that adsorption kinetics followed pseudo 2nd order model and isotherm data fitted well with Freundlich model (R² = 0.99803) as compared to Temkin and Langmuir. The ameliorating photocatalytic capability could be primarily accredited to the heterojunction created among Bi₂WO₆ and NH₂-MIL-88B(Fe) which facilitated the charge transfer and thus determines high catalytic efficiency. The enhanced photocatalyic effect was further verified by electrochemical impedance and photocurrent studies. The prepared composite also exhibited longer carrier lifetime (140.72 ns) compared to pure MOF (132.05 ns) and Bi₂WO₆ (136.39 ns). Further, based on the radical trapping investigations, role of superoxide radicals was dominant and detailed mechanism was proposed for the photocatalytic degradation process. The major intermediates formed during the course of reaction were also examined using LCMS analysis. The photodegradation was also carried over simulated hospital wastewater by the prepared heterostructure and 60.5% TOC was obtained under solar light in 390 min. Moreover, the synthesized heterostructure showed good recyclability up to three cycles depicting good stability.     

Synthesis and characterization of Bi2MoO6/MIL-101(Fe) as a novel composite with enhanced photocatalytic performance: Effect of water matrix and reaction mechanism

The integration of Bi₂MoO₆ with MIL-101(Fe) as a novel structure enhanced photocatalytic activity for RhB degradation. Bi₂MoO₆/MIL-101(Fe) composites were synthesized via the solvothermal procedure and characterized by XRD, EDX, FE-SEM, TEM, FT-IR, BET, TGA, UV–vis DRS, and PL. The optimal molar ratio Bi₂MoO₆:MIL-101(Fe) equal to 1:1 showed better photocatalytic activity than Bi₂MoO₆ and MIL-101(Fe) and other heterostructure composites. The effect of pH (5–9), reaction time (60–120 min), catalyst concentration (0.1–0.5 g/L), and dye concentration (10–20 ppm) were investigated on the removal performance of RhB by using central composite face-centered (CCF). In the optimal process factors where the [Catalyst]:0.4 g/L, [RhB]:20 ppm, pH: 6.5, irradiation time: 120 min, the RhB and TOC removal efficiency were 85% and 84.2%, respectively. The holes and superoxide radicals played a major role in the degradation of RhB. The addition of salt (NaCl, Na₂SO₄, and NaHCO₃) at different concentrations (100, 200, 400, and 800 ppm) revealed that the salts have an inhibitory role in the photocatalytic performance. At low concentrations of 100 ppm, the salts had a negative effect on removal efficiency (k_{Pure water} = 0.0155 min^?1, k_NaCl = 0.0075 min^?1, k_Na2SO4 = 0.0132 min^?1, k_NaHCO3 = 0.006 min^?1). Increasing the salt concentration to 800 ppm caused improved efficiency for NaCl (k_NaCl = 0.0141 min^?1), while for Na₂SO₄ this trend was decreasing (k_Na2SO4 = 0.011 min^?1), and for NaHCO₃ sharply diminished (k_NaHCO3 = 0.0026 min^?1).