Synthesis, characterization and photocatalytic properties of nanosized Bi2WO6, PbWO4 and ZnWO4 catalysts

Nanosized Bi₂WO₆, PbWO₄ and ZnWO₄ photocatalysts were synthesized by a mild hydrothermal crystallization process. The physical and photophysical properties of the catalysts were characterized by X-ray diffractometry, Brunauer-Emmet-Teller surface area and porosity measurements, transmission electron microscopy, Raman spectra, and diffused reflectance spectroscopy. The rhodamine-B photodegradation in aqueous medium was employed as a probe reaction to test the photoactivities of the as-prepared samples under four irradiation wavelengths. Bi₂WO₆ not only presented the photocatalytic activity in the wide spectral scope, including UV and visible light but also exhibited the strong photosensitized capability to transform RhB under visible light irradiation (λ > 490 nm). ZnWO₄ only displayed relatively high photoactivity under UV irradiation. However, PbWO₄ showed poor photoactivity under any light irradiation. On the basis of the calculated density functional theory (DFT), the photocatalytic mechanisms were discussed.     

Structural characterization and photocatalytic properties of novel Bi2YVO8

Bi₂YVO₈ was prepared by solid-state reaction for the first time. The structural and photocatalytic properties of Bi₂YVO₈ were studied. The results showed that this compound has the tetragonal crystal system with space group I4/mmm. The band gap of Bi₂YVO₈ was estimated to be about 2.09 eV by plotting (αhν)² versus hν and obtaining the hν axis intercept value according to Tauc's equation. For the photocatalytic water splitting reaction, H₂ or O₂ evolution was observed from pure water with Bi₂YVO₈ as the photocatalyst under ultraviolet light irradiation (wavelength = 390 nm). Degradation of aqueous methylene blue photocatalyzed by this compound was investigated under visible light irradiation. Bi₂YVO₈ showed higher photocatalytic activity compared to Bi₂YTaO₇, Bi₂InTaO₇ or TiO₂ (P-25). Complete removal of aqueous methylene blue was achieved after visible light irradiation for 170 min. The decrease of the total organic carbon and the formation of inorganic products such as SO₄²⁻ and NO₃⁻ revealed the continuous mineralization of aqueous methylene blue during photocatalytic reaction.     

Investigation of visible light photocatalytic behavior of Bi4V2O11−δ and BIMEVOX (ME = Al, Ga) oxides

A study of photocatalytic properties of Bi₄V₂O_11−δ for the degradation of common organic dyes such as methylene blue (MB) under visible light was carried out. Other identified bismuth based visible light photocatalysts such as Bi₂GaVO₇, Bi₂YVO₈ and Bi₂AlVO₇ were reinvestigated to understand their structural, and photocatalytic properties. Our experiments involving the synthesis of Bi₂YVO₈ indicated merely a mixture of BiYO₃ and BiVO₄, instead of the reported oxide containing bismuth in +3 and +5 oxidation states (J. Luan, et al., Mater. Res. Bull. 43 (2008) 3332). We have further shown the similarity of Bi₂AlVO₇ and Bi₂GaVO₇ photocatalysts with that of the metal ions substituted Bi₄V₂O_11−δ (BIMEVOX; ME = Al, Ga) based on the results of powder X-ray diffraction, UV-vis diffuse reflectance and photocatalytic studies. In general, photocatalytic behavior of Bi₄V₂O_11−δ and Bi₄V_2−xM_xO_11−δ (M = Al, Ga; x = 0.4) were found to be moderate for the decomposition of MB under visible light irradiation.     

Nest-like structures of Sr doped Bi2WO6: Synthesis and enhanced photocatalytic properties

A series of Sr-doped Bi₂WO₆ with three-dimensional (3D) nest-like structures were synthesized through simple hydrothermal route and characterized by XRD, FESEM, TEM, XPS, UV-vis DRS, etc. Morphology observation revealed that the as-synthesized Bi₂WO₆ were self-assembled three-dimensional (3D) nest-like structures, which were constructed from nanoplates. UV-vis diffuse reflectance spectra indicated that the samples had absorption in both UV and visible light areas. Their photocatalytic activities were evaluated by photodegradation of rhodamine B (RhB) under UV and visible light irradiation (λ > 420 nm). The photocatalytic properties were enhanced after Sr doping. Samples subsequently thermal treated at 500 °C showed higher photocatalytic activities. The reasons for the differences in the photocatalytic activities of these nest-like Bi₂WO₆ microstructures were further investigated.     

Preparation of grape-like Bi2O3/Ti photoanode and its visible light activity

Compact and grape-like bismuth oxide (Bi₂O₃) coated titania (Ti) anode was prepared by oxalic acid (H₂C₂O₄) etching, electrodeposition and calcination in order to explore its photoelectrocatalytic activities. The Bi₂O₃ coating was demonstrated to be full of pores, and a good combination between Bi₂O₃ layer and honeycomb-like Ti substrate was observed by scanning electron microscopy. The characteristic morphology of Bi₂O₃ coating indicated that the electrode is stable during degradation. The Bi₂O₃/Ti electrode was used in oxidative degradation of Acid Orange 7 by electrolysis, photocatalytic oxidation and photoelectrocatalytic oxidation processes. The pseudo-first order kinetics parameter (K_app) of photoelectrocatalytic process was 1.15 times of the sum of electrolysis and photocatalytic oxidation under visible light irradiation at 420 nm. The results indicated that the synergy of electrolysis and photocatalysis lead to an excellent photoelectrocatalytic property of the Bi₂O₃/Ti electrode.     

Substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of perovskite-structured Ba(In0.5Ta0.5−xBix)O3 semiconductors

We have investigated the substitution effect of pentavalent bismuth ions on the electronic structure and physicochemical properties of barium indium tantalate. X-ray diffraction, X-ray absorption spectroscopic, and energy dispersive spectroscopic microprobe analyses reveal that, under oxygen atmosphere of 1 atm, pentavalent Bi ions are successfully stabilized in the octahedral site of the perovskite tantalate lattice. According to diffuse reflectance UV-vis spectroscopic analysis, the Bi substitution gives rise to the significant narrowing of band gap of barium indium tantalate even at a low Bi content of ∼5%, underscoring a high efficiency of Bi substitution in the band gap engineering. Such an effective narrowing of the band gap upon the Bi substitution would be attributable to the lowering of conduction band position due to the high electronegativity of Bi^V substituent. As a result of band gap engineering, the Ba(In_0.5Ta_0.5−xBi_x)O₃ compounds with x ≥ 0.03 can generate photocurrents under visible light irradiation (λ > 420 nm). Based on the present experimental findings, it becomes clear that the substitution of highly electronegative p-block element like Bi^V ion can provide a very powerful tool for tailoring the electronic structure and physicochemical properties of wide band gap semiconductors.     

Synthesis and photocatalytic performance of novel CdS quantum dots sensitized Bi2WO6 photocatalysts

Novel quantum dots sensitized CdS-Bi₂WO₆ composite photocatalysts were synthesized to improve the visible-light-driven photocatalytic performance. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) UV-vis diffuse reflectance spectra (DRS). The photocatalytic activities of QDs sensitized CdS-Bi₂WO₆ samples were investigated based on the decomposition of methyl orange under visible light irradiation (λ > 420 nm). The DRS results revealed that CdS-Bi₂WO₆ samples have a red shift and stronger absorption in the visible light region. After being sensitized by quantum dots CdS, the Bi₂WO₆ samples showed the high efficiency for the degradation of methyl orange. This study may provide an approach to treatment of organic pollutants by using visible light.     

Enhancing solar photocatalytic activity of Bi5O7I photocatalyst with activated carbon heterojunction

Passive solar photocatalysis is one of the most efficient ways for the treatment of dye industry wastewater. Some dyes such as methyl orange are recalcitrant to photolysis; therefore, photocatalysts are used to expedite their degradation. Photocatalysts are semiconductors, and their activity can be improved by creating heterojunctions. In the current work, an active photocatalyst, Bi₅O₇I_, was modified with activated carbon (AC), obtained by controlled carbonization of pistachio shells, to give xAC-Bi₅O₇I photocatalysts. AC loading improved the surface area of the catalyst and decreased its bandgap to 1.8 eV, making it suitable for use as a visible light photocatalyst. Activated carbon enhances adsorption, while Bi₅O₇I scavenges adsorbed molecules increasing the efficiency. 5AC-Bi₅O₇I catalyst containing 5% activated carbon displayed the optimum photocatalytic activity, which was 3.4-fold higher than that of pristine Bi₅O₇I. 5AC-Bi₅O₇I achieved 99.9 % reduction in the concentration of methyl orange in 80 min under sunlight irradiation. 5% AC-Bi₅O₇I is more efficient than commercial Degussa P25 photocatalyst as well. The methyl orange degradation efficiency of the catalysts studied was: 5AC-Bi₅O₇I > Bi₅O₇I > Degussa P25.     

Preparation of monoclinic BiVO4 thin film by citrate route for photocatalytic application under visible light

A monoclinic BiVO₄ (mBiVO₄) film composed of nanoparticles with a size of 100 nm was prepared via a citrate-precursor chemical route. The BiVO₄ film was characterized by X-ray diffraction, scanning electron microscopy and absorption spectra. It was found that the mBiVO₄ film showed a photocatalytic activity of Acid Orange 7 (AO7) degradation in aqueous solution under visible-light irradiation (λ > 400 nm). The degradation efficiency was 78.9% in 3 h and basically remained constant in 10 repeated batch runs. The results demonstrated that the mBiVO₄ film had a high photocatalytic activity under visible light and good durability in repeated use.     

Photocatalytic degradation of an azo dye using Bi3.25M0.75Ti3O12 nanowires (M = La,Sm, Nd,and Eu)

Bi_3.25M_0.75Ti₃O₁₂ (BMT, M = La, Sm, Nd, and Eu) nanowires were synthesized through simple hydrothermal route and their structural and photocatalytic properties were investigated. XRD results indicated that these compounds are of layered perovskites structure. In addition, the band gaps of Bi_3.25La_0.75Ti₃O₁₂ (BLT), Bi_3.25Sm_0.75Ti₃O₁₂ (BST), Bi_3.25Nd_0.75Ti₃O₁₂ (BNT), and Bi_3.25Eu_0.75Ti₃O₁₂ (BET) were estimated to be about 2.403, 2.594, 2.525, and 2.335 eV, respectively. Their photocatalytic activities were evaluated by photocatalytic degradation of methyl orange (MO) under visible light irradiation (λ > 420 nm). Bi_3.25M_0.75Ti₃O₁₂ (M = La, Sm, Nd, and Eu) showed markedly higher catalytic activity compared to traditional N doped TiO₂ (N-TiO₂) and pure bismuth titanate (Bi₄Ti₃O₁₂, BIT) for MO photocatalytic degradation under visible light irradiation. The high photocatalytic performance of Bi_3.25M_0.75Ti₃O₁₂ photocatalysts could be attributed to the strong visible light absorption and the recombination restraint of the e^?/h⁺ pairs resulting from doping of rare earth metal ions. Furthermore, BET nanowires exhibited the highest photocatalytic activity.     

Preparation,characterization and photocatalytic activity of Bi2O3–MgO composites

A series of Bi₂O₃–MgO composites were synthesized by solvent-thermal method. It was found that the Bi₂O₃–MgO composites perform much better than TiO₂ (P25), Bi₂O₃ and MgO in the photocatalytic degradation of rhodamine B (RhB) in the presence of HCl and under irradiation of visible light (λ > 400 nm). The effects of Bi/Mg molar ratio, crystallization temperature of Bi₂O₃–MgO and reaction conditions on photocatalytic activity were studied. The best performance was observed over the composite with Bi:Mg molar ratio equal to 2:1 that had been subject to crystallization at 120 °C for 20 h. In addition, the photocatalytic efficiency of the composite can be significantly enhanced by the presence of hydrochloric acid. The prepared samples were characterized by XRD and UV–vis DRS techniques. The relationships between the structure and photocatalytic performance of the as-prepared Bi₂O₃–MgO samples were also investigated.     

Photocatalytic activity of Ca3Ti2O7 layered-perovskite doped with Rh under visible light irradiation

The photocatalytic activities of layered-perovskite Ca₃Ti₂O₇ doped with Rh were investigated with visible light irradiation. Although the Rh-doped Ca₃Ti₂O₇ as prepared showed low activity after an induction period, the photocatalytic activity was highly enhanced by treating the samples in reducing atmosphere without the need for an induction period. The rate of H₂ evolution from an aqueous methanol solution by 3 mol% Rh-doped Ca₃Ti₂O₇ after the reduction treatment was about 5 times higher than that before the reduction. The layered photocatalytic compounds, Ca₃Ti_2 − xRh_xO₇, showed higher stability in air than CaTi_1 − xRh_xO₃, which consists of a simple perovskite structure.     

Structural, photophysical and photocatalytic properties of Bi2MTaO7 (M = La and Y)

Bi₂MTaO₇ (M = Y and La) were synthesized by solid-state reaction method and their structural and photocatalytic properties were investigated. The results indicated that these compounds crystallize in the pyrochlore-type structure, cubic system with space group Fd-3 m. In addition, the band gaps of Bi₂LaTaO₇ and Bi₂YTaO₇ were estimated to be about 2.17(3) and 2.22(7) eV, respectively. For the photocatalytic water splitting reaction, H₂ or O₂ evolution was observed from pure water respectively with Bi₂MTaO₇ (M = Y and La) as the photocatalysts under ultraviolet light irradiation. Photocatalytic degradation of aqueous methylene blue (MB) dye over these compounds was further investigated under visible light irradiation. Bi₂MTaO₇ (M = Y and La) showed markedly higher catalytic activity compared to P-25 for MB photocatalytic degradation under visible light irradiation. Complete removal of aqueous MB was observed after visible light irradiation for 190 min with Bi₂LaTaO₇ as the photocatalyst and for 200 min with Bi₂YTaO₇ as the photocatalyst. The decrease of the total organic carbon (TOC) and the formation of inorganic products, SO₄²⁻ and NO₃⁻, demonstrated the continuous mineralization of aqueous MB during the photocatalytic process.     

New substitutions and novel derivatives of the Aurivillius phases, Bi5TiNbWO15 and Bi4Ti3O12

We investigated isomorphous substitution of several metal atoms in the Aurivillius structures, Bi₅TiNbWO₁₅ and Bi₄Ti₃O₁₂, in an effort to understand structure-property correlations. Our investigations have led to the synthesis of new derivatives, Bi₄LnTiMWO₁₅ (Ln = La, Pr; M = Nb, Ta), as well as Bi₄PbNb₂WO₁₅ and Bi₃LaPbNb₂WO₁₅, that largely retain the Aurivillius (n = 1) + (n = 2) intergrowth structure of the parent oxide Bi₅TiNbWO₁₅, but characteristically tend toward a centrosymmetric/tetragonal structure for the Ln-substituted derivatives. On the other hand, coupled substitution, 2Ti^IV → M^V + Fe^III in Bi₄Ti₃O₁₂, yields new Aurivillius phases, Bi₄Ti_3−2xNb_xFe_xO₁₂ (x = 0.25, 0.50) and Bi₄Ti_3−2xTa_xFe_xO₁₂ (x = 0.25) that retain the orthorhombic noncentrosymmetric structure of the parent Bi₄Ti₃O₁₂. Two new members of this family, Bi₂Sr₂Nb₂RuO₁₂ and Bi₂SrNaNb₂RuO₁₂ that are analogous to Bi₂Sr₂Nb₂TiO₁₂, possessing tetragonal (I4/mmm) Aurivillius structure have also been synthesized.     

Growth of quantum-confined CdS nanoparticles inside Ti-MCM-41 as a visible light photocatalyst

CdS nanocrystallites have been successfully incorporated into the mesopores of Ti-MCM-41 by a two-step method involving ion-exchange and sulfidation. The X-ray diffraction patterns (XRD), UV-vis absorption spectra (UV-vis), photoluminescence spectra (PL), Raman spectra and N₂ adsorption-desorption isotherms were used to characterize the structure of the composite materials. It is found that most of the CdS nanocrystallites are about 2.6 nm, less than the pore diameter of Ti-MCM-41. The CdS nanocrystallites inside the mesopores of Ti-MCM-41 host show a significant blue shift in the UV-vis absorption spectrum. Under irradiation of visible light (λ > 430 nm), the composite material has greater and more stable photocatalytic activity for hydrogen evolution than bulk CdS, which can be explained by the effective charge separation between the CdS nanocrystallites and mesoporous Ti-MCM-41.     

The enhanced visible light photocatalytic activity of nanosheet-like Bi2WO6 obtained by acid treatment for the degradation of rhodamine B

Bi₂WO₆ samples were fabricated by chemical solution decomposition (CSD) method and nanosheet-like Bi₂WO₆ samples could be obtained by concentrated nitric acid treatment at 70 °C for 20 min. The products were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), and UV-vis diffuse reflectance spectra. Photocatalytic activities of the samples were evaluated by the degradation of rhodamine B (RhB) under visible light irradiation. The temperature of acid treatment obviously influenced morphology and the visible light photocatalytic activity of the Bi₂WO₆ samples. The nanosheet-like Bi₂WO₆ photocatalysts obtained by acid treatment exhibited the highest photocatalytic activity under visible light irradiation.     

Preparation and crystal structure of a new bismuth vanadate, Bi3.33(VO4)2O2

Single crystals of a new bismuth vanadate, Bi_3.33(VO₄)₂O₂ was prepared by hydrothermal reaction using a hydrated sodium bismuthate, NaBiO₃·nH₂O as one of the starting compounds. The crystal structure was determined by using single crystal X-ray diffraction data. This compound crystallizes in the triclinic space group (#2) with a = 7.114(1), b = 7.844(2), c = 9.372(2) Å, α = 106.090(7), β = 94.468(7) and γ = 112.506(8)°, Z = 2 and the final R factors are R1 = 0.052 and wR2 = 0.14 for 2085 unique reflections. The crystal structure is composed by four bismuth atoms with the coordination number of 6 or 8 and two VO₄ tetrahedra, and one of four bismuth atoms is statistically distributed in the splitting sites with the distance of 0.83 Å. This compound exhibited photocatalytic behavior for decomposition of phenol under visible light irradiation and its activity was less than that of monoclinic BiVO₄.     

Photocatalytic degradation of 2,4-dichlorophenol wastewater using porphyrin/TiO2 complexes activated by visible light

The use of TiO₂ as photocatalyst to degrade the organic compounds is an effective method of oxidation process and has been widely studied in environmental engineering. However, TiO₂ absorbed the UV light which is only small part of sunlight reaching earth surface to activate photocatalytic procedure effectively is a major disadvantage. Therefore, studies on the development of new TiO₂ wherein its photocatalytic activity can be activated by visible light which is the major part of sunlight will be valuable for field application. In this study, we evaluate the photocatalytic degrading efficiency of porphyrins/TiO₂ complexes on the organic pollutants under irradiation with visible light (λ = 419 nm). The results showed that the photodecomposition efficiency of 2,4-dichlorophenol (2,4-DCP) wastewater by using porphyrin/TiO₂ irradiated under visible light for 4 h was up to 42-81% at pH 10. These evidences reveal that the system of porphyrin/TiO₂ complexes has also significantly efficiency of photocatalytic degradation for some hazardous or recalcitrant pollutants under visible light irradiation.     

Photoinduced charge property of nanosized perovskite-type LaFeO3 and its relationships with photocatalytic activity under visible irradiation

In this paper, ABO₃-type perovskite LaFeO₃ nanosized photocatalysts were synthesized by a sol-gel method, using citric acid (HOOCCH₂C(OH)(COOH)CH₂COOH) as complexing reagent and La(NO₃)₃·6H₂O and Fe (NO₃)₃·9H₂O as raw materials. The as-prepared samples also were characterized by several testing techniques, such as thermogravimetry-differential thermal analysis (TG-DTA), X-ray powder diffraction (XRD), Brunauer-Emmett-Teller (BET), infrared spectrum (IR), ultraviolet-visible diffuse reflection spectrum (UV-vis DRS), photoluminescence spectrum (PL), surface photovoltage spectroscopy (SPS) and electrical field induced surface photovoltage spectroscopy (EFISPS). The sample activity of different LaFeO₃ nanoparticles for degrading Rhodamine B solution under visible irradiation (λ > 400 nm) was evaluated. The effects of thermal treatment temperature on photoinduced charge property and photocatalytic activity were mainly investigated, together with their relationships. The results show that the LaFeO₃ sample calcined at 500 °C exhibits higher activity, and the activity decreases with increasing calcination temperature, which is in good agreement with the characterization results. The weaker is the PL and SPS signal, the higher is the photocatalytic activity. Moreover, the activity of all as-prepared LaFeO₃ samples is higher than that of international P-25 TiO₂ under visible irradiation.     

One step synthesis of Bi@Bi2O3@carboxylate-rich carbon spheres with enhanced photocatalytic performance

Bi@Bi₂O₃@carboxylate-rich carbon core-shell nanosturctures (Bi@Bi₂O₃@CRCSs) have been synthesized via a one-step method. The core–shell nanosturctures of the as-prepared samples were confirmed by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and Raman spectroscopy. The formation of Bi@Bi₂O₃@CRCSs core–shell nanosturctures should attribute to the synergetic roles of different functional groups of sodium gluconate. Bi@Bi₂O₃@CRCSs exhibits significant enhanced photocatalytic activity under visible light irradiation (λ > 420 nm) and shows an O₂-dependent feature. According to trapping experiments of radicals and holes, hydroxyl radicals were not the main active oxidative species in the photocatalytic degradation of MB, but O₂⁻ are the main active oxidative species.