Preparation and efficient visible light-induced photocatalytic activity of m-BiVO4 with different morphologies

The monoclinic scheelite BiVO₄ crystals with peanut-like, oval, twin-quadrangle and twin-four-pointed star morphologies were synthesized via a facile one step hydrothermal method by using sodium citrate as the chelating agent. The X-ray diffraction and scanning electron microscopy were employed to elucidate the structures and mophologies of the as-prepared BiVO₄ samples. The results showed that the formation of m-BiVO₄ with different morphologies relied on the pH value of the precursor solution. The band gaps values (E_g) of all the BiVO₄ samples were around 2.37–2.45 eV according to the UV–vis diffuse reflectance spectrum, which indicated that samples could strongly absorb in the visible light region. The photocatalytic activities of BiVO₄ crystals were evaluated by degradation of MB in aqueous solution under artificial solar-light. The BiVO₄ samples obtained at different pH values showed different photocatalytic activities during the sunlight-driven photodegradation of methylene blue (MB). The sample with peanut-like-shape prepared at pH=1 exhibited the highest activity, and the photocatalytic conversion could reach above 90% after 3 h of irradiation. The result suggested that m-BiVO₄ with peanut-like-shape could be used as an effective photocatalyst in practical application for organic pollutants degradation.     

Hydrothermal synthesis and photoelectric properties of BiVO4 with different morphologies: An efficient visible-light photocatalyst

Different morphologies of monoclinic BiVO₄ with smaller size were hydrothermal synthesized by simply adjusting the amount of surfactant (polyvinyl pyrrolidone PVP K30) added. The detailed field emission scanning electron microscope (FESEM) analysis revealed that the amount of PVP added could significantly affect the morphology and size of BiVO₄. Their photocatalytic activities were evaluated by the decolorization of methylene blue (MB) aqueous solution under visible-light irradiation (λ > 400 nm), and the as-prepared sample with well-assembled flower-like morphology showed a much higher photocatalytic activity due to larger specific surface area and higher separation efficiency of photo-induced carriers. The relationship between the behavior of photo-induced carriers and photocatalytic activity was studied using the surface photovoltage spectroscopy (SPS) and corresponding phase spectra.     

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.     

Efficient photocatalytic degradation of acid orange 7 on metal oxide p–n junction composites under visible light

MO(=CuO, Co₃O₄, NiO)/BiVO₄ p–n junction composites were synthesized by urea-precipitation and wet impregnation method. The physicochemical and optical properties of the as-prepared materials were investigated by X-ray diffraction (XRD), X-ray photoelectron spectra (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and UV–visible diffuse reflectance spectra. The photocatalytic performance of the as-prepared materials was investigated for decomposition of azo dye, acid orange 7. The CuO/BiVO₄ and Co₃O₄/BiVO₄ p–n junction composite photocatalysts exhibited the higher photocatalytic degradation of acid orange 7 than those of BiVO₄ and NiO/BiVO₄ as-prepared samples under visible light irradiation. We also discussed the mechanism of enhanced photocatalytic activity of p–n junctioned composites based on their energy band structures.     

Synthesis and characterization of MnWO4 nanoparticles encapsulated in mesoporous silica SBA-15 by fast microwave-assisted method

The MnWO₄ nanoparticles encapsulated in mesoporous silica (MnWO₄/SBA-15) was successfully synthesized by a fast microwave-assisted method. The products were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen absorption–desorption isotherm, and Fourier transform infrared spectroscopy (FTIR). Our results showed that the MnWO₄/SBA-15 nanocomposites have the ordered hexagonal meso-structure of SBA-15, indicating MnWO₄ nanoparticles were successfully distributed into the channels of SBA-15. The size of MnWO₄ nanoparticles in SBA-15 is significantly smaller than the size of MnWO₄ nanoparticles prepared without SBA-15, indicating that the MnWO₄/SBA15 nanocomposites would be very promising for improving photocatalytic activity of MnWO₄ nanoparticles.     

Visible-Light Activities of Erbium Doped BiVO4 Photocatalysts

采用水热合成法,制备出Er掺杂的BiVO₄复合光催化剂,并采用XRD、SEM、XPS和紫外-可见漫反射光谱技术对其进行分析表征．通过可见光下降解水溶液中甲基橙分子来考察其光催化性能,结果显示掺杂组份以氧化物Er₂O₃形式存在于的复合光催化剂中;且掺杂复合光催化剂的可见光吸收和催化活性都比纯BiVO₄有所增强．     

Multiwalled carbon nanotubes decorated with nitrogen, palladium co-doped TiO2 (MWCNT/N, Pd co-doped TiO2) for visible light photocatalytic degradation of Eosin Yellow in water

Multiwalled carbon nanotube (MWCNT/N), Pd co-doped TiO₂ nanocomposites were prepared by calcining the hydrolysis products of the reaction of titanium isopropoxide, Ti(OC₃H₇)₄ containing multiwalled carbon nanotubes with aqueous ammonia. The prepared samples were characterised by Fourier transform infrared spectroscopy, Raman spectroscopy, thermogravimetric analysis, diffuse reflectance UV?CVis spectrophotometry (DRUV?CVis), XRD, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). DRUV?CVis analysis confirmed the red shift in the absorption edge at lower MWCNT percentages. SEM and TEM images showed the complete coverage of the MWCNTs with clusters of anatase TiO₂ at low MWCNT percentages. Higher MWCNT levels led to their aggregation and consequently poor coverage by N, Pd co-doped TiO₂. The photocatalytic activities of the nanocomposites were monitored by photodegradation of Eosin Yellow under simulated solar and visible light irradiation (???>?450?nm). Irradiation with simulated solar radiation gave higher dye-degradation rates compared to visible radiation. The optimum MWCNT weight percentage in the composites was found to be 0.5. High degradation-rate constants of 3.42?×?10^?2 and 5.18?×?10^?3?min^?1 were realised for the 0.5% MWCNT/N, Pd co-doped TiO₂ composite, using simulated solar light and visible light, respectively.     

Urchin-like CdS/ZrO2 nanocomposite prepared by microwave-assisted hydrothermal combined with ion-exchange and its multimode photocatalytic activity

A series of urchin-like CdS/ZrO₂ nanocomposites with different mole ratios of Cd/Zr were prepared by a two-step method combining the microwave-assisted hydrothermal and ion exchange methods. The products were characterized by X-ray diffraction, ultraviolet–visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and N₂ adsorption–desorption measurements. The results of the study revealed that the CdS/ZrO₂ nanocomposites had mixed phases of tetragonal ZrO₂ and hexagonal CdS. Moreover, the samples prepared by the microwave-assisted hydrothermal method possessed the urchin-like structure with a surface composed of protrude-like nanoparticles in large quantities. The absorption in the visible region changed slightly with increasing mole ratio of Cd/Zr. Moreover, compared to the nanocomposites prepared by the conventional heating, the nanocomposites prepared by the microwave-assisted hydrothermal synthesis showed significantly different Brunauer–Emmett–Teller values, and the urchin-like CdS/ZrO₂ structures were obtained. The photocatalytic degradation of methyl orange under ultraviolet (UV) light irradiation indicated that the photocatalytic activity of the CdS/ZrO₂ nanocomposite with CdS/ZrO₂ molar ratio of 30 % was higher than those of CdS, ZrO₂, and other different ratios of CdS/ZrO₂ nanocomposites. Moreover, under UV light, visible light, and microwave-assisted multimode photocatalytic degradation, the urchin-like CdS/ZrO₂ nanocomposites significantly affected the photodegradation of various dyes. To understand the possible reaction mechanism of the photocatalysis by the CdS/ZrO₂ nanocomposites, a series of controlled experiments were performed, and the stability and reusability of the CdS/ZrO₂ nanocomposites were further investigated by the photocatalytic reaction.     

Ultrasonic-assisted preparation and characterization of CdS nanoparticles in the presence of a halide-free and low-cost ionic liquid and photocatalytic activity

An ultrasonic-assisted and environmentally favorable method is proposed for preparation of CdS nanoparticles in the presence of a halide-free and low-cost room-temperature ionic liquid (RTIL), 1-ethyl-3-methylimidazolium ethyl sulfate, ([EMIM][EtSO₄]). The prepared samples were characterized by powder X-ray diffraction (XRD), energy dispersive X-ray spectroscopy (EDX), scanning electron microscopy (SEM) and Fourier transform-infrared (FT-IR). Diffuse reflectance spectra (DRS) of the products reveal a blue shift of 1.45 eV relative to bulk CdS, which can be attributed to the quantum confinement effect of the prepared nanoparticles. Investigation of photocatalytic activity for the CdS nanoparticles towards photodegradation of methylene blue (MB) demonstrates that photodegradation of MB increases with RTIL content of the media using visible and UV irradiations.     

siRNA-loaded PEGylated porous silicon nanoparticles for lung cancer therapy

The BiPO₄/reduced graphene oxide (RGO) nanocomposites were prepared by a facile solvothermal approach. The prepared samples were characterized with Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, UV–vis diffuse reflectance spectroscopy, electrochemical impedance spectra, and Mott–Schottky and the photoluminescence spectra. A large quantity of BiPO₄ nanoparticles with sizes of ca. 150 nm were well dispersed on the RGO nanosheets. The absorbance of the BiPO₄/RGO nanocomposites is largely enhanced in the range of 400–800 nm compared with that of BiPO₄, and the BiPO₄/RGO showed better photocatalytic activities under simulated sunlight irradiation than the BiPO₄ nanocrystals.     

Rapid microwave-assisted hydrothermal synthesis of Bi12TiO20 hierarchical architecture with enhanced visible-light photocatalytic activities

Flower-like Bi₁₂TiO₂₀ hierarchical nanostructures composed of numerous nanobelts were synthesized at 180 °C within 1 h by a microwave-assisted hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB) for the first time. The as-prepared products were characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet–visible (UV–vis) absorption spectroscopy. Furthermore, the hierarchical Bi₁₂TiO₂₀ nanostructures exhibited higher photocatalytic activities in the degradation of Rhodamine B under visible-light irradiation than that of the samples prepared without CTAB. In addition, the role of CTAB cationic surfactant has been investigated thoroughly and a possible mechanism is proposed.     

Additive-free controllable fabrication of bismuth vanadates and their photocatalytic activity toward dye degradation

Bismuth vanadates (BiVO₄) with various crystal structures (tetragonal scheelite, monoclinic scheelite, and tetragonal zircon) and morphologies (sphere-, nanosheet-, dendrite-, and flower-like) were controllably fabricated by using a mild additive-free hydrothermal treatment process under the different preparation conditions. The crystal structures, morphologies, and photophysical properties of the products were well-characterized. Subsequently, their UV- as well as visible-light photocatalytic performance was evaluated via dyes rhodamine B (RB) and methylene blue (MB) degradation. Special attention was paid to evaluate the correlation of the reactivity with crystal structure, morphology, and electronic structure of as-prepared BiVO₄ samples.     

Low-temperature hydrothermal synthesis of highly photoactive mesoporous spherical TiO2 nanocrystalline

TiO₂ microspheres with mesoporous textural microstructures and high photocatalytic activity were prepared by hydrothermal treatment of mixed solution of titanium sulfate and urea with designed time. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and N₂ adsorption-desorption measurements. The photocatalytic activity was evaluated via the photocatalytic oxidation of acetone in air at room temperature. The results show that the hydrothermal time significantly influences on the morphology, microstructure and photocatalytic activity of the as-prepared samples. With increasing hydrothermal time, specific surface areas and pore volumes decrease, contrarily, the crystallite size and relative anatase crystallinity increase. The photocatalytic efficiency of the as-prepared samples is obviously higher than that of commercial Degussa P25 (P25) powders. Especially, the as-prepared TiO₂ powders by hydrothermal treatment for 7 h shows the highest photocatalytic activity, which exceeds that of P25 by a factor of more than 2 times.     

One-pot synthesis of Ag+ doped BiVO4 microspheres with enhanced photocatalytic activity via a facile hydrothermal method

The Ag⁺/BiVO₄ photocatalyst was fabricated through a facile hydrothermal method by using K₆V₁₀O₂₈·9H₂O as the vanadium source. The impact of Ag⁺ on the product's structure and morphology was studied. It was shown that the amount of Ag⁺ has no effect on the product’s crystal phases but plays an important role on the morphology of the nanoparticles that construct the shell of BiVO₄ microspheres. In addition, the Ag⁺-doped photocatalysts have much higher photocatalytic activities in removing RhB and MB under the UV light illumination than the pure BiVO₄. A possible photocatalytic mechanism was proposed in photoexcitation of the BiVO₄ electrons which subsequently captured by the dopant. The present work may offer a novel route to reach higher photocatalytic activity by doping the Ag⁺ in the semiconductor catalysts.     

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.     

Synthesis, characterization and photocatalytic activities of rare earth-loaded BiVO4 catalysts

The BiVO₄-based photocatalysts loaded with rare earth (RE=Ho, Sm, Yb, Eu, Gd, Nd, Ce and La) were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), diffuse reflectance spectroscopy (DRS), nitrogen adsorption for the BET specific surface area and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were evaluated by decolorization of methylene blue (MB) under visible light irradiation. The results of XRD, SEM and XPS analysis deduced that the rare earth ions were present as RE₂O₃ in the samples. The DRS analysis showed the shift in the absorbption edge from the UV to the visible range: Ho³⁺-BiVO₄ < Sm³⁺-BiVO₄ < Yb³⁺-BiVO₄ < Eu³⁺-BiVO₄ < Gd³⁺-BiVO₄ < Nd³⁺-BiVO₄ < La³⁺-BiVO₄ < Ce³⁺-BiVO₄ < BiVO_4. Gd³⁺-BiVO₄ had the highest photocatalytic activity among all the RE³⁺-BiVO₄ catalysts. The optimal Gd content was 8 at% under visible light irradiation. This beneficial effect was attributed to the specific electron structure characteristics of gadolinium and the increasing in the separation efficiency of the electron-hole pairs. On the contrast, the other rare earth ions had the detrimental effect on the photocatalytic decolorization of MB.     

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.     

Photo(electro)catalytic Activity of Cu-Modified TiO2 Nanorod Array Thin Films under Visible Light Irradiation

In the present study, a two-step method was applied to synthesise Cu²⁺-modified TiO₂ nanorod array thin films for photocatalytic processes. TiO₂ nanorod array thin films were synthesised by a hydrothermal method and then modified with an ultrasonic-assisted sequential cation adsorption method. The samples were characterised by X-ray diffraction (XRD), UV–vis diffuse reflectance spectra (DRS), scanning electron microscopy (SEM), photoluminescence (PL) spectroscopy and inductively coupled plasma mass spectroscopy (ICP-MS) analysis. The photoelectrochemical properties of the samples were evaluated by linear sweep voltammetry and Mott–Schottky analysis; photocatalytic activities were tested by methylene blue degradation under visible light. The photocurrent density of the TiO₂/FTO sample modified with 50 mM Cu²⁺ solution was 26 times higher than that of the unmodified TiO₂/FTO sample. Additionally, methylene blue degradation efficiency under visible light was increased 40% with respect to the efficiency of the unmodified sample. The mechanism of the photocatalytic activity enhancement of Cu²⁺-modified TiO₂ nanorod films was discussed.     

Observation of the diameter-dependent Raman dispersion effect in chemically oxidized multiwalled carbon nanotubes

Chemical oxidation of multiwalled carbon nanotubes (MWCNTs) using H₂SO₄/HNO₃ solution has been monitored by micro-Raman spectroscopy and X-ray absorption spectroscopy. The diameter distribution variation in MWCNTs due to chemical oxidation has been measured by scanning electron microscopy and transmission electron microscopy. The Raman dispersion behaviors of the intensity ratio and the band positions of the D, G, and G′ bands were found to be correlated with the MWCNT diameter distribution. It was also found that, during the nanotube unzipping process, defect formation complicates the observation of the diameter-dependent Raman dispersion effect. The curvature effect plays an important role in the intensity ratio trend. On the other hand, defect formation dominates the band position trend.     

Photocatalysis of novel reduced graphene oxide-CoSe nanocomposites with efficient interface-induced effect

In this work, reduced graphene oxide–CoSe (rGO–CoSe) nanocomposites were synthesized with chemical solution reaction and characterized by X-ray diffraction, scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, UV–vis spectroscopy, and photodegradation of toxicity malachite green in the water. The effects of rGO/CoSe ratio, initial solution pH, and H₂O₂ concentration on the photodegradation effeciency were studied. The nanocomposites showed excellent sunlight-excited photocatalytic activity to toxicity malachite green in the water. The photodegradation rate increased with increasing rGO/CoSe ratio and initial solution pH. Significantly, remarkable Fenton-like photocatalytic activity enhanced with increasing rGO/CoSe ratio and H₂O₂ concentration was observed. The photodegradation rate constant, k obs, was determined under pseudo-first order conditions. The interface-induced mechanism on enhanced photocatalysis with rGO/CoSe was suggested.