Facet-Dependent Fe2O3/BiVO4(110)/BiVO4(010)/Fe2O3 Dual S-Scheme Photocatalyst as an Efficient Visible-Light-Driven Peroxymonosulfate Activator for Norfloxacin Degradation.

A lack of eco-friendly, highly active photocatalyst for peroxymonosulfate (PMS) activation and unclear environmental risks are significant challenges. Herein, we developed a double S-scheme Fe2O3/BiVO4(110)/BiVO4(010)/Fe2O3 photocatalyst to activate PMS and investigated its impact on wheat seed germination. We observed an improvement in charge separation by depositing Fe2O3 on the (010) and (110) surfaces of BiVO4. This enhancement is attributed to the formation of a dual S-scheme charge transfer mechanism at the interfaces of Fe2O3/BiVO4(110) and BiVO4(010)/Fe2O3. By introducing PMS into the system, photogenerated electrons effectively activate PMS, generating reactive oxygen species (ROS) such as hydroxyl radicals (·OH) and sulfate radicals (SO4·-). Among the tested systems, the 20% Fe2O3/BiVO4/Vis/PMS system exhibits the highest catalytic efficiency for norfloxacin (NOR) removal, reaching 95% in 40 min. This is twice the catalytic efficiency of the Fe2O3/BiVO4/PMS system, 1.8 times that of the Fe2O3/BiVO4 system, and 5 times that of the BiVO4 system. Seed germination experiments revealed that Fe2O3/BiVO4 heterojunction was beneficial for wheat seed germination, while PMS had a significant negative effect. This study provides valuable insights into the development of efficient and sustainable photocatalytic systems for the removal of organic pollutants from wastewater.

A novel ternary heterogeneous TiO2/BiVO4/NaY-Zeolite nanocomposite for photocatalytic degradation of microcystin-leucine arginine (MC-LR) under visible light.

Microcystin-leucine arginine (MC-LR) is a carcinogenic toxin, produced by cyanobacteria. The release of this toxin into drinking water sources can threaten public health and environmental safety. Therefore, effective MC-LR removal from water resources is necessary. In the present study, the hydrothermal method was used to synthesize a novel ternary BiVO4/TiO2/NaY-Zeolite (B/T/N-Z) nanocomposite for MC-LR degradation under visible light. FESEM, FTIR, XRD, and DRS were performed for characterizing the nanocomposite structure. Also, the Response Surface Methodology (RSM) was applied to determine the impact of catalyst dosage, pH, and contact time on the MC-LR removal. High-performance liquid chromatography was performed to measure the MC-LR concentration. Based on the results, independent parameters, including contact time, catalyst dosage, and pH, significantly affected the MC-LR removal (P < 0.05). In other words, increasing the contact time, catalyst dosage, and acidic pH had positive effects on MC-LR removal. Among these variables, the catalyst dosage, with the mean square and F-value of 1041.37 and 162.84, respectively, had the greatest effect on the MC-LR removal efficiency. Apart from the interaction between the catalyst dosage and contact time, the interaction effects of other parameters were not significant. Also, the maximum MC-LR removal efficiency was 99.88% under optimal conditions (contact time = 120 min, catalyst dosage = 1 g/L, and pH = 5). According to the results, the B/T/N-Z nanocomposite, as a novel and effective photocatalyst could be used to degrade MC-LR from polluted water.

Transparent Nanostructured BiVO4 Double Films with Blue Light Shielding Capabilities to Prevent Damage to ARPE-19 Cells.

The hazards posed by blue light to human eyes are attracting significant attention owing to increasing exposure to electronic devices as well as artificial illumination. Therefore, in this study, nanostructured BiVO4 (BVO) double films were developed using an economical and environmentally friendly sol-gel spin-coating method; the films exhibited excellent blue light shielding capabilities. They could block 65.25% of the blue light in the 415-455 nm wavelength range while simultaneously maintaining an average transmittance greater than 85% in the 500-800 nm wavelength range. Moreover, the damp heat test (85 °C, 85% relative humidity) showed the excellent stability of the BVO filters as their transmittances remained unchanged for 15 days. Importantly, cell experiments were performed to further confirm the protective effects of the BVO filters against the hazards posed by blue light to ARPE-19 cells (human retinal pigment epithelium cell line). Furthermore, the blue light weighted radiance LB decreased by 34.32%, and the color rendering index showed negligible differences after applying an upscaled BVO filter to a phone screen. These cost-efficient, ecofriendly, highly reliable, and large-area nanostructured BVO films with high blue light shielding efficiency have potential applications in various areas.

Bio-photoelectrochemcial system constructed with BiVO4/RGO photocathode for 2,4-dichlorophenol degradation: BiVO4/RGO optimization, degradation performance and mechanism.

A single-chamber bio-photoelectrochemical system (BPES) constructed with BiVO4/reduced graphene oxide (RGO) photocathode was proposed for 2,4-dichlorophenol (2,4-DCP) degradation under simulated solar irradiation. The BiVO4/RGO (B/G) composites were synthesized, optimized and characterized by various techniques to analyze their physico-chemical and photocatalytic properties. Results showed that B/G (5 wt% - 9 h - 150 °C) exhibited the best photocatalytic activity for 2,4-DCP degradation, which was 1.5 times of that of BiVO4, due to its better light absorption, faster electrons transfer, and more efficient photo-generated e- - h+ separation. Reactive species trapping experiments revealed that ·OH was the main radical leading to 2,4-DCP degradation, and h+ also influenced 2,4-DCP removal. The 2,4-DCP (20 mg/L) removal rate and current output from the illuminated BPES were much higher than those of the unilluminated reactor (68.5 % vs. 41.8 %, 60.31 A/m3 vs. 40.07 A/m3) in 24 h, and the cathode potential was more negative, indicating that photocathode catalytic process was favorable to pollutants degradation and energy generation. Intermediates of 2,4-DCP degradation in the BPES were identified, and accordingly, possible degradation pathway and mechanism were proposed. This research advanced the development of efficient photocathode and mechanism of recalcitrant wastewater treatment in the BPES.

Bismuth vanadate-based semiconductor photocatalysts: a short critical review on the efficiency and the mechanism of photodegradation of organic pollutants.

The number of publications on photocatalytic bismuth vanadate-based materials is constantly increasing. Indeed, bismuth vanadate is gaining stronger interest in the photochemical community since it is a solar-driven photocatalyst. However, the efficiency of BiVO4-based photocatalyst under sunlight is questionable: in most of the studies investigating the photodegradation of organic pollutants, only few works identify the by-products and evaluate the real efficiency of BiVO4-based materials. This short review aims to (i) present briefly the principles of photocatalysis and define the photocatalytic efficiency and (ii) discuss the formation of reactive species involved in the photocatalytic degradation process of pollutants and thus the corresponding photodegradation mechanism could be determined. All these points are developed in a comprehensive discussion by focusing especially on pure, doped, and composite BiVO4. Therefore, this review exhibits a critical overview on different BiVO4-based photocatalytic systems with their real efficiency. This is a necessary knowledge for potential implementation of BiVO4 materials in environmental applications at larger scale than laboratory conditions.

Construction of plasmonic Ag modified phosphorous-doped ultrathin g-C3N4 nanosheets/BiVO4 photocatalyst with enhanced visible-near-infrared response ability for ciprofloxacin degradation.

To realize the full utilization of solar energy, the design of highly efficient photocatalyst with improved visible-near-infrared photocatalysis performance has attracted great attentions for environment pollutant removal. In this work, we rationally employed the surface plasmon resonance effect of metallic Ag in the phosphorus doped ultrathin g-C3N4 nanosheets (PCNS) and BiVO4 composites to construct a ternary Ag@PCNS/BiVO4 photocatalyst. It was applied for the photodegradation of ciprofloxacin (CIP), exhibiting 92.6% removal efficiency under visible light irradiation (λ>420nm) for 10mg/L CIP, and presenting enhanced photocatalytic ability than that of single component or binary nanocomposites under near-infrared light irradiation (λ>760nm). The improved photocatalytic activity of the prepared Ag@PCNS/BiVO4 nanocomposite can be attributed to the synergistic effect among the PCNS, BiVO4 and Ag, which not only improves the visible light response ability and hinders the recombination efficiency of the photogenerated electrons and holes, but also retains the strong the redox ability of the photogenerated charges. According to the trapping experiment and ESR measurements results, OH, h+ and O2- all participated in the photocatalytic degradation process. Considering the SPR effect of metallic Ag and the established local electric field around the interfaces, a dual Z-scheme electrons transfer mechanism was proposed.

Bandgap Tunability in Sb-Alloyed BiVO4 Quaternary Oxides as Visible Light Absorbers for Solar Fuel Applications.

The challenge of fine compositional tuning and microstructure control in complex oxides is overcome by developing a general two-step synthetic approach. Antimony-alloyed bismuth vanadate, which is identified as a novel light absorber for solar fuel applications, is prepared in a wide compositional range. The bandgap of this quaternary oxide linearly decreases with the Sb content, in agreement with first-principles calculations.

Synthesis of BiVO4@C Core-Shell Structure on Reduced Graphene Oxide with Enhanced Visible-Light Photocatalytic Activity.

Herein, a facile strategy for the controllable synthesis of BiVO4@C core-shell nanoparticles on reduced graphene oxide (RGO) is reported. The BiVO4 particle size can be controlled in the process by adjusting the volume ratio of glycerol in the sol-gel solution. The glycerol layers adsorbed on BiVO4 (BiVO4@glycerol) made it possible to form hydrogen bonds between BiVO4@glycerol and graphene oxide with the assistance of ultrasound. After thermal treatment, glycerol adsorbed on the BiVO4 particles formed amorphous carbon shells to link the particles and RGO. As a result, the obtained RGO-BiVO4@C nanocomposite showed a five times higher rate in O2 evolution from water under visible-light irradiation. Also, it demonstrated a six times higher photocatalytic performance enhancement than that of pure BiVO4 in the degradation of Rhodamine B. The enhanced performance is attributed to the carbon shells that restrict the growth of BiVO4 , the reduced graphene oxide that improves the electronic conductivity of the composite, and importantly, the bonds formed between the carbon shells and RGO that reduce the recombination loss of photogenerated charges effectively. The strategy is simple, effective, and can be extended to other ternary oxides with controlled size and high performance.

Remarkable enhancement in photocytotoxicity and hydrolytic stability of curcumin on binding to an oxovanadium(IV) moiety.

Oxovanadium(IV) complexes of polypyridyl and curcumin-based ligands, viz. [VO(cur)(L)Cl] (1, 2) and [VO(scur)(L)Cl] (3, 4), where L is 1,10-phenanthroline (phen in 1 and 3), dipyrido[3,2-a:2',3'-c]phenazine (dppz in 2 and 4), Hcur is curcumin and Hscur is diglucosylcurcumin, were synthesized and characterized and their cellular uptake, photocytotoxicity, intracellular localization, DNA binding, and DNA photo-cleavage activity studied. Complex [VO(cur)(phen)Cl] (1) has V(IV)N2O3Cl distorted octahedral geometry as evidenced from its crystal structure. The sugar appended complexes show significantly higher uptake into the cancer cells compared to their normal analogues. The complexes are remarkably photocytotoxic in visible light (400-700 nm) giving an IC50 value of <5 µM in HeLa, HaCaT and MCF-7 cells with no significant dark toxicity. The green emission of the complexes was used for cellular imaging. Predominant cytosolic localization of the complexes 1-4 to a lesser extent into the nucleus was evidenced from confocal imaging. The complexes as strong binders of calf thymus DNA displayed photocleavage of supercoiled pUC19 DNA in red light by generating ˙OH radicals as the ROS. The cell death is via an apoptotic pathway involving the ROS. Binding to the VO(2+) moiety has resulted in stability against any hydrolytic degradation of curcumin along with an enhancement of its photocytotoxicity.

Template-free hydrothermal synthesis different morphologies of visible-light-driven BiVO4 photocatalysts.

Monoclinic BiVO4 nano- and microstructures with a diversity of well-defined morphologies, such as nanoplates, dendrite leaves-like structures, sub-microrods, and microflowers were synthesized via a template-free hydrothermal process with bismuth nitrate and ammonium metavanadate as metal source. The crystal structures, morphologies and optical properties of the as-prepared samples were characterized by X-ray powder diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and UV-visible absorption spectra (UV-vis). Results showed that the pH value of the solution and the volume of ethylenediamine have great effect on the formation of these unique structures. The photocatalytic activity of these as-prepared samples had been tested by degradation of methylene blue under visible light, indicating that showed good photocatalytic performance.

Controlled synthesis of uniform BiVO4 microcolumns and advanced visible-light-driven photocatalytic activity for the degradation of metronidazole-contained wastewater.

Well-defined, uniform bismuth vanadate (BiVO4) microcolumns were synthesized through a refined hydrothermal route. During the fabrication process, a detailed orthogonal design on the synthetic conditions was performed, aiming to optimize the experimental parameters to produce BiVO4 materials (BiVO4 (Opt.)) with the most prominent visible-light-driven photocatalytic efficiency, where the catalytic activities of the synthesized materials were evaluated via the decolorization of methylene blue under visible light irradiation. The BiVO4 (Opt.) were then targetedly produced according to the determined optimal conditions and well characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, ultraviolet and visible diffuse-reflectance spectroscopy and photoluminescence spectroscopy. Compared with the commercial P25-TiO2 photocatalysts, the as-synthesized BiVO4 (Opt.) displayed superior visible-light-driven photocatalytic activities for the degradation of metronidazole-contained wastewater with the presence of H2O2. The degradation efficiency of metronidazole reached up to 70 % within 180 min, leading to a brief speculation on the possibly major steps of the visible-light-driven photocatalytic process. The current study provides a distinctive route to design novel shaped BiVO4 architectures with advanced photocatalytic capacities for the treatment of organic pollutants in the aqueous environment.

Effective visible light-active boron and europium co-doped BiVO4 synthesized by sol-gel method for photodegradion of methyl orange.

Eu-B co-doped BiVO4 visible-light-driven photocatalysts have been synthesized using the sol-gel method. The resulting materials were characterized by a series of joint techniques, including XPS, XRD, SEM, BET, and UV-vis DRS analyses. Compared with BiVO4 and B-BiVO4 photocatalysts, the Eu-B-BiVO4 photocatalysts exhibited much higher photocatalytic activity for methyl orange (MO) degradation under visible light irradiation. The optimal Eu doping content is 0.8 mol%. It was revealed that boron and europium were doped into the lattice of BiVO4 and this led to more surface oxygen vacancies, high specific surface areas, small crystallite size, a narrower band gap and intense light absorbance in the visible region. The doped Eu(III) cations can help in the separation of photogenerated electrons. The synergistic effects of boron and europium in doped BiVO4 were the main reason for improving visible light photocatalytic activity.

Three-dimensional ordered macroporous bismuth vanadates: PMMA-templating fabrication and excellent visible light-driven photocatalytic performance for phenol degradation.

Three-dimension ordered macroporous (3D-OM) bismuth vanadates with a monoclinic crystal structure and high surface area (18-24 m(2) g(-1)) have been prepared using ascorbic acid (AA)- or citric acid (CA)-assisted poly(methyl methacrylate) (PMMA)-templating strategy with bismuth nitrate and ammonium metavanadate as the metal sources, HNO(3) as the pH adjuster and ethylene glycol and methanol as the solvent. The materials were characterized by a number of analytical techniques. The photocatalytic performance of the porous BiVO(4) samples was evaluated for the degradation of phenol in the presence of a small amount of H(2)O(2) under visible light illumination. The effects of the initial phenol concentration and the H(2)O(2) amount on the photocatalytic activity of the photocatalyst were examined. It is shown that the chelating agent, AA or CA, and the amount in which it is added had a significant impact on the quality of the 3D-OM structure, with a "(Bi + V):chelating agent" molar ratio of 2:1 being the most appropriate. Among the as-prepared BiVO(4) samples, the one with a surface area of ca. 24 m(2) g(-1) showed the best visible light-driven photocatalytic performance for phenol degradation (phenol conversion = ca. 94% at phenol concentration = 0.1 mmol L(-1) and in the presence of 0.6 mL H(2)O(2)). A higher phenol conversion could be achieved within the same reaction time if the phenol concentration in the aqueous solution was lowered, but an excess amount of H(2)O(2) was not a favorable factor for the enhancement of the catalytic activity. It is concluded that the excellent photocatalytic activity of 3D-OM BiVO(4) is due to the high quality 3D-OM structured BiVO(4) that has a high surface area and surface oxygen vacancy density. We are sure that the 3D-OM material is a promising photocatalyst for the removal of organics from wastewater under visible light illumination.

CTAB-assisted synthesis of monoclinic BiVO4 photocatalyst and its highly efficient degradation of organic dye under visible-light irradiation.

A highly efficient monoclinic BiVO(4) photocatalyst (C-BVO) was synthesized by an aqueous method with the assistance of cetyltrimethylammonium bromide (CTAB). The structure, morphology and photophysical properties of the C-BVO were characterized by XRD, FE-SEM and diffuse reflectance spectroscopy, respectively. The photocatalytic efficiencies were evaluated by the degradation of rhodamine B (RhB) under visible-light irradiation, revealing that the degradation rate over the C-BVO was much higher than that over the reference BiVO(4) prepared by aqueous method and over the one prepared by solid-state reaction. The efficiency of de-ethylation and that of the cleavage of conjugated chromophore structure were investigated, respectively. The chemical oxygen demand (COD) values of the RhB were measured after the photocatalytic degradation over the C-BVO and demonstrated a 53% decrease in COD. The effects of CTAB on the synthesis of C-BVO were investigated, which revealed that CTAB not only changed the reaction process via the formation of BiOBr as an intermediate, but also facilitated the transition from BiOBr to BiVO(4). Comparison experiments were carried out and showed that the existence of impurity level makes significant contribution to the high photocatalytic efficiency of the C-BVO.