Visible-light-responsive γ-Fe2O3/PMMA/S-TiO2 core/shell nanocomposite: Preparation,characterization and photocatalytic activity

Organic-inorganic composite materials have demonstrated many potential applications in environmental field. This paper presented a facile preparation method for γ-Fe₂O₃/PMMA/S-TiO₂ nanocomposite with core-shell structure and its application in degradation of phenanthrene under visible light irradiation. Firstly, γ-Fe₂O₃/PMMA nanoparticles were synthesized by the modified-suspension-polymerization method. Then γ-Fe₂O₃/PMMA/S-TiO₂ core-shell nanocomposites were prepared by adding as-synthesized γ-Fe₂O₃/PMMA nanoparticles into the sol solution formed by sol-gel method using tetrabutyltitanate as Ti source and thiourea as sulfur source. The characterization result of the obtained products by X-ray diffraction, scanning electron microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy indicated that the layer of sulfur doped titania was successfully coated onto the surface of γ-Fe₂O₃/PMMA nanoparticles. Thermogravimetry (TG) analysis presented that the layer of sulfur doped TiO₂ could efficiently reduce the decomposition of polymethylmethacrylate (PMMA) even at higher temperature up to 500 °C. UV–vis diffuse reflectance spectroscopy showed that γ-Fe₂O₃/PMMA/S-TiO₂ nanocomposite clearly exhibits the red-shift of the absorption edge compared with γ-Fe₂O₃/PMMA/TiO_2. The photocatalytic activity evaluation showed that the γ-Fe₂O₃/PMMA/S-TiO₂ nanocomposite exhibited the best photocatalytic activity for degradation of phenanthrene under the conditions of 0.8 mol% of sulfur doping, calcination temperature at 300 °C and the addition concentration of 1.0 g/L. Moreover, the nanocomposites have good recovery ability by the recovery experiment.     

0D/3D ZnIn2S4/Ag6Si2O7 nanocomposite with direct Z-scheme heterojunction for efficient photocatalytic H2 evolution under visible light

Constructing heterojunction structure is a feasible way to realize an efficient and durable photocatalysts. Herein, a novel Z-scheme zero/three dimensional (0D/3D) ZnIn₂S₄/Ag₆Si₂O₇ (ZIS/ASO) composite was rationally designed, synthesized and analyzed. ZIS/ASO composite possesses a layer structure for increasing light response, a special 0D/3D structure for reducing the photo-induce carriers migration path, and numerous active sites for absorbing H₂O and producing H₂. This composite retains the high oxidation and reduction ability by facilitating separation and migration as well as limiting recombination of photo-induced carriers via the intimate interface between ZIS and ASO. Undoubtedly, the synthesized ZIS/ASO photocatalyst achieved a high photocatalytic H₂ activity, and the optimum sample shows a satisfactory H₂ evolution rate of 590.56 μmol g⁻¹ h⁻¹, distinctly better than that of pure ZIS. More importantly, this composite exhibits high stability and recyclability and is expected to be applied in practical application. Based on the H₂ evolution experimental results and electrochemical tests, the Z-scheme heterostructure construction of the composite was confirmed. This work expects to inspire a unique protocol for synthesizing Z-scheme photocatalysts for water splitting under visible light irradiation.     

Photo-electrochemistry of metallic titanium/mixed phase titanium oxide

In this study, the effect of potassium hydroxide concentration in anodization bath, anodization time, and calcination temperature on the photo-electrochemical behavior of metallic titanium/mixed phase titanium oxide is investigated. Further, the phase structure of a titanium oxide photocatalyst prepared on a titanium electrode through a high-voltage anodization method is examined. The study exploits photo-electrochemical, Fourier transform infrared spectroscopy attenuated total reflectance (FTIR–ATR), X-ray diffraction, and Raman spectroscopic methods to obtain better insights into the mechanism of mixed-phase titanium oxide formation. In this regard, the photo-electrochemical properties of the photocatalysts prepared in single excitation energy, violet light (410 nm), were investigated. The anodization time and the potassium hydroxide concentration in the anodization bath have significant effects on the photo-electrochemical properties of the photocatalysts. The experiments show that the effect of potassium hydroxide concentration is a function of the anodization potential applied, demonstrating different patterns as the anodization potential changes. Furthermore, FTIR-ATR, X-ray diffraction, and Raman spectroscopic studies reveal that the extended anodization times decrease the population of OH-containing groups, leading to lower photo-electrochemical performance. On the other hand, the formation of anatase phases becomes more favorable only in the extended anodization times before application of the calcination process. Additionally, the calcination temperature has a significant impact on the anatase to rutile ratio. Finally, increasing potassium hydroxide concentration leads to the formation of an amorphous titanium oxide layer. It can be concluded that the obtained information might have a significant impact on the preparation of titanium oxide and other metal oxide photocatalysts through the high voltage anodization process.     

Simultaneous degradation of RhB and reduction of Cr(VI) by MIL-53(Fe)/Polyaniline (PANI) with the mediation of organic acid

MIL-53(Fe)/polyaniline (PANI) composite was prepared by in situ depositing PANI on the surface of MIL-53(Fe) and their catalytic performances on the simultaneous removal of RhB and Cr(VI) were investigated. The elimination efficiency of both RhB and Cr(VI) reached more than 98% under pH=2 where hydrochloric acid and citric acid were used to adjust the pH. The results indicated that MIL-53(Fe)/PANI revealed an obvious pH response to the degradation of RhB, while citric acid promoted the Cr(VI) photoreduction. UV-Vis spectra, EIS, and photocurrent response experiments showed that MIL-53(Fe)/PANI had a better light response and carrier migration ability than MIL-53(Fe). The transient absorption spectra also exhibited that the lifetimes of photo-generated carriers were prolonged after the conductive polymer deposition on the MIL-53(Fe) surface. Scavenger experiments demonstrated that the main active species were ·O₂^- and OH. Combined with activity evaluation results, and the possible photocatalytic mechanism of MIL-53(Fe)/PANI on RhB oxidation and Cr(VI) reduction was proposed. The addition of conductive polymer can effectively improve the light response of the catalyst under acidic conditions, and meanwhile citric acid also provided a new mediation for the synergistic degradation of multiple pollutants. Good activity and stability of the catalysts made the scale-up purification of acid water feasible under UV-Vis light.     

Implementation of ZnSnO3 nanosheets and their RE (Er,Eu, and Pr) materials: Enhanced photocatalytic activity

ZnSnO₃, ZnSnO₃@Er, ZnSnO₃@Eu, and ZnSnO₃@Pr materials were synthesized by a hydrothermal method, these active materials characterized by XRD, Raman, DRS-UV, FT-IR, BET surface areas and Scanning electron microscopy studies. The ZnSnO₃ nanosheets meta-stable form was confirmed by XRD. Here, addressing to the pure and doped materials functional groups were evaluated by FT-IR spectroscopy. ZnSnO₃, ZnSnO₃@Er, ZnSnO₃@Eu, and ZnSnO₃@Pr rotational vibrations frequency modes were predicted by the Raman spectroscopy. Our results are marvelously, the obtained bandgap energies at 3.5 eV for pure sample and ZnSnO₃@Er, ZnSnO₃@Eu and ZnSnO₃@Pr energies at 3.06 eV, 3.04 eV and 3.02 eV. The synthesized pure samples get a sheet-like morphology and doped for RE metals than morphology was changing for nanocubes. We assess for all samples that were focused on photocatalytic dye degradation for Methylene blue dye; hence, we are discussing these approaches, ZnSnO₃@Pr/Methylene blue sample was a great improvement and high decolorization efficiency compared with ZnSnO₃@Er, ZnSnO₃@Eu nanocubes. The ZnSnO₃@Pr sample surface area was investigated by BET analysis. In addition, we are testing the phenol degradation with wastewater. The ZnSnO₃@Er, ZnSnO₃@Eu catalysts were determined to the less efficiency when comparing to the ZnSnO₃@Pr material. The ZnSnO₃@Pr material results have more efficiency and a very good recyclable stability nature.     

Synthesis and characterization of ZnO NRs with spray coated GO for enhanced photocatalytic activity

Zinc oxide nanorods, ZnO NRs, were synthesized on a clean glass and coated with graphene oxide (GO) using spray coating method to enhance the photocatalytic activity in wastewater treatment. The ZnO NRs were synthesized using the solution process synthesis that was optimized using Taguchi method. Several synthesis parameters have been optimized and studied to determine the best synthesis parameter to grow ZnO NRs for the photodegradation of organic contaminants. Field emission scanning electron microscopy (FESEM) with EDX, X-ray diffraction (XRD), Raman, ultraviolet visible near-infrared (UV-VIS-NIR), and photoluminescence (PL) spectroscopies were used to investigate the structural and optical properties of the produced nanorods. FESEM images revealed the vertical growth of ZnO NRs as well as layers of GO covering the ZnO NRs' top surface. The Raman study demonstrates the combination peak of GO and ZnO, hence proving the GO layer's successful coating. After the GO coating, decrease in the bandgap of the synthesized photocatalyst was detected by PL and UV–Vis absorption measurements. Under UVC exposure with treatment time of 6 h, the degradation of MB with ZnO NRs/GO photocatalyst reached a degradation percentage of 97.86%, which is greater than the degradation percentage achieved using pristine ZnO NRs, which is 93.28%. The results validated that the coating of GO enhances the photocatalytic activity of the host material, ZnO NRs.     

A novel nonmetal intercalated high crystalline g-C3N4 photocatalyst for efficiency enhanced H2 evolution

Introducing nickel foam as assistant, a novel nonmetal intercalated high crystalline graphitic carbon nitride (g-C₃N₄) catalyst was successfully fabricated by β-cyclodextrin (β-CD) pretreated melamine with one step thermal polymerization process. The final results show that 0.3-NCCN presented a remarkably visible-light (λ > 400 nm) photocatalytic H₂ evolution reaching 9297  μmol g^?1 h^?1, and the reaction process follows the zero-order kinetic model. The increase in crystallization of 0.3-NCCN implies a higher-ordered arrangement of tris-s-triazine. The nonmetal interlayer formed by oxygen-contained graphitized carbon can extend the π-conjugated system. Both above significantly benefit the rapid migration and separation of charge-carrier. Moreover, the narrowed band gap provides a stronger thermodynamic driving force for improving the photocatalytic water splitting efficiency. Our work paved a new method to construct high performance photocatalyst for water splitting.     

2D sodium titanate nanosheet encapsulated Ag2O-TiO2 p-n heterojunction photocatalyst: Improving photocatalytic activity by the enhanced adsorption capacity

In a photocatalytic reaction, maintaining the high efficiency of photocatalyst under a low concentration of pollutants is a key challenge. In this work, a new 2D sodium titanate nanosheet encapsulated Ag₂O-TiO₂ (2D NTO/Ag₂O-TiO₂) p-n heterojunction photocatalyst is proposed to deal with this dilemma. Through a simple plasma electrolytic oxidation (PEO) treatment and ion exchange treatment, a classic Ag₂O-TiO₂ p-n heterojunction structure is prepared and used as the photoelectric conversion unit in the photocatalyst. Then, through a subsequent hydrothermal treatment, a 2D NTO film that serves as the adsorption unit in the photocatalyst can be produced on the surface of the Ag₂O-TiO₂ p-n heterojunction layer. Finally, the desired 2D NTO/Ag₂O-TiO₂ structure is formed. The photocatalyst exhibits superior photocatalytic performance including high degradation rate as well as excellent catalytic stability and durability by combining the high sunlight utilization efficiency and high photoelectric utilization efficiency of the Ag₂O-TiO₂ p-n heterojunction and the outstanding adsorption performance of the 2D NTO film. Therefore, the problem of photocatalytic slow kinetics under low pollutants concentration is perfectly solved. This work provides a new strategy for the structural design of high-performance photocatalysts.     

Heterostructured dysprosium vanadate – ZnO for photo-electrocatalytic and self-cleaning applications

In this article, we report fabrication of 5 wt% of Dy as DyVO₄ supported ZnO by template-free hydrothermal-thermal decomposition method and its photocatalytic activity towards degradation of azo dyes Rhodamine-B (Rh-B) and Trypan Blue (TB) in solar light, Electrocatalytic activity in methanol oxidation and Self-cleaning properties. The as prepared DyVO₄-ZnO was characterized by surface analytical and spectroscopic techniques. The results suggested that Dysprosium vanadate doping on ZnO has increased its photocatalytic efficiency with high reusability. DyVO₄-ZnO exhibits higher electrocatalytic activity than prepared ZnO for methanol electrooxidation in alkaline medium, revealing its promising potential as the anode in direct methanol fuel cells. Hydrophobicity of ZnO increases by doping of DyVO_4.     

Visible light-driven mesoporous Au–TiO2/SiO2 photocatalysts for advanced oxidation process

Au–TiO₂/SiO₂ heterogeneous catalysts with different Au contents were successfully synthesized by a facile hydrothermal process and their photocatalytic activity towards reduction of Rose Bengal (RB), Methyl Blue (MB), Rhodamine B (RhB) and Congo Red (CR) was investigated in the presence of sodium borohydride (NaBH₄) for advanced oxidation process (AOP). The results reveal that 3 wt% Au loaded in TiO₂/SiO₂ can significantly degrade high RB concentration dye (>95%, 0.3 g/L, 12 pH) within 20 min of irradiation time. All catalysis reaction followed the pseudo-first order rate reaction with high correlation coefficient. The effect of loading of Au nanoparticles (1–5 wt%) along with variation in dye concentration (100–500 ppm), pH of solution (2–12), catalysts dosage (0.1–0.5 g/L), and reaction temperature (30–80 °C) were also studied. The present works shows the superior performance of Au–TiO₂/SiO₂ heterogeneous catalysts to be related to the high dispersion of Au nanoparticles in the TiO₂/SiO₂ and to the catalytic effect between gold and TiO₂.