Photoelectrochemical property of ZnFe2O4/TiO2 double-layered films

ZnFe₂O₄/TiO₂ double-layered films on indium-tin oxide (ITO) substrate were prepared by a dip-coating method, and the optical absorption and photocurrent of the as-prepared films were measured. In the double-layered films, the onset of fundamental absorption edge shifts to a longer wavelength, and even shifts to a longer wavelength than that of ZnFe₂O₄-only film as the ZnFe₂O₄ layer thickness increases. Application of the coupled photoanodes double-layered films composed of ZnFe₂O₄ and TiO₂ can obviously increase the photocurrent. It was found that the photocurrent density of ZnFe₂O₄/TiO₂ double-layered films first increased and then decreased with increasing the ZnFe₂O₄ layer thickness. A five-fold increase in the photocurrent density was obtained compared with TiO₂-only films under optimum condition.     

Preparation of nitrogen doped TiO2 photocatalyst by oxidation of titanium nitride with H2O2

Nitrogen doped anatase TiO₂ (N-TiO₂) were prepared by hydrothermally treating TiN with H₂O₂. The as-synthesized samples were characterized by X-ray diffraction (XRD), transmission electron microscope (TEM), UV-vis diffuse reflectance spectrum (DRS), Fourier transform infrared spectra (FT-IR) and X-ray photoelectron spectroscopy (XPS) techniques. The results confirmed that the hydrothermal oxidation is an effective method to prepare N-doped TiO₂ anatase. The nitrogen concentration in TiO₂ could be controlled by the concentration of H₂O₂ solution. Photocatalytic degradation of methyl orange (MO) was carried out under visible light and UV-visible light irradiation, respectively. The as-prepared optimal N-TiO₂ showed higher photocatalytic activity than N-P25 and P25, and exhibited excellent reusability.     

Fabrication of ultrafine ZnFe2O4 nanoparticles for efficient photocatalytic reduction CO2 under visible light illumination

A one-pot, solvent-thermal process was used to create the ultrafine ZnFe₂O₄ nanoparticles photocatalyst. During the solvent-thermal process, the in situ self-forming NaCl not only served as a “cage” to confine the ion diffusion, but also acted as a microreactor for nanocrystallite growth. An average particle size of ～10 nm and a high-specific surface area of ～112.9 m²/g were observed for the ultrafine ZnFe₂O₄ nanoparticles Owing to the synergistic effect of ultrafine particle size, the full utilization of the visible light region and high conduction band (CB) position, ultrafine ZnFe₂O₄ photocatalyst displayed an efficient photocatalytic CO₂ reduction under visible light illumination. Besides, the ultrafine ZnFe₂O₄ photocatalyst showed high production selectivity for CH₃CHO and C₂H₅OH generation in aqueous CO₂/NaHCO₃ solution. This work may provide a new idea for the synthesis of new high-efficiency photocatalysts.     

Facile synthesis and characterization of ZnFe2O4/α-Fe2O3 composite hollow nanospheres

ZnFe₂O₄/α-Fe₂O₃ composite hollow nanospheres were successfully fabricated via a facile one-pot solvothermal method, utilizing polyethylene glycol as soft template. X-ray diffraction and scanning electron microscopy analysis revealed that the prepared nanospheres with cubic spinel and rhombohedra composite structure had a uniform diameter of about 370 nm, and the hollow structure could be further confirmed by transmission electron microscopy. Energy dispersive X-ray, X-ray photoelectron spectroscopy and Fourier transform infrared techniques were also applied to characterize the elemental composition and chemical bonds in the hollow nanospheres. The ZnFe₂O₄/α-Fe₂O₃ composite hollow nanospheres show attractive light absorption property for potential applications in electronics, optics, and catalysis.     

Room temperature synthesis of nearly monodisperse rodlike rutile TiO2 nanocrystals

A new method was developed to synthesize uniform rodlike rutile TiO₂ nanocrystals by the hydrolysis of tetrabutyl titanate [Ti(OC₄H₉)₄] in hydrochloric acid-alcohol aqueous solutions at room temperature. The hydrolytic sol-gel reaction generated 44 nm (diameter) × 200 nm (length) sized rutile TiO₂ nanocrystals. Transmission electron microscopic images showed that the particles have a uniform shape and narrow size distribution. X-ray diffraction and electron diffraction patterns combined with high-resolution transmission electron microscopic image showed that the rodlike TiO₂ nanoparticles prepared at room temperature were crystalline rutile structure grown along the [001] direction. The morphology and photocatalytic activity of the TiO₂ nanocrystals formed at different urea concentrations were showed. The rutile TiO₂ nanocrystals formed in the absence of urea exhibited higher photocatalytic activity than the commercial photocatalyst P25 on the photocatalytic degradation of Rhodamine B.     

Synthesis and photocatalytic activity of cobalt oxide doped ZnFe2O4-Fe2O3-ZnO mixed oxides

Novel cobalt oxide doped ZnFe₂O₄-Fe₂O₃-ZnO mixed oxides with the Zn/Fe molar ratio of 1/2 were synthesized with a citric acid complex method. The effects of cobalt oxide and calcination temperature on phase composition and photocatalytic activity of the mixed oxides were investigated. X-ray diffraction (XRD) analysis revealed that there were mainly ZnFe₂O₄, α-Fe₂O₃, amorphous ZnO and Fe₂O₃ in the 6 mol% cobalt oxide doped products calcined at 500 °C. 5-10 mol% cobalt oxide doping could significantly enhance the formation of ZnFe₂O₄ and altered the phase composition of the mixed oxides. Experimental results showed that cobalt oxide doping could remarkably improve the photocatalytic activity of the mixed oxides for phenol degradation. The 6 mol% cobalt oxide doped mixed oxides calcined at 500 °C exhibited better photocatalytic activity as compared with other samples.     

A citrate complex process to prepare nanocrystalline PbBi2Nb2O9 at a low temperature

PbBi₂Nb₂O₉ nanocrystals with a perovskite-type structure were successfully synthesized at a relative low temperature via a citrate complex method. Metal ions were dispersed by citric acid in ethanol and ethylene glycol solvent, and then reacted with NH₄H₂[NbO(C₂O₄)₃·3H₂O] to form the gel. XRD results showed that pure PbBi₂Nb₂O₉ nanocrystals could be obtained after calcined treatment of xerogel at 800 °C. The average particles size was 57 nm. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) revealed that the sintering process led to the agglomeration of the nanoparticles. The photocatalytic test showed that the sample prepared by the citrate complex method exhibited a higher photocatalytic activity than that of the sample prepared by the solid-state reaction.     

The effect of support on the structure and photocatalytic activity of ternary ZnO-ZnFe2O4/palygorskite composite photocatalysts

The ternary ZnO-ZnFe₂O₄/palygorskite composite photocatalysts were fabricated via a solvothermal method followed by thermal treatment. The structure, morphology and photoelectric performances of samples were characterized, and the results indicated that ZnO/ZnFe₂O₄ nanoparticles with size of 25–30 nm were adequately anchored on the palygorskite fibers surface. Compared with ZnO, ZnFe₂O₄, ZnO/ZnFe₂O₄ and ZnO/palygorskite, the ZnO-ZnFe₂O₄/palygorskite composite photocatalysts exhibited significantly improved photocatalytic activity in degradation of methylene blue (MB). Especially, the optimal photocatalyst (ZF1.5) displayed the highest photocatalytic activity, achieving 99.68% and 99.48% degradation efficiency after 90 min of UV–vis (350 ≤ λ ≤ 780 nm) and 100 min of visible-light (λ ≥ 420 nm) irradiation, respectively. The photocatalysis degradation process matched well with the Langmuir-Hinshelwood kinetics. The obtained improvement of photocatalytic activity was ascribed to the synergetic effect of superior visible-light utilization; effective charge carrier separation and palygorskite support effect (optimize nanoparticles dispersibility, developed mesoporous structure, enlarge specific surface area and increase adsorption capacity).     

Controlled synthesis of Mn3O4 and MnCO3 in a solvothermal system

Controlled synthesis of Mn₃O₄ nanocrystals and MnCO₃ aggregates was achieved by a facile solvothermal method using different divalent manganese source in the solvent of N,N-dimethylformamide (DMF) with/without the introduction of poly(vinylpyrrolidone) (PVP). PVP was used as a co-reducing reagent in the controlled formation of MnCO₃ crystal. The products were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and selected-area electron diffraction (SAED), Fourier transform infrared (FTIR) spectra, Raman spectrum and magnetic measurement. Higher process temperature and longer solvothermal time were favorable for the formation of MnCO₃ single phase using MnCl₂ as the manganese source. Mn₃O₄ nanocrystals were prepared at a relatively lower temperature. MnCO₃ aggregates consisted by small nanoparticles have a certain orientation, showing that the nanocrystals formed earlier through oriented aggregation. The size of Mn₃O₄ nanocrystals was 22.5 ± 7.3 nm and 7.3 ± 1.4 nm prepared using MnCl₂ and Mn(CH₃COO)₂, respectively, at 160 °C for 24 h. Raman spectra showed size-dependent characteristics. Smaller Mn₃O₄ nanoparticle resulted in a red-shift in Raman spectra. Magnetic property of the prepared Mn₃O₄ nanoparticle was influenced by the size distribution and crystallinity.     

Nonaqueous sol-gel synthesis and growth mechanism of single crystalline TiO2 nanorods with high photocatalytic activity

In this paper, we report on a nonaqueous synthesis of single crystalline anatase TiO₂ nanorods by reaction between TiCl₄ and benzyl alcohol at a low temperature of 80 °C. The resulting samples were characterized with X-ray diffraction, scanning electron microscopy, transmission electron microscopy, high resolution transmission electron microscopy, nitrogen adsorption, X-ray photoelectron spectrometry and UV-vis diffuse reflectance spectroscopy. We proposed that the TiO₂ nanorods were formed through an oriented attachment mechanism. More importantly, these single crystalline anatase TiO₂ nanorods exhibited significantly higher photocatalytic activities than commercial photocatalyst P25. This study provides an environmentally friendly and economic approach to produce highly active TiO₂ photocatalyst.     

Heterostructured Fe3O4/Bi2O2CO3 photocatalyst: Synthesis,characterization and application in recyclable photodegradation of organic dyes under visible light irradiation

Heterostructured Fe₃O₄/Bi₂O₂CO₃ photocatalyst was synthesized by a two-step method. First, Fe₃O₄ nanoparticles with the size of ca. 10 nm were synthesized by chemical method at room temperature and then heterostructured Fe₃O₄/Bi₂O₂CO₃ photocatalyst was synthesized by hydrothermal method at 180 °C for 24 h with the addition of 10 wt% Fe₃O₄ nanoparticles into the precursor suspension of Bi₂O₂CO₃. The pH value of synthesis suspension was adjusted to 4 and 6 with the addition of 2 M NaOH aqueous solution. By controlling the pH of synthesis suspension at 4 and 6, sphere- and flower-like Fe₃O₄/Bi₂O₂CO₃ photocatalysts were obtained, respectively. Both photocatalysts demonstrate superparamagnetic behavior at room temperature. The UV–vis diffuse reflectance spectra of the photocatalysts confirm that all the heterostructured photocatalysts are responsive to visible light. The photocatalytic activity of the heterostructured photocatalysts was evaluated for the degradation of methylene blue (MB) and methyl orange (MO) in aqueous solution over the photocatalysts under visible light irradiation. The heterostructured photocatalysts prepared in this study exhibit highly efficient visible-light-driven photocatalytic activity for the degradation of MB and MO, and they can be easily recovered by applying an external magnetic field.     

Fabrication and photocatalytic activity of porous TiO2 nanowire microspheres by surfactant-mediated spray drying process

A novel, porous TiO₂ nanowire microsphere with a diameter of 3-8 μm was successfully fabricated via spray drying of TiO₂ nanowire suspension with the assistance of surfactant (F127). The products were characterized by FESEM, XRD and N₂ adsorption-desorption analysis and results revealed that the resulting TiO₂ nanowire microspheres possessed a hierarchically macro/mesoporous structure, as well as a high BET surface area of 38.2 m²/g. Systematic studies showed that the presence of surfactant in the suspension feed for spray drying was critical in the formation of porous microspheres. The structure of the fabricated microspheres depends on the nanowire concentration in the feed. The TiO₂ nanowire microspheres exhibited significant photocatalytic degradation of Methylene blue (MB) as compared to commercial TiO₂ nanoparticles (P25). It was also revealed that the microspheres have excellent stability on photocatalytic activity and mechanical strength, which are both crucial factors when considering reuse of these photocatalysts.     

A low-temperature process to synthesize rutile phase TiO2 and mixed phase TiO2 composites

This works employed K₂Ti₄O₉, a novel Ti source, to prepare TiO₂ powders. By a “low-temperature dissolution-reprecipitation process” (LTDRP), rutile phase TiO₂ was successfully synthesized after reacting at 50 °C for 48 h. The obtained sample showed a specific surface area about 45 m²/g, and excellent activity in photo-destruction of NO_x gas. The coupling of rutile phase TiO₂ with commercial anatase TiO₂ showed significant effect in further enhancing the photocatalytic activity.     

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.     

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.     

Effect of photocatalytic activities of nano-sized copper molybdate (CuMoO4)-doped bismuth titanate (Bi2Ti4O11) (CMBT) alloy

Different compositions of [CuMoO₄]_x-doped Bi₂Ti₄O₁₁ nanophotocatalyst (x = 0.05, 0.1, 0.5) have been prepared by chemical precursor decomposition (CPD) method using triethanolamine (TEA) and HNO₃. Cu(II) is one of reactive species on the catalyst surface and Mo(VI) ion helps to generate charge compensation of lattice having poor catalytic properties. The photocatalytic properties based on the prepared samples for photodecolorization of thymol blue (TB) solutions are examined by Hg-lamp. The crystal structures of the prepared nano-powders are characterized by XRD, EDAX, UV-vis spectra, specific surface area (BET), and HRTEM analyses. The average particle size of copper molybdate-doped bismuth titanate ranges 32 ± 5 nm measured from TEM. Results show doping of copper molybdate of 5 mol% with bismuth titanate can significantly increase the photoactivity of bismuth titanate compared all the compositions studied except degussa P25 titania. The observed increased photocatalytic activity of copper molybdate-doped bismuth titanate ((CuMoO4)_x(Bi₂Ti₄O₁₁)_1−x; CM_xBT_1−x) is attributed to the strong absorption of OH groups at the surface of the catalyst.     

FTIR study of the photocatalytic degradation of gaseous benzene over UV-irradiated TiO2 nanoballs synthesized by hydrothermal treatment in alkaline solution

In this study, photocatalysts of TiO₂ nanoballs were obtained via a hydrothermal treating of commercial P25 in alkaline solution, and then characterized with SEM, XRD, BET and surface photovoltage spectroscopy techniques. The UV-assisted photodegradation of gaseous benzene over P25 and the prepared TiO₂ nanoballs was monitored by an in situ infrared technique. The results demonstrated that the prepared TiO₂ nanoballs in anatase form were more active than commercial P25 in photocatalytic oxidation of gaseous benzene. The promoted activity of the hydrothermal-treated TiO₂ is attributed to the increasing specific surface area and larger band gap induced by the reduced crystallite size. The spectra of FTIR indicated that weakly adsorbed phenol was formed as the reaction progress. Hydroxyl groups on the surface of TiO₂ nanoballs are able to react with photo-produced phenol, which is then retained on the catalyst surface leading to the progressive deactivation of the catalyst in the gas-solid system.     

Photocatalytic activity of Li-Rb-Y doped or codoped TiO2 under sunlight irradiation

Doped TiO₂ particles were synthesized by solid grinding and sol-gel methods. The ensuing powders were analysed by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and ground state diffuse reflectance absorption spectroscopy (GSDR). The doped samples prepared by solid grinding at 400 °C were in the anatase form, while those synthesised via sol-gel method and calcinated at the same temperature were dominated by the rutile phase. The X-ray photoelectron spectroscopy (XPS) revealed a surface segregation of the doping elements namely for Y, Rb and Rb-Y. The photocatalytic activity of the prepared catalysts, under sunlight irradiation, was evaluated using 2-naphthol as a pollutant model. Results showed a great enhancement in the photocatalytic efficiency with incorporation of Y in samples prepared by solid grinding, while in samples prepared via sol-gel process both Rb and Y dopants greatly improve the photocatalytic activity. The Langmuir-Hinshelwood model was used to describe the photocatalytic reactions from which a pseudo-first-order kinetics was established. The repeatability of photocatalytic activity was also tested for several degradation cycles.     

Complete oxidation of acetaldehyde on Pt/CeO2-ZrO2-Bi2O3 catalysts

Pt/CeO₂-ZrO₂-Bi₂O₃ catalysts for catalytic combustion of acetaldehyde, which is one of volatile organic compounds (VOCs), were prepared by a wet impregnation method in the presence of polyvinylpyrrolidone K25 (PVP). The addition of PVP in the preparation process was effective to enhance the specific surface area and the Pt²⁺ ratio on the surface. Additionally, the pore volume and size of the catalysts were modified by the PVP addition. The Pt/CeO₂-ZrO₂-Bi₂O₃ catalysts are specific for the total acetaldehyde oxidation and CO and any acetaldehyde-derivative compounds were not observed as by-products. The catalytic activity of the Pt/CeO₂-ZrO₂-Bi₂O₃ catalysts was significantly promoted by the PVP addition and the total oxidation temperature decreased. By the optimization of the amount of platinum, the complete oxidation of acetaldehyde was realized at a temperature as low as 140 °C on a 10 wt%Pt/CeO₂-ZrO₂-Bi₂O₃ catalyst.