Synthesis and Photocatalytic Performance of Bi<Subscript>12</Subscript>O<Subscript>17</Subscript>Cl<Subscript>2</Subscript> Semiconductors Calcined at Different Temperatures

In the current investigation a series of oxygen-rich bismuth oxychloride Bi₁₂O₁₇Cl₂ samples through an ethylene glycol-solvothermal route were constructed at different calcination temperatures and fully characterized by X-ray diffraction patterns, scanning electron microscopy, Fourier transformed infrared spectroscopy, X-ray photoelectron spectroscopy, UV–Vis diffuse reflectance spectra, X-ray energy dispersion spectroscopy, and photoluminescence spectra. It was demonstrated that the calcination temperatures indeed had a crucial effect on the crystallinity, grain size, morphology, optical property, and charge carrier separation of Bi₁₂O₁₇Cl₂ series. These Bi₁₂O₁₇Cl₂ samples showed significantly improved photocatalytic degradation over dye Rhodamine B and colorless antibiotic tetracycline hydrochloride. Particularly, the best candidate, the sample 350 °C—Bi₁₂O₁₇Cl₂ could show apparent reaction rate constants that were nearly 28.2, 1.2 times of N–TiO₂ over Rhodamine B and tetracycline hydrochloride, respectively. The possible reason of enhancing photocatalytic performance by various Bi₁₂O₁₇Cl₂ samples calcined at different temperatures was discussed and major oxidative radicals maybe generated during photocatalytic processes were detected.     

Purification of textile wastewater by using coated Sr/S/N doped TiO<Subscript>2</Subscript> nanolayers on glass orbs

Simultaneous doping of TiO₂ nanoparticles with three elements including Sr, S, and N is reported. The resulting material shows superior photocatalytic performance toward degradation of textile waste under visible and sunlight. The pure and doped TiO₂ nanolayers were prepared by sol-gel method and were fixed on a bed of glass orbs. The immobilized TiO₂ were characterized by a variety of techniques: X-ray diffraction (XRD), scanning electron microscopy (SEM), spectroscopy diffusion reflection (DRS), energy dispersive X-ray spectrometry (EDS) and elemental analysis (CHNS). The photocatalytic activity of the prepared fixed-bed materials toward degradation of the textile wastes was determined by using ultraviolet-visible spectroscopy (UV-Vis) and measurement of the chemical oxygen demand testing (COD). The best photocatalytic activity was observed with the use of Sr/S/N-TiO₂ nano-layers. Afterwards, the experimental conditions were optimized by tuning reaction parameters, including amount of doped metal ion on photocatalyst structure, sample solution pH and photoreactor output flow rate. The results confirmed that at natural pH 5.9 of sample solution, maximum decomposition of 91-99% of azo dyes was obtained in 8 h under visible irradiation. Finally, the experiments were repeated under 1.5 AM sunlight with high volume of reactants in order to confirm the cost-effectiveness of the designed photocatalyst.     

Preparation and characterization of TiO2 photocatalysts by Fe doping together with Au deposition for the degradation of organic pollutants

Fe³⁺ doped TiO₂ deposited with Au (Au/Fe–TiO₂) was successfully prepared with an attempt to extend light absorption of TiO₂ into the visible region and reduce the rapid recombination of electrons and holes. The samples were characterized by X-ray diffraction (XRD), N₂ physical adsorption, Raman spectroscopy, atomic absorption flame emission spectroscopy (AAS), UV–vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), and photoluminescence (PL) spectra. The photocatalytic activities of the samples were evaluated for the degradation of 2,4-chlorophenol in aqueous solutions under visible light (λ > 420 nm) and UV light irradiation. The results of XRD, XPS and high-resolution transmission electron microscopy (HRTEM) analysis indicated that Fe³⁺ substituted for Ti⁴⁺ in the lattice of TiO₂, Au existed as Au⁰ on the surface of the photocatalyst and the mean particle size of Au was 8 nm. Diffuse reflectance measurements showed an extension of light absorption into the visible region for Au/Fe–TiO₂, and PL analysis indicated that the electron–hole recombination rate has been effectively inhibited when Au deposited on the surface of Fe-doped TiO₂. Compared with Fe doped TiO₂ sample and Au deposited TiO₂ sample, the Au/Fe–TiO₂ photocatalyst exhibited excellent visible light and UV light activity and the synergistic effects of Fe³⁺ and Au was responsible for improving the photocatalytic activity.     

Preparation of hydrophobic SiO<Subscript>2</Subscript>@(TiO<Subscript>2</Subscript>/MoS<Subscript>2</Subscript>) composite film and its self-cleaning properties

TiO₂/MoS₂ composite was encapsulated by hydrophobic SiO₂ nanoparticles using a sol–gel hydrothermal method with methyltriethoxysilane (MTES), titanium tetrachloride (TiCl₄), and molybdenum disulfide (MoS₂) as raw materials. Then, a novel dual functional composite film with hydrophobicity and photocatalytic activity was fabricated on a glass substrates via the combination of polydimethylsiloxane adhesives and hydrophobic SiO₂@(TiO₂/MoS₂) composite particles. The influence of the mole ratios of MTES to TiO₂/MoS₂ (M:T) on the wettability and photocatalytic activity of the composite film was discussed. The surface morphology, chemical compositions, and hydrophobicity of the composite film on the glass substrate were investigated by scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and water contact angle (water CA) measurements. The results indicated that the composite film exhibited stable superhydrophobicity and excellent photocatalytic activity for degradation of methyl orange (MO) even after five continuous cycles of photocatalytic reaction when M/T was 7:1. The water CA and degradation efficiency for MO remained at 154° and 94%, respectively. Further, the composite film showed a good non-sticking characteristic with the water sliding angle (SA) at about 4°. The SiO₂@(TiO₂/MoS₂) composite consisting of hydrophobic SiO₂ nanoparticles and TiO₂/MoS₂ heterostructure could provide synergistic effects for maintaining long-term self-cleaning performance.     

Research of mica/Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> pearlescent pigment by co-precipitation

Experiments on preparation of mica/Fe₃O₄ pearlescent pigment were performed to discuss influences of several crucial parameters on final products. The samples were characterized by XRD, HRSEM, FTIR and color measurement, the content of Fe₃O₄ on the mica surface was also analyzed by XPS. It was found that the smoothness, compactness and colour deepness of the coating were influenced by different pH values and temperatures. The optimum preparation parameters of mica/Fe₃O₄ pearlescent pigment were obtained: the value of pH ≥ 9.2; the concentration of sodium hydroxide was 0.5 mol/l; the concentration ratio of Fe³⁺ to Fe²⁺ was 1.6 : 1; the velocity of magnetic stirring was 138 ≤ v ≤ 151 r/min; reaction temperature was 70–80°C; calcination temperature was 350°C and calcination time was 3 h.     

Visible light-irradiated degradation of alachlor on Fe-TiO<Subscript>2</Subscript> with assistance of H<Subscript>2</Subscript>O<Subscript>2</Subscript>

0.1 Fe/Ti mole ratio of Fe-TiO₂ catalysts were synthesized via solvothermal method and calcined at various temperatures: 300, 400, and 500 °C. The calcined catalysts were characterized by XRD, N₂-adsorption-desorption, UV-DRS, XRF, and Zeta potential and tested for photocatalytic degradation of alachlor under visible light. The calcined catalysts consisted only of anatase phase. The BET specific surface area decreased with the calcination temperatures. The doping Fe ion induced a red shift of absorption capacity from UV to the visible region. The Fe-TiO₂ calcined at 400 °C showed the highest photocatalytic activity on degradation of alachlor with assistance of 30 mM H₂O₂ at pH 3 under visible light irradiation. The degradation fitted well with Langmuir-Hinshelwood model that gave adsorption coefficient and the reaction rate constant of 0.683 L mg⁻¹ and 0.136 mg/L·min, respectively.     

Synthesis and thermal behavior of Fe<Subscript>3</Subscript>O<Subscript>2</Subscript>(BO<Subscript>4</Subscript>) oxoborate

Iron oxoborate Fe₃O₂(BO₄) has been first produced in solid-phase chemical reactions. Its thermal behavior in the temperature range 20–900°C is studied with the use in-situ high-temperature powder X-ray diffraction. It is shown that Fe₃O₂(BO₄) begins decomposing with the formation of Fe₂O₃ in the temperature range 660–900°C. Thermal expansion is sharply anisotropic at room temperature (α_max/α_min = 7) and becomes more isotropic with an increase in the temperature (α_max/α_min = 1.2). The degree of oxidation of Fe³⁺ has been confirmed by Mössbauer spectroscopy (at a room temperature), and two nonequivalent positions in the structure have been detected, which are occupied by iron atoms with the octahedral environment of the oxygen atoms.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> composite oxide and its photocatalytic degradation of rhodamine B

The composite semiconductor photocatalyst TiO₂/SiO₂ was prepared by template-hydrothermal method using carbon spheres as the template. The structural and optical properties of TiO₂/SiO₂ were characterized by XRD, SEM, BET, UV–Vis DRS, TG-DTA, PL techniques. The formation of hydroxyl radical on the surface of TiO₂/SiO₂ was studied with terephthalic acid as the probe molecule, combined with fluorescence technique. The results showed that the specific surface area of TiO₂/SiO₂ composite was 327.9 m²/g, and the specific surface area of TiO₂/SiO₂ was larger than that of pure TiO₂. Photocatalytic degradation of rhodamine B showed that TiO₂/SiO₂ composite oxide under visible light illumination 40 min, the degradation rate was 98.6 % and the degradation rate of pure TiO₂ was only 11.9 %. The apparent first-order rate constant of TiO₂/SiO₂ was 33 times that of pure TiO₂ and more than 6 times that of P25 when the molar ratio of Ti to Si was 1:1 under visible light irradiation. Moreover, it’s also as much as 5 times that of pure TiO₂ and is more than 1 times that of P25 under UV light irradiation 25 min. Based on the experimental results, ^·O₂ ^? and h⁺ were suggested to be the major active species which was responsible for the degradation reaction. The increased photocatalytic activity of TiO₂/SiO₂ may be mainly attributed to effectively suppressing the recombination of hole/electron pairs. After the photocatalyst TiO₂/SiO₂ was reused 5 times, the degradation rate of rhodamine B could reach 89.2 % under visible light irradiation. Moreover, The composite semiconductor photocatalyst TiO₂/SiO₂ was selective towards the degradation of rhodamine B.     

Synergistic effects of doped Fe3+ and deposited Au on improving the photocatalytic activity of TiO2

Fe³⁺ doped together with Au deposited TiO₂ (Au/Fe³⁺–TiO₂) was successfully prepared, which shows excellent photocatalytic activity for degradation of methyl orange (MO) under both UV and visible light (λ > 420 nm) illumination. Fe³⁺ has been confirmed by EPR to substitute for Ti⁴⁺ in the TiO₂ lattice, and Au exists as Au⁰ on the surface of the photocatalyst indicated by the results of XRD. Fe³⁺ and Au have synergistic effects on improving the photocatalytic activity of TiO₂. A proposed mechanism concerning the synergistic effects is discussed to explain the improvement of the photocatalytic activities.     

Photocatalytic Activity of a TiO<Subscript>2</Subscript> Photocatalyst Doped with C<Superscript>4+</Superscript> and S<Superscript>4+</Superscript> Ions Having a Rutile Phase Under Visible Light

C⁴⁺ and S⁴⁺-codoped titanium dioxide (TiO₂) having a rutile phase was prepared. By doping C⁴⁺ and S⁴⁺ ions into a TiO₂ lattice, the absorption edge of rutile TiO₂ powder was largely shifted from 400 to 700 nm. 2-Methylpyridine and methyleneblue were photocatalytically oxidized at high efficiency on C⁴⁺ and S⁴⁺-doped TiO₂ under visible light at a wavelength longer than 5 nm.     

Ni<Superscript>2+</Superscript> reduction under solar irradiation over CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript>/TiO<Subscript>2</Subscript> catalysts

The photo-electrochemical characterization of the hetero-system CoFe₂O₄/TiO₂ was undertaken for the Ni²⁺ reduction under solar light. The spinel CoFe₂O₄ was prepared by nitrate route at 940 °C and the optical gap (1.66 eV) was well matched to the sun spectrum. The flat band potential (-0.21 V_SCE) is more cathodic than the potential of Ni²⁺/Ni couple (-0.6 V_SCE), thus leading to a feasible nickel photoreduction. TiO₂ with a gap of 3.2 eV is used to mediate the electrons transfer. The reaction is achieved in batch configuration and is optimized with respect to Ni²⁺ concentration (30 ppm); a reduction percentage of 72% is obtained under sunlight, the Ni²⁺ reduction is strongly enhanced and follows a first order kinetic with a rate constant of 4.6×10^-2 min^-1 according to the Langmuir-Hinshelwood model.     

Photocatalytic activity of metal-decorated SiO<Subscript>2</Subscript>@TiO<Subscript>2</Subscript> hybrid photocatalysts under water splitting

We report the fabrication of a metal-decorated hybrid nanocomposite with TiO₂ encapsulation (Metal/SiO₂@TiO₂, Metal=Pt or Ru) using a simple surface-modification chemical process. Metal nanoparticles capped with polyvinylpyrrolidone were successfully assembled on functionalized SiO₂ via electrostatic interactions, after which a thin layer of TiO₂ was coated on the surface by the sol-gel process to avoid agglomeration of the coated silica spheres. Transmission electron microscopy studies confirmed that the metal nanoparticles were uniformly distributed throughout the surface of the SiO₂ with a thin layer of TiO₂. In addition, X-ray diffraction was employed to ensure the crystal structure of the uniformly coated thin TiO₂ layer. Even after calcination at 500 °C, the structure remained intact, confirming high thermal stability. The photocatalytic activity of the metal-decorated SiO₂/TiO₂ nanocomposites was evaluated using the H₂ evolution reaction. The Metal/SiO₂@TiO₂ catalysts show the photocatalytic water splitting efficiency for H₂ generation (i.e., 0.14% for Pt/SiO₂@TiO₂ and 0.12% for Ru/SiO₂@TiO₂), while there is no generation of H₂ on the Metal/SiO₂ without a coating layer. These results indicate that the anatase crystalline coating layer has good thermal and chemical stability and plays a significant role in photocatalytic H₂ production.     

In situ DRIFTS study of photocatalytic CO<Subscript>2</Subscript> reduction under UV irradiation

Photocatalytic reduction of CO₂ on TiO₂ and Cu/TiO₂ photocatalysts was studied by in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) under UV irradiation. The photocatalysts were prepared by sol-gel method via controlled hydrolysis of titanium (IV) butoxide. Copper precursor was loaded onto TiO₂ during sol-gel procedure. A large amount of adsorbed H₂O and surface OH groups was detected at 25°C on the TiO₂ photocatalyst after being treated at 500°C under air stream. Carbonate and bicarbonate were formed rapidly due to the reaction of CO₂ with oxygen-vacancy and OH groups, respectively, on TiO₂ surface upon CO₂ adsorption. The IR spectra indicated that, under UV irradiation, gas-phase CO₂ further combined with oxygen-vacancy and OH groups to produce more carbonate or bicarbonate. The weak signals of reaction intermediates were found on the IR spectra, which were due to the slow photocatalytic CO₂ reduction on photocatalysts. Photogenerated electrons merge with H⁺ ions to form H atoms, which progressively reduce CO₂ to form formic acid, dioxymethylene, formaldehyde and methoxy as observed in the IR spectra. The well-dispersed Cu, acting as the active site significantly increases the amount of formaldehyde and dioxymethylene, thus promotes the photoactivity of CO₂ reduction on Cu/TiO₂. A possible mechanism of the photocatalytic CO₂ reduction is proposed based on these intermediates and products on the photocatalysts.     

Highly efficient photocatalytic degradation of methylene blue using carbonaceous WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> composites

Recent improvements in the performance of photocatalysts made it possible to tackle pollution through environment friendly methods. This study investigates the modification of the photocatalytic activity of TiO₂ by employing WO₃ and conductive polymers, namely, polyaniline (Pani) and polypyrrole (Ppy). Basing on our previous improvement of TiO₂ using a conductive polymer and activated carbon (AC), this study determines the activated carbon forms of TiO₂. The prepared composites are characterized using X-ray powder diffraction, transmission electron microscopy, Fourier transform infrared, thermogravimetric analysis, Brunauer–Emmet–Teller, and UV–Vis spectroscopy. The specific surface area of the mesoporous composites is as follows: WO₃/TiO₂·AC (Pani) > WO₃/TiO₂·AC (Ppy) > WO₃/TiO₂·Pani > WO₃/TiO₂·Ppy (127 > 98 > 68 > 44 m² g^?1), which exhibited a similar trend to the photocatalytic performances (100 > 95 > 91 > 72 % conversion rate). This result could be attributed to higher porosity, surge of charge separation, and photo-responding range extension induced by the synergistic effect of WO₃, conducting polymers, and TiO₂ in the samples.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript>-coated coal fly ash for photocatalyst

In order to more easily separate TiO₂ photocatalyst from treated wastewater, TiO₂ photocatalyst is immobilized on coal fly ash by precipitation method. The titanium hydroxide precipitated on coal fly ash by neutralization of titanium chloride is transformed into titanium dioxide by heat treatment in the temperature range of 300–700 ‡C. The crystalline structure of the titanium dioxide shows anatase type in all ranges of heat treatment temperature. The crystal size of anatase increases with increasing heat treatment temperature, with the drawback being the lower removal ability of NO gas. When the coal fly ash coated with 10 wt% of TiO₂ was calcined at 300 and 400 ‡C for 2 hrs, the average crystal size of anatase appeared about 9 nm, and the removal rates of NO gas were 63 and 67.5%, respectively. The major iron oxide, existing in coal fly ash as impurity, is magnetite (Fe₃O₄). Phase transformation of magnetite into hematite (Fe₂O₃) by heat treatment improves the removal rate of NO gas for TiO₂-coated coal fly ash.     

A Resumable Fluorescent Probe BHN-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>@SiO<Subscript>2</Subscript> Hybrid Nanostructure for Fe<Superscript>3+</Superscript> and its Application in Bioimaging

A multifunctional fluorescent probe BHN-Fe₃O₄@SiO₂ nanostructure for Fe³⁺ was designed and developed. It has a good selective response to Fe³⁺ with fluorescence quenching and can be recycled using an external magnetic field. With adding EDTA (2.5?×?10^?5 M) to the consequent product Fe³⁺-BHN-Fe₃O₄@SiO₂, Fe³⁺ can be removed from the complex, and its fluorescence probing ability recovers, which means that this constituted on-off type fluorescence probe could be reversed and reused. At the same time, the probe has been successfully applied for quantitatively detecting Fe³⁺ in a linear mode with a low limit of detection 1.25?×?10^?8 M. Furthermore, the BHN-Fe₃O₄@SiO₂ nanostructure probe is successfully used to detect Fe³⁺ in living HeLa cells, which shows its great potential in bioimaging detection.     

Preparation and Characterization of Multi-functional Titanium Dioxide Photocatalysts

Recent research trends of the preparation and characterization of highly efficient titanium oxide-based photocatalysts modified by different methods are reviewed on the basis of studies done in our laboratory. Special attention is focused on the preparation and characterization of TiO₂ photocatalysts prepared by the transitional metal doping and noble metal deposition method, especially combining above two methods. Fe³⁺ doped together with Au deposited TiO₂ (Au/Fe³⁺–TiO₂) was successfully prepared, which shows excellent photocatalytic activity for degradation of methyl orange (MO) under both UV and visible light (λ > 420 nm) illumination. Fe³⁺ has been confirmed by EPR to substitute for Ti⁴⁺ in the TiO₂ lattice, and Au exists as Au⁰ on the surface of the photocatalyst indicated by the results of XRD. Fe³⁺ and Au have synergistic effects on improving the photocatalytic activity of TiO₂. A proposed mechanism concerning the synergistic effects is discussed to explain the improvement of the photocatalytic activities.     

Effect of Ni Doping on the Structural and Optical Properties of TiO<Subscript>2</Subscript> Nanoparticles at Various Concentration and Temperature

TiO₂ nanopowders doped by Ni were prepared by sol–gel method. The effects of Ni ion (transition metal ion) doping on the physical structural and optical properties of TiO₂ have been investigated by X-ray diffraction (XRD), scanning electron microscopy and UV–Vis absorption spectroscopy. XRD results suggest that adding impurities has a significant effect on anatase phase stability, crystallinity, and particle size of TiO₂. The phase transformation from anatase to rutile was inhibited by Ni ion doped TiO₂ at temperatures 675 °C. The lowest band gap value (2.83 eV) was obtained for TiO₂-4%Ni sample calcined at 675 °C.     

Developments in photocatalytic antibacterial activity of nano TiO<Subscript>2</Subscript>: A review

TiO₂, which is one of the most explored materials, has emerged as an excellent photocatalyst material for environmental and energy fields, including air and water purification, self-cleaning surfaces, antibacterial and water splitting. This review summarizes recent research developments of TiO₂-based photocatalyst used for photocatalytic antibacterial applications. Several strategies to enhance the efficiency of TiO₂ photocatalyst are discussed, including doping with metal ions, noble metals, non-metals, and coupling with other materials. The mechanism of photocatalytic antibacterial activity in the presence of nano-sized TiO₂ is also discussed. The modified TiO₂ photocatalyst significantly inhibits the growth of bacterial cells in response to visible light illumination. TiO₂ photocatalysis appears to be promising as a route of advanced oxidation process for environmental remediation.     

Synthesis and Photocatalytic Properties of HTaWO<Subscript>6</Subscript> Intercalated with Oxide Materials

Transition metal oxides (TiO₂, MnO₂, Cr₂O₃, Fe₂O₃, NiO, CuO) were intercalated into the interlayer of HTaWO₆ by (1) hydrothermal reaction on HTaWO₆ with 1 M soluble metal nitrate aqueous solution at 130C for 12 h followed by calcination at 250C for 3 h and (2) sol reaction on HTaWO₆/n-C₃H₇NH₂ precursor with metal oxide sol, followed by UV irradiation. The gallery height of transition metal oxide in the interlayer of HTaWO₆ is changed from 0.42 to 0.71 nm, the band gap energies of intercalated materials are less than 3 eV. HTaWO₆/Cr₂O₃, HTaWO₆/MnO, HTaWO₆/Fe₂O₃, HTaWO₆/NiO and HTaWO₆/CuO porous materials are capable of photocatalytic decomposing methyl orange, and the photocatalytic activity of HTaWO₆/TiO₂ is superior to that of unsupported TiO₂.