Combined effects of adsorption and photocatalysis by hybrid TiO2/ZnO-calcium alginate beads for the removal of copper

The use of nanosized titanium dioxide(TiO_2) and zinc oxide(ZnO) in the suspension form during treatment makes the recovering and recycling of photocatalysts difficult.Hence,supported photocatalysts are preferred for practical water treatment applications.This study was conducted to investigate the efficiency of calcium alginate(CaAlg) beads that were immobilized with hybrid photocatalysts,TiO_2/ZnO to form TiO_2/ZnO-CaAlg.These immobilized beads,with three different mass ratios of TiO_2:ZnO(1:1,1:2,and 2:1) were used to remove Cu(Ⅱ) in aqueous solutions in the presence of ultraviolet light.These beads were subjected to three cycles of photocatalytic treatment with different initial Cu(Ⅱ) concentrations(10-80 ppm).EDX spectra have confirmed the inclusion of Ti and Zn on the surface of the CaAlg beads.Meanwhile,the surface morphology of the beads as determined using SEM,has indicated differences of before and after the photocatalytic treatment of Cu(Ⅱ).Among all three,the equivalent mass ratio TiO_2/ZnO-CaAlg beads have shown the best performance in removing Cu(Ⅱ) during all three recycling experiments.Those TiO_2/ZnO-CaAlg beads have also shown consistent removal of Cu,ranging from 7.14-52.0 ppm(first cycle) for initial concentrations of10-80 ppm.In comparison,bare CaAlg was only able to remove 6.9-48 ppm of similar initial Cu concentrations.Thus,the potential use of TiO_2/ZnO-CaAlg beads as environmentally friendly composite material can be further extended for heavy metal removal from contaminated water.     

Kinetic study on photocatalytic degradation of Acid Orange 52 in a baffled reactor using TiO2 nanoparticles

In this study, a baffled photocatalytic reactor was used for the treatment of colored wastewater containing the azo dye of Acid Orange 52(AO52). A study on the active species of the photocatalytic process using TiO_2 nanoparticles indicated that hydroxyl radical and superoxide have the greatest contribution to the dye degradation process respectively.Given that a level of biological oxygen demand/chemical oxygen demand(BOD5/COD) equal to 0.4 was achieved after about 5 hr from the beginning of the experiment, the reactor seems to be capable of purifying the wastewater containing AO52 dye after this time in order to discharge into a biological treatment system to continue the treatment process.The results of the liquid chromatography-mass spectrometry(LC-MS) test showed that during the first 4 hr of the experiment, with the breakdown of the azo bond, the contaminant was decomposed into the benzene annular compounds with less toxicity indicating a reduction in the toxicity of wastewater after removing the dye agent. The study on the kinetics of these reactions followed the pseudo-first-order kinetic model in all conditions and corresponded well to Langmuir–Hinshelwood model. According to the kinetic model for the simultaneous occurrence of possible pathways, the kinetic constant of production and degradation of intermediate products in optimal conditions was estimated to be between 0.0029 and 0.0391 min~(-1).     

Highly efficient Zr doped-TiO2/glass fiber photocatalyst and its performance in formaldehyde removal under visible light

Zr-doped-TiO_2 loaded glass fiber(ZT/GF) composite photocatalysts with different Zr/Ti ratios were prepared with a sol–gel process. Zr4+can replace Ti4+in the TiO_2 lattice, which is conducive to forming the anatase phase and reducing the calcination temperature. The glass fiber carrier was responsible for better dispersion and loading of Zr-doped-TiO_2 particles, improving the applicability of the Zr-doped-TiO_2. The ZT/GF photocatalysts were characterized by X-ray diffraction(XRD), scanning electron microscope(SEM), Fourier transform infrared spectroscopy(FT-IR), ultraviolet–visible spectroscopy(UV–vis) and Barrett–Joyner–Halenda(BJH). The performance of photocatalysts with different loading was evaluated in formaldehyde degradation under visible light at room temperature. ZT/GF0.2exhibited the highest activity, with a formaldehyde removal rate as high as 95.14% being observed, which is better than that of the photocatalyst particles alone. The stability of the catalyst was also tested, and ZT/GF exhibited excellent catalytic performance with 94.38%removal efficiency, even after seven uses.     

Construction of Ag2CO3/BiOBr/CdS ternary composite photocatalyst with improved visible-light photocatalytic activity on tetracycline molecule degradation

Photocatalytic degradation was considered as a best strategy for the removal of antibiotic drug pollutants from wastewater. The photocatalyst of ABC (Ag₂CO₃/BiOBr/CdS) composite synthesized by hydrothermal and precipitation method. The ABC composite used to investigate the degradation activity of tetracycline (TC) under visible light irradiation. The physicochemical characterization methods (e.g. scanning electron microscopy (SEM), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), ultraviolet visible spectroscopy (UV), photoluminescence (PL) and time resolved photoluminescence (TRPL) clearly indicate that the composite has been construct successfully that enhances the widened visible light absorption, induces charge transfer and separation efficiency of electron – hole pairs. The photocatalytic activity of all samples was examined through photodegradation of tetracycline in aqueous medium. The photocatalytic degradation rate of ABC catalyst could eliminate 98.79% of TC in 70 min, which is about 1.5 times that of Ag₂CO_3, 1.28 times that of BiOBr and 1.1 times that of BC catalyst, respectively. The role of operation parameters like, TC concentration, catalyst dosage and initial pH on TC degradation activity were studied. Quenching experiment was demonstrated that ·OH and O₂^·− were played a key role during the photocatalysis process that was evidently proved in electron paramagnetic resonance (EPR) experiment. In addition, the catalyst showed good activity perceived in reusability and stability test due to the synergistic effect between its components. The mechanism of degradation of TC in ABC composite was proposed based on the detailed analysis. The current study will give an efficient and recyclable photocatalyst for antibiotic aqueous pollutant removal.     

Synergistic effect of N-and F-codoping on the structure and photocatalytic performance of TiO2

Three types of Ti O2 nanostructures were synthesized via a facile hydrolysis method at195 °C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of Ti O2 were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller porosimetry, ultraviolet–visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase Ti O2 had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure Ti O2. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N–F-Ti O2 nanomaterial shows considerable potential for water treatment under sunlight irradiation.     

Understanding the multifunctionality in Cu-doped BiVO4 semiconductor photocatalyst

A visible light-induced, Cu-doped BiVO_4 photocatalyst was synthesized by a microwave hydrothermal method. The photocatalytic efficiency was investigated in the degradation of model water pollutants like Methylene Blue(dye) and ibuprofen(pharmaceuticals), as well as the inactivation of Escherichia coli(bacteria). The Cu-doped BiVO4 samples showed better efficiency than undoped BiVO_4, and the 1 wt.% Cu-doped BiVO_4 sample showed the best efficiency. The degradation of Methylene Blue reached 95%, while the degradation of ibuprofen reached 75%, and the inactivation of E. coli reached 85% in irradiation with visible light. The appearance of additional absorption band shoulders and widening of the optical absorption in the visible range makes the prepared powder an efficient visible light-driven photocatalyst. Moreover, the formation of an in-gap energy state just above the valance band as determined by density functional theory(DFT) first principle calculation, facilitates the wider optical absorption range of the doped system. Similarly, this in-gap energy state also acts as an electron trap, which is favorable for the efficient separation and photoexcited charge carriers' transfer process. The formation of oxygen vacancies due to doping also improved the separation of the charge carrier, which promoted the trapping of electrons and inhibited electron hole recombination, thus increasing the photocatalytic activity. No decrease in the efficiency of the 1 wt.% Cu-doped BiVO_4 photocatalyst in the degradation of ibuprofen over three consecutive cycles revealed the stability of the photocatalyst towards photocorrosion. These findings highlight the multifunctional applications of Cu-doped BiVO_4 in wastewater containing multiple pollutants.     

Synthesis, characterization and application of ZnO-Ag as a nanophotocatalyst for organic compounds degradation, mechanism and economic study

The current work deals with ZnO-Ag nanocomposites (in the wide range of x in the Zn_1 − xO-Ag_x chemical composition) synthesized using microwave assisted solution combustion method. The structural, morphological and optical properties of the samples were characterized by XRD (X-ray diffraction), FTIR (Fourier transform infrared spectrometry), SEM (scanning electron microscopy technique), EDX (energy dispersive X-ray spectrum), ICP (inductively coupled plasma technique), TEM (transmission electron microscopy), BET (Brunauer–Emmett–Teller method), UV–Vis (ultraviolet–visible spectrophotometer) and photoluminescence spectrophotometer. The photocatalytic activity of the ZnO-Ag was investigated by photo-degradation of Acid Blue 113 (AB 113) under UV illumination in a semi-batch reactor. This experiment showed that ZnO-Ag has much more excellent photocatalytic properties than ZnO synthesized by the same method. The enhanced photocatalytic activity was due to the decrease in recombination of photogenerated electron-holes. The results showed the improvement of ZnO photocatalytic activity and there is an optimum amount of Ag (3.5 mol%) that needs to be doped with ZnO. The effect of operating parameters such as pH, catalyst dose and dye concentration were investigated. The reaction byproducts were identified by LC/MS (liquid chromatography/mass spectrometry) analysis and a pathway was proposed as well. Kinetic studies indicated that the decolorization process follows the first order kinetics. Also, the degradation percentage of AB 113 was determined using a total organic carbon (TOC) analyzer. Additionally, cost analysis of the process, the mechanism and the role of Ag were discussed.     

纳米二氧化钛/针铁矿的制备及其光催化性能的研究

采用溶胶-凝胶法,以钛酸丁酯为原料制备纳米级二氧化钛,将其负栽于采用化学沉淀法以九水硝酸铁为原料制备的针铁矿上,对复合材料进行透射电镜分析,确定了制备的最佳影响因素,将2种溶胶进行复合提膜,研究其光催化效率.     

Acid-treated Fe-doped TiO2 as a high performance photocatalyst used for degradation of phenol under visible light irradiation

The photocatalytic activity of Fe-doped TiO2 nanoparticles is significantly increased by an acid-treatment process. The photocatalyst nanoparticles were prepared using sol–gel method with 0.5 mol% ratio of Fe:Ti in acidic pH of 3. The nanoparticles were structurally characterized by means of X-ray diffraction(XRD), high-resolution transmission electron microscope(HRTEM), energy-dispersive X-ray spectroscopy(EDX), X-ray photoelectron spectroscopy(XPS) and diffuse reflectance spectroscopy(DRS). It was observed that the photocatalytic activity suffered from an iron oxide contaminating layer deposited on the surface of the nanoparticles. This contamination layer was removed using an HCl acidtreatment process. The photocatalytic activity using 500 mg/L of Fe0.5-TiO2 in a 10 mg/L of phenol solution increased significantly from 33% to 57%(about 73% increase in the performance), within 90 min of reaction time under visible light irradiation. This significant improvement was achieved by removing the iron oxide contamination layer from the surface of the nanoparticles and adjusting p H to mild acidic and basic pHs.     

Synergistic effect of N- and F-codoping on the structure and photocatalytic performance of TiO2

Three types of TiO₂ nanostructures were synthesized via a facile hydrolysis method at 195 °C. Effects of the preparation method and doping with N and F on the crystal structure and photocatalytic performance of TiO₂ were investigated. The nanomaterials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller porosimetry, ultraviolet–visible diffuse reflectance spectroscopy and fluorescent emission spectra. Their photo-catalytic activity was examined by the photodegradation of methylene blue in aqueous solution under both ultra-violet and visible light irradiation. The results show that nitrogen and fluorine co-doped anatase TiO₂ had the characteristics of a smaller crystalline size, broader light absorption spectrum and lower charge recombination than pure TiO₂. Most importantly, more efficient photocatalytic activity under both ultra-violet and visible light was observed. The obtained N–F-TiO₂ nanomaterial shows considerable potential for water treatment under sunlight irradiation.