Photocatalytic degradation of C.I. Acid Orange 7 by TiO2 nanoparticles immobilized onto/into chitosan‐based hydrogel

Photocatalytic degradation of dye C.I. Acid Orange 7 in aqueous solution using TiO₂/hydrogel nanocomposite under solar light simulating source was studied. Hydrogel based on chitosan, itaconic and methacrylic acid was modified with colloidal TiO₂ nanoparticles synthetized by acidic hydrolysis of TiCl₄ and commercial Degussa P25 TiO₂ nanoparticles. SEM/EDX analysis confirmed the presence of TiO₂ nanoparticles onto/into hydrogel. It was found that both types of photocatalysts efficiently removed the dye from solution, but sorption rates and photodegradation efficiency were higher in the case of colloidal TiO₂ nanoparticles. They ensured complete discoloration of dye solution. The efficiency of the reused TiO₂/hydrogel nanocomposite showed that photodegradation activity was maintained at satisfactory level after three repeated cycles of illumination. POLYM. COMPOS., 35:806–815, 2014. © 2013 Society of Plastics Engineers     

A unique Cu2O/TiO2 nanocomposite with enhanced photocatalytic performance under visible light irradiation

A unique Cu₂O/TiO₂ nanocomposite with high photocatalytic activity was synthesized via a two-step chemical solution method and used for the photocatalytic degradation of organic dye. The structure, morphology, composition, optical and photocatalytic properties of the as-prepared samples were investigated in detail. The results suggested that the Cu₂O/TiO₂ nanocomposite is composed of hierarchical TiO₂ hollow microstructure coated by a great many Cu₂O nanoparticles. The photocatalytic performance of Cu₂O/TiO₂ nanocomposite was evaluated by the photodegradation of methylene blue (MB) under visible light, and compared with those of the pure TiO₂ and Cu₂O photocatalysts synthesized by the identical synthetic route. Within 120 min of reaction time, nearly 100% decolorization efficiency of MB was achieved by Cu₂O/TiO₂ photocatalyst, which is much higher than that of pure TiO₂ (26%) or Cu₂O (32%). The outstanding photocatalytic efficiency was mainly ascribed to the unique architecture, the extended photoresponse range and efficient separation of the electron-hole pairs in the Cu₂O/TiO₂ heterojunction. In addition, the Cu₂O/TiO₂ nanocomposite also retains good cycling stability in the photodegradation of MB.     

Preparation of interpenetrating polymer network gel beads for dye absorption

Preparation of interpenetrating polymer network (IPN) gel beads for dye absorption was carried out by using simultaneous crosslinking method. First, sodium alginate (SA), 3‐(methacrylamido) propyl trimethyl ammonium chloride (MAPTAC), and/or acrylamide (AM), K₂S₂O₈, and N,N′‐methylenebisacrylamide (MBAM) were mixed in aqueous solution. The beads were prepared using K₂S₂O₈ and MBAM as the initiator and crosslinking agent, respectively. Then, the solution was dropped into CaCl₂ solution mixed with N,N,N′,N′‐tetramethylethylenediamine (TMEDA). The former was used as the crosslinking agent of alginate and the latter was used as the accelerator for the polymerization of monomer in the alginate solution. The gel bead composed of only alginate was also prepared to compare the properties with IPN gel bead. The components in IPN gel bead were examined by FTIR analysis. The factors effecting the particle size of alginate and IPN gel beads were investigated. In alginate gel bead, the concentration of solution affected the particle size, whereas type of monomer affected the particle size of IPN gel bead. The IPN gel bead had smooth surface (from SEM results), different from the alginate bead. Alginate content caused the swelling behavior of dried IPN beads. Cationic dye was absorbed by crosslinked alginate gel bead. The absorption of reactive dye by IPN gel bead was a result of its cationic charge. The absorption density of IPN gel beads was the reciprocal of the absorbent dosage. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1585–1591, 2006     

Photocatalytic activity of TiO2 nanopowders supported on a new persistent luminescence phosphor

TiO₂ nanoparticles were supported on a new persistent luminescence (3ZnO:Ga₂O₃:2GeO₂):Cr^3 + material. The sample was characterized by means of X-ray powder diffraction, scanning electron microscopy and radioluminescence. The photoactivity was evaluated for the degradation of methylene blue (MB) in aqueous solution especially in the darkness. A MB photodegradation occurred also in the absence of an external illumination. In fact, the persistent luminescence material stores and provides the necessary photons to the TiO₂ allowing the photocatalysis process even in the darkness.     

Effect of the grain size of nanoparticle dye‐coated titanium dioxide on the short‐circuit current density and open‐circuit voltage of an indium tin oxide/titanium dioxide/poly(acrylonitrile)–propylene carbonate–lithium perchlorate/graphite solar cell

A dye‐sensitized indium tin oxide (ITO)/titanium dioxide (TiO₂)/polyacrylonitrile (PAN)–propylene carbonate (PC)–lithium perchlorate (LiClO₄)/graphite solar cell was fabricated, and its performance was tested in the dark and under the illumination of a 100 mW/cm² light. Three TiO₂ samples were used in the device, namely, uncoated TiO₂, a TiO₂ film coated with methyl red dye, and a TiO₂ film coated with coumarin dye. The films were deposited onto an ITO‐covered glass substrate by a controlled hydrolysis technique assisted with a spin‐coating technique. The films were characterized by scanning electron microscopy to determine their average grain size. The smallest grain size (48 nm) was obtained for the uncoated film. An electrolyte of PAN–LiClO₄ with PC plasticizer was prepared by a solution‐casting technique. A graphite electrode was prepared on a glass slide by an electron‐beam evaporation technique. The device showed rectification properties in the dark and showed a photovoltaic effect under illumination. The device with the uncoated TiO₂ film showed the highest short‐circuit current density (2.0 μA/cm²) and an open‐circuit voltage of 0.64 V because it possessed the smallest grain size. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photocatalysis of methylene blue on titanium dioxide nanoparticles synthesized by modified sol-hydrothermal process of TiCl4

Titanium dioxide nanoparticles were synthesized by the hydrolysis and condensation of TiCl₄, an economic titanium precursor, in a mixed solvent of iso-propyl alcohol and water. As-prepared powders were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), energy filtering transmission electron microscopy (EF-TEM). To examine the photocatalytic activity of the as-prepared TiO₂, the photodegradation of MB which is a typical dye resistant to biodegradation has been investigated on TiO₂ powders in aqueous heterogeneous suspensions. The photocatalytic activity of TiO₂ powders prepared by the hydrolysis of TiCl₄ in the mixed solutions of iso-PrOH/H₂O exceeded that of commercial TiO₂ powders. The apparent first order rate constants (k _app) for the photodegradation of methylene blue (MB) showed a good correlation with the absorbance area obtained by UV-VIS DRS on wavelength in the limits of used lamp emission 300∼420 nm.     

Synthesis of Octa(maleimidophenyl) silsesquioxane–SiO2/TiO2 Hybrid Nanocomposites: Adsorption Behavior for the Removal of an Organic Methylene Blue Dye and Antimicrobial Activity against Pathogens

In this study, a sol–gel process was used to prepare hybrid nanocomposite consisting of octa(maleimidophenyl) silsesquioxane-silica/titania (maleimide–POSS (polyhedral oligomeric silsesquioxanes)–SiO₂/TiO₂) to use in methylene blue (MB) adsorption and as an antibacterial agent. The structure, surface, and morphological characteristics were confirmed through Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and transmission electron microscopy. The optical and thermal stabilities were studied by conducting UV–visible and thermogravimetric analysis–differential scanning electron calorimetry analysis. The experimental results showed a maximum dye adsorption capacity of 92% achieved using 0.5?g of hybrid nanocomposite after 2.5?h at pH 9. We also investigated the effect that the adsorbent dosage, pH, and contact time had on the removal efficiency of the MB dye in aqueous solution. The recycling experiment showed a good adsorption capacity of the MB dye, even after five repeated cycles. Furthermore, the hybrid nanocomposite was tested against pathogenic bacteria, such as Bacillus cereus, Lactobacillus, Escherichia coli, and Pseudomonas aeruginosa. The nanocomposite was observed to be highly sensitive to E. coli, B. cereus, and P. aeruginosa, as confirmed by the size of the zone inhibition.     

Effect of Carbon Nanotubes and Carbon Nanotubes/Gold Nanoparticles Composite on the Photocatalytic Activity of TiO2 and TiO2‐SiO2

A carbon nanotube (CNT)/gold nanoparticle (NP) nanocomposite was synthesized by simultaneously reducing the Au ions and depositing Au NPs on the surface of a CNT. The functional groups were investigated with Fourier transform infrared spectra. From the Raman spectra, the D‐band and G‐band of the CNT were identified. The deposition of nanometer‐sized Au NPs on the CNT sites was observed by transmission electron microscopy. The photodegradation of methylene blue (MB) in aqueous solutions was studied using various photocatalysts, including TiO₂, TiO₂‐SiO₂, CNT/TiO₂, CNT/TiO₂‐SiO₂, Au/TiO₂, CNT‐Au/TiO₂, and CNT‐Au/TiO₂‐SiO₂ composites. CNT addition leads to a synergic effect, improving the photoactivity of the catalysts. A possible physically based mechanism was proposed involving the reduction of electron‐hole recombination and fast electron‐transfer possibility.     

A novel approach for the synthesis of highly active ZnO/TiO2/Ag2O nanocomposite and its photocatalytic applications

The present work is focused on the preparation of hybrid ZnO/TiO₂/Ag₂O nanocomposite for enhanced photocatalytic activity. The resultant samples are characterized by using XRD, SEM, EDX, HR-TEM, UV-DRS, BET and XPS techniques. X-ray diffraction analysis indicates the co-existence of wurtzite, anatase and cubic phases in ZnO/TiO₂/Ag₂O nanocomposite. The band gap energy value of the photocatalyst is 3.39 eV, which has been evidenced from UV–visible diffuse reflectance spectroscopy measurements. Photocatalytic degradation of methylene blue dye has been investigated by using UV–visible spectrophotometer. From the result, it has been concluded that ZnO/TiO₂/Ag₂O nanocomposite has proven to be an efficient photocatalyst under UV irradiation when compared to that of mono and binary oxide systems. Further, the possible photodegradation mechanism is proposed to support the enhancement of photocatalytic activity towards degradation of dyes.     

Preparation of aerochitin‐TiO2 composite for efficient photocatalytic degradation of methylene blue

An aerochitin–titania (TiO₂) composite was successfully synthesized and characterized by Fourier transform infrared spectroscopy, X‐ray diffraction, thermogravimetric analysis, field emission scanning electron microscopy, and N₂ adsorption isotherms. The photocatalytic activity of the composite was investigated on the degradation of the model organic pollutant, methylene blue (MB) dye, under UV irradiation. The aerochitin–TiO₂ composite showed excellent adsorptive and photocatalytic activity with a degradation degree of 98% for MB. The first‐order rate constants for the photodegradation MB by TiO₂ nanoparticles and aerochitin–TiO₂ composite were found to be (3.49 ± 0.04) × 10^?3 and (1.82 ± 0.02) × 10^?2 min^?1. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45908.     

Adsorption of Methylene Blue on Poly (Methacrylic Acid) Modified Chitosan and Photocatalytic Regeneration of the Adsorbent

The preparation of poly(methacrylic acid) modified chitosan microspheres (PMAA-GLA-CTS) and its application for the removal of cationic dye, methylene blue (MB), in aqueous solution in a batch system were described. The modified chitosan was characterized using FTIR and XPS analysis. The effects of the pH of the solution, contact time, and initial dye concentration were studied. The adsorption capacity of the microspheres for MB increased significantly after the modification as a large number of carboxyl groups were introduced. The equilibrium process was better described by the Langmuir rather than the Freundlich isotherm. According to the Langmuir equation, the maximum adsorption capacity was 1 g · g^?1 for MB. Kinetic studies showed better correlation coefficients for a pseudo-second-order kinetic model, confirming that the sorption rate was controlled by a chemisorption process. Photocatalytic regeneration of spent PMAA-GLA-CTS using UV/TiO₂ is effective. Further, the regenerated PMAA-GLA-CTS exhibits 90% efficiency for a subsequent adsorption cycle with MB aqueous solutions.     

Hydrothermal preparation of Sn3O4/TiO2 nanotube arrays as effective photocatalysts for boosting photocatalytic dye degradation and hydrogen production

The efficient TiO₂ NTs/Sn₃O₄ photocatalysts were synthesized by the hydrothermal deposition of Sn₃O₄ on TiO₂ nanotube arrays (TiO₂ NTs), and the morphology, microstructure and photocatalytic property were adjusted by changing the alkali kind. The TiO₂ NTs/Sn₃O₄ prepared with NaOH exhibited the outstanding photoelectric conversion and photocatalytic environment remediation/H₂ evolution. The methylene blue (MB) dye and Cr(VI) could be removed by the as-prepared photocatalysts under visible light irradiation, and ?O₂^?/?OH radicals were the main active species for MB photodegradation. Furthermore, the high photocatalytic H₂ evolution rate was as high as 6.49 μmol cm^?2 h^?1. The outstanding photocatalytic activity and stability of TiO₂ NTs/Sn₃O₄ photocatalysts would exhibit attractive prospect in the wastewater remediation and electric energy/hydrogen generation.     

Preparation of transparent PVA/TiO2 nanocomposite films with enhanced visible-light photocatalytic activity

Polymer/semiconductor oxide nanocomposite films have been intensively investigated for various applications. In this work, we reported a simple hydrothermal method to fabricate highly transparent poly(vinyl alcohol)/titanium dioxide (PVA/TiO₂) nanocomposite films with enhanced visible-light photocatalytic activity. The as-prepared PVA/TiO₂ nanocomposite films showed high optical transparency in the visible region even at a high TiO₂ content (up to 40 wt.%). The determination of photocatalytic activity by photodegradation of methyl orange (MO) and colorless phenol showed that PVA/TiO₂ nanocomposite films exhibited enhanced visible-light photocatalytic activity and excellent recycle stability. This work provided new insights into fabrication of polymer/TiO₂ nanocomposites as high performance photocatalysts in waste water treatment.     

Laser-Induced Silver Nanoparticles on Titanium Oxide for Photocatalytic Degradation of Methylene Blue

Silver nanoparticles doped on titanium oxide (TiO₂) were produced by laser-liquid interaction of silver nitrate (AgNO₃) in isopropanol. Characteristics of Ag/TiO₂ (Ag doped TiO₂) nanoparticles produced by the methods presented in this article were investigated by XRD, TEM, SEM, EDX, and UV-Vis. From the UV-Vis measurements, the absorption of visible light of the Ag/TiO₂ photocatalysts was improved (additional absorption at longer wavelength in visible light region) obviously. The photocatalytic efficiency of Ag/TiO₂ was tested by the degradation of methylene blue (MB) in aqueous solution. A maximum of 82.3% MB degradation is achieved by 2.0 wt% Ag/TiO₂ photocatalyst under 2 h illumination with a halogen lamp.     

Enhancing Effects of Ultrasound Treatment on the Preparation of TiO2 Photocatalysts

TiO₂ nanoparticles were synthesized by the hydrolysis and condensation of TiCl₄ in a mixed solvent of iso-propyl alcohol and water with or without ultrasound treatment. As-prepared powders were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), energy filtering transmission electron microscopy (EF-TEM), particle size analysis and BET surface area analysis. The specific surface area, thermal stability and crystallization of the as-prepared samples treated with ultrasound were higher than those of samples treated without ultrasound. To examine the photocatalytic activity of the as-prepared TiO₂, the photodegradation of MB which is a typical dye resistant to biodegradation has been investigated on TiO₂ powders in aqueous heterogeneous suspensions. The photocatalytic degradation of a aqueous solution of methylene blue shows a remarkable increase when it is carried out with ultrasound in all cases.     

Adsorption and photocatalytic properties of TiO<Subscript>2</Subscript>/mesoporous silica composites from two silica sources (acid-leached kaolinite and Si-alkoxide)

Two different mesoporous silicas (MPS) were synthesized by hydrothermal treatment in NaOH solution of two SiO₂ sources. These were microporous silica (MicroPS) derived from selectively acid leached metakaolinite and tetraethylorthosilicate (TEOS). The hydrothermal syntheses of the MPSs were performed at a ratio of SiO₂/cetyltrimethyl- ammonium bromide (CTABr)/NaOH/H₂O = 1/0.1/0.3/150. The specific surface areas (S _BET) of the MPSs from MicroPS (MPS(M)) and TEOS (MPS(T)) were 1070 and 1020 m²/g, respectively. Composites of MPS (75 mass%) with TiO₂ (25 mass%) were prepared using both SiO₂ and two commercial TiO₂ powders, P25 and ST-01. The adsorption–desorption behavior of methylene blue (MB) by the four resulting composites and the two MPSs alone was unique in showing partially reversible behavior. The maximum MB adsorption, observed in the composite of ST-01 with MPS(M), designated (S/M), was 0.034 mmol/g. The rates of MB adsorption in the dark and photodecomposition under UV illumination were considerably different for the four composites and two TiO₂ powers, and followed the order ST-01 < S/T < P25 < P/T ≈ P/M ≪ S/M. The removal rate of MB by the composite S/M by adsorption and photodecomposition was further enhanced by heating at 700 °C. Direct photodecomposition of MB without adsorption in the dark was greatly enhanced in the composites, especially in that composed of MPS(M) and ST-01.     

Multifunctional Fe3O4@Ag@TiO2-xNx core-shell composite particles for dye adsorption and visible-light photocatalysis

This study prepares Fe₃O₄@Ag@TiO₂ (FAT) particles via a solvothermal route, then thermally treats the particles over a temperature range from 300 to 500 °C in flowing nitrogen atmosphere to form Fe₃O₄@Ag@TiO_2-xN_x (x = 0.056 to 0.15) (FATN) core-shell composite particles. The FATN particles comprise an outermost TiO_2-xN_x shell of about 20–50 nm in thickness, a Brunauer-Emmett-Teller surface area of 103.2–152.5 m²/g, and a Barrett-Joyner-Halenda pore size of 12.9–30.2 nm. The particles show dye adsorption and visible-light photocatalysis against a model methylene-blue (MB) dye in water. For the FATN particles being treated at 400 °C, they show a dark adsorption of 54.8% and an additional visible-light photodegradation of 25.1% when using a dyed wastewater with an initial MB concentration of 5 × 10^-6 M. This compares favorably to those being treated at other nitridation temperatures. The 500 °C-treated FATN particles yet exhibit a dark adsorption of 99.1% against the MB solution. Use of an external magnet can facilely recycle the composite particles. The recycled particles remain greater than 72% of their initial MB removal capability after use of five times. The intermediate Ag nanolayer can release Ag ions to the surrounding water medium through the mesoporous shell channel. The time-dependent Ag release appears to follow the Voigt-Maxwell model and reaches 0.764 ppm after 48 h, suggesting a long-time releasing efficacy.     

Aerosol processing of Ag/TiO2 composite nanoparticles for enhanced photocatalytic water treatment under UV and visible light irradiation

In this study, we investigated the effect of Ag addition on the photocatalytic reactivity of TiO₂ nanoparticles (NPs). Controlled amounts of Ag were incorporated in TiO₂ NPs using aerosol spray pyrolysis and subsequent calcination. Ag/TiO₂ composite NPs containing different amounts of Ag (e.g., 0, 0.5, 1, 2, and 5 wt%) were successfully fabricated. The photodegradation performances of the as-prepared Ag/TiO₂ composite NPs were tested using methylene blue (MB) solution under UV and visible light irradiation. Upon increasing the Ag content to 1 wt%, the resulting Ag/TiO₂ composite NPs exhibited increased photocatalytic reactivity due to lowered bandgap energy, which promoted both charge generation and separation. However, when the Ag content exceeded 1 wt%, the photocatalytic reactivity of the resulting Ag/TiO₂ composite NPs was considerably deteriorated due to the masking effect of the excess Ag on the reactive sites of TiO₂. Hence, the incorporation of an optimized amount of Ag in the TiO₂ matrix promotes the photocatalytic reactivity of Ag/TiO₂ composite NPs by controlling their bandgap energy and charge generation and separation processes. These results could lead to the development of photodegradation active substances for water treatment in organic solutions.     

Ag nanoparticles loaded TiO2/MWCNT ternary nanocomposite: A visible-light-driven photocatalyst with enhanced photocatalytic performance and stability

A visible light active photocatalyst, Ag/TiO₂/MWCNT was synthesized by loading of Ag nanoparticles onto TiO₂/MWCNT nanocomposite. The photocatalytic activity of Ag/TiO₂/MWCNT ternary nanocomposite was evaluated for the degradation of methylene blue dye under UV and visible light irradiation. Ag/TiO₂/MWCNT ternary nanocomposite exhibits (~9 times) higher photocatalytic activity than TiO₂/MWCNT and (~2 times) higher than Ag/TiO₂ binary nanocomposites under visible light irradiation. The enhancement in the photocatalytic activity is attributed to the synergistic effect between Ag nanoparticles and MWCNT, which enhance the charge separation efficiency by Schottky barrier formation at Ag/TiO₂ interface and role of MWCNT as an electron reservoir. Effect of different scavengers on the degradation of methylene blue dye in the presence of catalyst has been investigated to find the role of photogenerated electrons and holes. Simultaneously, the Ag/TiO₂/MWCNT shows excellent photocatalytic stability. This work highlights the importance of Ag/TiO₂/MWCNT ternary nanocomposite as highly efficient and stable visible-light-driven photocatalyst for the degradation of organic dyes.     

Synthesis and photocatalytic performance of PVA/TiO2/graphene‐MWCNT nanocomposites for dye removal

TiO₂/graphene‐MWCNT nanocomposite was prepared using solvothermal reaction for the effective distribution of TiO₂ nanoparticles on carbonaceous materials. TiO₂/graphene‐MWCNT nanocomposite was immobilized in poly(vinyl alcohol) (PVA) matrix for a convenient recovery after wastewater purification. MWCNT was incorporated in a nanocomposite not only to prevent the restacking of graphene but also to increase the electron transfer from TiO₂. The detailed characterization of the nanocomposite was performed using SEM, EDX, XRD, XPS, and FTIR. The photocatalytic performance of PVA/TiO₂/graphene‐MWCNT nanocomposite was investigated by UV spectroscopy on the basis of degradation of organic pollutants. PVA/TiO₂/graphene‐MWCNT nanocomposite showed improved photocatalytic decomposition of more than 70% of residual dye left in case of using PVA/TiO₂/graphene nanocomposite due to the improved electron transfer and the higher adsorption of organic pollutants. PVA/TiO₂/graphene‐MWCNT nanocomposite was suitable as a promising material for the recyclable photocatalytic wastewater purification system. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40715.