Hydrothermal preparation of ZnO:CNT and TiO<Subscript>2</Subscript>:CNT composites and their photocatalytic applications

ZnO:CNT and TiO₂:CNT composites were fabricated under mild hydrothermal conditions (T = 150–240 °C) with an autogenous pressure. The as prepared composites were characterized using X-ray diffraction, Scanning electron microscopy and FTIR spectroscopy. Photocatalytic applications of the composites were investigated using indigo caramine dye. The effect of the catalyst content, pH of the medium, source and intensity of illumination on the photodegradation of the indigo caramine dye was studied and the efficiency of the composites were investigated based on different parameters like percent transmittance (%T), percent decomposition, and chemical oxygen demand of the dye solution to obtain optimum treatment conditions. The results obtained exhibit higher photocatalytic activity when compared to the reagent grade ZnO, TiO₂ and hydrothermally prepared ZnO:AC and TiO₂:AC composites.     

A new method to prepare high-surface-area N-TiO2/activated carbon

A new method, combining impregnation and vapor-hydrolysis, was developed to prepare hybrid photocatalyst: nitrogen doped TiO₂ coated activated carbon (N-TiO₂/AC). The activated carbon (AC) was impregnated into titanium tetraethoxide/urea/methanol solution, and then the impregnated AC powder was kept in water vapor at 90 °C for 3 h for hydrolysis. Then it was calcinated to fabricate N-TiO₂/AC. Transmission electron microscopy (TEM) results showed that the nitrogen doped TiO₂ (N-TiO₂) in the as-synthesized hybrid was anatase TiO₂ powder with 10-20 nm in grain size, and the bandgap was about 3.08 eV. Moreover, the hybrid photocatalyst (8 wt.% N-TiO₂) had high specific surface area that was up to 1321 m²/g. The hybrid photocatalyst is expected to have high photocatalytic performance with visible irradiation.     

Hydrothermal preparation and characterization of TiO2:AC composites

A new photocatalyst titania:activated carbon (TiO₂:AC) composite was prepared by impregnating anatase type TiO₂ nanoparticulates onto the activated carbon surface through a mild hydrothermal route. A varied ratio of TiO₂ to AC was considered for impregnation. As-prepared TiO₂:AC composite was characterized by various techniques such as powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), BET surface area and positron annihilation lifetime spectroscopy (PALS). Powder XRD results showed the persisting nature of anatase phase of TiO₂ deposited on the activated carbon surface. The BET, FTIR and PALS results revealed the impregnation threshold. The TiO₂ particulates were well adhered and uniformly dispersed on the carbon surface as confirmed by SEM.     

Photocatalytic degradation of reactive black-5 dye using TiO<Subscript>2</Subscript> impregnated ZSM-5

In the present study, photocatalytic degradation of reactive black-5 (RB-5) dye was investigated using supported TiO₂ photocatalyst based adsorbent as a semiconductor photocatalyst in a batch reactor. The synthesized photocatalyst composition was developed using TiO₂ as photoactive component and zeolite (ZSM-5) as the adsorbents. Attempts were also made to optimize the composition of the supported catalyst and to study the reliability of prepared catalyst. The optimum formulation of supported catalyst was found to be (TiO₂: ZSM-5 = 0·15:1) which gave the highest efficiency with 98% degradation of 50 mg/L RB-5 solution in 90 min. Effect of different parameters such as initial concentration of dye solution, catalyst amount on the rate of photodegradation was also studied. The reduction in the chemical oxygen demand (COD, 88%) proves the mineralization of the RB-5 dye along with the colour removal. The supported TiO₂ was found to be stable for repeated use.     

Impregnation of ZnO onto activated carbon under hydrothermal conditions and its photocatalytic properties

Zinc oxide photocatalyst was impregnated onto the activated carbon under mild hydrothermal conditions (T=150°C, P = 20–30 bars) to form a ZnO:AC composite material. The ZnO:AC composite was characterized using powder X-ray diffraction (XRD), Fourier infrared spectroscopy (FTIR), BET surface area measurements and scanning electron microscopy (SEM). As-prepared ZnO:AC composite exhibited higher photocatalytic activity when compared to the commercial ZnO and untreated activated carbon; this was testified by the degradation of acid violet dye using ZnO:AC and commercial ZnO. The effect of various parameters such as initial dye concentration, catalyst loading, pH of the medium, source and intensity of illumination on the photocatalytic degradation of acid violet using ZnO:AC were investigated. Real time textile effluents have also been considered for the degradation using ZnO:AC composites. The reduction in the chemical oxygen demand (COD) values of the treated effluents revealed a complete destruction of the organic molecules along with the color removal.     

Effects of Ni doping on photocatalytic activity of TiO<Subscript>2</Subscript> thin films prepared by liquid phase deposition technique

The TiO₂ thin films doped by Ni uniformly and non-uniformly were prepared on glass substrate from an aqueous solution of ammonium hexa-fluoro titanate and NiF₂ by liquid phase deposition technique. The addition of boric acid as an F ⁻ scavenger will shift the equilibrium to one side and thereby deposition of the film is progressed. The rate of the reaction and the nature of deposition depend on growing time and temperature. The resultant films were characterized by XRD, EDAX, UV and SEM. The result shows that the deposited films have amorphous background, which becomes crystalline at 500°C. The EDAX data confirms the existence of Ni atoms in TiO₂ matrix. XRD analysis reveals the peaks corresponding to Ni but no peak of crystalline NiO was found. The transmittance spectra of Ni uniformly and non-uniformly doped TiO₂ thin films show ‘blue shift and red shift’, respectively. Ni-doped TiO₂ thin films can be used as photocatalyst for the photodegradation of methyl orange dye. It was found that, organic dye undergoes degradation efficiently in presence of non-uniformly Ni-doped TiO₂ thin films when compared to uniformly doped films and pure TiO₂ films under visible light. The photocatalytic activity increases with increase in the concentration of Ni in case of nonuniformly doped thin films but decreases with the concentration when uniformly doped thin films were used.     

On the synthesis,characterization and photocatalytic applications of nanostructured TiO<Subscript>2</Subscript>

Nanocrystalline semiconducting materials are attracting much attention due to their potential applications in solar energy conversion, nonlinear optics, and heterogeneous photocatalysis. In the present investigation, we have synthesized nanostructured TiO₂ photocatalysts, which have been used in the photocatalytic degradation of phenol (one of the most common water pollutants). These catalysts have been prepared through sol-gel technique using titanium tetra-isopropoxide as a raw material for synthesis. Characterization techniques such as XRD, SEM and TEM have been employed for structural/microstructural investigations. XRD results show that the as synthesized TiO₂ nanopowder exhibit anatase phase, TiO₂. The average sizes of the TiO₂ nanopowders are ∼ 5–10 nm. The optical properties of the samples were investigated through UV-visible and fluorescence techniques. It has been observed that absorption edge corresponds to ∼ 410 nm (bandgap, ∼ 3.02 eV). The emission peak in the fluorescence spectrum at ∼ 418 nm corresponds to the bandgap energy of ∼ 2.97 eV. Concentration of phenol (initial concentration, ∼ 100 ppm) with illumination time was monitored by measuring the absorbance of pure and illuminated phenol through UV-visible spectrophotometer. Salient feature of this study relates to the fact that the present sol-gel synthesized TiO₂ nanopowders have been found to be better photocatalysts for phenol degradation than the presently employed commercial TiO₂ (P-25, Degussa) photocatalyst. Thus, whereas phenol concentration, with the presently synthesized TiO₂ nanopowders, the concentration of phenol decreases up to ∼ 32% but for commercial TiO₂ nanopowder (P-25, Degussa), it decreased only up to ∼ 25%. The improved surface area is considered as an important factor for the aforesaid decrease in phenol concentration.     

Treatment of nano-sized rutile TiO<Subscript>2</Subscript> powder in hydrogen peroxide under microwave irradiation and investigation on its sonocatalytic activity

In this work, a novel nano-sized mixed-crystal TiO₂ catalyst was obtained under microwave irradiation in hydrogen peroxide solution and its sonocatalytic activity was also investigated through degradation of congo red dye. It was found that the sonocatalytic degradation effect of congo red using nano-sized mixed-crystal TiO₂ powder was much higher than that using pure nano-sized rutile phase TiO₂ powder. At last, the congo red dyes in aqueous solution were degraded completely and became some simple inorganic ions such as NO₃⁻, SO₄²⁻ and so on. The experiments indicated that the degradation method using such treated nano-sized rutile TiO₂ powder as sonocatalyst could be used to treat those non- or low-transparent wastewaters effectively. The article is published in the original.     

The optical properties of nanoporous structured titanium dioxide and the photovoltaic efficiency on DSSC

This study examined the characterization of nanoporous structured titanium dioxide and its application to dye-sensitized solar cells (DSSCs). TEM revealed nanopore sizes of 10.0 nm with a regular hexagonal form. When nanoporous structured TiO₂ was applied to DSSC, the energy conversion efficiency was enhanced considerably compared with that using nanometer sized TiO₂ prepared using a hydrothermal method. The energy conversion efficiency of the DSSC prepared from nanoporous structured TiO₂ was approximately 8.71% with the N719 dye under 100 mW cm⁻² simulated light. FT-IR spectroscopy showed that the dye molecules were attached perfectly to the surface and more dye molecules were absorbed on the nanoporous structured TiO₂ than on the nano-sized TiO₂ particles prepared using a conventional hydrothermal method. Electrostatic force microscopy (EFM) showed that the electrons were transferred rapidly to the surface of the nanoporous structured TiO₂ film.     

An investigation on synthesis and photocatalytic activity of polyaniline sensitized nanocrystalline TiO<Subscript>2</Subscript> composites

Polyaniline (PAn) sensitized nanocrystalline TiO₂ composite photocatalyst (PAn/TiO₂) with high activity and easy separation was facilely prepared by in situ chemical oxidation of aniline from the surfaces of the TiO₂ nanoparticles. The morphology, structure, and light absorption properties of composite photocatalyst were examined in term of its application to photocatalysis. The photocatalytic activity of PAn/TiO₂ nanocomposites for the degradation of methylene blue (MB) aqueous solution was investigated and compared with pure TiO₂. The spectra analyses illustrated that, when PAn deposited on the surface of TiO₂, the crystalline behavior of PAn was hampered and the degree of crystallinity decreased, and the characteristic peaks of the PAn were shifted indicating that there was a strong interaction between PAn and TiO₂ nanoparticles. PAn was able to sensitize TiO₂ efficiently and the composite photocatalyst could be activated by absorbing both the ultraviolet and visible light (λ = 190–800 nm), whereas pure TiO₂ absorbed ultraviolet light only (λ < 400 nm). Photocatalytic experiments showed that under natural light irradiation, MB could be degraded more efficiently on the PAn/TiO₂ than on the pure TiO₂, due to the charge transfer from PAn to TiO₂ and efficient separation of e⁻-h⁺ pairs on the interface of PAn and TiO₂ in the excited state. More significantly, the PAn/TiO₂ composite photocatalyst exhibited easy separation and less deactivation after several runs. The advantages of the obtained PAn/TiO₂ composite photocatalyst revealed its great practical potential in wastewater treatment.     

Fabrication of SiO<Subscript>2</Subscript>/TiO<Subscript>2</Subscript> double layer thin films with self-cleaning and photocatalytic properties

Transparent antireflective SiO₂/TiO₂ double layer thin films were prepared using a sol–gel method and deposited on glass substrate by spin coating technique. Thin films were characterized using XRD, FE-SEM, AFM, UV–Vis spectroscopy and water contact angle measurements. XRD analysis reveals that the existence of pure anatase phase TiO₂ crystallites in the thin films. FE-SEM analysis confirms the homogeneous dispersion of TiO₂ on SiO₂ layer. Water contact angle on the thin films was measured by a contact angle analyzer under UV light irradiation. The photocatalytic performance of the TiO₂ and SiO₂/TiO₂ thin films was studied by the degradation of methylene blue under UV irradiation. The effect of an intermediate SiO₂ layer on the photocatalytic performance of TiO₂ thin films was examined. SiO₂/TiO₂ double layer thin films showed enhanced photocatalytic activity towards methylene blue dye.     

Optimization of TiO<Subscript>2</Subscript>/MWCNT composites for efficient dye sensitized solar cells

This paper deals with the effects of introducing multiwall carbon nanotubes (MWCNTs) into photoanodes of dye sensitized solar cells (DSSCs). Mesoporous titanium dioxide (TiO₂) nanoparticles were synthesized using sol–gel technique. TiO₂/MWCNT composites were prepared by adding functionalized MWCNTs to TiO₂ nanoparticles using two different surfactants (α-terpineol and Triton X-100). Nanoparticles and composites were characterized using Dynamic Light Scattering spectrophotometer, Raman spectrometer, X-ray diffractometer, field emission scanning electron microscope, Brunauer–Emmett–Teller surface area analyzer and UV–Vis spectrophotometer. FESEM depicted that particles were spherical in shape and their size decreased due to addition of MWCNTs. This was attributed to the decrease in the crystallite size which in turn confirmed by XRD. UV–Vis absorption spectra showed the better absorbance for the visible range of light, as the content of MWCNT is increased. From the Tauc plot optical band gap was calculated and noted that it declined gradually with the content of MWCNTs. BET surface area increased drastically which was attributed to the formation of more number of pores in the nanocomposites as visualized from FESEM. UV–Vis spectra of dye desorbed from the photoanode revealed that the dye adsorption increased as a function of MWCNT wt%. I–V studies were carried out under the illumination of 100 mW/cm² simulated sunlight. Photoanodes prepared by both the methods showed better performance compared to pristine TiO₂ photoanode, because of high conducting path and high surface area provided by MWCNTs. Photoanodes with 0.19 wt% MWCNTs in them were able to achieve maximum efficiency of 3.54 and 3.86% for method A and B respectively.     

Evaluation of magnetic nanoparticles performance as photocatalyst for the catalytic treatment of direct red 28 dye in synthetic and real water effluents

Integrated water resources management practice is gaining popularity as an alternative water source due to the limited supply of freshwater. The present study was carried out on the photocatalytic degradation of Direct red 28 (DR-28) dye using magnetic nanoparticles (MNPs; Fe₃O₄) as a photocatalyst. The study was conducted on the photocatalytic degradation of DR-28 dye in synthetic dye effluent water, to understand the effects of different photoreaction parameters on the degradation kinetics. The influence of different parameters such as time, amount of photocatalyst, concentration of H₂O₂ and pH was investigated. At the optimum dosage of MNPs (0.6?g/L) with 4?mmol/L of H₂O₂, significant photocatalytic degradation of DR-28 dye (93.2%) was observed. The kinetic study revealed that the photocatalytic degradation followed pseudo-first-order kinetics. The degradation performance of Fe₃O₄ nanoparticles as a photocatalyst for DR-28 dye was compared with titanium dioxide (TiO₂) and it was found that the performance of Fe₃O₄ as a photocatalyst is superior to TiO₂ photocatalyst. The real dye effluent was also degraded at optimum conditions and promising results were achieved.     

Scalable production of ultra small TiO2 nano crystal/activated carbon composites by atomic layer deposition for efficient removal of organic pollutants

A high surface area photo-catalytic composite material is synthesized by depositing thin films of titanium dioxide (TiO₂) on activated carbon (AC) particles using atomic layer deposition (ALD). A rotary ALD reactor is developed for scalable fabrication of powder and grams of the catalyst is prepared in each batch. The processes of TiO₂ ALD are monitored by mass spectrometry. Saturated ALD surface reactions are confirmed so that the entire surface of the AC support is covered by conformal coatings of TiO₂. For composites fabricated by 3 or more ALD cycles of TiO₂, the amorphous oxide layers can be converted to crystalline films by high temperature annealing. The as-prepared TiO₂/AC composites are highly reactive in photo-catalyzed degradation of methyl orange. The excellent catalytic performance is attributed to the abundant and uniformly dispersed active phase, formation of very active ultra small (<5 nm) TiO₂ crystals, and easy accessibility of the active sites.     

Solar photocatalytic degradation of rhodamine B by heat-treated nanometer anatase TiO<Subscript>2</Subscript> powder

The partial phase transformation of nanometer TiO₂ powder from anatase to rutile was realized by heat-treatment, and then a novel photocatalyst which could utilize solarlight was obtained. The heat-treated nanometer TiO₂ powders at different transition stage were characterized by XRD, TEM and UV-vis spectra. In addition, the photocatalytic activity of heat-treated nanometer TiO₂ powder was tested out through the degradation of Rhodamine B dye in aqueous solution under solarlight irradiation. The results reveal that the nanometer anatase TiO₂ powder heat-treated at 500°C for 80 min exhibites the highest photocatalytic activity. That is, Rhodamine B dye can effectively degraded under solarlight irradiation in the presence of heat-treated nanometer TiO₂ powder.     

Preparation,characterization and photocatalytic activity of TiO<Subscript>2</Subscript> / Methylcellulose nanocomposite films derived from nanopowder TiO<Subscript>2</Subscript> and modified sol–gel titania

TiO₂—methylcellulose (MC) nanocomposite films processed by the sol-gel technique were studied for phocatalytic applications. Precalcined TiO₂ nanopowder was mixed with a sol and heat treated. The sol suspension was prepared by first adding titanium tetra isopropoxide (Ti(OPr)₄ or TTP) to a mixture of ethanol and HCl (molar ratio TTP:HCl:EtOH:H₂O = 1:1.1:10:10) and then adding a 2 wt.% solution of methylcellulose (MC). The TiO₂ nanopowder was dispersed in the sol and the mixture was deposited on a microscope glass slide by spin coating. Problems of film inhomogeneity and defects which caused peeling and cracking during calcinations, because of film shrinkage, were overcome by using MC as a dispersant. Effect of MC on the structure evaluation, crystallization behavior and mechanical integrity with thermal treatment up to 500 °C are followed by SEM, XRD and scratch test. XRD Scanning electron microscopy (SEM) showed that the composite films with MC have much rougher surface than films made without MC. Composite films heat treated at approximately 500 °C have the greatest hardness values. For the composite thick film, the minimum load which caused the complete coating removal was 200 g/mm², an indication of a strong bond to the substrate. Photocatalytic activities of the composite film were evaluated through the degradation of a model pollutant, the textile dye, Light Yellow X6G (C.I. Reactive Yellow 2) and were compared with the activity of (i) a similar composite film without MC, and (ii) a TiO₂ nanopowder. The good mechanical integrity make this composite film an interesting candidate for practical catalytic applications.     

Functionalization of electrospun magnetically separable TiO<Subscript>2</Subscript>-coated SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript> nanofibers: strongly effective photocatalyst and magnetic separation

Magnetically separable TiO₂-coated SrFe₁₂O₁₉ electrospun nanofibers were obtained successfully by means of sol–gel, electrospinning, and coating technology, followed by heat treatment at 550–650 °C for 3 h. The average diameter of the electrospun fibers was 500–600 nm. The fibers were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscope (TEM), and vibrating sample magnetometer (VSM). The optimized calcining temperature was determined by XRD and the analysis of decolorizing efficiency of methylene blue (MB) under UV–vis irradiation. The photocatalytic activity of the TiO₂-coated SrFe₁₂O₁₉ fibers was investigated using ultraviolet–visible absorbance by following the photooxidative decomposition of a model pollutant dye solution, MB in a photochemical reactor. In contrast to pure TiO₂ fibers, the TiO₂-coated SrFe₁₂O₁₉ fibers have higher absorption in 250–750 nm wavelength regions. The presence of SrFe₁₂O₁₉ not only broadened the response region of visible-light, but also enhanced the absorbance for UV light. The decolorizing efficiency of MB under UV–vis irradiation was up to 98.19%, which was a little higher than that of Degussa P25 (97.68%). Furthermore, these fibers could be recollected easily with a magnet in a photocatalytic process and had effectively avoided secondary pollution of treated water.     

Synthesis of highly-active single-crystalline TiO2 nanorods and its application in environmental photocatalysis

Highly-active anatase TiO₂ nanorods have been successfully synthesized via a simple two-step method, hydrothermal treatment of anatase/rutile titanium dioxide nanoparticle powder in a composite-hydroxide eutectic system of 1:1 M KOH/NaOH, followed by acid post-treatment. The morphology and crystalline structure of the obtained nanorods were characterized using XRD, TEM, SEM/EDX and BET surface area analyzer. The obtained TiO₂ nanorods have a good crystallinity and a size distribution (about 4-16 nm); with the dimensions of 200-300 nm length and of 30-50 nm diameter. Compared with its precursor anatase/rutile TiO₂ nanoparticles and the titanate nanotubes, the pure anatase TiO₂ nanorods have a large specific surface area with a mesoporous structure. The photocatalytic performance of the prepared nanorods was tested in the degradation of the commercial Cibacrown Red (FN-R) textile dye, under UV irradiation. Single-crystalline anatase TiO₂ nanorods are more efficient for the dye removal.     

Synthesis of nanocrystalline TiB<Subscript>2</Subscript> powder from TiO<Subscript>2</Subscript>, B<Subscript>2</Subscript>O<Subscript>3</Subscript> and Mg reactants through microwave-assisted self-propagating high-temperature synthesis method

In this research work, microwave-assisted self-propagating high-temperature synthesis (SHS) process was employed for the fabrication of titanium diboride (TiB₂) compound from TiO₂–B₂O₃–Mg mixtures. Thermodynamic evaluations of this system and its relevant subsystems revealed that TiB₂–MgO composite powder can be easily produced by a SHS reaction. However, experimental results of a TiO₂ : B₂O₃ : 5Mg mixture heated in a domestic oven showed the formation of some intermediate compounds such as Mg₃B₂O₆, presumably due to some degree of Mg loss. The optimum amount of Mg in TiO₂ : B₂O₃ : xMg mixtures, yielding the highest amount of TiB₂ phase, was found to be around 7 mol, i.e., 40 mol% more than the stoichiometric amount. Experimental results revealed that a pure TiB₂ compound could be obtained by leaching the unwanted by-products in an HCl acid solution. Scanning electron microscopic observations and Scherrer calculations showed that the produced TiB₂ contains sub-micron (150–200 nm) particles, where each particle consists of a number of nanosized (32 nm) crystallites.     

Photo-catalytic degradation of toxic dye amaranth on TiO2/UV in aqueous suspensions

The photo-catalytic degradation of an azo dye − Amaranth (AM) - has been investigated in TiO₂/UV aqueous suspensions. The results obtained from the experiments during H₂O₂/TiO₂ addition show that the highest decolorization rate is provided by the combination of (UV + TiO₂ + H₂O₂). The decolorization efficiencies were 17%, 26%, 38% and 64% in the runs UV, UV + H₂O₂, UV + TiO₂ and (UV + TiO₂ + H₂O₂) after approximately 100 min illumination periods, respectively. The observed dye degradation rates followed pseudo-first order kinetics with respect to the substrate concentration under the experimental conditions used. Different experimental conditions, such as temperature, pH and presence of electron acceptor were investigated. The temperature effect was investigated at the range of 293-313 K and it was observed that decolorization rate increased by the increase in temperature. Chemical oxygen demand and dye absorbance of the photodegraded dye solution substantially decreased. Effect of pH was also investigated and it was observed that the lower the pH the higher the degradation. In addition, an enhancement in the photodegradation rate was observed by the addition of hydrogen peroxide as an electron acceptor. The adsorption trends of Amaranth at various initial concentrations followed the Langmuir isotherm trend. This work adds to the global discussion on the role of the advanced oxidation processes in water treatment.