Comparative study on the photodegradation of Indigo Caramine dye using commercial TiO<Subscript>2</Subscript> and natural rutile

The photocatalytic degradation of Indigo Caramine dye using commercial TiO₂ and fine grained natural rutile has been carried out. The commercial TiO₂ and natural rutile were characterized using powder X- ray diffraction (XRD) and Fourier transformed infra red spectroscopy (FTIR). The study on the photodegradation of Indigo Caramine dye using commercial TiO₂ and natural rutile were investigated both under Solar and UV irradiation. The degradation of Indigo Caramine dye was checked by the following parameters like Chemical Oxygen Demand (COD), %T, irradiation time and duration. In both cases using commercial TiO₂ and natural rutile, the COD of the dye solution was reduced from 288 mg/L to less than 20 mg/L, and similarly the %T was increased from 76% to 97% and the percentage decomposition upto 97% within the irradiation duration of 3.5 hrs. The preliminary results obtained on the photodegradation of Indigo Caramine dye are highly encouraging and further work is being carried out for the use of the natural rutile or anatase sources for the other organic decomposition and treatment of industrial effluents.     

Photocatalytic performance of TiO<Subscript>2</Subscript> and WO<Subscript>3</Subscript>/TiO<Subscript>2</Subscript> nanoparticles coated on urban green infrastructure materials in removing nitrogen oxide

This study investigated the performance of UV light active TiO₂ and UV–visible light active WO₃/TiO₂ nanoparticles as air purifying materials that can be potentially applied to urban green infrastructures such as rain gardens and pervious pavements. Using a laboratory-scale continuous gas flow photoreactor, the removal efficiency of gaseous nitrogen oxide (NO _x ) by two different photocatalytic nanoparticles coated on natural zeolites and pervious concrete blocks was evaluated. The results showed that the TiO₂- and WO₃/TiO₂-coated zeolites are excellent photoactive materials providing enhanced air purification function (~95% removal efficiency of NO _x ) under UV and UV–visible light irradiation, respectively. In contrast, both of the TiO₂- and WO₃/TiO₂-coated pervious concrete blocks showed a measurable NO _x removal (~60%) only under UV irradiation, whereas the visible light activity of the WO₃/TiO₂-coated concrete block was significantly reduced (~20%) mainly due to the decrease in the photocatalytic reaction sites for visible light. This study revealed the potential utility of photocatalytic nanoparticles in improving urban air quality, in the form of the surface component of various urban infrastructures.     

Visible light N-TiO<Subscript>2</Subscript>-induced photodegradation of Congo red: characterization,kinetics and mechanistic study

In this study, the photocatalytic degradation of Congo red has been investigated in N-doped TiO₂ (N-TiO₂) aqueous suspensions under visible light irradiation. Visible light-active N-TiO₂ was successfully prepared at three different weight contents (2.5, 5, and 7%) employing sol–gel method. It was able to harvest the visible irradiation with wavelength suitable for activation. X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectrometer, diffused reflectance UV–Vis spectroscopy, nitrogen adsorption Brunauer–Emmert–Teller, Raman spectroscopy, photoluminescence and X-ray photoelectron spectrometer were used to characterize the doped catalyst. The samples had a relatively large specific Brunauer–Emmert–Teller surface areas of about 42 m² g^?1 with average X-ray diffraction crystalline size of 52 nm and showed visible light photocatalytic activity at about 408 nm. The impacts of several operating parameters on the Congo red photodegradation process were examined. Langmuir–Hinshelwood model exhibited pseudo-first-order degradation kinetics. N-TiO₂-assisted plausible photodegradation mechanism has been suggested based on the qualitatively detected intermediate compounds.     

Photocatalytic treatment of oil and grease spills in wastewater using coated N-doped TiO<Subscript>2</Subscript> polyscales under sunlight as an alternative driving energy

To enhance the overall efficiency of oil and grease removal in wastewater coated N-doped TiO₂ photocatalytic polyscales were fabricated through sol–gel technique. The materials fabricated were characterized using powder X-ray diffraction, Fourier transmission infrared spectroscopy, scanning electron microscopy, and UV–Vis spectroscopy. In order to enhance degradation efficiency of organic pollutant under natural sun light, shifting of absorption range of TiO₂ to visible spectrum, various modifications such as surface modification and size optimization were carried out by doping of nitrogen under sol–gel processes. To ease recovery of suspended catalysts from aqueous media, the coated N-doped TiO₂ were prepared by decorating photocatalytic particles onto suitable substrates. N-doped TiO₂ polyscales with desired functionalities were coated onto the spherical supporting substrates using a binding agent. The photocatalytic treatment studies clearly indicated the considerable level of the oil and grease and other organic pollutants removal from wastewater (up to 85–90 % ± 2) using coated N-doped TiO₂ under natural sunlight as an alternative driving energy source. Removal of oil and grease along with other organic pollutants in wastewater using coated N-doped TiO₂ polyscales is a versatile, economical, and environmental friendly technique due to the ease of handling and recovery, utilization of natural sunlight which is renewable energy source.     

Study of photocatalytic degradation of environmentally harmful phthalate esters using Ni-doped TiO<Subscript>2</Subscript> nanoparticles

Undoped and Ni-doped TiO₂ nanoparticles are synthesized using sol–gel technique. The physical, structural, optical and thermal properties of the samples are investigated using X-ray powder diffraction, Fourier transform infrared spectroscopy, transmittance electron microscopy, UV–visible diffuse reflectance and thermogravimetric analysis. The photocatalytic activity of the samples is investigated by the photocatalytic degradation of phthalate esters. Phthalate esters have been considered as endocrine disrupting compounds. Ni-doped TiO₂ samples show better photocatalytic activity as compared to undoped TiO₂ sample. The greater photocatalytic activity of doped samples as compared to undoped TiO₂ can be attributed to the production of more number of electron–hole pairs in doped samples.     

Incorporation of chitosan and glass substrate for improvement in adsorption,separation, and stability of TiO<Subscript>2</Subscript> photodegradation

It is demonstrated that single titanium dioxide (TiO₂) has high potential for photodegradation of pollutants. However, it is still far from becoming an effective photocatalyst system, due to issues of adsorption process, separation, as well as dissolution. Therefore, this study highlights the high adsorption capacity, simplified separation, and the promising stability of TiO_2(SY) (synthesized via sol–gel method) photocatalyst, fabricated using chitosan–TiO_2(SY) and supported by glass substrate (Cs–TiO_2(SY)/glass substrate) photocatalysts. Chitosan (Cs), with abundant –R–NH and NH₂ groups, promotes the adsorption sites of methyl orange (MO) and OH groups for major attachment to TiO_2(SY). Meanwhile, the glass substrate increases stability and assists separation of the photocatalysts. Initially, nano-TiO_2(SY) has been characterized using high-resolution transmission electron microscope. Cs–TiO_2(SY)/glass substrate was fabricated via dip-coating. The distribution and interface between the photocatalytic components were characterized by Fourier transform infrared absorption spectroscopy, UV–Vis diffuse reflectance spectroscopy, field emission scanning electron microscopy, and energy-dispersive spectrometer. UV–Vis analysis of the multilayer photocatalyst (2, 4, 6, and 8 layers) was further carried out by the adsorption–photodegradation, with MO as model of pollutant. Seventy percent of the total removal of MO via optimized eight layers of photocatalyst was achieved within 1 h of UV irradiation. The adsorption photocatalyst achieved 50 % with no exposure to UV light for 15 min of irradiation. It is concluded that suitable photocatalytic conditions and sample parameters possessing the multilayer photocatalyst of Cs–TiO_2(SY) are beneficial toward the adsorption–photodegradation process in wastewater treatment.     

Photocatalytic activity evaluation of TiO<Subscript>2</Subscript> nanoparticles based on COD analyses for water treatment applications: a standardization attempt

Evaluation of the photocatalytic activities of TiO₂ nanomaterials based on the chemical oxygen demand (COD) analyses under identical experimental conditions was not previously reported. In this work, COD has been selected as an adequate industrial water quality measure toward the establishment of a representative standard test method. The initial COD values of six organic pollutants representing dye, surfactants, phenols and alcohol were set at 30 ± 2 mg/L. Ten of different commercial and synthesized TiO₂ samples representing anatase, rutile and mixed phases were used and characterized. The data of photocatalytic processes were compared to that obtained using the commonly widespread Degussa-P25 TiO₂ (TD). The COD of all pollutants was completely removed by TD at UV exposure dose ≤9.36 mWh/cm². Consequently, the maximum irradiation dose was set at this value in all experiments. The percentages of COD removal as well as the values of the accumulated UV doses required for complete removal of pollutants were measured using the different TiO₂ samples. TiO₂ samples show different performance abilities toward the various pollutants compared to TD. Based on the obtained data, TiO₂ photocatalysts were divided into two categories according to the hydroxyl radical formation rates. Comparison with previous studies reveals that the photocatalytic efficiency evaluation depends on the method of measurement. COD is recommended to be used as an adequate technique of analysis that meets the purpose of water treatment applications.     

Ag/TiO<Subscript>2</Subscript>/EP: a low-cost and floating plasmonic photocatalyst for degrading furfural under visible light irradiation

A low-cost visible light-driven silver/titanium oxide/expanded perlite (Ag/TiO₂/EP) as a floating plasmonic photocatalyst is fabricated by a simple hydrolysis method. Photocatalytic properties of Ag/TiO₂/EP have been studied by scanning electron microscope, X-ray diffraction, UV–Vis (DRS), EDAX, FTIR, chemiluminescence, photoluminescence and X-ray photoelectron spectroscopy methods. The photocatalytic activity of resulting Ag/TiO₂/EP with different Ag contents (3 and 5%) was evaluated by its ability to degrade furfural solution under visible light irradiation. The Ag/TiO₂/EP exhibits wide absorption in the visible light region and shows visible light-driven photocatalytic activities in furfural degradation compared with TiO₂/EP photocatalyst. The Ag/TiO₂/EP (5%) was the best concentration of photocatalyst dosage with almost 80% furfural degradation under visible light. The antibacterial character of Ag/TiO₂/EP with different Ag contents has been tested against Escherichia Coli under visible light. The photocatalytic activity of Ag/TiO₂/EP can be attributed to the plasmonic effect of silver in the separation of photoinduced electrons and holes in resulting photocatalyst. The Ag/TiO₂/EP (5%) as a floating photocatalyst combined with its ability to absorb visible light makes it of significant interest for the purification of industrial wastewater.     

Synthesis of rare earth-doped yttrium vanadate polyscale crystals and their enhanced photocatalytic degradation of aqueous dye solution

In this study, a series of RE³⁺:YVO₄ catalysts were successful synthesized by environmentally friendly mild hydrothermal and supercritical hydrothermal techniques. The rare earth-doped YVO₄ photocatalysts were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectroscopy, photoluminescence spectroscopy. The X-ray diffraction analysis reveals that the as-prepared YVO₄ crystals are of tetragonal phase. Further, the Fourier transform infrared spectroscopy result shows the absence of OH– molecules. The photoluminescence spectroscopy curves and UV–Vis spectra suggest that the band gap energy of YVO₄ is shifted to lower energy level due to doping of Nd³⁺ and Er³⁺ ions. The catalytic activities of the as-prepared RE³⁺:YVO₄ samples were tested for the photodegradation of amaranth aqueous dye solution under sunlight irradiation. Remarkably, the rare earth-doped YVO₄ nanocrystal sample showed outstanding photocatalytic degradation activities than undoped YVO₄ nanocrystal sample with good reusability. Under full spectrum irradiation, the as-prepared Nd³⁺-doped YVO₄ nanocrystals exhibited about 83% degradation efficiency. The apparent rate constant k for as-prepared Nd³⁺-doped YVO₄ nanocrystals with 50 mg of photocatalyst exhibits highest k value (0.32 min^?1), which is 2.9% higher than pure YVO₄ nanocrystals (0.11 min^?1).     

Response surface methodology (RSM) optimization approach for degradation of Direct Blue 71 dye using CuO–ZnO nanocomposite

The present study highlights the synthesis of CuO–ZnO nanocomposite via facile hydrothermal method at 150 °C and autogenous pressure. The structural and textural features of prepared composite material was characterized by several characterization techniques such as X-ray powder diffraction, Fourier transform infrared spectroscopy, Scanning electron microscopy, and energy-dispersive X-ray spectroscopy. The optimized prepared nanocomposite was utilized for photocatalytic degradation of aromatic Direct Blue 71 dye (DB71) under natural sunlight conditions. The catalytic activity results by CuO–ZnO nanocomposite were observed to be higher than the reagent-grade zinc oxide under visible light conditions. The response surface methodology protocol (RSM) with central composite design was optimized by different photodegradation operational parameters such as pH, dye concentration, catalyst amount, and reaction time. The optimized RSM results demonstrated that a quadratic polynomial model was found suitable to define the relation between the photocatalytic activity and operational parameters. Moreover, the observed high R ² value (0.9786) confirms a strong evaluation of experimental data. To achieve maximum DB71 degradation, optimized condition was found at 177.13 min of contact time, 3.93 solution pH, and 24.34 mg/L of dye concentration with 1.85 g/L of catalyst dose The identical optimum conditions resulted maximum 89.58% DB71 degradation.     

Photocatalytic degradation of azo dye Orange II in aqueous solutions using copper-impregnated titania

During dyeing process, industries consume large quantity of water and subsequently produce large volume of wastewater. This wastewater is rich in color and contains different dyes. Orange II is one of them. In this article, metal-impregnated TiO₂ P-25 catalyst was used to enhance the photocatalytic degradation of Orange II dye. Photodegradation percentage was followed spectrophotometrically by the measurements of absorbance at λ _max = 483 nm. The effect of copper-impregnated TiO₂ P-25 photocatalyst for the degradation of Orange II has been investigated in terms of percentage removal of color, chemical oxygen demand (COD) and total organic carbon (TOC). As such 98 % color removal efficiency, 97 % percentage removal of COD and 89 % percentage removal of TOC was achieved with TiO₂ P-25/Cu catalysts under typical conditions. Copper-impregnated TiO₂ P-25 photocatalyst showed comparatively higher activity than UV/H₂O₂ homogeneous photodegradation. The relative electrical energy consumption for photocatalytic degradation was considerably lower with TiO₂ P-25/Cu photocatalyst than that with homogeneous photodegradation. Transmission electron microscopic analysis was used for catalyst characterization.     

Photocatalytic degradation of imidacloprid in aqueous suspension of TiO<Subscript>2</Subscript> supported on H-ZSM-5

The composite of TiO₂ and zeolite H-ZSM-5 has great photocatalytic ability for organic contaminants over a very large specific surface area and highlighted adsorption capacity. To describe abiotic degradation of imidacloprid, the photoinduced degradation of the pesticide imidacloprid in aqueous solutions, in the presence of TiO₂ supported on H-ZSM-5 as photocatalyst, was performed. The study focused on the comparison of the imidacloprid degradation between photolysis and photocatalysis. The experimental results showed that the degradation of imidacloprid was more rapid in the condition of photocatalytic than that of photolysis or TiO₂-only. The identification of possible intermediate products during the degradation was investigated by the high-performance liquid chromatography coupled with electrospray time-of-flight mass spectrometry (HPLC/TOF-MS). The main photocatalytic products were identified as chloronictinic acid, 1-[(6-chloro-3-pyridinyl) methyl]-2-imidazolidinone and 1-[(6-chloro-3-pyridinyl) methyl]-N-nitroso-2-imidazolidimine.     

Transition metals (Mn,Ni, Co) doping in TiO<Subscript>2</Subscript> nanoparticles and their effect on degradation of diethyl phthalate

Transition metal-doped TiO₂ nanoparticles are synthesized by sol–gel method. The as-prepared samples are characterized by various techniques to correlate structural and optical properties with chemical nature of dopants and their effect on photocatalytic degradation of diethyl phthalate esters. X-ray diffraction (XRD) reveals that all the samples are crystalline and exhibit anatase as a major phase. Chemical nature of dopants could not affect the formation of anatase and its volume fraction. The crystallite size of undoped and doped TiO₂ nanoparticles varies between 10 and 12 nm as confirmed by XRD and transmission electron microscope. The lowest optical band gap observed is 2.47 eV in Mn-doped TiO₂. Among all the samples, Ni-doped TiO₂ sample shows better photocatalytic activity and degradation of diethyl phthalate due to its lower crystallite size and higher surface area than those of Mn- and Co-doped TiO₂ samples.     

Photodegradation of amaranth in aqueous solution catalyzed by immobilized nanoparticles of titanium dioxide

The use of suspensions of nanoparticles of titanium dioxide in photocatalytic degradation of dye solution has disadvantages of inconvenient separation of fine particles for reuse and limited penetration of light for effective degradation. These problems can be minimized by supporting titanium dioxide on various inert supports. The present study involves the preparation of immobilized titanium dioxide films by three different techniques and characterization of the prepared films. The immobilized films of nanocrystals of titanium dioxide were prepared using sol?Cgel technique, polyvinyl alcohol?Cformaldehyde binder and acrylic emulsion. The photocatalytic performance of the prepared films for degradation of amaranth dye has also been evaluated and compared. Combination of photodegradation and adsorption processes induces strong beneficial effects on removal of dyes. Addition of high adsorption capacity activated carbon to photoactive titanium dioxide in photodegradation of dyes improves the efficiency of dye mineralization. The activated carbon has also been immobilized along with titanium dioxide in the present work to examine the dual effect of photodegradation and adsorption in the removal of amaranth. The films formed with the help of polyvinyl alcohol?Cformaldehyde binder showed better dye degradation capabilities.     

Comparison of different phases of bismuth silicate nanofibers for photodegradation of organic dyes

Two different phases of bismuth silicate nanofibers [Bi₂SiO₅ and Bi₄(SiO₄)₃] were synthesized using electrospinning technique. BS nanofibers were tested for the photocatalytic degradation of methyl orange and safranin O dyes. Different phases of BS affect the photodegradation efficiency of nanofibers. Impressive enhancement in photocatalytic efficiency and BET surface area of Bi₄(SiO₄)₃ was observed over Bi₂SiO₅. A speedy reduction in dyes concentration was attributed to the rapid formation of oxygenated radicals by the capture of electrons and holes, generated in the BS nanofiber by UV irradiation. Therefore, the photocatalytic mechanism was elucidated using impedance spectroscopy at room temperature. The lower impedance value of Bi₄(SiO₄)₃ nanofibers had improved high-efficiency charge transfer capability. The cycling efficiency (30 times) and recovery characteristics pointed out that Bi₄(SiO₄)₃ nanofibers photocatalysts had high constancy, resilience, and regeneration ability.     

Photo-induced degradation of emamectin benzoate: effect of iron amendments and solvent system

Photodegradation is the major dissipation pathway for emamectin benzoate (EB) in water. Therefore, the photolysis of EB was studied in distilled water (DW) and methanol under different irradiation conditions such as natural sunlight, UV tube, and artificially stimulated light (mercury lamp 125 W). The results of the study showed that EB degrades rapidly in DW than in methanol as evidenced by a photodegradation efficiency of about 75 % achieved in DW, after 24 h of irradiation with UV light, while in methanol, it was only 59.3 %. The addition of iron to EB solution in DW further enhanced its photodegradation. The rate of photodegradation of EB was recorded to be increased from 5.5 × 10^?2 to 1.0 × 10^?1 k/h after amendment with iron. The order for the rate of photodegradation of EB was DW + Fe > DW > methanol, with their respective t _1/2 values of 6.5, 12.6, and 18.7 h. Fe amendment was also found to enhance the degradation efficiency of EB even in the absence of any light (dark).     

Facile synthesis of hexamine–silicotungstic acid hybrid and its photocatalytic activity toward degradation of dyes

A new organic hybrid of silicotungstic acid was prepared by means of an easily available, very cheap, and non-toxic amine via a facile precipitation method. Characterization of hybrid was carried out by elemental analyses, Fourier transform infrared spectroscopy, powder X-ray diffraction, thermogravimetric analysis, differential scanning calorimetry, and scanning electron microscopy. Dye adsorption and photocatalytic properties of the prepared water-insoluble hybrid were examined by studying the decolorization of model dyes such as methylene blue and methyl, orange and their mixture solutions under ultraviolet, visible, and sunlight irradiation. The effect of different factors containing the initial concentration, pH, catalyst dosage, H₂O₂ dosage, and salt adding was investigated on the decolorization of dyes. The results showed that the hybrid is a good heterogeneous photocatalyst in the degradation of methylene blue, methyl orange and their mixture and can be recovered and reused. The methylene blue is removed via combination of adsorption and photocatalytic degradation under ultraviolet, visible, and sunlight through direct oxidation by hybrid. The methyl orange is removed via ultraviolet and solar photocatalytic degradation through indirect oxidation by ^·OH radicals. While the visible light is not able to degrade methyl orange solution alone in the presence of hybrid, it degrades the methyl orange mixed with methylene blue solution.     

A novel continuous magnetic nano-Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/perlite fixed bed reactor for catalytic wet peroxide oxidation of dyes: reactor structure

In the present work, a continuous catalytic wet peroxide oxidation fixed bed reactor was employed to treat a simulated wastewater sample with malachite green dye, as a contaminant. Natural perlite particle-supported nano-Fe₃O₄ catalyst was used as a fixed bed inside a reactor, and it was immobilized by a persistent magnetic field. The range of (perlite) particle sizes was from 100 to 1000 nm. The effects of various operating parameters, including temperature of the reactor, pH, initial hydrogen peroxide concentration and initial dye concentration, were investigated on the percentage removal of malachite green dye. Load of catalyst of 2 g and volumetric flow rate of 1 L/h were selected for all the tests. Maximum malachite green degradation was 99.5 ± 0.3%. This removal percentage was attained at temperature of 80 °C, pH = 6, initial dye concentration of 6 mg/L and initial hydrogen peroxide concentration of 100 mg/L. The process was isotherm, and the catalyst showed high catalytic activity in the steady-state condition. The loss of catalyst was less than 0.3%.     

Temperature-jump induced cation exchange kinetics in (Co<Subscript>0.1</Subscript>Mg<Subscript>0.9</Subscript>)<Subscript>2</Subscript>SiO<Subscript>4</Subscript> olivine: an in situ optical spectroscopic study

In the olivine crystal structure, cations are distributed over two inequivalent octahedral sites, M1 and M2. Kinetics of cation exchange between the two octahedral sites in (Co_0.1Mg_0.9)₂SiO₄ single crystal have been studied in the temperature range from 600 to 800°C by monitoring the time evolution of the absorbance of Co²⁺ ions in M1 or M2 sites using optical spectroscopy after rapid temperature jumps. It was found from such temperature-jump induced relaxation experiments that with increasing temperature the absorbance of Co²⁺ ions in the M1 site decreases while that in the M2 site increases. This indicates a tendency of Co²⁺ cations to populate the M2 site with increasing temperatures and vice versa. The experimental relaxation data can be modeled using a triple exponential equation based on theoretical analysis. Activation energies of 221 ± 4 and 213 ± 10 kJ/mol were derived from relaxation experiments on the M2 site and M1 site, respectively, for the cation exchange processes in (Co_0.1Mg_0.9)₂SiO₄ olivine. Implications for cation diffusion at low temperatures are discussed.