Abstract: One-dimensional (1D) nanostructures like nanowires, nanotubes, and nanorods find variety of practical application owing to their unique physico-chemical properties. In this work, TiO2 nanowires were synthesized by direct oxidation of titanium particles in a unique microwave plasma jet reactor. The prepared TiO2 nanowires manifested the flexible features, and were characterized by using X-ray diffraction, Brunauer-Emmett-Teller (BET) surface area analyzer, UV-Visible and FTIR spectrophotometers, Scanning electron microscope, and Transmission electron microscope. Further, the photodegradation efficiency of these nanowires were tested against toxic organic dye like methylene blue (MB) and the results were compared with the commercial TiO2. It was found that TiO2 nanowires exhibited superior photocatalytic performance (89%) as compared to commercial TiO2 (75%) after 60 min of reaction. This is attributed to the lower recombination rate and increased interfacial charge transfer in TiO2 nanowire. Pseudo-first order kinetic modelling performed with the experimental results revealed that the rate constant of photodegradation in case of TiO2 nanowire was 1.3 times higher than that of commercial TiO2. Superoxide radical (O2˙−) was found to be the major contributor in the photodegradation mechanism. Based on the trapping experiments, a plausible mechanism of the photocatalytic reaction is discussed.
Abstract: Phenol is a hazardous material found in many industrial wastewaters. Photocatalytic degradation and furthermore catalyst doping are promising techniques in purpose of effective phenol removal, which have been studied comprehensively in this decade. In this study, Fe, Cr codoped TiO2 were prepared by sol-gel method, and its photocatalytic activity was investigated through degradation of phenol under visible light. The catalyst was characterized by XRD, SEM, FT-IR, BET, and EDX. The results showed that nanoparticles possess anatase phase, and the average size of nanoparticles was about 21 nm. Also, photocatalyst has significant surface area. Effect of experimental parameters such as pH, irradiation time, pollutant concentration, and catalyst concentration were investigated by using Design-Expert® software. 98% of phenol degradation was achieved after 6h of irradiation.
Abstract: Solar-light activated titanium dioxide photocatalysts were prepared by hydrolysis of titanium (IV) isopropoxide with thiourea, followed by calcinations at 450 °C. The experiments demonstrated that methyl orange in aqueous solutions were successfully degraded under solar light using doped TiO2. The photocatalytic oxidation of a mono azo methyl-orange dye has been investigated in multi ion doped TiO2 and solar light. Solutions were irradiated by solar-light until high removal was achieved. It was found that there was no degradation of methyl orange in the dark and in the absence of TiO2. Varieties of laboratory prepared TiO2 catalysts both un-doped and doped using titanium (IV) isopropoxide and thiourea as a dopant were tested in order to compare their photoreactivity. As a result, it was found that the efficiency of the process strongly depends on the working conditions. The highest degradation rate of methyl orange was obtained at optimum dosage using commercially produced TiO2. Our work focused on laboratory synthesized catalyst and the maximum methyl orange removal was achieved at 81% with catalyst loading of 0.04 g/L, initial pH of 3 and methyl orange concentration of 0.005 g/L using multi-ion doped catalyst. The kinetics of photocatalytic methyl orange dye stuff degradation was found to follow a pseudo-first-order rate law. The presence of the multi-ion dopant (thiourea) enhanced the photoefficiency of the titanium dioxide catalyst.
Abstract: Organic compounds in wastewaters coming from textile and pharmaceutical industry generated multiple harmful effects on the environment and the human health. One of them is the methyl orange (MeO), an azoic dye considered to be a recalcitrant compound. The heterogeneous photocatalysis emerges as an alternative for treating this type of hazardous compounds, through the generation of OH radicals using radiation and a semiconductor oxide. According to the author’s knowledge, catalysts such as TiO2 doped with metals show high efficiency in degrading MeO; however, this presents economic limitations on industrial scale. Black sand can be considered as a naturally doped catalyst because in its structure is common to find compounds such as titanium, iron and aluminum oxides, also elements such as zircon, cadmium, manganese, etc. This study reports the photocatalytic activity of the mineral black sand used as semiconductor in the discoloration of MeO by oxidation and reduction photocatalytic techniques. For this, magnetic composites from the mineral were prepared (RM, M1, M2 and NM) and their activity were tested through MeO discoloration while TiO2 was used as reference. For the fractions, chemical, morphological and structural characterizations were performed using Scanning Electron Microscopy with Energy Dispersive X-Ray (SEM-EDX), X-Ray Diffraction (XRD) and X-Ray Fluorescence (XRF) analysis. M2 fraction showed higher MeO discoloration (93%) in oxidation conditions at pH 2 and it could be due to the presence of ferric oxides. However, the best result to reduction process was using M1 fraction (20%) at pH 2, which contains a higher titanium percentage. In the first process, hydrogen peroxide (H2O2) was used as electron donor agent. According to the results, black sand mineral can be used as natural semiconductor in photocatalytic process. It could be considered as a photocatalyst precursor in such processes, due to its low cost and easy access.
Abstract: A systematic study was conducted to explore the photocatalytic reduction of carbon dioxide (CO2) into methanol on TiO2 loaded copper ferrite (CuFe2O4) photocatalyst under visible light irradiation. The phases and crystallite size of the photocatalysts were characterized by X-ray diffraction (XRD) and it indicates CuFe2O4 as tetragonal phase incorporation with anatase TiO2 in CuFe2O4/TiO2 hetero-structure. The XRD results confirmed the formation of spinel type tetragonal CuFe2O4 phases along with predominantly anatase phase of TiO2 in the CuFe2O4/TiO2 hetero-structure. UV-Vis absorption spectrum suggested the formation of the hetero-junction with relatively lower band gap than that of TiO2. Photoluminescence (PL) technique was used to study the electron–hole (e−/h+) recombination process. PL spectra analysis confirmed the slow-down of the recombination of electron–hole (e−/h+) pairs in the CuFe2O4/TiO2 hetero-structure. The photocatalytic performance of CuFe2O4/TiO2 was evaluated based on the methanol yield with varying amount of TiO2 over CuFe2O4 (0.5:1, 1:1, and 2:1) and changing light intensity. The mechanism of the photocatalysis was proposed based on the fact that the predominant species of CO2 in aqueous phase were dissolved CO2 and HCO3- at pH ~5.9. It was evident that the CuFe2O4 could harvest the electrons under visible light irradiation, which could further be injected to the conduction band of TiO2 to increase the life time of the electron and facilitating the reactions of CO2 to methanol. The developed catalyst showed good recycle ability up to four cycles where the loss of activity was ~25%. Methanol was observed as the main product over CuFe2O4, but loading with TiO2 remarkably increased the methanol yield. Methanol yield over CuFe2O4/TiO2 was found to be about three times higher (651 μmol/gcat L) than that of CuFe2O4 photocatalyst. This occurs because the energy of the band excited electrons lies above the redox potentials of the reaction products CO2/CH3OH.
Abstract: In recent years, visible-light activated photocatalysis has become a major field of intense researches for the higher efficiency of solar energy utilizations. Many attempts have been made on the modification of wide band gap semiconductors, while more and more efforts emphasize on cost-effective synthesis of visible-light activated catalysts. In this work, BiOBr nanoplates with band gap of visible-light range are synthesized through a promising microwave solvothermal method. The treatment time period and temperature dependent BiOBr nanosheets of various particle sizes are investigated through SEM. BiOBr synthesized under the condition of 160°C for 60 mins shows the most uniform particle sizes around 311 nm and the highest surface-to-volume ratio on account of its smallest average particle sizes compared with others. It exhibits the best photocatalytic behavior among all samples in RhB degradation.
Abstract: Carbon dioxide (CO2) emission to the environment is inevitable which is responsible for global warming. Photocatalytic reduction of CO2 to fuel, such as methanol, methane etc. is a promising way to reduce greenhouse gas CO2 emission. In the present work, Bi2S3/CdS was synthesized as an effective visible light responsive photocatalyst for CO2 reduction into methanol. The Bi2S3/CdS photocatalyst was prepared by hydrothermal reaction. The catalyst was characterized by X-ray diffraction (XRD) instrument. The photocatalytic activity of the catalyst has been investigated for methanol production as a function of time. Gas chromatograph flame ionization detector (GC-FID) was employed to analyze the product. The yield of methanol was found to increase with higher CdS concentration in Bi2S3/CdS and the maximum yield was obtained for 45 wt% of Bi2S3/CdS under visible light irradiation was 20 μmole/g. The result establishes that Bi2S3/CdS is favorable catalyst to reduce CO2 to methanol.
Abstract: Ultraviolet photocatalytic oxidation (UV-PCO)
technology has been recommended as a green approach to health
indoor environment when it is integrated into mechanical ventilation
systems for inorganic and organic compounds removal as well as
energy saving due to less outdoor air intakes. Although much research
has been devoted to UV-PCO, limited information is available on the
UV-PCO behavior tested by the mixtures in literature. This project
investigated UV-PCO performance and by-product generation using a
single and a mixture of acetone and MEK at 100 ppb each in a
single-pass duct system in an effort to obtain knowledge associated
with competitive photochemical reactions involved in. The
experiments were performed at 20 % RH, 22 °C, and a gas flow rate of
128 m3/h (75 cfm). Results show that acetone and MEK mutually
reduced each other’s PCO removal efficiency, particularly negative
removal efficiency for acetone. These findings were different from
previous observation of facilitatory effects on the adsorption of
acetone and MEK on photocatalyst surfaces.
Abstract: Poly vinyl acetate (PVA)-based titania (TiO2)–carbon
nanotube composite nanofibers (PVA-TCCNs) with various
PVA-to-solvent ratios and PVA-based TiO2 composite nanofibers
(PVA-TN) were synthesized using an electrospinning process,
followed by thermal treatment. The photocatalytic activities of these
nanofibers in the degradation of airborne monocyclic aromatics under
visible-light irradiation were examined. This study focuses on the
application of these photocatalysts to the degradation of the target
compounds at sub-part-per-million indoor air concentrations. The
characteristics of the photocatalysts were examined using scanning
electron microscopy, X-ray diffraction, ultraviolet-visible
spectroscopy, and Fourier-transform infrared spectroscopy. For all the
target compounds, the PVA-TCCNs showed photocatalytic
degradation efficiencies superior to those of the reference PVA-TN.
Specifically, the average photocatalytic degradation efficiencies for
benzene, toluene, ethyl benzene, and o-xylene (BTEX) obtained using
the PVA-TCCNs with a PVA-to-solvent ratio of 0.3 (PVA-TCCN-0.3)
were 11%, 59%, 89%, and 92%, respectively, whereas those observed
using PVA-TNs were 5%, 9%, 28%, and 32%, respectively.
PVA-TCCN-0.3 displayed the highest photocatalytic degradation
efficiency for BTEX, suggesting the presence of an optimal
PVA-to-solvent ratio for the synthesis of PVA-TCCNs. The average
photocatalytic efficiencies for BTEX decreased from 11% to 4%, 59%
to 18%, 89% to 37%, and 92% to 53%, respectively, when the flow
rate was increased from 1.0 to 4.0 L min1. In addition, the average
photocatalytic efficiencies for BTEX increased 11% to ~0%, 59% to
3%, 89% to 7%, and 92% to 13%, respectively, when the input
concentration increased from 0.1 to 1.0 ppm. The prepared
PVA-TCCNs were effective for the purification of airborne aromatics
at indoor concentration levels, particularly when the operating
conditions were optimized.
Abstract: Thin ZnO films are deposited on glass substrates via
sol–gel method and dip-coating. The films are prepared from zinc
acetate dehydrate as a starting reagent. After that the as-prepared
ZnO sol is aged for different periods (0, 1, 3, 5, 10, 15 and 30 days).
Nanocrystalline thin films are deposited from various sols. The
effect ZnO sols aging time on the structural and photocatalytic
properties of the films is studied. The films surface is studied by
Scanning Electron Microscopy. The effect of the aging time of the
starting solution is studied in the photocatalytic degradation of
Reactive Black 5 (RB5) by UV-vis spectroscopy. The experiments
are conducted upon UV-light illumination and in complete darkness.
The variation of the absorption spectra shows the degradation of RB5
dissolved in water, as a result of the reaction, occurring on the surface
of the films and promoted by UV irradiation. The initial
concentrations of dye (5, 10 and 20 ppm) and the effect of the aging
time are varied during the experiments. The results show, that the
increasing aging time of starting solution with respect to ZnO
generally promotes photocatalytic activity. The thin films obtained
from ZnO sol, which is aged 30 days have best photocatalytic
degradation of the dye (97,22%) in comparison with the freshly
prepared ones (65,92%). The samples and photocatalytic
experimental results are reproducible. Nevertheless, all films exhibit
a substantial activity in both UV light and darkness, which is
promising for the development of new ZnO photocatalysts by sol-gel
method.
Abstract: Rhodamine B (RB) is a toxic dye used extensively in
textile industry, which must be remediated before its drainage to
environment. In the present study, supported gold nanoparticles on
commercially available titania and zincite were successfully prepared
and then their activity on the photodegradation of RB under UV A
light irradiation were evaluated. The synthesized photocatalysts were
characterized by ICP, BET, XRD, and TEM. Kinetic results showed
that Au/TiO2 was an inferior photocatalyst to Au/ZnO. This
observation could be attributed to the strong reflection of UV
irradiation by gold nanoparticles over TiO2 support.
Abstract: Microfibrous palygorskite and tubular halloysite clay mineral combined with nanocrystalline TiO2 are incorporating in the preparation of nanocomposite films on glass substrates via sol-gel route at 450oC. The synthesis is employing nonionic surfactant molecule as pore directing agent along with acetic acid-based sol-gel route without addition of water molecules. Drying and thermal treatment of composite films ensure elimination of organic material lead to the formation of TiO2 nanoparticles homogeneously distributed on the palygorskite or halloysite surfaces. Nanocomposite films without cracks of active anatase crystal phase on palygorskite and halloysite surfaces are characterized by microscopy techniques, UV-Vis spectroscopy, and porosimetry methods in order to examine their structural properties.
The composite palygorskite-TiO2 and halloysite-TiO2 films with variable quantities of palygorskite and halloysite were tested as photocatalysts in the photo-oxidation of Basic Blue 41 azo dye in water. These nanocomposite films proved to be most promising photocatalysts and highly effective to dye’s decoloration in spite of small amount of palygorskite-TiO2 or halloysite-TiO2 catalyst immobilized onto glass substrates mainly due to the high surface area and uniform distribution of TiO2 on clay minerals avoiding aggregation.
Abstract: Cu-mesoporous TiO2 is developed for removal acid
odor cooperated with ozone assistance and online- regeneration
system with/without UV irradiation (all weather) in study. The results
showed that Cu-mesoporous TiO2 present the desirable adsorption
efficiency of acid odor without UV irradiation, due to the larger
surface area, pore sizeand the additional absorption ability provided by
Cu. In the photocatalysis process, the material structure also benefits
Cu-mesoporous TiO2 to perform the more outstanding efficiency on
degrading acid odor. Cu also postponed the recombination of
electron-hole pairs excited from TiO2 to enhance photodegradation
ability. Cu-mesoporous TiO2 could gain the conspicuous increase on
photocatalysis ability from ozone assistance, but without any benefit
on adsorption. In addition, the online regeneration procedure could
process the used Cu-mesoporous TiO2 to reinstate the adsorption
ability and maintain the photodegradtion performance, depended on
scrubbing, desorping acid odor and reducing Cu to metal state.
Abstract: Laboratory experiments have been performed to investigate photocatalytic detoxification by using TiO2 photocatalyst for treating dairy effluent. Various operational parameters such as catalyst concentration, initial concentration, angle of tilt of solar flat plate reactor and flow rate were investigated. Results indicated that the photocatalytic detoxification process can efficiently treat dairy effluent. Experimental runs with dairy wastewater can be used to identify the optimum operational parameters to perform wastewater degradation on large scale for recycling purpose. Also effect of two different types of reactors on degradation process was analyzed.
Abstract: In our recent study, we have used ZnO nanoparticles assisted with UV light irradiation to investigate the photocatalytic degradation of Phenol Red (PR). The ZnO photocatalyst was characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), specific surface area analysis (BET) and UVvisible spectroscopy. X-ray diffractometry result for the ZnO nanoparticles exhibit normal crystalline phase features. All observed peaks can be indexed to the pure hexagonal wurtzite crystal structures, with the space group of P63mc. There are no other impurities in the diffraction peak. In addition, TEM measurement shows that most of the nanoparticles are rod-like and spherical in shape and fairly monodispersed. A significant degradation of the PR was observed when the catalyst was added into the solution even without the UV light exposure. In addition, the photodegradation increases with the photocatalyst loading. The surface area of the ZnO nanomaterials from the BET measurement was 11.9 m2/g. Besides the photocatalyst loading, the effect of some parameters on the photodegradation efficiency such as initial PR concentration and pH were also studied.
Abstract: New lead-free ferroelectric relaxor ceramics were
prepared by conventional solid-state synthesis in the BaTiO3-Bi2O3-
Y2O3 systems. Some of these ceramics present a ferroelectric relaxor
with transition temperature close to room temperature. These new
materials are very interesting for applications and can replace leadbased
ceramic to prevent the toxic pollutions during the preparation
state. In the other hand, the energy band diagram shows the
potentiality of these compounds for the solar energy conversion.
Thus, some compositions have been tested successfully for H2
production upon visible light. The best activity occurs in alkaline
media with a rate evolution of about 0.15 mL g-1 mn-1 and a quantum
yield of 1% under polychromatic light.
Abstract: ZnO nanocrystals with mean diameter size 14 nm
have been prepared by precipitation method, and examined as
photocatalyst for the UV-induced degradation of insecticide diazinon
as deputy of organic pollutant in aqueous solution. The effects of
various parameters, such as illumination time, the amount of
photocatalyst, initial pH values and initial concentration of
insecticide on the photocatalytic degradation diazinon were
investigated to find desired conditions. In this case, the desired
parameters were also tested for the treatment of real water containing
the insecticide. Photodegradation efficiency of diazinon was
compared between commercial and prepared ZnO nanocrystals. The
results indicated that UV/ZnO process applying prepared
nanocrystalline ZnO offered electrical energy efficiency and
quantum yield better than commercial ZnO. The present study, on the
base of Langmuir-Hinshelwood mechanism, illustrated a pseudo
first-order kinetic model with rate constant of surface reaction equal
to 0.209 mg l-1 min-1 and adsorption equilibrium constant of 0.124 l
mg-1.
Abstract: The photocatalytic activity efficiency of TiO2 for the degradation of Toluene in photoreactor can be enhanced by nano- TiO2/LDPE composite film. Since the amount of TiO2 affected the efficiency of the photocatalytic activity, this work was mainly concentrated on the effort to embed the high amount of TiO2 in the Polyethylene matrix. The developed photocatalyst was characterized by XRD, UV-Vis spectrophotometer and SEM. The SEM images revealed the high homogeneity of the deposition of TiO2 on the polyethylene matrix. The XRD patterns interpreted that TiO2 embedded in the PE matrix exhibited mainly in anatase form. In addition, the photocatalytic results show that the toluene removal efficiencies of 30±5%, 49±4%, 68±5%, 42±6% and 33±5% were obtained when using the catalyst loading at 0%, 10%, 15%, 25% and 50% (wt. cat./wt. film), respectively.
Abstract: A study concerning the photocatalytic decolourization
of Congo red (CR) dye, over artificial UV irradiation is presented.
Photocatalysts based on a commercial titanium dioxide (TiO2)
modified with transition metals (Ni, Cu and Zn) were used. The
dopage method used was wet impregnation. A TiO2 sample without
salt was subjected to the same hydrothermal treatment to be used as
reference. Congo red solutions to several pH conditions (natural and
basic) were used to evaluate photocatalytic performance of each
doped catalysts. Photodecolourization percentage was measured
spectrofotrometically after 3 h of treatment to 499 nm as response
variable. Kinetics investigations of photodegradation indicated that
reactions obey to Langmuir-Hinshelwood model and pseudo–first
order law. The rate constant studies of photocatalytic decolourization
reactions for Zn–TiO2 and Cu–TiO2 photocatalysts indicated that in
all cases the rate constant of the reaction was higher than that of TiO2
undoped. These results show that nature of the metal modifying the
TiO2 influence on the efficiency of the photocatalyst evaluated in
process. Ni does not present an additional effect compared with TiO2,
while Zn enhances the photoactivity due to its electronic properties.
Abstract: The accelerated sonophotocatalytic degradation of
Reactive Red (RR) 120 dye under visible light using dye sensitized
TiO2 activated by ultrasound has been carried out. The effect of
sonolysis, photocatalysis and sonophotocatalysis under visible light
has been examined to study the influence on the degradation rates by
varying the initial substrate concentration, pH and catalyst loading to
ascertain the synergistic effect on the degradation techniques.
Ultrasonic activation contributes degradation through cavitation
leading to the splitting of H2O2 produced by both photocatalysis and
sonolysis. This results in the formation of oxidative species, such as
singlet oxygen (1O2) and superoxide (O2
-●) radicals in the presence of
oxygen. The increase in the amount of reactive radical species which
induce faster oxidation of the substrate and degradation of
intermediates and also the deaggregation of the photocatalyst are
responsible for the synergy observed under sonication. A
comparative study of photocatalysis and sonophotocatalysis using
TiO2, Hombikat UV 100 and ZnO was also carried out.