Given that drugs and their degradation products are likely to occur as concoctions in wastewater, the degradation of a mixture of two nonsteroidal anti-inflammatory drugs (NSAIDs), diclofenac (DCF) and naproxen (NPX), was investigated by solar photolysis and titanium dioxide (TiO2)-mediated solar photocatalysis using an immersion-well photoreactor. An equimolar ratio (1:1) of both NSAIDs in distilled water, drinking water, and river water was subjected to solar degradation. Solar photolysis of the DCF and NPX mixture was competitive particularly in drinking water and river water, as both drugs have the ability to undergo photolysis. However, the addition of TiO2 in the mixture significantly enhanced the degradation rate of both APIs compared to solar photolysis alone. Mineralization, as measured by chemical oxygen demand (COD), was incomplete under all conditions investigated. TiO2-mediated solar photocatalytic degradation of DCF and NPX mixtures produced 15 identifiable degradants corresponding to degradation of the individual NSAIDs, while two degradation products with much higher molecular weight than the parent NSAIDs were identified by liquid chromatography mass spectrometry (LC-MS) and Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS). This study showed that the solar light intensity and the water matrix appear to be the main factors influencing the overall performance of the solar photolysis and TiO2-mediated solar photocatalysis for degradation of DCF and NPX mixtures.
The objective of this study was to examine the effects of adsorbability and number of sulfonate group on solar photocatalytic degradation of mono azo methyl orange (MO) and diazo Reactive Green 19 (RG19) in single and binary dye solutions. The adsorption capacity of MO and RG19 onto the TiO₂ was 16.9 and 26.8 mg/g, respectively, in single dye solution, and reduced to 5.0 and 23.1 mg/g, respectively, in the binary dye solution. The data obtained for photocatalytic degradation of MO and RG19 in single and binary dye solution were well fitted with the Langmuir-Hinshelwood kinetic model. The pseudo-first-order rate constants of diazo RG19 were significant higher than the mono azo MO either in single or binary dye solutions. The higher number of sulfonate group in RG19 contributed to better adsorption capacity onto the surface of TiO₂ than MO indicating greater photocatalytic degradation rate.
In this study, the zinc oxide (ZnO) layer was synthesised on the surface of Zn plates by three different techniques, i.e. electrolysis, hydrogen peroxide and heat treatment. The synthesised ZnO layers were characterised using scanning electron microscopy, X-ray diffraction, UV-visible diffuse reflectance and photoluminescence spectroscopy. The photocatalytic activity of the ZnO layer was further assessed against methylene blue (MB) degradation under UV irradiation. The photocatalytic degradation of MB was achieved up to 84%, 79% and 65% within 1 h for ZnO layers synthesised by electrolysis, heat and hydrogen peroxide treatment, respectively. The reusability results show that electrolysis and heat-treated ZnO layers have considerable photocatalytic stability. Furthermore, the results confirmed that the photocatalytic efficiency of ZnO was directly associated with the thickness and enlarged surface area of the layer. Finally, this study proved that the ZnO layers synthesised by electrolysis and heat treatment had shown better operational stability and reusability.
Graphene (Gr)/gold (Au) and graphene-oxide (GO)/Au nanocomposites (NCPs) were synthesized by performing pulsed-laser-induced photolysis (PLIP) on hydrogen peroxide and chloroauric acid (HAuCl4) that coexisted with Gr or GO in an aqueous solution. A 3-month-long aqueous solution stability was observed in the NCPs synthesized without using surfactants and additional processing. The synthesized NCPs were characterized using absorption spectroscopy, transmission electron microscopy, Raman spectroscopy, energy dispersive spectroscopy, and X-ray diffraction to prove the existence of hybrid Gr/Au or GO/Au NCPs. The synthesized NCPs were further evaluated using the photocatalytic reaction of methylene blue (MB), a synthetic dye, under UV radiation, visible light (central wavelength of 470 nm), and full spectrum of solar light. Both Gr/Au and GO/Au NCPs exhibited photocatalytic degradation of MB under solar light illumination with removal efficiencies of 92.1% and 94.5%, respectively.
Multiwall carbon nanotube (CNT)-filled high density polyethylene (HDPE) nanocomposites were prepared by extrusion and considered for their suitability in the offshore sheathing applications. Transmission electron microscopy was conducted to analyse dispersion after bulk extrusion. Monolithic and nanocomposite samples were subjected to accelerated weathering and photodegradation (carbonyl and vinyl indices) characterisations, which consisted of heat, moisture (seawater) and UV light, intended to imitate the offshore conditions. The effects of accelerated weathering on mechanical properties (tensile strength and elastic modulus) of the nanocomposites were analysed. CNT addition in HDPE produced environmentally resilient nanocomposites with improved mechanical properties. The energy utilised to extrude nanocomposites was also less than the energy used to extrude monolithic HDPE samples. The results support the mass substitution of CNT-filled HDPE nanocomposites in high-end offshore applications.
Solar photocatalysis is a green technology that takes advantage of sustainable solar energy for enhancing oxidation process of numerous harmful water contaminants. In this study, a custom solar driven zinc oxide (ZnO)-mediated photocatalytic system was developed and its efficiency to remove organic contaminants as well as to disinfect selected bacteria was investigated. Methylene blue (MB) dye was used as the model organic contaminant, while Escherichia coli(E.coli) was used as the model fecal coliform bacteria in contaminated water. A series of photodegradation experiments were conducted on water contaminated with either 10 mg/L of MB or ~1010CFU/ml of E.coli. The experiments were completed under sunlight irradiation in the presence of 1 g/L of nano ZnO photocatalyst for up to 6 hours. Using a solar thermal collector, the photoreactor operated in the temperature range of 25 to 50 oC. The findings revealed that the combination of solar thermal with solar photocatalysis usingZnO intensified the degradation of MB and disinfection of E.coli. 98.08% of MB dye and 99.99% of E.coliwere successfully removed from the water within the first 3 hours of treatment. Almost complete removal was eventually achieved after 6 hours of treatment. It is therefore suggested that ZnO-based solar photocatalytic system developed in this study is highly efficient at enhancing water decontamination process.
There are various approaches to enhancing the catalytic properties of TiO₂, including modifying its morphology by altering the surface reactivity and surface area of the catalyst. In this study, the primary aim is to enhance the photocatalytic activity by changing the TiO₂ nanotubes' architecture. The highly ordered infrastructure is favorable for a better charge carrier transfer. It is well known that anodization affects TiO₂ nanotubes' structure by increasing the anodization duration which in turn influence the photocatalytic activity. The characterizations were conducted by FE-SEM (fiend emission scanning electron microscopy), XRD (X-ray diffraction), RAMAN (Raman spectroscopy), EDX (Energy dispersive X-ray spectroscopy), UV-Vis (Ultraviolet visible spectroscopy) and LCMS/MS/MS (liquid chromatography mass spectroscopy). We found that the morphological structure is affected by the anodization duration according to FE-SEM. The photocatalytic degradation shows a photodegradation rate of k = 0.0104 min-1. It is also found that a mineralization of Simazine by our prepared TiO₂ nanotubes leads to the formation of cyanuric acid. We propose three Simazine photodegradation pathways with several intermediates identified.
Disposal of dye wastewater into water streams without treatment endangers human and marine lives. This work focused on the second largest class of textile dyes after azo dyes due to its high resistivity to biodegradation and high toxicity. The photocatalytic degradation of Reactive Blue 4 (RB4), an anthraquinone dye, has been investigated using pure anatase nano titanium (IV) oxide (TiO2). The dye molecules were fully degraded and the addition of hydrogen peroxide (H2O2) enhanced the photodegradation efficiency. It is found that the degradation as the hydroxyl radicals in the bulk solution is sufficient for complete mineralisation. The disappearance of the dye follows pseudo-first-order kinetics. The effect of pH, amount of photocatalyst, UV-light intensity, light source and concentration of hydrogen peroxide was ascertained.
Zinc oxide (ZnO) utilization in advanced oxidation process (AOP) via solar-photocatalytic process was a promising method for alternative treating wastewater containing phenol. The ZnO photocatalyst semiconductor was synthesized by sol-gel method. The morphology of the ZnO nanostructures was observed by using scanning electron microscope (SEM) and the crystallite phase of the ZnO was confirmed by x-ray diffraction (XRD). The objective of this study was to synthesis ZnO nanoparticles through a sol-gel method for application as a photocatalyst in the photodegradation of phenol under solar light irradiation. The photodegradation rate of phenol increased with the increasing of ZnO loading from 0.2 until 1.0 g. Only 2 h were required for synthesized ZnO to fully degrade the phenol. The synthesized ZnO are capable to totally degrade high initial concentration up until 45 mg L-1 within 6 h of reaction time. The photodegradation of phenol by ZnO are most favoured under the acidic condition (pH3) where the 100% removal achieved after 2 h of reaction. The mineralization of phenol was monitored through chemical oxygen demand (COD) reduction and 92.6% or removal was achieved. This study distinctly utilized natural sunlight as the sole sources of irradiation which safe, inexpensive; to initiate the photocatalyst for degradation of phenol.
The polyvinyl alcohol (PVA) and neem extract were grafted onto coupled oxides (3ZT-CO) via reflux process to stabilize the particles to form 3ZT-CO/PVA and 3ZT-CO/Neem. These were then incorporated into LLDPE by melt blending process to give LLDPE/3ZT-CO/PVA and LLDPE/3ZT-CO/Neem composites. The Neem and PVA stabilized particles showed high zeta potential and dispersed homogeneously in water. The stabilization process altered the shape of the particles due to plane growth along the (002) polar direction. The stabilizers acted as capping agents and initiated the one-dimensional growth. The alkyl chain groups from PVA increased the polarity of the LLDPE/3ZT-CO/PVA and played a dominant role in the water adsorption process to activate the photocatalytic activity. This was further enhanced by the homogeneous distribution of the particles and low degree of crystallinity (20.87%) of the LLDPE composites. LLDPE/3ZT-CO/PVA exhibited the highest photodegradation (93.95%), which was better than the non-stabilized particles. Therefore, the photocatalytic activity of a polymer composite can be enhanced by grafting PVA and neem onto couple oxides. The LLDPE/3ZT-CO/PVA composite was further used to treat textile effluent. The results showed the composite was able to remove dye color by 93.95% and to reduce biochemical oxygen demand (BOD) and chemical oxygen demand (COD) by 99.99%.
The objective of this study was to investigate several operating parameters, such as open circuit, different external resistance, pH, supporting electrolyte, and presence of aeration that might enhance the degradation rate as well as electricity generation of batik wastewater in solar photocatalytic fuel cell (PFC). The optimum degradation of batik wastewater was at pH 9 with external resistor 250 Ω. It was observed that open circuit of PFC showed only 17.2 ± 7.5% of removal efficiency, meanwhile the degradation rate of batik wastewater was enhanced to 31.9 ± 15.0% for closed circuit with external resistor 250 Ω. The decolorization of batik wastewater in the absence of photocatalyst due to the absorption of light irradiation by dye molecules and this process was known as photolysis. The degradation of batik wastewater increased as the external resistor value decreased. In addition, the degradation rate of batik wastewater also increased at pH 9 which was 74.4 ± 34.9% and at pH 3, its degradation rate was reduced to 19.4 ± 8.7%. The presence of aeration and sodium chloride as supporting electrolyte in batik wastewater also affected its degradation and electricity generation. The maximum absorbance of wavelength (λmax) of batik wastewater at 535 nm and chemical oxygen demand gradually decreased as increased in irradiation time; however, batik wastewater required prolonged irradiation time to fully degrade and mineralize in PFC system.
For the synthesis of a highly active TiO2-chitosan nanocomposite, pH plays a crucial role towards controlling its morphology, size, crystallinity, thermal stability, and surface adsorption properties. The presence of chitosan (CS) biopolymer facilitates greater sustainability to the photoexcited electrons and holes on the catalysts' surface. The variation of synthesis pH from 2 to 5 resulted in different physico-chemical and photocatalytic properties, whereby a pH of 3 resulted in TiO2-chitosan nanocomposite with the highest photocatalytic degradation (above 99 %) of methylene orange (MO) dye. This was attributed to the efficient surface absorption properties, high crystallinity, and the presence of reactive surfaces of -NH2 and -OH groups, which enhances the adsorption-photodegradation effect. The larger surface oxygen vacancies coupled with reduced electron-hole recombination further enhanced the photocatalytic activity. It is undeniable that the pH during synthesis is critical towards the development of the properties of the TiO2-chitosan nanocomposite for the enhancement of photocatalytic activity.
Photocatalysis is an ecofriendly technique that emerged as a promising alternative for the degradation of many organic pollutants. The weaknesses of the present photocatalytic system which limit their industrial applications include low-usage of visible light, fast charge recombination, and low migration ability of the photo-generated electrons and holes. Therefore, various elements such as noble metals and transition metals as well as non-metals and metalloids (i.e., graphene, carbon nanotube, and carbon quantum dots) are doped into the photocatalyst as co-catalysts to enhance the photodegradation performance. The incorporation of the co-catalyst which alters the photocatalytic mechanism was discussed in detail. The application of photocatalysts in treating persistent organic pollutants such as pesticide, pharmaceutical compounds, oil and grease and textile in real wastewater was also discussed. Besides, a few photocatalytic reactors in pilot scale had been designed for the effort of commercializing the system. In addition, hybrid photocatalytic system integrating with membrane filtration together with their membrane fabrication methods had also been reviewed. This review outlined various types of heterogeneous photocatalysts, mechanism, synthesis methods of biomass supported photocatalyst, photocatalytic degradation of organic substances in real wastewater, and photocatalytic reactor designs and their operating parameters as well as the latest development of photocatalyst incorporated membrane.
This study reported the synthesis and assessment of zinc oxide/iron oxide (ZnO/Fe2O3) nanocomposite as photocatalysts for the degradation of a mixture of methylene red and methylene blue dyes. X-ray diffraction analysis confirms that the crystallite of zinc oxide (ZnO) has a hexagonal wurtzite phase and iron oxide (Fe2O3) has a rhombohedral phase. Fourier Transform Infra-Red spectrum confirms the presence of Zn-O vibration stretching at 428, 480 and 543 cm-1 stretching confirming Fe-O bond formation. Scanning Electron Microscope images exhibited a diverse size and shape of the nanocomposites. The ZnO-90%/Fe2O3-10% and ZnO-10%/Fe2O3-90% nanocomposites reveal good photocatalytic activity with reaction rate constants of 1.5 × 10-2 and 0.66 × 10-2; and 1.3 × 10-2 and 0.60 × 10-2 for methylene blue and methyl red dye respectively. The results revealed that the synthesized ZnO/Fe2O3 nanocomposite is the best catalyst for dye degradation and can be used for industrial applications in future.
Photocatalytic oxidation of crosslinked chitosan-epichlorohydrin (CS-ECH) film was successfully achieved via an immobilized TiO2/CS-ECH photocatalyst system on a glass plate. Oxidation process of CS-ECH film was carried out by irradiating the system with a 45-W fluorescent lamp for 10h in ultra-pure water. The results indicate the formation of carbonyl functional groups and partial elimination of amine groups in the molecular structure of the oxidized CS-ECH film. This oxidized CS-ECH film has different optical properties, ionic conductivity, degree of transparency, swelling index and chemical stability than the fresh CS-ECH film. In the environmental applications, the TiO2/oxidized-CS-ECH photocatalyst system can have photodegradation and faster mineralization rate of phenol than both fresh TiO2/CS-ECH and TiO2/oxidized-CS photocatalyst systems. This simple photocatalyst system, therefore can be considered as an environmental friendly method to oxidize synthetic biopolymer and to improve the photocatalytic efficiency of TiO2 to treat wastewater.
Dyeing wastewater was known to have strong color and refractory organic pollutants. In this study irradiation alone was used for dyes wastewater treatment. This paper studies the effect of the concentrations of pollutants to its removal at various dosages using electron beam technology. Irradiation was effective in removing the highly colored and refractory organic compounds. The color removal for initial concentrations of 255 CU, 520 CU, 990 CU and 1900 CU treated using irradiation at 0.5 kGy were 61%, 48%, 28% and 16%, respectively. However, at the dose of 108 kGy and higher, the color removal between 87% and 96% were recorded with no apparent trend. COD removal also reported similar trend but at relatively lower removal percentage. The COD removal at 0.5 kGy for initial COD concentrations of 57 mg/l and 515 mg/l were 10% and 0%, respectively. At irradiation dose of 108 kGy, the removal for initial COD concentrations of 57 mg/l and 515 mg/l were 37% and 13%, respectively. This showed that concentrations of pollutants and dose of irradiation applied to remove color and COD were dependent to each other.
ZnS and CdS nanoparticles were prepared by a simple microwave irradiation method under mild conditions. The obtained nanoparticles were characterized by XRD, TEM and EDX. The results indicated that high purity of nanosized ZnS and CdS was successfully obtained with cubic and hexagonal crystalline structures, respectively. The band gap energies of ZnS and CdS nanoparticles were estimated using UV-visible absorption spectra to be about 4.22 and 2.64 eV, respectively. Photocatalytic degradation of methylene blue was carried out using physical mixtures of ZnS and CdS nanoparticles under a 500-W halogen lamp of visible light irradiation. The residual concentration of methylene blue solution was monitored using UV-visible absorption spectrometry. From the study of the variation in composition of ZnS:CdS, a composition of 1:4 (by weight) was found to be very efficient for degradation of methylene blue. In this case the degradation efficiency of the photocatalyst nanoparticles after 6 h irradiation time was about 73% with a reaction rate of 3.61 × 10-3 min-1. Higher degradation efficiency and reaction rate were achieved by increasing the amount of photocatalyst and initial pH of the solution.
The optical properties of a ZnO photocatalyst were enhanced with various dopant concentrations of Fe(3+). Doped ZnO nanoparticles were synthesized via a sol-gel method without the use of capping agents or surfactants and was then characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and ultraviolet-visible (UV-Vis) spectroscopy. The results showed that ZnO has a wurtzite, hexagonal structure and that the Fe(3+) ions were well incorporated into the ZnO crystal lattice. As the Fe(3+) concentration increased from 0.25 wt.% to 1 wt.%, the crystal size decreased in comparison with the undoped ZnO. The spectral absorption shifts of the visible light region (red shift) and the band gap decreases for each Fe-ZnO sample were investigated. The photocatalytic activities of the ZnO and Fe-ZnO samples were evaluated based on the degradation of 2-chlorophenol in aqueous solution under solar radiation. The samples with a small concentration of Fe(3+) ions showed enhanced photocatalytic activity with an optimal maximum performance at 0.5 wt.%. The results indicated that toxicity removal of 2-chlorophenol at same line of degradation efficiency. Small crystallite size and low band gap were attributed to high activities of Fe-ZnO samples under various concentrations of Fe(3+) ions compared to undoped ZnO.
MWCNTs/TiO2 nanocomposite was prepared by oxidising MWCNT in H2SO4/HNO3 then decorating it with TiO2-p25 nanopowder. The composites were characterised using XRD, TEM, FT-IR PL and UV-vis spectroscopy. The TEM images have shown TiO2 nanoparticles immobilised onto the sidewalls of the MWCNTs. The UV-vis spectrum confirms that the nanocomposites can significantly absorb more light in the visible regions compared with the commercial TiO2 (P25). The catalytic activity of these nanocomposites was determined by photooxidation of MB aqueous solution in the presence of visible light. The MWCNTs/TiO2 (1:3) mass ratio showed maximum degradation efficiency. However, its activity was more favourable in alkaline and a neutral pH than an acidic medium.
Methylene blue (MB) is a dye pollutant commonly present in textile wastewater. We investigate and critically evaluate the applicability of BaTiO3/GO composite for photodegradation of MB in synthetic wastewater under UV-vis irradiation. To enhance its performance, the BaTiO3/GO composite is varied based on the BaTiO3 weight. To compare and evaluate any changes in their morphologies and crystalline structures before and after treatment, BET (Brunauer-Emmett-Teller), XRD (X-ray diffraction), FTIR (Fourier transform infrared spectroscopy), SEM (scanning electron microscopy) and TEM (transmission electron microscopy) tests are conducted, while the effects of reaction time, pH, dose of photocatalyst and initial MB concentration on its photodegradation by the composite are also investigated under identical conditions. The degradation pathways and removal mechanisms of MB by the BaTiO3/GO are elaborated. It is evident from this study that the BaTiO3/GO composite is promising for MB photodegradation through ·OH. Under optimized conditions (0.5 g/L of dose, pH 9.0, and 5 mg/L of MB concentration), the composite with 1:2 dose ratio of BaTiO3/GO has the highest MB degradation rate (95%) after 3 h of UV vis irradiation. However, its treated effluents still could not comply with the discharge standard limit of less than 0.2 mg/L imposed by national environmental legislation. This suggests that additional biological treatments are still required to deal with the remaining oxidation by-products of MB, still present in the wastewater samples such as 3,7-bis (dimethyl-amino)-10H-phenothiazine 5-oxide.