Tungsten-loaded TiO(2) photocatalyst has been successfully prepared and characterized. TEM analysis showed that the photocatalysts were nanosize with the tungsten species forming layers of coverage on the surface of TiO(2), but not in clustered form. This was confirmed by XRD and FT-Raman analyses where tungsten species were well dispersed at lower loading (<6.5 mol%), but were in crystalline WO(3) at higher loadings (>12 mol%). In addition, loading with tungsten could stabilize the anatase phase from transforming into inactive rutile phase and did not shift the optical absorption to the visible region as shown by DRUV-vis analysis. PZC value of TiO(2) was found at 6.4, but the presence of tungsten at 6.5 mol% WO(3), decreased the PZC value to 3. Tungsten-loaded TiO(2) was superior to unmodified TiO(2) with 2-fold increase in degradation rate of methylene blue, and equally effective for the degradation of different class of dyes such as methyl violet and methyl orange at 1 mol% WO(3) loading.
Palm ash, an agriculture waste residue from palm-oil industry in Malaysia, was investigated as a replacement for the current expensive methods of removing direct blue 71 dye from an aqueous solution. The experimental data were analyzed by the Langmuir and Freundlich models of adsorption. Equilibrium data fitted well with Freundlich model in the range of 50-600mg/L. The equilibrium adsorption capacity of the palm ash was determined with the Langmuir equation and found to be 400.01mg dye per gram adsorbent at 30 degrees C. The rates of adsorption were found to conform to the pseudo-second-order kinetics with good correlation. The results indicate that the palm ash could be employed as a low-cost alternative to commercial activated carbon.
Electrochemical-assisted photodegradation of methyl orange has been investigated using TiO2 thin films. The films were prepared by sol-gel dip-coating method. Several operational parameters to achieve optimum efficiency of this electrochemical-assisted photodegradation system have been tested. Photoelectrochemical degradation was studied using different light sources and light intensity. The light sources chosen ranged from ultraviolet to visible light. The effect of agitation of the solution at different speeds has also been studied. Slight improvement of photodegradation rate was observed by applying higher agitation speed. Investigation on the electrode after repeated usages show the electrode can be reused up to 20 times with percentage of deficiency less than 15%. The study on the effect of solution temperature indicated that the activation energy of the methyl orange degradation is 18.63 kJ mol(-1).
Fenton oxidation, an advanced oxidation process, is an efficient method for the treatment of recalcitrant wastewaters. Unfortunately, it utilizes H2O2 and iron-based homogeneous catalysts, which lead to the formation of high volumes of sludge and secondary pollutants. To overcome these problems, an alternate option is the usage of heterogeneous catalyst. In this study, a heterogeneous catalyst was developed to provide an alternative solution for homogeneous Fenton oxidation. Iron Zeolite Socony Mobile-5 (Fe-ZSM-5) was synthesized using a new two-step process. Next, the catalyst was characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, fourier transform infrared spectroscopy, and Brunauer-Emmett-Teller analysis and tested against a model wastewater containing the azo dye Acid Blue 113. Results showed that the loading of iron particles reduced the surface area of the catalyst from 293.59 to 243.93 m2/g; meanwhile, the average particle size of the loaded material was 12.29 nm. Furthermore, efficiency of the developed catalyst was evaluated by performing heterogeneous Fenton oxidation. Taguchi method was coupled with principal component analysis in order to assess and optimize mineralization efficiency. Experimental results showed that under optimized conditions, over 99.7% degradation and 77% mineralization was obtained, with a 90% reduction in the consumption of the developed catalyst. Furthermore, the developed catalyst was stable and reusable, with less than 2% leaching observed under optimized conditions. Thus, the present study proved that newly developed catalyst has enhanced the oxidation process and reduced the chemicals consumption.
In Malaysia, most colored wastewater from dyeing factories is discharged to the environment causing serious problems. In this paper the influence of several reacting conditions, i.e. H2O2, pH, Ultraviolet (UV) intensity and dye concentration, on the performance of the immobilized system is discussed. The pH of the solution was varied from 3 to 11 while H2O2 concentration tested was from 10(-4) M to 5 x 10(-2) M. UV was tested at 365 nm and 254 nm, while dye concentration ranged from 2.5 x 10(-4) M to 10(-3) M. The influence of the reacting conditions was assessed based on absorbance. Using an OG concentration of 10(-3) M, the degradation increases from 17.8% to 49.7%. Optimum concentration of H2O2 was found to be 5 x 10(-3) M for degradation. Increasing the intensity of the UV light via shorter light wavelength also improves the performance of the system. Increasing the concentration of the dye reduces the overall performance of the system. Using the dye concentration of 2.5 x 10(-4) M (H2O2 = 10(-2) M, lambda = 254 nm, pH = 11), gives a degradation of 93.2%. At dye concentration of 10(-3) M, the performance was reduced to 53.1%.
Chitosan-polyethyleneimine with calcium chloride as ionic cross-linker (CsPC) was synthesized as a new kind of adsorbent using a simple, green and cost-effective technique. The adsorption properties of the adsorbent for Acid Red 88 (AR88) dye, as a model analyte, were investigated in a batch system as the function of solution pH (pH 3-12), initial AR88 concentration (50-500 mg L-1), contact time (0-24 h), and temperature (30-50 °C). Results showed that the adsorption process obeyed the pseudo-first order kinetic model and the adsorption rate was governed by both intra-particle and liquid-film mechanism. Equilibrium data were well correlated with the Freundlich isotherm model, with the calculated maximum adsorption capacity (qm) of 1000 mg g-1 at 30 °C. The findings underlined CsPC to be an effective and efficient adsorbent, which can be easily synthesized via one-step process with promising prospects for the removal of AR88 or any other similar dyes from the aqueous solutions.
NiS-SiO2 and Cr2S3-TiO2 synthesized by Ultrasound-Microwave method was tested for the photo-degradation of methyl red as azo dye under ultraviolet (UV) light. The structure and morphology of the synthesized materials were examined through scanning electron microscopy, X-ray diffraction and photoelectron spectroscopy, energy-dispersive spectroscopy, dynamic light scattering and the band gap energy differences were determined through diffuse reflectance spectroscopy (DRS). The crystallite size and band gap values of SiO2, TiO2, NiS-SiO2 and Cr2S3-TiO2-1 were obtained from XRD and UV-vis DRS analysis and found insignificant 44.22, 54.11, and 57.11 nm, and 8.9, 3.2, 3.0, 2.7 eV, respectively. The NiS-SiO2 and Cr2S3-TiO2 nanocomposites exhibited good stability and catalytic performance in the azo dye degradation; the composite provides a complete degradation after 50 min under UV irradiation. The effects of different quencher compounds on the Methyl red dye degradation were also investigated. The result for this experiment shows the system without the quencher was highly degradation of Methyl red. The antibacterial influence of the SiO2, TiO2, NiS-SiO2 and Cr2S3-TiO2-1 were studied versus two species bacteria. The antifungal performance of this nanoparticle was analyzed versus two species fungi as the C. albicans and P. funiculosum. Biological data demonstrated that the prepared catalyst has great bactericidal and fungicidal properties.
Grafting of crosslinked chitosan with monomer, N-vinyl-2-pyrrolidone, has been carried out to investigate its adsorption capacity toward Orange G (OG) from aqueous solutions. The adsorption performance of modified chitosan (cts(x)-g-PNVP) was examined and compared with that of the unmodified chitosan. The effects of initial pH, contact time and initial dye concentration were investigated in a batch system. The experimental data were correlated with the Langmuir and Freundlich isotherm models. The maximum adsorption capacity of cts(x)-g-PNVP (63.7mgg-1) based on Langmuir equation was relatively higher than that of the unmodified chitosan (1.7mgg-1). The kinetic studies showed that the adsorption process was consistent with the pseudo-second order kinetic model. Interaction mechanisms between OG and cts(x)-g-PNVP were also proposed. The overall results suggested that the prepared cts(x)-g-PNVP stands a good candidate as adsorbent for removal of anionic dye from aqueous solutions.
This study aims to develop a highly efficient adsorbent material. CNTs are prepared using a chemical vapor deposition method with acetylene and synthesized mesoporous Ni-MCM41 as the carbon source and catalyst, respectively, and are then functionalized using 3-aminopropyltriethoxysilane (APTES) through the co-condensation method and loaded with commercial TiO2. Results of X-ray powder diffraction (XRD), Raman spectra, and Fourier transform infrared spectroscopy (FTIR) confirm that the synthesized CNTs grown are multi-walled carbon nanotubes (MWNTs). Transmission electron microscopy shows good dispersion of TiO2 nanoparticles onto functionalized-CNTs loaded TiO2, with the diameter of a hair-like structure measuring between 3 and 8 nm. The functionalized-CNTs loaded TiO2 are tested as an adsorbent for removal of methyl orange (MO) in aqueous solution, and results show that 94% of MO is removed after 10 min of reaction, and 100% after 30 min. The adsorption kinetic model of functionalized-CNTs loaded TiO2 follows a pseudo-second order with a maximum adsorption capacity of 42.85 mg/g. This study shows that functionalized-CNTs loaded TiO2 has considerable potential as an adsorbent material due to the short adsorption time required to achieve equilibrium.
Fabrication of an immobilized cross-linked chitosan-epichlorohydrine thin film (CLCETF) onto glass plate for adsorption of reactive orange 16 (RO16) dye was successfully studied using the direct casting technique. Adsorption experiments were performed as a function of contact time, initial dye concentration (25mg/L to 350mg/L), and pH (3-11). The adsorption isotherm followed the Langmuir model. The adsorption capacity of CLECTF for RO16 was 356.50mg/g at 27±2°C. The kinetics closely followed the pseudo-second-order model. Results supported the potential use of an immobilized CLECTF as effective adsorbent for the treatment of reactive dye without using filtration process.
Azo dyes are widely used in textile, fiber, cosmetic, leather, paint and printing industries. Besides their characteristic coloring function, azo compounds are reported as antibacterial, antiviral, antifungal and cytotoxic agents. They have the ability to be used as drug carriers, either by acting as a 'cargo' that entrap therapeutic agents or by prodrug approach. The drug is released by internal or external stimuli in the region of interest, as observed in colon-targeted drug delivery. Besides drug-like and drug carrier properties, a number of azo dyes are used in cellular staining to visualize cellular components and metabolic processes. However, the biological significance of azo compounds, especially in cancer chemotherapy, is still in its infancy. This may be linked to early findings that declared azo compounds as one of the possible causes of cancer and mutagenesis. Currently, researchers are screening the aromatic azo compounds for their potential biomedical use, including cancer diagnosis and therapy. In this review, we highlight the medical applications of azo compounds, particularly related to cancer research. The biomedical significance of cis-trans interchange and negative implications of azo compounds are also discussed in brief.
The global attention has been focused on degradation of the environmental organic pollutants through green methods such as advanced oxidation processes (AOPs) under sunlight. However, AOPs have not yet been efficient in function of the photocatalyst that has been used. In this work, firstly, CaCu3Ti4O12 nanocomposite was simultaneously synthesized and decorated in different amounts of graphene oxide to enhance photodegradation of the organics. The result of the photocatalyst characterization showed that the sample with 8% graphene presented optimum photo-electrical properties such as low band gap energy and a great surface area. Secondly, the photocatalyst was applied for photodegradation of an organic model in a batch photoreactor. Thirdly, to scale up the process and optimize the efficiency, the photodegradation was modeled by multivariate semi-empirical methods. As the optimized condition showed, 45 mg/L of the methyl-orange has been removed at pH 5.8 by 0.96 g/L of the photocatalyst during 288 min of the light irradiation. Moreover, the photodegradation has been scaled up for industrial applications by determining the importance of the input effective variables according to the following organics order > photocatalyst > pH > irradiation time.
Supramolecular building blocks, such as cucurbit[n]uril (CB[n])-based host-guest complexes, have been extensively studied at the nano- and microscale as adhesion promoters. Herein, we exploit a new class of CB[n]-threaded highly branched polyrotaxanes (HBP-CB[n]) as aqueous adhesives to macroscopically bond two wet surfaces, including biological tissue, through the formation of CB[8] heteroternary complexes. The dynamic nature of these complexes gives rise to adhesion with remarkable toughness, displaying recovery and reversible adhesion upon mechanical failure at the interface. Incorporation of functional guests, such as azobenzene moieties, allows for stimuli-activated on-demand adhesion/de-adhesion. Macroscopic interfacial adhesion through dynamic host-guest molecular recognition represents an innovative strategy for designing the next generation of functional interfaces, biomedical devices, tissue adhesives, and wound dressings.
In this study, chitosan/polyvinyl alcohol/TiO2 nanofiber was fabricated via electrospinning at a pump rate of 1.5 mL/h and voltage 6 kV. Field-emission scanning electron microscopic images showed bead free finer nanofiber. Fourier transform infrared spectra proved the formation of strong bond among chitosan, polyvinyl alcohol and TiO2. X-ray powder diffraction showed that TiO2 became amorphous in the composite nanofiber. Toughness and thermal stability of the chitosan/PVA nanofibrous membrane was increased with addition TiO2. The chitosan/PVA/TiO2 nanofibrous membrane was stable at basic medium. But degraded in acidic and water medium after 93 and 162 h, respectively. The adsorption mechanism of congo red obeyed the Langmuir isotherm model. On the other hand, adsorption characteristic of methyl orange fitted well with both Langmuir and Freundlich isotherm models. The maximum adsorption capacity of the resulting membrane for congo red and methyl orange is 131 and 314 mg/g, respectively. However, a high dose of adsorbent was required for congo red.
In this work, chitosan (Chi) was cross-linked with glyoxal (Gly) and deposited onto glass plate to be a superior adsorbent film for two structurally different reactive orange 16 (RO-16) and methyl orange (MO) dyes by using non-conventional adsorption system without filtration process. The characterizations indicate that the cross-linked chitosan-glyoxal (Chi-Gly) film has a low swelling index, high adherence strength on glass plate, amine group (NH2) content was 32.52%, and pHpzc of ∼6.0 indicating a negative surface charge occurs above pHpzc. The adsorption isotherm data of RO-16 and MO by Chi-Gly film were in agreement with Langmuir isotherm, with maximum adsorption capacities of 1554.3 mg/g and 1451.9 mg/g, respectively. The pseudo-first-order kinetic model best described the kinetic data. The adsorption process was spontaneous and exothermic in nature at Chi-Gly film thickness of 8.55 μm, and pH ~3. The mechanism of adsorption included mainly electrostatic attractions, dipole-dipole hydrogen bonding interactions, n-π stacking attractions, and Yoshida H-bonding. This study reveals that immobilized Chi-Gly film as a good candidate for adsorption of reactive and acid dyes as it does not require any filtration process and adsorbent recovery during and post-adsorption process.
Extensive use of recalcitrant azo dyes in textile and paper industries poses a direct threat to the environment due to the carcinogenicity of their degradation products. The aim of this study was to investigate the efficiency of Curvularia clavata NZ2 in decolorization of azo dyes. The ability of the fungus to decolorize azo dyes can be evaluated as an important outcome as existing effluent treatment is unable to remove the dyes effectively. C. clavata has the ability to decolorize Reactive Black 5 (RB5), Acid Orange 7 (AO7), and Congo Red azo dyes, utilizing these as sole sources of carbon and nitrogen. Ultraviolet-visible (UV-vis) spectroscopy and Fourier infrared spectroscopy (FTIR) analysis of the extracted RB5's metabolites along with desorption tests confirmed that the decolorization process occurred due to degradation and not merely by adsorption. Enzyme activities of extracellular enzymes such as carboxymethylcellulase (CMCase), xylanase, laccase, and manganese peroxidase (MnP) were also detected during the decolorization process. Toxicity expressed as inhibition of germination was reduced significantly in fungal-treated azo dye solution when compared with the control. The cultivation of C. clavata under sequential batch system also recorded a decolorization efficiency of above 90%. The crude enzyme secreted by C. clavata also showed excellent ability to decolorize RB5 solutions with concentrations of 100 ppm (88-92%) and 1000 ppm (70-77%) without redox mediator. This proved that extracellular enzymes produced by C. clavata played a major role in decolorization of RB5.
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.
This study examined the anti-adipogenic effects of extracts of Ficus deltoidea var. deltoidia and var. angustifolia, a natural slimming aid, on 3T3-L1 adipocytes.
Fish scale (FS) loaded TiO2 composites were investigated as photocatalysts in degradation of Methyl Orange under solar light irradiation. Composites were prepared through sol-gel method by varying mass ratio of TiO2/FS at 90:10, 70:30 and 50:50, respectively. The catalysts prepared in this study were characterized by using XRD, SEM, FT-IR and nitrogen sorption. The effects of solar irradiation, mass ratio of TiO2/FS composites, irradiation time and catalyst loadings were studied. Synergistic effect was found in TiO2/FS of 90:10 composite which performed higher photocatalytic degradation than synthesized TiO2 under solar light irradiation. However, further increasing fish scale content in the composites reduced the photocatalytic activity drastically. Under solar light irradiation, all the catalysts in this study exhibited photocatalytic activity, except TiO2/FS of 50:50 composite that only acted as a weak biosorbent without performing any photocatalytic property. Photocatalytic degradation increased with increasing catalyst loading and irradiation time but decreased with increased of initial dye concentration.
A renewable waste tea activated carbon (WTAC) was coalesced with chitosan to form composite adsorbent used for waste water treatment. Adsorptive capacities of crosslinked chitosan beads (CCB) and its composite (WTAC-CCB) for Methylene blue dye (MB) and Acid blue 29 (AB29) were evaluated through batch and fixed-bed studies. Langmuir, Freundlich and Temkin adsorption isotherms were tested for the adsorption process and the experimental data were best fitted by Langmuir model and least by Freundlich model; the suitability of fitness was adjudged by the Chi-square (χ(2)) and Marquadt's percent standard deviation error functions. Judging by the values of χ(2), pseudo-second-order reaction model best described the adsorption process than pseudo-first-order kinetic model for MB/AB29 on both adsorbents. After five cycles of adsorbents desorption test, more than 50% WTAC-CCB adsorption efficiency was retained while CCB had <20% adsorption efficiency. The results of this study revealed that WTAC-CCB composite is a promising adsorbent for treatment of anionic and cationic dyes in effluent wastewaters.