Photocatalytic fuel cell (PFC) was employed to provide renewable power sources to photoelectro-Fenton (PEF) process to fabricate a double-chambered hybrid system for the treatment of azo dye, Amaranth. The PFC-PEF hybrid system was interconnected by a circuit attached to the electrodes in PFC and PEF. Circuit connection is the principal channel for the electron transfer and mobility between PFC and PEF. Thus, different circuit connections were evaluated in the hybrid system for their influences on the Amaranth dye degradation. The PFC-PEF system under the complete circuit connection condition attained the highest decolourization efficiency of Amaranth (PFC: 98.85%; PEF: 95.69%), which indicated that the complete circuit connection was crucial for in-situ formation of reactive species in dye degradation. Besides, the pivotal role of ultraviolet (UV) light irradiation in the PFC-PEF system for both dye degradation and electricity generation was revealed through various UV light-illuminating conditions applied for PFC and PEF. A remarkable influence of UV light irradiation on the production of hydrogen peroxide and generation and regeneration of Fe2+ in PEF was demonstrated. This study provided a comprehensive mechanistic insight into the dye degradation and electricity generation by the PFC-PEF system.
In this study, a magnetic chitosan grafted-benzaldehyde (CS-BD/Fe3O4) was hydrothermally prepared using benzaldehyde as a grafting agent to produce a promising adsorbent for the removal of acid red 88 (AR88) dye. The CS-BD/Fe3O4 was characterized by infrared spectroscopy, surface area analysis, scanning electron microscopy-energy dispersive X-ray, vibrating sample magnetometry, powder X-ray diffraction, CHN elemental analysis, and point of zero charge (pHPZC). The Box-Behnken design (BBD) was adopted to study the role of variables that influence AR88 dye adsorption (A: CS-BD/Fe3O4 dose (0.02-0.1 g), B: pH (4-10), and time C: (10-90 min)). The ANOVA results of the BBD model indicated that the F-value for the AR88 removal was 22.19 %, with the corresponding p-value of 0.0002. The adsorption profiles at equilibrium and dynamic conditions reveal that the Temkin model and the pseudo-first-order kinetics model provide an adequate description of the isotherm results, where the maximum adsorption capacity (qmax) with the AR88 dye was 154.1 mg/g. Several mechanisms, including electrostatic attraction, n-π interaction, π-π interaction, and hydrogen bonding, regulate the adsorption of AR88 dyes onto the CS-BD/Fe3O4 surface. As a result, this research indicates that CS-BD/Fe3O4 can be utilized as an effective and promising bio-adsorbent for azo dye removal from contaminated wastewater.
Para-arsanilic acid (p-ASA) has been widely used in the poultry industry to promote growth and prevent dysentery. It is excreted unchanged in the manure and released into non-target sites causing organoarsenic pollution risk to the environment and living system. Therefore, simple and effective analytical strategies are demanded for determining the samples that contain p-ASA. However, direct determination of both p-ASA and ortho-arsanilic acid (o-ASA) using differential pulse cathodic stripping voltammetry (DPCSV) gives the similar voltammograms that directly hamper the analysis used by the DPCSV technique. In this study, a method to determine and differentiate p-ASA from o-ASA via diazotization and coupling reaction of the amine groups followed by the direct DPCSV determination of diazo compounds is presented. The diazotization reaction carried out at pH 1.5 and 0 ± 1°C for 10 min showed two reduction peaks in DPCSV at-70 mV and -440 mV vs. Ag/AgCl (KCl 3 M). However, when the diazotization reaction was performed at pH 12.5 and 0 ± 1°C for 40 min, a coloured azo compound was produced and the DPCSV showed only one reduction peak that appeared at -600 mV vs. Ag/AgCl (3 M of KCl). The results of this study show that only p-ASA compound gave a reduction peak, whereas o-ASA compound did not give any peak. The detection limit of p-ASA was found to be 4 × 10(-8 )M. As a result, the proposed electro-analytical technique might be a good candidate to determine and differentiate the p-ASA present in the poultry and environmental samples.
The objectives of this study were: (1) to investigate the role of mixed culture of biomass in the regeneration of mono-amine modified silica (MAMS) and granular activated carbon (GAC) loaded with Acid Orange 7 (AO7), (2) to quantify and compare the bioregeneration efficiencies of AO7-loaded MAMS and GAC using the sequential adsorption and biodegradation approach and (3) to evaluate the reusability of bioregenerated MAMS. The results show that considerably higher bioregeneration efficiency of AO7-loaded MAMS as compared to that of AO7-loaded GAC was achieved due to higher reversibility of adsorption of MAMS for AO7 and favorable pH factor resulting in more AO7 desorption. The progressive loss of adsorption capacity of MAMS for AO7 with multiple cycles of use suggests possible chemical and microbial fouling of the adsorption sites.
A modified hydrophilic penta-bismuth hepta-oxide nitrate (Bi5O7NO3) surface was synthesized via a precipitation method using TiO2 and Ag as modified agents. The synthesized product was characterized by different analytical techniques. The removal efficiency was evaluated using mono- and di-sulphonated azo dyes as model pollutants. Different kinetic, isotherm and diffusion models were chosen to describe the adsorption process. X-ray photoelectron spectroscopy (XPS) results revealed no noticeable differences in the chemical states of modified adsorbent when compared to pure Bi5O7NO3; however, the presence of hydrophilic centres such as TiO2 and Ag developed positively charged surface groups and improved its adsorption performance to a wide range of azo dyes. Dyes removal was found to be a function of adsorbent dosage, initial dye concentration, solution pH and temperature. The reduction of Langmuir 1,2-mixed order kinetics to the second or first-order kinetics could be successfully used to describe the adsorption of dyes onto the modified adsorbent. Mass transfer can be described by intra-particle diffusion at a certain stage, but it was not the rate limiting step that controlled the adsorption process. Homogenous behavior of adsorbent surface can be explored by applying Langmuir isotherm to fit the adsorption data.
In this study, calcined Lapindo volcanic mud (LVM) was used as an adsorbent to remove an anionic dye, methyl orange (MO), from an aqueous solution by the batch adsorption technique. Various conditions were evaluated, including initial dye concentration, adsorbent dosage, contact time, solution pH, and temperature. The adsorption kinetics and equilibrium isotherms of the LVM were studied using pseudo-first-order and -second-order kinetic equations, as well as the Freundlich and Langmuir models. The experimental data obtained with LVM fits best to the Langmuir isotherm model and exhibited a maximum adsorption capacity (q(max)) of 333.3 mg g(-1); the data followed the second-order equation. The intraparticle diffusion studies revealed that the adsorption rates were not controlled only by the diffusion step. The thermodynamic parameters, such as the changes in enthalpy, entropy, and Gibbs free energy, showed that the adsorption is endothermic, random and spontaneous at high temperature. The results indicate that LVM adsorbs MO efficiently and could be utilized as a low-cost alternative adsorbent for the removal of anionic dyes in wastewater treatment.
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.
A stab-culture method was adapted to screen for azo dyes-decolorizing bacteria from soil and water samples. Decolorized azo dye in the lower portion of the solid media indicates the presence of anaerobic azo dyes-decolorizing bacteria, while aerobic decolorizing bacteria decolorizes the surface portion of the solid media. Of twenty soil samples tested, one soil sample shows positive results for the decolourisation of two azo dyes; Biebrich scarlet (BS) and Direct blue 71 (DB) under anaerobic conditions. A gram negative and oxidase negative bacterial isolate was found to be the principal azo dyes degrader The isolate was identified by using the Biolog identification system as Serratia marcescens.
In this paper, the newly explored TiO(2)-Chitosan/Glass was suggested as a promising alternative material to conventional means of wastewater treatment. Characterization of TiO(2)-Chitosan/Glass photocatalyst was studied with SEM-EDX, XRD, and Fourier transform infrared spectroscopy (FTIR) analysis. The combination effect of photodegradation-adsorption process for the removal of methyl orange (MO), an acid dye of the monoazo series occur promisingly when four layers of TiO(2)-Chitosan/Glass photocatalyst was used for MO removal. Approximately, 87.0% of total MO removal was achieved. The reactive -NH(2), -OH, and metal oxide contents in the prepared photocatalyst responsible for the photodegradation-adsorption effect were confirmed by FTIR study. Similarly, MO removal behavior was well supported by SEM-EDX and XRD analysis. Significant dependence of MO removal on the TiO(2)-Chitosan loading can be explained in terms of relationship between quantum yield of photocatalytic reactions and photocatalyst structure/activity. Hence, the research work done thus far suggests a new method, having both the advantages of photodegradation-adsorption process in the abatement of various wastewater pollutants.
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.
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.
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.
Due to environmental concern, the research to date has tended to focus on how textile dye removal can be carried out in a greener manner. Therefore, this study aims to evaluate the decolorization and biotransformation pathway of Mordant Orange-1 (MO-1) by Cylindrocephalum aurelium RY06 (C. aurelium RY06). Decolorization study was conducted in a batch experiment including the investigation of the effects of physio-chemical parameters. Enzymatic activity of C. aurelium RY06 during the decolorization was also investigated. Moreover, transformation and biodegradation of MO-1 by C. aurelium RY06 were observed using the gas chromatography-mass spectrometry. Manganese peroxidase, lignin peroxidase, laccase, 1,2-dioxygenase, and 2,3-dioxygenase enzymes were detected during the decolorization. In general, the present work concluded that the MO-1 was successfully degraded by C. aurelium RY06 and transformed to be maleic acid and to be isophtalic acid.
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.