This study investigated the effect of different supporting electrolyte (Na2SO4, MgSO4, NaCl) in degradation of Reactive Black 5 (RB5) and generation of electricity. Zinc oxide (ZnO) was immobilized onto carbon felt acted as photoanode, while Pt-coated carbon paper as photocathode was placed in a single chamber photocatalytic fuel cell, which then irradiated by UV lamp for 24 h. The degradation and mineralization of RB5 with 0.1 M NaCl rapidly decreased after 24-h irradiation time, followed by MgSO4, Na2SO4 and without electrolyte. The voltage outputs for Na2SO4, MgSO4 and NaCl were 908, 628 and 523 mV, respectively, after 24-h irradiation time; meanwhile, their short-circuit current density, J SC, was 1.3, 1.2 and 1.05 mA cm(-2), respectively. The power densities for Na2SO4, MgSO4 and NaCl were 0.335, 0.256 and 0.245 mW cm(-2), respectively. On the other hand, for without supporting electrolyte, the voltage output and short-circuit current density was 271.6 mV and 0.055 mA cm(-2), respectively. The supporting electrolyte NaCl showed greater performance in degradation of RB5 and generation of electricity due to the formation of superoxide radical anions which enhance the degradation of dye. The mineralization of RB5 with different supporting electrolyte was measured through spectrum analysis and reduction in COD concentration.
The photocatalytic fuel cell (PFC) system was developed in order to study the effect of several operating parameters in degradation of Reactive Black 5 (RB5) and its electricity generation. Light irradiation, initial dye concentration, aeration, pH and cathode electrode are the operating parameters that might give contribution in the efficiency of PFC system. The degradation of RB5 depends on the presence of light irradiation and solar light gives better performance to degrade the azo dye. The azo dye with low initial concentration decolorizes faster compared to higher initial concentration and presence of aeration in PFC system would enhance its performance. Reactive Black 5 rapidly decreased at higher pH due to the higher amount of OH generated at higher pH and Pt-loaded carbon (Pt/C) was more suitable to be used as cathode in PFC system compared to Cu foil and Fe foil. The rapid decolorization of RB5 would increase their voltage output and in addition, it would also increase their Voc, Jsc and Pmax. The breakage of azo bond and aromatic rings was confirmed through UV-Vis spectrum and COD analysis.
The role of azo dye Reactive Black 5 (RB5) as an electron donor and/or electron acceptor could be distinguished in dual chamber of photocatalytic fuel cell (PFC). The introduction of RB5 in anode chamber increased the voltage generation in the system since degradation of RB5 might produce electrons which also would transfer through external circuit to the cathode chamber. The removal efficiency of RB5 with open and closed circuit was 8.5% and 13.6%, respectively and removal efficiency for open circuit was low due to the fact that recombination of electron-hole pairs might happen in anode chamber since without connection to the cathode, electron cannot be transferred. The degradation of RB5 in cathode chamber with absence of oxygen showed that electrons from anode chamber was accepted by dye molecules to break its azo bond. The presence of oxygen in cathode chamber would improve the oxygen reduction rate which occurred at Platinum-loaded carbon (Pt/C) cathode electrode. The Voc, Jsc and Pmax for different condition of ultrapure water at cathode chamber also affected their fill factor. The transportation of protons to cathode chamber through Nafion membrane could decrease the pH of ultrapure water in cathode chamber and undergo hydrogen evolution reaction in the absence of oxygen which then increased degradation rate of RB5 as well as its electricity generation.
Hydrothermal method has been proven to be an effective method to synthesise the nanostructured titanium dioxide (TiO2) with good morphology and uniform distribution at low temperature. Despite of employing a well-known and commonly used glass substrate as the support to hydrothermally synthesise the nanostructured TiO2, this study emphasised on the application of kaolin hollow fibre membrane as the support for the fabrication of kaolin/TiO2 nanorods (TNR) membrane. By varying the hydrothermal reaction times (2 h, 6 h, and 10 h), the different morphology, distribution, and properties of TiO2 nanorods on kaolin support were observed by field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDX), atomic force microscope (AFM), X-ray diffraction (XRD) and Fourier transform infrared spectroscopy (FTIR). It was found that the well-dispersed of TiO2 nanorods have improved the surface affinity of kaolin/TNR membrane towards water, allowing kaolin/TNR membrane prepared from 10 h of hydrothermal reaction to exhibit the highest water permeation of 165 L/h.m2.bar. In addition, this prepared membrane also showed the highest photocatalytic activity of 80.3% in the decolourisation of reactive black 5 (RB5) under UV irradiation. On top of that, the kaolin/TNR membrane prepared from 10 h of hydrothermal reaction also exhibited a good resistance towards photocorrosion, enabling the reuse of this membrane for three consecutive cycles of photocatalytic degradation of RB5 without showing significant reduction in photocatalytic efficiency towards the decolourisation of RB5.
Comparison studies in suspension and hybrid photocatalytic membrane reactor (HPMR) system was investigated by using Reactive Black 5 (RB5) as target pollutant under UVA light irradiation. To achieve this aim, hybrid TiO2/clinoptilolite (TCP) photocatalyst powder was prepared by solid-state dispersion (SSD) methods and embedded at the outer layer of dual layer hollow fiber (DLHF) membranes fabricated via single step co-spinning process. TiO2 and CP photocatalyst were also used as control samples. The samples were characterized by Scanning Electron Microscopy (SEM), Energy Dispersion of X-ray (EDX), X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) analyses. The result shows that TCP was actively functioned as photocatalyst in suspension system and 86% of RB5 photocatalytic degradation achieved within 60 min; however the additional step is required to separate the catalyst with treated water. In the HPMR system, even though the RB5 photocatalytic degradation exhibits lower efficiency however the rejection of RB5 was achieved up to 95% under UV irradiation due to the properties of photocatalytic membranes. The well dispersed of TCP at the outer layer of DLHF membrane have improved the surface affinity of DL-TCP membrane towards water, exhibit the highest pure water flux of 41.72 L/m2.h compared to DL-TiO2 membrane. In general, CP can help on improving photocatalytic activity of TiO2 in suspension, increased the RB5 removal and the permeability of DLHF membrane in HPMR system as well.
The mineralisation of remazol black B (RBB) was studied at concentrations ranging from 20-1000 mgL(-1). The work was aimed at investigating the Fenton-like peroxidation of RBB at a concentration typically obtained in Batik cottage industries. Other response parameters were degradation and colour removal efficiencies. The parameters that were measured included total organic carbon (TOC), chemical oxygen demand (COD) as well as absorbance for mineralisation, degradation and colour. To optimise the process, the interaction effects of several controlling variables on the treatment process were examined using dispersion matrix-optimal design and response surface analysis. Four specific variables: initial dye concentration (Dye)o; the molar ratio of oxidant to dye organic strength (H2O2):(COD); the mass ratio of the oxidant to the catalyst (H2O2):(Fe3+) and reaction time (t(r)), were observed. Three reduced empirical models, one for each response, were developed for describing the treatment process. For 20, 510 and 1000 mgL(-1), the optimum %TOC reduction and oxidation times were 44% for 95 min, 52% for 52.5 min and 68% for 10 min corresponding to 67, 81 and 75% COD reduction, respectively. The optimum COD reduction and oxidation times were 89% for 95 min, 91% for 10 min and 84% for 95 min for concentrations of 20, 510 and 1000 mg L(-1), respectively. For all concentrations, total colour removal was achieved. A comparison of the results obtained in this study with literature values for traditional Fenton, photo-Fenton and photo-Fenton-like oxidation indicated that the TOC reduction obtained using the Fenton-like process was satisfactory.
Tubular nanofiltration membrane performance to treat water for reuse was carried out by choosing C.I. Acid Black 210 dye as a model dye. It has been shown that increasing pH causes reduction in irreversible fouling factor (IFF) and the dye removal is also affected by solution pH. The total organic carbon removal for pH 4, pH 7, pH 8 and pH 10 is 97.9, 92.3, 94.5 and 94.6%, respectively. The conductivity removal for pH 4, pH 7, pH 8 and pH 10 is 85.1, 88.3, 87.8 and 90.7% respectively. The increase in the initial dye concentration causes rapid increase in fouling until 100 mg/l. Then the fouling increases gradually as it reaches a maximum IFF around 13%. This study also shows that the colour of permeate changes from colourless to light greenish/yellowish (initial concentration of 2,000 and 4,000 mg/l) as the initial dye concentration increases. The conductivity removal was also reduced as the initial dye concentration increased due to screening of the Donnan effect with the presence of salt.
A non-cyclic tetrameric structure has been suggested for calcichrome (calcion). This structure is consistent with its mass spectrum, proton NMR spectrum, elemental composition and complexing ability with polyaromatic hydrocarbons in water. The stability constants of the 1:1 complexes formed between calcichrome and seven polyaromatic hydrocarbons in water at room temperature have been measured.
In this study, the construction and test of tapered plastic optical fiber (POF) sensors, based on an intensity modulation approach are described. Tapered fiber sensors with different diameters of 0.65 mm, 0.45 mm, and 0.35 mm, were used to measure various concentrations of Remazol black B (RBB) dye aqueous solutions at room temperature. The concentrations of the RBB solutions were varied from 0 ppm to 70 ppm. In addition, the effect of varying the temperature of the RBB solution was also investigated. In this case, the output of the sensor was measured at four different temperatures of 27 °C, 30 °C, 35 °C, and 40 °C, while its concentration was fixed at 50 ppm and 100 ppm. The experimental results show that the tapered POF with d = 0.45 mm achieves the best performance with a reasonably good sensitivity of 61 × 10(-4) and a linearity of more than 99%. It also maintains a sufficient and stable signal when heat was applied to the solution with a linearity of more than 97%. Since the transmitted intensity is dependent on both the concentration and temperature of the analyte, multiple linear regression analysis was performed to combine the two independent variables into a single equation. The resulting equation was then validated experimentally and the best agreement between the calculated and experimental results was achieved by the sensor with d = 0.45 mm, where the minimum discrepancy is less than 5%. The authors conclude that POF-based sensors are suitable for RBB dye concentration sensing and, with refinement in fabrication, better results could be achieved. Their low fabrication cost, simple configuration, accuracy, and high sensitivity would attract many potential applications in chemical and biological sensing.
Effluent containing colour/dyes, especially reactive dyes, becomes a great concern of wastewater treatment because it is toxic to human life and aquatic life. In this study, reactive dye of Black B was separated using the supported liquid membrane process. Commercial polypropylene membrane was used as a support of the kerosene-tridodecylamine liquid membrane. Several parameters were tested and the result showed that almost 100% of 70 ppm Black B was removed and 99% of 70 ppm Black B was recovered at pH 2 of the feed phase containing 0.00001 M Na2SiO3, flow rate of 150 ml/min and 0.2 M NaOH. The membrane support also remained stable for up to 36 hours under an optimum condition.
Monoazo and diazo dyes [New coccine (NC), Acid orange 7 (AO7), Reactive red 120 (RR120) and Reactive green 19 (RG19)] were employed as electron acceptors in the abiotic cathode of microbial fuel cell. The electrons and protons generated from microbial organic oxidation at the anode which were utilized for electrochemical azo dye reduction at the cathodic chamber was successfully demonstrated. When NC was employed as the electron acceptor, the chemical oxygen demand (COD) removal and dye decolourisation efficiencies obtained at the anodic and cathodic chamber were 73±3% and 95.1±1.1%, respectively. This study demonstrated that the decolourisation rates of monoazo dyes were ∼50% higher than diazo dyes. The maximum power density in relation to NC decolourisation was 20.64mW/m2, corresponding to current density of 120.24mA/m2. The decolourisation rate and power output of different azo dyes were in the order of NC>AO7>RR120>RG19. The findings revealed that the structure of dye influenced the decolourisation and power performance of MFC. Azo dye with electron-withdrawing group at para substituent to azo bond would draw electrons from azo bond; hence the azo dye became more electrophilic and more favourable for dye reduction.
In this work, poly(MBAAm-co-SBMA) zwitterionic polymer nanoparticles were synthesized in one-step via distillation-precipitation polymerization (DPP) and were characterized. [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl)ammonium hydroxide (SBMA) as monomer and N, N'-methylene bis(acrylamide) (MBAAm) as cross-linker are used for the synthesis of nanoparticles. As far as our knowledge, this is the first such report on the synthesis of poly(MBAAm-co-SBMA) nanoparticles via DPP. The newly synthesized nanoparticles were further employed for the surface modification of polysulfone (PSF) hollow fiber membranes for dye removal. The modified hollow fiber membrane exhibited the improved permeability (56 L/ m2 h bar) and dye removal (>98% of Reactive Black 5 and >80.7% of Reactive orange 16) with the high permeation of salts. Therefore, the as-prepared membrane can have potential application in textile and industrial wastewater treatment.
Nanofiltration membranes technology commonly used for wastewater treatment especially
wastewater containing charged and/or uncharged species. Commonly, textile wastewater
possesses high chemical oxygen demand (COD) and non-biodegradable compounds such as
pigments and dyes which lead to environmental hazard and serious health problem. Therefore, the
objective of this study was to investigate the effects of hydrophilic surfactant on the preparation and
performance of Active Nanofiltration (ANF) membrane. The polymeric ANF membranes were
prepared via dry/wet phase inversion technique by immersion precipitation process. The
Cetyletrimethylammonium bromide (CTAB) as cationic surfactant was added in casting solution at
concentrations from 0 to 2.5 wt%. The synthesized membrane performance was evaluated in terms
of pure water permeation (PWP) and dye rejection. The experimental data showed that the
membrane demonstrated good increment of PWP ranging from 0.27 to 10.28 L/m2
h at applied
pressure from 100 to 500kPa, respectively. Meanwhile, the ANF membranes achieved high
removal of Methyl Blue and Reactive Black 5 dye up to 99.5% and 91.6%, respectively.
As sulfate-radical (SR)-based advanced oxidation processes are increasingly implemented, Oxone has been frequently-used for generation of SR. While Co3O4 nanoparticle (NP) has been widely-accepted as a promising catalyst for activating Oxone, Co3O4 NPs tend to aggregate in water, losing their reactivity. Thus, many attempts have immobilized Co3O4 NPs on supports, especially carbonaceous substrates, because combination of Co NPs with carbon substrates offers synergistic effects for boosting catalytic activities. Moreover, carbon substrates doped with hetero-atoms (N and S) further increase electron transfer and reactivity. Therefore, it is even promising to immobilize Co NPs onto N/S-doped carbon (NSC) to form Co-embedded NSC (denoted as CoNSC) for enhancing Oxone activation. In this study, a convenient and facile technique is proposed to prepare such a CoNSC via a simple carbonization treatment of a coordination polymer of Co and trithiocyanuric acid (TTCA). The resulting CoNSC exhibits the sheet-like hexagonal morphology with the core-shell configuration, and Co NPs are well-embedded into the N/S-doped carbonaceous matrix, making it an advantageous heterogeneous catalyst for Oxone activation. As Azorubine S (ARS) decolorization is employed as a model reaction of Oxone activation, CoNSC exhibits a higher catalytic activity than pristine Co3O4 and NSC for Oxone activation to decolorize ARS. In comparison to the other reported catalysts, CoNSC also possesses a much lower Ea for ARS decolorization. CoNSC can be also reusable and stable for Oxone activation over multiple cycles without loss of catalytic activity. These features validate that CoNSC is a promising and useful Co-based catalyst for Oxone activation.
Mixed microbial culture used in this study was developed from sludge that was taken from local textile wastewater treatment tank. Acclimatization process was performed before starting the biodegradation experiment to obtain a microbial culture with high degradation properties. Kinetic studies by the mixed microbial culture were determined quantitatively for the model pollutant, Reactive Black 5 (RB 5). By using Michaelis-Menten model, the constants were found to be 11.15 mg l-1 h -1 and 29.18 mg l-1 for Vm and Km respectively. The values of kinetic constants for Monod model were found to be 33.11 mg l-1 cell h-1 for the maximum specific microbial growth rate, µm and 86.62 mg l-1 for Monod constant, Ks. The effects of process parameters such as pH, inoculum size and initial dye concentration on the biodegradation of azo dye, RB 5 were systematically investigated. Maximum removal efficiencies observed in this study were 75% for pH 6, 100% for 15% inoculum concentration and 75% for 20 ppm of initial dye concentration.
The treatment of single and binary azo dyes, as well as the effect of the circuit connection, aeration, and plant on the performance of UFCW-MFC, were explored in this study. The decolorization efficiency of Remazol Yellow FG (RY) (single dye: 98.2 %; binary dye: 92.3 %) was higher than Reactive Black 5 (RB5) (single: 92.3 %; binary: 86.7 %), which could be due to monoazo dye (RY) requiring fewer electrons to break the azo bond compared to the diazo dye (RB5). In contrast, the higher decolorization rate of RB5 in binary dye indicated the removal rate was affected by the electron-withdrawing groups in the dye structure. The closed circuit enhanced about 2% of color and 4% of COD removal. Aeration improved the COD removal by 6%, which could be contributed by the mineralization of intermediates. The toxicity of azo dyes was reduced by 11-26% and the degradation pathways were proposed. The dye removal by the plants was increased with a higher contact time. RB5 was more favorable to be uptook by the plant as RB5 holds a higher partial positive charge. 127.39 (RY), 125.82 (RB5), and 58.66 mW/m3 (binary) of maximum power density were generated. The lower power production in treating the binary dye could be due to more electrons being utilized for the degradation of higher dye concentration. Overall, the UFCW-MFC operated in a closed circuit, aerated, and planted conditions achieved the optimum performance in treating binary azo dyes containing wastewater (dye: 87-92%; COD: 91%) compared to the other conditions (dye: 83-92%; COD: 78-87%).
The theme of present research demonstrates performance of copper (II) sulfate (CuSO4) as catalyst in thermolysis process to treat reactive black 5 (RB 5) dye. During thermolysis without presence of catalyst, heat was converted to thermal energy to break the enthalpy of chemical structure bonding and only 31.62% of color removal. With CuSO4 support as auxiliary agent, the thermally cleaved molecular structure was further destabilized and reacted with CuSO4. Copper ions functioned to delocalize the coordination of π of the lone paired electron in azo bond, C=C bond of the sp2 carbon to form C-C of the sp3 amorphous carbon in benzene and naphthalene. Further, the radicals of unpaired electrons were stabilized and RB 5 was thermally decomposed to methyl group. Zeta potential measurement was carried out to analyze the mechanism of RB 5 degradation and measurement at 0 mV verified the critical chemical concentration (CCC) (0.7 g/L copper (II) sulfate), as the maximum 92.30% color removal. The presence of copper (II) sulfate catalyst has remarkably increase the RB 5 dye degradation as the degradation rate constant without catalyst, k1 is 6.5224 whereas the degradation rate constant with catalyst, k2 is 25.6810. This revealed the correlation of conversion of thermal energy from heat to break the chemical bond strength, subsequent fragmentation of RB 5 dye molecular mediated by copper (II) sulfate catalyst. The novel framework on thermolysis degradation of molecular structure of RB 5 with respect to the bond enthalpy and interfacial intermediates decomposition with catalyst reaction were determined.
One of the biggest challenges of using single-chamber microbial fuel cells (MFCs) that utilize proton-exchange membrane (PEM) air cathode for bioenergy recovery from recalcitrant organic compounds present in wastewater is mainly attributed to their high internal resistance in the anodic chamber of the single microbial fuel cell (MFC) configurations. The high internal resistance is due to the small surface area of the anode and cathode electrodes following membrane biofouling and pH splitting conditions as well as substrate and oxygen crossover through the membrane pores by diffusion. To address this issue, the fabrication of new PEM air-cathode single-chamber MFC configuration was investigated with inner channel flow open assembled with double PEM air cathodes (two oxygen reduction activity zones) coupled with spiral-anode MFC (2MA-CsS-AMFC). The effect of various proton-exchange membranes (PEMs), including Nafion 117 (N-117), Nafion 115 (N-115), and Nafion 212 (N-212) with respective thicknesses of 183, 127, and 50.08 μ, was separately incorporated into carbon cloth as PEM air-cathode electrode to evaluate their influences on the performance of the 2MA-CsS-AMFC configuration operated in fed-batch mode, while Azorubine dye was selected as the recalcitrant organic compound. The fed-batch test results showed that the 2MA-CsS-AMFC configuration with PEM N-115 operated at Azorubine dye concentration of 300 mg L-1 produced the highest power density of 1022.5 mW m-2 and open-circuit voltage (OCV) of 1.20 V coupled with enhanced dye removal (4.77 mg L h-1) compared to 2MA-CsS-AMFCs with PEMs N-117 and N-212 and those in previously published data. Interestingly, PEM 115 showed remarkable reduction in biofouling and pH splitting. Apart from that, mass transfer coefficient of PEM N-117 was the most permeable to oxygen (KO = 1.72 × 10-4 cm s-1) and PEM N-212 was the most permeable membrane to Azorubine (KA = 7.52 × 10-8 cm s-1), while PEM N-115 was the least permeable to both oxygen (KO = 1.54 × 10-4) and Azorubine (KA = 7.70 × 10-10). The results demonstrated that the 2MA-CsS-AMFC could be promising configuration for bioenergy recovery from wastewater treatment under various PEMs, while application of PEM N-115 produced the best performance compared to PEMs N-212 and N-117 and those in previous studies of membrane/membrane-less air-cathode single-chamber MFCs that consumed dye wastewater.
In this work a novel anode configuration consisting of an iron mesh double layer is proposed for the electrochemical treatment of wastewater. The removal of Reactive Black 5 dye (RB5) from synthetic contaminated water was used as a model system. At a constant anode surface area, identical process operating parameters and batch process mode, the iron mesh double layer electrode showed better performance compared to the conventional single layer iron mesh. The double layer electrode was characterized by RB5 and chemical oxygen demand (COD) removal efficiency of 98.2% and 97.7%, respectively, kinetic rate constant of 0.0385/min, diffusion coefficient of 4.9×10(-5)cm(2)/sec and electrical energy consumption of 20.53kWh/kgdye removed. In the continuous flow system, the optimum conditions suggested by Response Surface Methodology (RSM) are: initial solution pH of 6.29, current density of 1.6mA/cm(2), electrolyte dose of 0.15g/L and flow rate of 11.47mL/min which resulted in an RB5 removal efficiency of 81.62%.
Acid denaturation of champedak galactose-binding (CGB) lectin was studied in the pH range, 7.0-1.0 using intrinsic fluorescence and ANS fluorescence measurements. The lectin remained stable up to pH 5.0 and showed local disordering in the vicinity of the protein fluorophores within the pH range, 5.0-3.5. Decrease in the pH from pH 3.5 to pH 2.5 led to structural transition, marked by the decrease in the intrinsic fluorescence and increase in the ANS fluorescence signals. This can be ascribed to the dissociation of the tetrameric lectin into monomeric forms. Further decrease in the pH up to pH 1.5 produced another transition, which specified the unfolding of monomers as reflected from the decrease in both intrinsic fluorescence and ANS fluorescence signals. Characterization of the conformational states obtained at pH 7.0, pH 2.5 and pH 1.5 based on intrinsic and ANS fluorescence spectra, gel chromatographic behavior and thermal denaturation confirmed the existence of folded monomeric forms at pH 2.5 and unfolded states at pH 1.5. However, the aciddenatured state of CGB lectin at pH 1.5 retained significant residual structure, as evident from the greater loss of both secondary and tertiary structures in the presence of 6 M guanidine hydrochloride at low pH values. Anion-induced refolding below pH 1.5 was also seen using ANS fluorescence measurements.