Water pollution caused by dyes has been a serious problem affecting human health and environment. The surface of polyacrylonitrile (PAN) nanofiber membranes was modified by mild hydrolysis and coupled with bovine serum albumin (BSA) obtained from the laboratory wastes, resulting in the synthesis of P-COOH and P-COOH-BSA nanofibers. The nanofibers with specific functional groups may enhance their potential applications toward the removal of ionic dyes in wastewater. Toluidine blue O (TBO) was applied as an example of cationic dye to evaluate the removal efficiency of P-COOH-BSA nanofiber. Results showed that the equilibrium dissociation constant and maximum removal capacity were 0.48 mg/mL and 434.78 mg/g, respectively, at pH 12, where the TBO removal can be explained based on Langmuir isotherm and pseudo-second-order model. Desorption studies have shown that TBO adsorbed on P-COOH-BSA protein membrane can be completely eluted with either 1 M NaCl or 50% glycerol. The results of repeated studies indicated that after five consecutive adsorption/desorption cycles, the removal efficiency of TBO can be maintained at ~97%. P-COOH-BSA has shown to be promising adsorbent in TBO dye removal from dye wastewater.
In current research work, chitosan (Chi) was subjected to subsequent physical and chemical modifications by incorporating kaolin clay (KA) into its polymeric structure, and crosslinking process with a covalent cross-linker namely epichlorohydrin (ECH) respectively. The final product of crosslinked chitosan-epichlorohydrin/kaolin (Chi-ECH/KA) composite was successfully applied for color removal and chemical oxygen demand (COD) reduction of textile dye namely reactive blue 19 dye (RB19) from aqueous environment. The influence of pertinent parameters, i.e. A: Chi-ECH/KA dose (0.02-0.1 g), B: pH (4-10), and C: time (5-30 min) on the RB19 color removal and COD reduction were statistically optimized by using response surface methodology with Box-Behnken design (RSM-BBD). The experimental data of the adsorption kinetic and the adsorption isotherm demonstrated a better fitness to pseudo-second order model and Langmuir isotherm model respectively. Excellent absorption ability of 560.9 mg/g was recorded for Chi-ECH/KA composite. The calculated thermodynamic functions clarified that the RB19 adsorption process was endothermic and spontaneous in nature. The mechanism of RB19 adsorption onto the Chi-ECH/KA may include electrostatic interactions, hydrogen bonding, Yoshida H-bonding, and n-π interactions. This study introduces Chi-ECH/KA composite as an eco-friendly, potential and multi-function composite bio adsorbent for removal of textile dye and COD reduction from aqueous environment.
Adsorption of lysozyme on the dye-affinity nanofiber membranes was investigated in batch and dynamic modes. The membrane matrix was made of electrospun polyacrylonitrile nanofibers that were grafted with ethylene diamine (EDA) and/or chitosan (CS) for the coupling of Reactive Blue 49 dye. The physicochemical properties of these dye-immobilized nanofiber membranes (P-EDA-Dye and P-CS-Dye) were characterized microscopically, spectroscopically and thermogravimetrically. The capacities of lysozyme adsorption by the dye-affinity nanofiber membranes were evaluated under various conditions, namely pH, dye immobilized density, and loading flow rate. The adsorption of lysozyme to the dye-affinity nanofiber membranes was well fitted by Langmuir isotherm and pseudo-second kinetic models. P-CS-Dye nanofiber membrane had a better performance in the dynamic adsorption of lysozyme from complex chicken egg white solution. It was observed that after five cycles of adsorption-desorption, the dye-affinity nanofiber membrane did not show a significant loss in its capacity for lysozyme adsorption. The robustness as well as high dynamic adsorption capability of P-CS-Dye nanofiber membrane are promising for the efficient recovery of lysozyme from complex feedstock via nanofiber membrane chromatography.
Renewable solar energy is the key target to reduce fossil fuel consumption, minimize global warming issues, and indirectly minimizes erratic weather patterns. Herein, the authors synthesized an ultrathin reduced graphene oxide (rGO) nanosheet with ~47 nm via an improved Hummer's method. The TiO2 was deposited by RF sputtering onto an rGO nanosheet with a variation of temperature to enhance the photogenerated electron or charge carrier mobility transport for the photoanode component. The morphology, topologies, element composition, crystallinity as well as dye-sensitized solar cells' (DSSCs) performance were determined accordingly. Based on the results, FTIR spectra revealed presence of Ti-O-C bonds in every rGO-TiO2 nanocomposite samples at 800 cm-1. Besides, XRD revealed that a broad peak of anatase TiO2 was detected at ~25.4° after incorporation with the rGO. Furthermore, it was discovered that sputtering temperature of 120 °C created a desired power conversion energy (PCE) of 7.27% based on the J-V plot. Further increase of the sputtering temperature to 160 °C and 200 °C led to excessive TiO2 growth on the rGO nanosheet, thus resulting in undesirable charge recombination formed at the photoanode in the DSSC device.
Chitosan (CS) was physically modified with fly ash (FA) powder and subjected to chemical cross-linking reaction with tripolyphosphate (TPP) to produce a cross-linked CS-TPP/FA composite as adsorbent for removal of reactive orange 120 (RR120) dye. Different ratios of FA such as 25% FA particles (CS-TPP/FA-25) and 50% FA particles (CS-TPP/FA-50) were loaded into the molecular structure of CS-TPP. Box-Behnken design (BBD) was applied to optimize the input variables that affected the synthesis of the adsorbent and the adsorption of RR120 dye. These variables included FA loading (A: 0-50%), adsorbent dose (B: 0.04-0.1 g), solution pH (C: 4-10), temperature (D: 30 °C-60 °C), and time (E: 30-90 min). Results revealed that the highest removal (88.8%) of RR120 dye was achieved by CS-TPP/FA-50 at adsorbent dosage of 0.07 g, solution of pH 4, temperature of 45 °C, and time of 60 min. The adsorption equilibrium was described by the Freundlich model, with 165.8 mg/g at 45 °C as the maximum adsorption capacity of CS-TPP/FA-50 for RR120 dye. This work introduces CS-TPP/FA-50 as an ideal composite adsorbent for removal of textile dyes from the aqueous environment.
Biochar (BC) has attracted much attention owing to its superior sorption capacity towards ionized organic contaminants. However, the mechanism of ionized organics sorption occurring within BC containing large amounts of minerals is still controversial. In this study, we demonstrate the physicochemical structure of high-salinity microalgal residue derived biochar (HSBC) and elucidate the corresponding sorption mechanisms for four ionized dyes along with determining the crucial role of involved minerals. The results indicate that sodium and calcium minerals mainly exist within HSBCs, and the pyrolysis temperature can dramatically regulate the phases and interfacial property of both carbon matrix and minerals. As a result, the HSBC shows a higher sorption potential, benefiting from abundant functional groups and high content of inorganic minerals. Using theoretical calculations, the activities of electron donor-acceptor interaction between HSBCs and different dyes are clearly illustrated, thereby identifying the critical role of Ca2+ in enhancing the removal of ionized dyes in HSBCs. In addition, Ca-containing minerals facilitate the sorption of ionized dyes in HSBCs by forming ternary complexes through metal-bridging mechanism. These results of mineral-induced dye sorption mechanisms help to better understand the sorption of ionized organics in high-salt containing BC and provide a new disposal strategy for hazardous microalgal residue, as well as provide a breakthrough in making the remediation of ionized organic contaminated microalgal residue derived absorbent feasible.
Proper remediation of aquatic environments contaminated by toxic organic dyes has become a research focus globally for environmental and chemical engineers. This study evaluates the adsorption potential of a polymer-based adsorbent, thiourea-modified poly(acrylonitrile-co-acrylic acid) (T-PAA) adsorbent, for the simultaneous uptake of malachite green (MG) and methylene blue (MB) dye ions from binary system in a continuous flow adsorption column. The influence of inlet dye concentrations, pH, flow rate, and adsorbent bed depth on adsorption process were investigated, and the breakthrough curves obtained experimentally. Results revealed that the sorption capacity of the T-PAA for MG and MB increase at high pH, concentration and bed-depth. Thomas, Bohart-Adams, and Yoon-Nelson models constants were calculated to describe MG and MB adsorption. It was found that the three dynamic models perfectly simulate the adsorption rate and behavior of cationic dyes entrapment. Finally, T-PAA adsorbent demonstrated good cyclic stability. It can be regenerated seven times (or cycles) with no significant loss in adsorption potential. Overall, the excellent sorption capacity and multiple usage make T-PAA polymer an attractive adsorbent materials for treatment of multicomponent dye bearing effluent in a fixed-bed column system.
This study investigates the effects of stirring duration on the synthesis of graphene oxide (GO) using an improved Hummers' method. Various samples are examined under different stirring durations (20, 40, 60, 72, and 80 h). The synthesized GO samples are evaluated through X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), and Raman spectroscopy. The GO sample with 72 h stirring duration (GO72) has the highest d-spacing in the XRD results, highest atomic percentage of oxygen in EDX (49.57%), highest intensity of oxygen functional group in FTIR spectra, and highest intensity ratio in Raman analysis (ID/IG = 0.756). Results show that GO72 with continuous stirring has the highest degree of oxidation among other samples. Electrochemical impedance spectroscopy analysis shows that GO72-titanium dioxide (TiO2) exhibits smaller charge transfer resistance and higher electron lifetime compared with the TiO2-based photoanode. The GO72 sample incorporating TiO2 nanocomposites achieves 6.25% photoconversion efficiency, indicating an increase of more than twice than that of the mesoporous TiO2 sample. This condition is fully attributed to the efficient absorption rate of nanocomposites and the reduction of the recombination rate of TiO2 by GO in dye-sensitized solar cells.
A developed colorimetric pH sensor film based on edible materials for real-time monitoring of food freshness is described. The mixed natural dyes from edible plants Clitoria sp and Brassica sp were extracted and incorporated into ι-carrageenan film as a colorimetric pH sensor film for monitoring food spoilage and its freshness. The color changes of the developed colorimetric sensor film were measured with chromametry and UV-vis spectroscopy, respectively. Experimental results show that colorimetric pH sensor film demonstrated statistically significant differences (p < 0.05) between CIE-L*a*b* coordinates color system indicated that the developed colorimetric sensor film was able to give a gradual change in color over a wide pH range. The color of the colorimetric sensor film also changes discretely and linearly with factors that contribute to food spoilage using shrimp and durian samples. Moreover, the developed colorimetric pH sensor film has the potential to be used as a safe, non-destructive testing and also a flexibly visual method for direct assessment of food freshness indicator during storage.
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.
Nanofiber membrane chromatography integrates liquid membrane chromatography and nanofiber filtration into a single-step purification process. Nanofiber membrane can be functionalised with affinity ligands for promoting binding specificity of membrane. Dye molecules are a good affinity ligand for nanofiber membrane due to their low cost and high binding affinity. In this study, a dye-affinity nanofiber membrane (P-Chitosan-Dye membrane) was prepared by using polyacrylonitrile nanofiber membrane modified with chitosan molecules and immobilized with dye molecules. Reactive Orange 4, commercially known as Procion Orange MX2R, was found to be the best dye ligand for membrane chromatography. The binding capacity of P-Chitosan-Dye membrane for lysozyme was investigated under different operating conditions in batch mode. Furthermore, desorption of lysozyme using the P-Chitosan-Dye membrane was evaluated systematically. The recovery percentage of lysozyme was found to be ~100%. The optimal conditions obtained from batch-mode study were adopted to develop a purification process to separate lysozyme from chicken egg white. The process was operated continuously using the membrane chromatography and the characteristic of the breakthrough curve was evaluated. At a lower flow rate (i.e., 0.1 mL/min), the total recovery of lysozyme and purification factor of lysozyme were 98.59% and 56.89 folds, respectively.
The utilization of renewable and functional group enriched nano-lignin as bio-additve in fabricating composite has become the focus of attention worldwide. Herein, lignin nanoparticles in the form of hollow spheres with the diameter of the order of 138 ± 39 nm were directly prepared from agro-industrial waste (palm kernel shell) using recyclable tetrahydrofuran in an acidified aqueous system without any chemical modification steps. We then fabricated a new chitosan/nano-lignin composite material as highly efficient sorbent, as demonstrated by efficient removal (~83%) of methylene blue (MB) dye under natural pH conditions. The adsorption process obeyed pseudo-second-order kinetics and adequate fitting of the adsorption data using Langmuir model suggested a monolayer adsorption with a maximum adsorption capacity of 74.07 mg g-1. Moreover, thermodynamic study of the system revealed spontaneous and endothermic nature of the sorption process. Further studies revealed that chitosan composite with nano-lignin showed better performance in dye decontamination compared to native chitosan and chitosan/bulk lignin composite. This could essentially be attributed to synergistic effects of size particularity (nano-effect) and incorporated functionalities due to lignin nanoparticles. Recyclability study performed in four repeated adsorption/regeneration cycles revealed recyclable nature of as-prepared composite, whilst adsorption experiments using spiked real water samples indicated recoveries as high as 89%. Based on this study, as-prepared bio-nanocomposite may thus be considered as an efficient and reusable adsorptive platform for the decontamination of water supplies.
Aim: Time-based microfluidic absorption sampling was proposed using cotton fiber-based device made in swab stick. The assay was optimized and compared with conventional pipetted drop sampling using the same device. Materials & methods: Reagents were integrated into cotton fiber device for assessing concentration of analytes by the colorimetric detection method through time-based absorption sampling microfluidic system. All assay parameters were first optimized using conventional pipette-based drop sampling. Results: The color intensity is linear in the relevant concentration range of the analytes. The LOD are 0.189 mM for glucose and 6.56 μM for nitrite, respectively. These values are better than conventional drop sampling. The fiber-containing swab itself functions as sampling, assay and calibration device. Conclusion: Microfluidic cotton fiber-based assay device was fabricated and can determine analyte concentration in artificial salivary samples, colorimetrically, by time-based absorption sampling without the need of complex equipments.
The remediation of wastewater requires treatment technologies which are robust, efficient, simple to operate and affordable such as adsorption. Lately, three-dimensional (3D) graphene based materials have attracted significant attention as effective adsorbents for wastewater treatment. The intrinsic properties of 3D graphene structure such as large surface area and interconnected porous structure can facilitate the transport of pollutants into the 3D network and provide abundant active sites for trapping the pollutants. For the synthesis of 3D graphene structure, ice-templating is commonly practiced due to its facile steps, cost effectiveness and high scalability potential. This review covers the ice-templating fabrication technique for 3D graphene based materials and their application as adsorbents in eliminating dyes and heavy metals from aqueous media. The assembly mechanisms of the ice-templating fsynthesis are comprehensively discussed. Further discussion on the fundamental principles, critical process parameters and characteristics of ice-templated 3D graphene structures is also included. A thorough review on the mechanisms for batch adsorption of dyes and heavy metals is presented based on the structures and properties of the 3D graphene materials. The review further evaluates the dynamic adsorption in packed columns and the regeneration of 3D graphene based materials.
Magnetic beads (AO-γ-Fe2O3) of alginate (A) impregnated with citrate coated maghemite nanoparticles (γ-Fe2O3) and oxidized multiwalled carbon nanotubes (OMWCNTs) were synthesized and used as adsorbent for the removal of methylene blue from water. The XRD analysis revealed that the diameter of γ-Fe2O3 is 10.24 nm. The mass saturation magnetization of AO-γ-Fe2O3 and γ-Fe2O3 were found to be 27.16 and 42.63 emu·g-1, respectively. The adsorption studies revealed that the data of MB isotherm were well fitted to the Freundlich model. The Langmuir isotherm model exhibited a maximum adsorption capacity of 905.5 mg·g-1. The adsorption was very dependent on initial concentration, adsorbent dose, and temperature. The beads exhibited high adsorption stability in large domain of pH (4-10). The thermodynamic parameters determined at 283, 293, 303, and 313 K revealed that the adsorption occurring was spontaneous and endothermic in nature. Adsorption kinetic data followed the intraparticle diffusion model. The AO-γ-Fe2O3 beads were used for six cycles without significant adsorptive performance loss. Therefore, the eco-friendly prepared AO-γ-Fe2O3 beads were considered as highly recyclable and efficient adsorbent for methylene blue as they can be easily separated from water after treatment.
Graphene oxide/chitosan aerogel (GOCA) was prepared by a facile ice-templating technique without using any cross-linking reagent for metanil yellow dye sequestration. The adsorption performance of GOCA was investigated by varying the adsorbent mass, shaking speed, initial pH, contact time, concentration and temperature. The combined effects of adsorption parameters and the optimum conditions for dye removal were determined by response surface methodology. GOCA exhibited large removal efficiencies (91.5-96.4%) over a wide pH range (3-8) and a high adsorption capacity of 430.99 mg/g at 8 mg adsorbent mass, 400 mg/L concentration, 35.19 min contact time and 175 rpm shaking speed. The adsorption equilibrium was best represented by the Langmuir model. GOCA could be easily separated after adsorption and regenerated for re-use in 5 adsorption-desorption cycles thereby maintaining 80% of its adsorption capability. The relatively high adsorption and regeneration capabilities of GOCA render it an attractive adsorbent for treatment of azo dye-polluted water.
The adsorption of rhodamine B (RhB) using acid modified banana peels has been examined. Chemical characteristics of the adsorbents were observed in order to determine active functional groups. The major functional groups on the surface were OH, C = O, C = C and C-O-C. Interactions between operational parameters were studied using the central composite design (CCD) of response surface methodology (RSM). The predictions of the model output indicated that operational factors influenced responses at a confidence level of 95% (P<0.05). The optimum conditions for adsorption were pH 2 at a 0.2 g/L dose within 60 minutes of contact time. Isotherm studies were carried out using the optimized process variables. The data revealed that RhB adsorption fitted the Langmuir isotherm equation while the reduction of COD followed the Freundlich isotherm. Kinetic experiments fitted the pseudo second order model for RhB removal and COD reduction. The adsorption mechanism was not the only rate controlling step. Diffusion through the boundary layer described the pattern of adsorption.
Dye-ligand affinity chromatography in a stirred fluidized bed has been developed for the rapid recovery of malate dehydrogenase (MDH) from highly turbid baker's yeast cell homogenate in a single step. The most suitable dye, namely Reactive Orange 4, in its optimal immobilized concentration of 8.78 mg/mL was immobilized onto high-density STREAMLINE matrix. To further examine optimal adsorption and elution conditions, the enzyme recovery operation was carried out using unclarified cell homogenates in stirred fluidized bed system. Aiming to develop a non-specific eluent, namely NaCl, to effectively elute the MDH adsorbed, direct recovery of MDH from highly turbid cell homogenate (50% w/v) in a stirred fluidized bed adsorption system was performed. The proposed system successfully achieved a recovery yield of 73.6% and a purification factor of 73.5 in a single step by using 0.6 M NaCl as an eluent at a high liquid velocity of 200 cm/h.
The adsorption behavior of basic, methylene blue (MB), and reactive, remazol brilliant violet 5R (RBV), dyes from aqueous solution onto Intsia bijuga sawdust-based activated carbon (IBSAC) was executed via batch and column studies. The produced activated carbon was characterized through Brunauer-Emmett-Teller (BET) surface area and pore structural analysis, proximate and ultimate, scanning electron microscopy (SEM), and Fourier transform infrared spectroscopy (FTIR). Batch studies were performed to investigate the effects of contact time, initial concentration, and solution pH. The equilibrium data for both MB and RBV adsorption better fits Langmuir model with maximum adsorption capacity of 434.78 and 212.77 mg/g, respectively. Kinetic studies for both MB and RBV dyes showed that the adsorption process followed a pseudo-second-order and intraparticle diffusion kinetic models. For column mode, the breakthrough curves were plotted by varying the flow rate, bed height, and initial concentration and the breakthrough data were best correlated with the Yoon-Nelson model compared to Thomas and Adams-Bohart model. The adsorption activity of IBSAC shows good stability even after four consecutive cycles.