Congo red (CR) is an anionic azo dye widely used in many industries including pharmaceutical, textile, food and paint industries. The disposal of huge amount of CR into the various streams of water has posed a great threat to both human and aquatic life. Therefore, it has become an important aspect of industries to remove CR from different water sources. Molecular imprinting technology is a very slective method to remove various target pollutant from environment. In this study a precipitation polymerization was employed for the effective and selective removal of CR from contaminated aqueous media. A series of congo red molecularly imprinted polymers (CR-MIPs) of uniform size and shape was developed by changing the mole ratio of the components. The optimum ratio (0.1:4: 20, template, functional monomer and cross-linking monomer respectively) for CR1-MIP from synthesized polymers was able to rebind about 99.63% of CR at the optimum conditions of adsorption parameters (contact time 210 min, polymer dosage 0.5 g, concentration 20 ppm and pH 7). The synthesized polymers were characterized by various techniques such as Fourier Infra-red spectroscopy (FTIR), scanning electron microscopy (SEM), Thermogravimetric analysis (TGA), energy-dispersive X-ray spectroscopy (EDX), and Brumauer-Emmett-Teller (BET). The polymer particles have successfully removed CR from different aqueous media with an efficiency of about ~ 90%.
The presence of metal with microwave irradiation has always invited controversial arguments as the metal will catch on fire easily. But interestingly, researchers found that arc discharge phenomena provide a promising way for molecule cracking to synthesize nanomaterials. This study developed a single-step yet affordable synthesis approach that combines microwave heating and arcing in transforming crude palm oil into magnetic nanocarbon (MNC), which can be considered a new alternative for the palm oil sectors. It involves synthesizing the medium at a partial inert condition with constant coiled stainless steel metal wire (dielectric media) and ferrocene (catalyst). This approach successfully demonstrates heating at a temperature ranging from 190.9 to 472.0 °C with different synthesis times (10-20 min). The produced MNC shows formations of spheres with average sizes of 20.38-31.04 nm, mesoporous structure (SBET: 14.83-151.95 m2/g), and high content of fixed carbon (52.79-71.24wt%), and the ratio of the D and G bands (ID/IG) is 0.98-0.99. The formation of new peaks in the FTIR spectra (522.29-588.48 cm-1) supports the appearance of the FeO compounds from the ferrocene. The magnetometer shows high magnetization saturation (22.32-26.84 emu/g) in ferromagnetic materials. The application of the MNC in wastewater treatment has been demonstrated by evaluating their adsorbent capability with Methylene Blue (MB) adsorption test at a different concentrations varying between 5 and 20 ppm. The MNC produced at synthesis time (20 min) shows the highest adsorption efficiency (10.36 mg/g) compared to others, with 87.79% removal of MB dye. As a result, the value for Langmuir is not promising compared to Freundlich, with R2 being around 0.80, 0.98, and 0.99 for MNC synthesized at 10 min (MNC10), 15 min (MNC15), and 20 min (MNC20), respectively. Hence, the adsorption system is in a heterogeneous condition. The microwave-assisted arcing thereby presents a promising approach to transforming CPO into MNC that could remove the hazardous dye.
The purpose of this work is to remove Pb(II) from the aqueous solution using a type of hydrogel composite. A hydrogel composite consisting of waste linear low density polyethylene, acrylic acid, starch, and organo-montmorillonite was prepared through emulsion polymerization method. Fourier transform infrared spectroscopy (FTIR), Solid carbon nuclear magnetic resonance spectroscopy (CNMR)), silicon(-29) nuclear magnetic resonance spectroscopy (Si NMR)), and X-ray diffraction spectroscope ((XRD) were applied to characterize the hydrogel composite. The hydrogel composite was then employed as an adsorbent for the removal of Pb(II) from the aqueous solution. The Pb(II)-loaded hydrogel composite was characterized using Fourier transform infrared spectroscopy (FTIR)), scanning electron microscopy (SEM)), and X-ray photoelectron spectroscopy ((XPS)). From XPS results, it was found that the carboxyl and hydroxyl groups of the hydrogel composite participated in the removal of Pb(II). Kinetic studies indicated that the adsorption of Pb(II) followed the pseudo-second-order equation. It was also found that the Langmuir model described the adsorption isotherm better than the Freundlich isotherm. The maximum removal capacity of the hydrogel composite for Pb(II) ions was 430mg/g. Thus, the waste linear low-density polyethylene-g-poly (acrylic acid)-co-starch/organo-montmorillonite hydrogel composite could be a promising Pb(II) adsorbent.
This present research aims to synthesize and investigate the adsorption potential of sugarcane bagasse (SCB) impregnated with iron oxide (Fe3O4) for dye removal. The surface morphology and functional groups of the newly developed adsorbent (ISCB) were studied using Scanning Electron Microscopy/Energy-dispersive X-ray spectroscopy (SEM/EDX), Fourier transforms infrared spectroscopy (FTIR), and X-ray powder diffraction (XRD) analysis. The effects of the operating parameters, including initial dye concentration, adsorbent dosage, contact time and initial pH of the dye solution on the adsorption efficiency were investigated to identify an optimal condition. The characterization of SEM-EDX and FTIR analyses shows that ISCB has a porous structure and carbon-containing functional groups. The adsorption result revealed that ISCB removed 93.7% of dye, 88.8% of color and had a dye adsorption capacity of 7.2 mg/g within 6 h of contact time using 0.7 g/L of ISCB at pH 8.4. The result obtained fitted well for Langmuir isotherms, and adsorption process followed the pseudo-second-order kinetic model. In conclusion, this study proved that ISCB has the potential to be used as an effective and low-cost adsorbent to remove dyes from wastewater.
A chitosan/polyvinyl alcohol (PVA)/zeolite composite was fabricated in this study. The composite was analyzed through field emission scanning electron microscopy, Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), thermogravimetric analysis, and weight loss test. FTIR and XRD results revealed a strong interaction among chitosan, PVA, and zeolite. Weight loss test results indicated that the composite was stable in acidic and basic media. Congo red was removed through flocculation, and the removal rate was 94% at an initial concentration of 100mg/L for a dose of 1g/L. The removal rate of methyl orange was controlled by adsorption at an initial concentration of less than 100mg/L. Flocculation occurred at high concentrations. The removal rate was also 94% at an initial concentration of 500mg/L for a dose of 5g/L. The adsorption behavior of the composite for the removal of methyl orange and Cr(VI) was described by using a pseudo-second-order kinetic model. The adsorption capacity of the composite for Cr(VI) was 450mg/g. Therefore, the synthesized composite exhibited versatility during the removal of dyes and heavy metals.
Chitosan-ethylene glycol diglycidyl ether/TiO2 nanoparticles (CS-EGDE/TNP) composite was synthesized to be biosorbent for the removal of reactive orange 16 (RO16) dye from aqueous solution. The CS-EGDE/TNP composite was characterized via BET, XRD, FTIR, and SEM-EDX techniques. Response surface methodology (RSM) with Box-Behnken design (BBD) was applied to optimize the adsorption key parameters such as adsorbent dose (A: 0.02-0.08 g/L), RO16 dye concentration (B: 20-80 mg/L), solution pH (C: 4-10), temperature (D: 30-50 °C), and contact time (E: 30-90 min). The adsorption isotherm followed Freundlich model and pseudo-second order (PSO) kinetic model. The adsorption capacity of CS-EGDE/TNP for RO16 dye was 1407.4 mg/g at 40 °C. The adsorption mechanism of RO16 dye on the surface of CS-EGDE/TNP can be attributed to various interactions such as electrostatic attraction, n-π interaction, Yoshida H-bonding, and H-bonding. Results supported the potential use of CS-EGDE/TNP as effective adsorbent for the treatment of acid reactive dye.
In this research article, novel starch phosphate grafted polyvinyl imidazole (StP-g-PIMDZs) was synthesized. Firstly, a phosphate group was attached to starch polymer via a phosphorylation reaction. Next, 1-vinyl imidazole (VIMDZ) was grafted on the backbone of starch phosphate (StP) through a free radical polymerization reaction. The synthesis of these modified starches was confirmed by 1H NMR, 31P NMR and FT-IR techniques. The grafting of vinyl imidazole onto StP diminished the crystallinity. Due to the insertion of the aromatic imidazole ring, the StP-g-PIMDZs demonstrated greater thermal stability. The StP and StP-g-PIMDZs were used as sorbents for the adsorption of methylene blue dye (MBD) from the model solution. The maximum removal percentage for starch, StP, StP-g-PIMDZ 1, StP-g-PIMDZ 2 and StP-g-PIMDZ 3 was found to be 60.6%, 66.7%, 74.2%, 85.3 and 95.4%, respectively. The Pseudo second order kinetic model and Langmuir adsorption isotherm were best suited to the experimental data with R2 = 0.999 and 0.99, respectively. Additionally, the thermodynamic parameters showed that the adsorption process was feasible, spontaneous, endothermic and favored chemi-sorption mechanism.
The present study synthesized nano-magnetite (Fe3O4) from milled steel chips using the high energy ball milling (HEBM) method, characterized it, and then utilized it as a sorbent to remediate boron concentration at various pH (4-9), dosages (0.1-0.5 g), contact times (20-240 min), and initial concentrations (10-100 mg/L). The nano-sorbents were characterized based on SEM structure, elemental composition (EDX), surface area analysis (BET), crystallinity (XRD), and functional group analysis (FTIR). The highest adsorption capacity of 8.44 mg/g with removal efficiency of 84% was attained at pH 8, 0.5 g dosage, contact time of 180 min, and 50 mg/L initial concentration. The experimental data fit best with the pseudo-second-order kinetic model with R2 of 0.998, while the Freundlich adsorption isotherm describes the adsorption process with an R2 value of 0.9464. A regeneration efficiency of 47% was attained even after five cycles of reusability studies. This efficiency implies that the nano-magnetite has the potential for sustainable industrial application.
High concentration of fluoride in wastewater discharge from various industries is threatening the environment due to its hazardous effects and properties. This research work aims to develop an efficient adsorbent for fluoride removal in wastewater. Graphite oxide (GO) was impregnated
with ZnO nanoparticles as an adsorbent, and the effect of synthesis parameters of GO-ZnO adsorbent for fluoride removal were studied (sonication temperature, synthesis time, and ratio of GO to ZnO). The surface functional groups of these synthesized adsorbents were analyzed by
using FTIR. The synthesis parameters that contribute to the highest adsorption capacity and percentage removal are 5:1 ratio of GO-ZnO, 45 ºC of sonication temperature and 60 minutes of synthesis time, respectively. The highest value of adsorption capacity obtained from the fluoride
removal is 55.5 mg/g. The functional groups contained in the GO-ZnO adsorbent are hydroxyl group (O-H), C=O group, aromatics group, carboxyl group (C-O), epoxy group and alkoxy group. These functional groups showed significant impact towards fluoride adsorption due to the bonding of fluoride ion to the functional groups.
A molecularly imprinted polymer (MIP), with the ability to bind Pb(II) ion, was prepared using the non-covalent molecular imprinting methods and evaluated as a sorbent for the Pb(II) ion uptake. 4-vinylbenzoic acid was chosen as the complexing monomer. The imprinted polymer was synthesized by radical polymerization. The template (Pb(II) ions) was removed using 0.1 M HCl. As a result, the efficient adsorption was found to occur at pH 7. The result also showed the applicability of the Langmuir model for the sorption, with the maximum sorption capacity of 204.08 μg/mg.
β-Cyclodextrin-ionic liquid polymer (CD-ILP) was first synthesized by functionalized β-cyclodextrin (CD) with 1-benzylimidazole (BIM) to form monofunctionalized CD (βCD-BIMOTs) and was further polymerized using a toluene diisocyanate (TDI) linker to form insoluble CD-ILP (βCD-BIMOTs-TDI). The βCD-BIMOTs-TDI polymer was characterized using various tools and the results obtained were compared with those derived from the native β-cyclodextrin polymer (βCD-TDI). The SEM result shows that the presence of ionic liquid (IL) increases the pore size, while the thermo gravimetric analysis (TGA) result shows that the presence of IL increases the stability of the polymer. Meanwhile, Brunauer-Emmett-Teller (BET) results show that βCD-BIMOTs-TDI polymer has 1.254 m(2)/g surface areas and the Barret-Joyner-Halenda (BJH) pore size distribution result reveals that the polymer exhibits macropores with a pore size of 77.66 nm. Preliminary sorption experiments were carried out and the βCD-BIMOTs-TDI polymer shows enhanced sorption capacity and high removal towards phenols and As(V).
The recent implication of circular economy in Australia spurred the demand for waste material utilization for value-added product generations on a commercial scale. Therefore, this experimental study emphasized on agricultural waste biomass, rice husk (RH) as potential feedstock to produce valuable products. Rice husk biochar (RB) was obtained at temperature: 180 °C, pressure: 70 bar, reaction time: 20 min with water via hydrothermal carbonization (HTC), and the obtained biochar yield was 57.9%. Enhancement of zeta potential value from - 30.1 to - 10.6 mV in RB presented the higher suspension stability, and improvement of surface area and porosity in RB demonstrated the wastewater adsorption capacity. Along with that, an increase of crystallinity in RB, 60.5%, also indicates the enhancement of the catalytic performance of the material significantly more favorable to improve the adsorption efficiency of transitional compounds. In contrast, an increase of the atomic O/C ratio in RB, 0.51 delineated high breakdown of the cellulosic component, which is favorable for biofuel purpose. 13.98% SiO2 reduction in RB confirmed ash content minimization and better quality of fuel properties. Therefore, the rice husk biochar through HTC can be considered a suitable material for further application to treat wastewater and generate bioenergy.
A magnetic graphene oxide (MGO) was developed for the adsorption of As(III) from aqueous solution. The characteristics of MGO were investigated using Fourier-transform infrared (FTIR), X-ray diffraction and field emission scanning electron microscope-E/energy-dispersive X-ray analyses. Batch adsorption experiments were designed using central composite design, and the effects of adsorbent dosage, pH, contact time and concentration of As(III) were investigated. The MGO showed an excellent performance, removing up to 99.95% of As(III) under the following condition: initial As(III) concentration = 100 mg/L, pH = 7, adsorbent dosage = 0.3 g/L and contact time = 77 min. MGO dosage and initial pH were the most significant parameters influencing the process performance. FTIR analysis of the used adsorbent confirms the adsorption of As(III) through complexation between surface functional groups of the MGO and the oxyanions of As(III). The adsorbent maintained a significant level of performance even after four cycles of adsorption. Thus, the developed MGO has the potential to be used for the abatement of arsenic pollution.
In this study, adsorption behavior of anthill-eggshell composite (AEC) for the removal of hexavalent chromium (Cr6+) from aqueous solution was investigated. The raw AEC sample was thermally treated at 864 °C for 4 h and characterized using Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and X-ray fluorescence (XRF) techniques. The effects of adsorption process variables including initial Cr6+ concentration, contact time, and adsorbent dosage on the Cr6+ removal efficiency were investigated using central composite design (CCD) of response surface methodology (RSM). Equilibrium adsorption isotherm and kinetic were also studied. From the analysis of variance (ANOVA), the three variables proved to be significant and the optimum conditions for Cr6+ adsorption were obtained to be 150 mg/L initial Cr6+ concentration, 45.04-min contact time, and 0.5 g adsorbent dosage, which resulted in 86.21% of Cr6+ adsorbed. Equilibrium isotherm study showed that Freundlich model fitted well to the experimental data. The pseudo-second-order kinetic model appeared to better describe the experimental data. The study showed that mixed anthill-eggshell is a promising adsorbent for removing Cr6+ from aqueous solution.
The acid corrosion inhibition process of mild steel in 1 M HCl by azelaic acid dihydrazide has been investigated using electrochemical impedance spectroscopy (EIS), potentiodynamic polarization, open circuit potential (OCP) and electrochemical frequency modulation (EFM). Azelaic acid dihydrazide was synthesized, and its chemical structure was elucidated and confirmed using spectroscopic techniques (infrared, nuclear magnetic resonance and mass spectroscopy). Potentiodynamic polarization studies indicate that azelaic acid dihydrazide is a mixed-type inhibitor. The inhibition efficiency increases with increased inhibitor concentration and reaches its maximum of 93% at 5 × 10(-3) M. The adsorption of the inhibitor on a mild steel surface obeys Langmuir's adsorption isotherm. The effect of te perature on corrosion behavior in the presence of 5 × 10(-3) M inhibitor was studied in the temperature range of 30-60 °C. The results indicated that inhibition efficiencies were enhanced with an increase in concentration of inhibitor and decreased with a rise in temperature. To inspect the surface morphology of inhibitor film on the mild steel surface, scanning electron microscopy (SEM) was used before and after immersion in 1.0 M HCl.
The development of new adsorbent has rapidly increased in order to overcome the problem
of waste water treatment from heavy metal pollution. The ability of nickel (II)-ion imprinted
polymer (Ni-IIP) as an alternative adsorbent for the removal of nickel ion from aqueous has
been investigated. The Ni-IIP was prepared via bulk polymerization by using functional
monomers; methylacrylic acid (MAA) with picolinic acid as a co-monomer. Nickel ion was
used as template, AIBN as initiator and EGDMA as cross-linking agent. Non-imprinted control
polymer (NIP) was prepared in the same manner as Ni-IIP but in the absence of nickel
ion. The resultant of Ni-IIP and NIP were characterized by using Fourier Transform Infrared
(FTIR) spectroscopy and Scanning Electron Microscope (SEM). Result showed that, the adsorption
of nickel ion onto Ni-IIP increased as the adsorbent dosage increased and contact
time is prolonged. The adsorption isotherm model for Ni-IIP and NIP were fitted well with
Freundlich and Langmuir, respectively. Kinetic study for both Ni-IIP and NIP were followed
the pseudo-second order, indicates that the rate-limiting step is the surface adsorption that
involves chemisorption. Selectivity studies showed that the distribution coefficient of Ni2+
was higher compared to Zn2+, Mg2+ and Pb2+. The present work has successfully synthesized
Ni-IIP particles with good potential in recognition of Ni2+ ions in an aqueous medium.
The main objectives of this study are to synthesize a new solid-supported ionic liquid (SSIL) that has a covalent bond between the solid support, i.e., activated silica gel, with thiosalicylate-based ionic liquid and to evaluate the performance of this new SSIL as an extractant, labelled as Si-TS-SSIL, and to remove Pb(II) ions from an aqueous solution. In this study, 1-methyl-3-(3-trimethoxysilylpropyl) imidazolium thiosalicylate ([MTMSPI][TS]) ionic liquid was synthesized and the formation of [MTMSPI][TS] was confirmed through structural analysis using NMR, FTIR, IC, TGA, and Karl Fischer Titration. The [MTMSPI][TS] ionic liquid was then chemically immobilized on activated silica gel to produce a new thiosalicylate-based solid-supported ionic liquid (Si-TS-SSIL). The formation of these covalent bonds on Si-TS-SSIL was confirmed by solid-state NMR analysis. Meanwhile, BET analysis was performed to study the surface area of the activated silica gel and the prepared Si-TS-SSIL (before and after washing with solvent) with the purpose to show that all physically immobilized [MTMSPI][TS] has been washed off from Si-TS-SSIL, leaving only chemically immobilized [MTMSPI][TS] on Si-TS-SSIL before proceeding with removal study. The removal study of Pb(II) ions from an aqueous solution was carried out using Si-TS-SSIL as an extractant, whereby the amount of Pb(II) ions removed was determined by AAS. In this removal study, the experiments were carried out at a fixed agitation speed (400 rpm) and fixed amount of Si-TS-SSIL (0.25 g), with different contact times ranging from 2 to 250 min at room temperature. The maximum removal capacity was found to be 8.37 mg/g. The kinetics study was well fitted with the pseudo-second order model. Meanwhile, for the isotherm study, the removal process of Pb(II) ions was well described by the Freundlich isotherm model, as this model exhibited a higher correlation coefficient (R2), i.e., 0.99, as compared to the Langmuir isotherm model.
Mesoporous silica materials (MSMs) were synthesized economically using silica (SiO2) as a precursor via a modified alkaline fusion method. The MSM prepared at 500°C (MSM-500) had the highest surface area, pore size, and volume, and the results of isotherms and the kinetics of ibuprofen (IBP) removal indicated that MSM-500 had the highest sorption capacity and fastest removal speed vs. SBA-15 and zeolite. Compared with commercial granular activated carbon (GAC), MSM-500 had a ~100 times higher sorption rate at neutral pH. IBP uptake by MSM-500 was thermodynamically favorable at room temperature, which was interpreted as indicating relatively weak bonding because the entropy (∆adsS, -0.07 J mol(-1) K(-1)) was much smaller. Five times recycling tests revealed that MSM-500 had 83-87% recovery efficiencies and slower uptake speeds due to slight deformation of the outer pore structure. In the IBP delivery test, MSM-500 drug loading was 41%, higher than the reported value of SBA-15 (31%). The in vitro release of IBP was faster, almost 100%, reaching equilibrium within a few hours, indicating its effective loading and unloading characteristics. A cost analysis study revealed that the MSM was ~10-70 times cheaper than any other mesoporous silica material for the removal or delivery of IBP.
The influence of an anionic surfactant, a cationic surfactant, and salinity on adsorbed methane (CH4) in shale was assessed and modeled in a series of systematically designed experiments. Two cases were investigated. In case 1, the crushed Marcellus shale samples were allowed to react with anionic sodium dodecyl sulfate (SDS) and brine. In case 2, another set of crushed Marcellus shale samples were treated with cetyltrimethylammonium bromide (CTAB) and brine. The surfactant concentration and salinity of brine were varied following the Box-Behnken experimental design. CH4 adsorption was then assessed volumetrically in the treated shale at varying pressures (1-50 bar) and a constant temperature of 30 °C using a pressure equilibrium cell. Mathematical analysis of the experimental data yielded two separate models, which expressed the amount of adsorbed CH4 as a function of SDS/CTAB concentration, salinity, and pressure. In case 1, the highest amount of adsorbed CH4 was about 1 mmol/g. Such an amount was achieved at 50 bar, provided that the SDS concentration is kept close to its critical micelle concentration (CMC), which is 0.2 wt %, and salinity is in the range of 0.1-20 ppt. However, in case 2, the maximum amount of adsorbed CH4 was just 0.3 mmol/g. This value was obtained at 50 bar and high salinity (∼75 ppt) when the CTAB concentration was above the CMC (>0.029 wt %). The findings provide researchers with insights that can help in optimizing the ratio of salinity and surfactant concentration used in shale gas fracturing fluid.
Biochar/layered double hydroxide (LDH) composites have gained considerable attention in recent times as low-cost sustainable materials for applications in water treatment. This paper critically evaluates the latest development in applications of biochar/LDH composites in water treatment with an emphasis on adsorption and catalytic degradation of various pollutants. The adsorption of various noxious contaminants, i.e., heavy metals, dyes, anions, and pharmaceuticals onto biochar/LDH composites are described in detail by elaborating the adsorption mechanism and regeneration ability. The synergistic effect of LDH with biochar exhibited significant improvement in specific surface area, surface functional groups, structure heterogeneity, stability, and adsorption characteristics of the resulting biochar/LDH composites. The major hurdles and challenges associated with the synthesis and applications of biochar/LDH composites in water remediation are emphasized. Finally, a roadmap is suggested for future research to assure the effective applications of biochar/LDH composites in water purification.