Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TU-poly(AN-co-AA)) adsorbent was a surface modification of poly(acrylonitrile-co-acrylic acid) synthesized by facile redox polymerization. Surface functionalization with thiourea was carried out to provide hydrophilicity on the surface of a polymeric adsorbent. Fourier transform infrared (FTIR) spectrometer, scanning electron microscope (SEM), and Zetasizer characterized the morphology and structures of TU-poly(AN-co-AA). Copolymerization of poly(acrylonitrile-co-acrylic acid) and its successful incorporation of the thioamide group was confirmed by the FTIR spectra. The SEM micrographs depicted uniform and porous surface morphologies of polymeric particles. The average diameter of modified and unmodified poly(acrylonitrile-co-acrylic acid) was 289 nm and 279 nm, respectively. Zeta potentials of TU-poly(AN-co-AA) revealed the negatively charged surface of the prepared polymer. Adsorption capacities of hydrophilic TU-poly(AN-co-AA) were investigated using malachite green (MG) as an adsorbate by varying experimental conditions (pH, initial concentration, and temperature). Results showed that the pseudo-second-order reaction model best described the adsorption process with chemisorption being the rate-limiting step. Furthermore, Elovich and intraparticle diffusions play a significant role in adsorption kinetics. The equilibrium isotherm has its fitness in the following order: Freundlich model > Temkin model > Langmuir model. Thermodynamic analysis indicates that the sorption process is spontaneous and exothermic in nature. The reusability results suggested potential applications of the TU-poly(AN-co-AA) polymer in adsorption and separation of cationic malachite green dye from wastewater.
The paper evaluates the adsorptive potential of thiourea-modified poly(acrylonitrile-co-acrylic acid), (TA-poly(AN-co-AA)) for the uptake of cationic methylene blue (MB) from aquatic environments via a batch system. TA-poly(AN-co-AA) polymer was synthesized through redox polymerization and modified with thiourea (TA) where thioamide groups were introduced to the surface. Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), CHNS and Zetasizer were used to characterize the physico-chemical and morphological properties of prepared TA-poly(AN-co-AA). Afterwards, it was confirmed that incorporation of thioamide groups was successful. The adsorption kinetics and equilibrium adsorption data were best described, respectively, by a pseudo-second-order model and Freundlich model. Thermodynamic analysis showed the exothermic and spontaneous nature of MB uptake by TA-poly(AN-co-AA). The developed TA-poly(AN-co-AA) polymer demonstrated efficient separation of MB dye from the aqueous solution and maintained maximum adsorption capacity after five regeneration cycles. The findings of this study suggested that synthesized TA-poly(AN-co-AA) can be applied successfully to remove cationic dyes from aquatic environments.
In this study, simultaneous adsorption of cationic dyes was investigated by using binary component solutions. Thiourea-modified poly(acrylonitrile-co-acrylic acid) (TMPAA) polymer was used as an adsorbent for uptake of cationic dyes (malachite green, MG and methylene blue, MB) from aqueous solution in a binary system. Adsorption tests revealed that TMPAA presented high adsorption of MG and MB at higher pH and higher dye concentrations. It suggested that there are strong electrostatic attractions between the surface functional groups of the adsorbent and cationic dyes. The equilibrium analyses explain that both extended Langmuir and extended models are suitable for the description of adsorption data in the binary system. An antagonistic effect was found, probably due to triangular (MG) and linear (MB) molecular structures that mutually hinder the adsorption of both dyes on TMPAA. Besides, the kinetic studies for sorption of MG and MB dyes onto adsorbent were better represented by a pseudo-second-order model, which demonstrates chemisorption between the polymeric TMPAA adsorbent and dye molecules. According to experimental findings, TMPAA is an attractive adsorbent for treatment of wastewater containing multiple cationic dyes.
Ethylene glycol dimethacrylate (EGDMA) is used as a crosslinker in poly(acrylonitrile (AN)-co-vinylbenzyl chloride (VBC)) to investigate the effect of long-chain crosslinker to the porosity of the terpolymer system. Poly(AN-co-EGDMA-co-VBC) is synthesized by using precipitation polymerization method and further hypercrosslinked by Friedel-Crafts reaction. FT-IR spectra of poly(AN-co-EGDMA-co-VBC) show that the absorption bands at ~1290 cm−1 that are assigned to the C–Cl vibrations are almost disappeared in hypercrosslinked (HXL) poly(AN-co-EGDMA-co-VBC) polymers, confirming that the hypercrosslinking reaction is successful. SEM images show that the morphologies of the polymers are retained through the hypercrosslinking reactions. Brunauer–Emmett–Teller (BET) analysis shows that hypercrosslinked polymers had a specific surface area up to 59 m2·g−1. The preliminary performance of the terpolymer adsorbent to capture polar analyte is evaluated by adsorbing salicylic acid and mefenamic acid from aqueous solution in a batch system. The maximum adsorption capacity of salicylic acid and mefenamic acid were up to 416.7 mg·g−1 and 625 mg·g−1, respectively, and the adsorption kinetic data obeyed pseudo-second-order rate equation.
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.
Emerging dye pollution from textile industrial effluents is becoming more challenging for researchers worldwide. The contamination of water by dye effluents affects the living organisms in an ecosystem. Methylene blue (MB) and malachite green (MG) are soluble dyes with a high colour intensity even at low concentration and are hazardous to living organisms. The adsorption method is used in most wastewater plants for the removal of organic pollutants as it is cost-effective, has a high adsorption capacity, and good mechanical stabilities. In this study, a composite adsorbent was prepared by impregnating iron modified silica (FMS) onto polyurethane (PU) foam to produce an iron modified silica/polyurethane (FMS/PU) composite. The composite adsorbent was utilised in batch adsorption of the cationic dyes MB and MG. The effect of adsorption parameters such as the adsorbent load, pH, initial dye concentration, and contact time were discussed. Adsorption kinetics and isotherm were implemented to understand the adsorption mechanism for both dyes. It was found that the adsorption of MB and MG followed the pseudo-second order model. The Langmuir model showed a better fit than the Freundlich model for the adsorption of MB and MG, indicating that the adsorption occurred via the monolayer adsorption system. The maximum adsorption capacity of the FMS/PU obtained for MB was 31.7 mg/g, while for MG, it was 34.3 mg/g. The thermodynamic study revealed that the adsorption of MB and MG were exothermic and spontaneous at room temperature. In addition, the regeneration of FMS/PU was conducted to investigate the composite efficiency in adsorbing dyes for several cycles. The results showed that the FMS/PU composite could be regenerated up to four times when the regeneration efficiency dropped drastically to less than 20.0%. The impregnation of FMS onto PU foam also minimised the adsorbent loss into the environment.