Agar/graphene oxide hydrogels as nano-bioadsorbents: a comparative analysis for dye removal.

Nano-biocomposite hydrogel samples were produced using graphene oxide (GO) and agar and applied as adsorbents of organic components in water. The hydrogels were prepared by varying the wt% of Agar and GO. The samples were characterized, and batch adsorption experiments evaluated the effect of initial pH, equilibrium isotherms, and kinetics for the adsorption of the anionic dye Acid Orange 7 (AO) and the cationic dyes Nile Blue A (NB) and methylene blue (MB) in an aqueous medium. Overall, both hydrogel samples exhibited satisfactory results for removing NB and MB; however, there was no effective removal for the anionic dye AO. Adsorption equilibrium isotherms were obtained, and Freundlich, Langmuir, and Sips models were fitted to the experimental equilibrium data; moreover, kinetic data were adjusted to driving force models and particle mass balance. The maximum experimental adsorption capacities, 141.48 mg·g-1 (MB) and 284.69 mg·g-1 (NB), were obtained, on a dry basis, for the sample produced with 70 wt% of agar and 30 wt% of GO. Both hydrogels exhibited remarkable regenerative potential for NB and MB, with the adsorption capacity remaining constant, even after five adsorption/desorption cycles.

Adsorption of chloroquine, propranolol, and metformin in aqueous solutions using magnetic graphene oxide nanocomposite.

The work proposes the application of a nanocomposite formed by graphene oxide and magnetite to remove chloroquine, propranolol, and metformin from water. Tests related to adsorption kinetics, equilibrium isotherms and adsorbent reuse were studied, and optimization parameters related to the initial pH of the solution and the adsorbent dosage were defined. For all pharmaceuticals, adsorption tests indicated that removal efficiency was independent of initial pH at adsorbent dosages of 0.4 g L-1 for chloroquine, 1.2 g L-1 for propranolol, and 1.6 g L-1 for metformin. Adsorption equilibrium was reached within the first few minutes, and the pseudo-second-order model represented the experimental data well. While the equilibrium data fit the Sips isotherm model at 298 K, the predicted maximum adsorption capacities for chloroquine, propranolol, and metformin were 44.01, 16.82, and 12.23 mg g-1, respectively. The magnetic nanocomposite can be reused for three consecutive cycles of adsorption-desorption for all pharmaceuticals, being a promising alternative for the removal of different classes of pharmaceuticals in water.

Synthesis and application of graphene oxide as a nanoadsorbent to remove Cd (II) and Pb (II) from water: adsorption equilibrium, kinetics, and regeneration.

In this work, graphene oxide (GO) was synthesized by the modified Hummers method. The nanomaterial was characterized by FTIR and Raman spectroscopy, SEM, and pH at the point of zero charge. GO exhibited typical characteristics of graphene-based materials, indicating that graphite oxidation and exfoliation occurred successfully. Cd (II) and Pb (II) adsorption onto GO was carried out in batch systems, in which the effect of adsorbent dosage, contact time, and initial adsorbate concentration were evaluated. Langmuir, Freundlich, and Sips isotherm models, as well as pseudo order models and Elovich kinetic equation were applied to adsorption experimental data. Results indicated that increasing adsorbent mass, the removal efficiency of Cd (II) and Pb (II) increased. Freundlich isotherm better described Pb (II) adsorption (R2 = 0.96), while Cd (II) isotherm showed linear behavior. From the Akaike's AIC parameter, kinetic data were satisfactorily described by pseudo-first order (Cd (II)) and pseudo-n order (Pb (II)) models. GO was successfully subjected to five regeneration cycles, maintaining high efficiency (> 90%) in all cycles. GO showed high potential for the adsorption of Cd (II) and Pb (II) from aqueous solution, due to its high adsorption capacity, rapid Cd (II) and Pb (II) intakes, and great regeneration performance.

Removal of textile dyes by benefited marine shells wastes: From circular economy to multi-phenomenological modeling.

Marine shell wastes were thermally activated and characterized as aragonite and calcite phases and were used in the removal of synthetic anionic dyes, Bright Blue Acid (NB180) and Reactive Red 133 (RR133). Benefited marine shells were classified as low-cost (USD 0.33/g of adsorbent) in comparison with other reported materials. Furthermore, the absence of chemicals in the adsorbent preparation allows its further employment in economic activities. The coexistence of adsorption and exchange-precipitation reaction was responsible for up to 93% of dye removal, whilst the maximum adsorption capacities were 225 mg g-1 for NB180 and 36 mg g-1 for RR133. The observed kinetic behavior of the dye removal by the adsorbent allowed the proposal of a mechanism for dye-adsorbent interaction in liquid-solid interface considering both adsorption and exchange-precipitation reaction. Contribution of the exchange-precipitation reaction in the removal process was quantified as being approximately 75% for NB180 and 25% for RR133. The mathematical model that phenomenologically described the kinetic behavior of the dye removals gave the magnitude order of the kinetic parameters as kads = 8.67-9.49 min-1 and kp = 1.18-2.84 min-1, due to the adsorption and the (exchange-reaction)-precipitation, respectively. This work indicates the step (exchange reaction)-precipitation as an additional contribution to improve the dye removal from aqueous effluents, achieving in the evolution of the process up to 24% in terms of kinetic selectivity of removal.

Detoxification of sisal bagasse hydrolysate using activated carbon produced from the gasification of açaí waste.

Due to its recalcitrance and difficult disruption, biomass requires severe treatment conditions to produce bioproducts. These processes also generate substances that inhibit microbial metabolism, resulting in low conversion of sugars into bioproducts. To minimize this, in this work the sisal bagasse acid hydrolysate was detoxified using the activated carbon obtained from residues of the gasification of açaí endocarp. The adsorbent properties were analyzed, and the effects of experimental parameters related to furfural adsorption were evaluated. Then, the validation of the adsorption experiments was carried out in acid hydrolyzed liquor from sisal bagasse, the fermentation tests being performed with Saccharomyces cerevisiae. Overall, the furfural adsorption in the activated carbon was fast since most of the furfural was removed in the first minutes of the experiment. The Sips isotherm fit the experimental data best, with maximum adsorption capacity of 48.02 mg.g-1. Kinetic data fitted LDF, QDF and FD models, and diffusivity parameters were obtained. After detoxification, the activated carbon from açaí waste removed 52% of furfural, 100% of HMF and 40.4% of acetic acid with moderate loss of sugars (17%). The results confirmed that the adsorbent is effective and promising for removing furfural and other fermentation inhibitors.

Amino-Fe3O4-functionalized multi-layered graphene oxide as an ecofriendly and highly effective nanoscavenger of the reactive drimaren red.

Amino-functionalized multilayer graphene oxide (Am-nGO) has been synthesized and applied to remove the reactive drimaren red (DR) from aqueous solutions. Infrared spectroscopy evidenced amine and amide presence by peaks at 1579 cm-1 and a band between 3300 and 3500 cm-1. Raman spectroscopy showed an increment in ID/IG ratio after amino-Fe3O4-functionalization of nGO from 1.05 to 1.20, referent to an increase in sp3 domain disorder. The isoelectric point of Am-nGO was pH 8.1. From kinetic study, the equilibrium was achieved within 90 min; moreover, pseudo-n-order model satisfactorily fitted to the experimental data. Kinetic constant (kn) was 0.71 mg1-n g1-n min-1 and modeled equilibrium sorption capacity (qe) 219.17 mg g-1. Equilibrium experiments showed monolayer adsorption capacity (qm) of 219.75 mg g-1, and BET model best fitted to the equilibrium data, indicating that the adsorption process happened with multiple layers formation. From sorption thermodynamics, the standard free energy of Gibbs and enthalpy were respectively - 31.91 kJ mol-1 (at 298 K) and 66.43 kJ mol-1. Such data evidence the spontaneous and chemical behavior of DR adsorption as a consequence of strong electron donor-receptor interactions between the dye and the nanosorbent. By phytotoxicity assessment, Am-nGO showed inexpressive inhibitory potential to American lettuce seeds in comparison with its precursor nGO and graphite nanoplatelets.

Graphene-based materials production and application in textile wastewater treatment: color removal and phytotoxicity using Lactuca sativa as bioindicator.

The dyes used in textile industries are usually difficult to degrade in aquatic environments, being highly toxic to micro fauna and flora. Thus, textile wastewater treatments have been developed, among them, one that stands out is adsorption process. With the rise of nanomaterials applied to adsorption, graphene oxide (GO) shows promise in the removal of dyes. This work aimed to produce a more economical and environmentally friendly GO by reducing H2SO4 concentration during the synthesis. Adsorption tests were performed with methylene blue (MB) and brilliant blue (BB), adsorbent regeneration tests, as well as a kinetic study using real wastewater, and toxicological assays with lettuce seeds. Results showed that the sample produced with less H2SO4 (GO-21) performed better for MB (99% removal) and BB (29% removal); and recycling test showed that despite the decrease in removal efficiency, it remained high in the first cycles. Kinetics showed that equilibrium was reached in 30 min, removing 67.43% of color and 90.23% of the effluent's turbidity. Phytotoxicity assays indicated that the wastewater treated with GO-21 was the least toxic, compared to other wastewater samples analyzed. Therefore, GO has demonstrated its potential to be an effective and less toxic option to treat textile effluents.[Formula: see text].

Environmentally friendly route for graphene oxide production via electrochemical synthesis focused on the adsorptive removal of dyes from water.

This work shows a promising, environmentally friendly and greener alternative for the production and application of electrochemically produced Graphene Oxide (GO) for the adsorptive removal of Methylene Blue (MB) dye in an aqueous medium. During the adsorption tests, GO produced via electrochemical route reached the equilibrium in only 10 min of contact, exhibiting a percentage removal of MB over 97%. It could also be observed that the experimental data better fitted to the pseudo-second order kinetic model. By analysing the isotherms, it was verified the maximum adsorptive capacity was 500 mg g-1 (303.15 K) and that in overall, adsorptive capacity decreases with the increase in temperature. Experimental equilibrium data were better fitted to the Freundlich isotherms in all temperatures studied (303.15, 318.15 and 333.15 K). The thermodynamic analysis confirmed the exothermic nature of the process, and that MB adsorption onto GO occurs spontaneously. ΔH◦ and ΔG◦ values suggested that physisorption occurred, which is mainly due to π-π interactions and electrostatic interactions between MB and oxygen functional groups on the GO surface. Cost-effectiveness analysis showed there is a lower cost involved in the production of electrochemical GO, as compared to the Hummers method; and in the reusability study, even after 5 cycles GO removed ≥ 90% MB. Thus, the electrochemically produced GO seems to be an efficient, cost-effective and environmentally friendly alternative for colour removal from water, as it uses less hazardous and expensive reagents when compared to those applied in the traditional GO synthesis, without losing, however, the efficiency in colour removal from water.

Removal of azo dye from water via adsorption on biochar produced by the gasification of wood wastes.

It was the aim of this work to evaluate the adsorptive performance of the biochar obtained from the gasification of wood residues onto a solution of Indosol Black NF1200 dye. The study was performed by means of factorial design 22, having as control variables: pH and adsorbent's granulometry. Batch tests were carried out at 200 rpm for 3 h (T = 28 °C). As output variable, the percentage removal of dye was determined. The best operating conditions were pH = 2 and 100 mesh granulometry. Also, adsorbent dosage studies were carried out, as well as equilibrium and adsorption kinetics. Both kinetics and equilibrium of adsorption tests were proceeded in basic and acid medium. For a basic pH value (pH = 12), it was concluded the equilibrium was reached in about 3 h of experiment, the experimental qmax value was near 12 mg g-1, and the equilibrium data fitted the Langmuir model. On the other hand, for tests with pH = 2, the equilibrium was reached after 5 min of experiment, the experimental qmax value was over 185 mg g-1, and the equilibrium data fitted both the Langmuir and Freundlich models. Thus, the biochar produced via gasification of wood wastes appears to be a promising adsorbent for the removal of azo dyes from textile wastewater, especially when working at lower pH values. Also, for a 10-kg/h consumption of wood residue, approximately 10 kW of energy is generated and 1 kg of biochar is produced, which represents another advantage from the environmentally friendly point of view. Graphical abstract.