Cellulose nanocrystals as promising adsorbents for the removal of cationic dyes

Cellulose nanocrystals (CNCs) prepared from cellulose fibre via sulfuric acid hydrolysis was used as an adsorbent for the removal of methylene blue (MB) from aqueous solution. The effects of pH, adsorbent dosage, temperature, ionic strength, initial dye concentration were studied to optimize the conditions for the maximum adsorption of dye. Adsorption equilibrium data was fitted to both Langmuir and Freundlich isotherm models, where the Langmuir model better described the adsorption process. The maximum adsorption capacity was 118 mg dye/g CNC at 25 °C and pH 9. Calculated thermodynamic parameters, such as free energy change (ΔG = ?20.8 kJ/mol), enthalpy change (ΔH = ?3.45 kJ/mol), and entropy change (ΔS = 0.58 kJ/mol K) indicates that MB adsorption on CNCs is a spontaneous exothermic process. Tunability of the adsorption capacity by surface modification of CNCs was shown by oxidizing the primary hydroxyl groups on the CNC surface with TEMPO reagent and the adsorption capacity was increased from 118 to 769 mg dye/g CNC.     

Symmetry breaking in cationic and anionic polymethine dyes

The electron density distribution and equilibrium molecular geometry of ionic polymethine dyes containing both the simplest terminal groups and carbo and heterocyclic residues were investigated by ab initio and AM1 methods. It is shown that charge waves and wave of the carbon–carbon bond lengths in the conjugated chain are of solitonic nature. The dimensions of the charge (electron or hole) soliton and geometrical (topological) soliton are practically unsensitive to the chain lengths, while the wave shape depends on the donor/acceptor strength of the terminal groups. If the length of the chromophore exceeds the dimension of the solitons, then the soliton center in the substituted ionic conjugated systems shifted to one of the chain ends, what leads to an appearance of the asymmetrical form. The conditions of this symmetry breaking (crucial number of the vinylene groups in the chain, effective length and donor/acceptor strength of the terminal residues, total charge) was found and was established that no moving of the solitons occurs in the unsubstituted conjugated ions.     

Interaction of chromophores in cationic/anionic dyes

The spectral properties of dyes containing colored organic cations and anions have been investigated in solvents differing in polarity. It has been established that the color of cationic/anionic dyes in low-polarity solvents is governed by the properties of the ion pairs that are formed. The chromophores in the ion pairs of cationic/anionic dyes interact, and this moves the absorption bands away from each other and redistributes their intensities.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 1, pp. 47–53, January–February, 1989.     

Graphene oxide functionalized magnetic nanoparticles as adsorbents for removal of phthalate esters

We show that magnetic nanoparticles can be functionalized with graphene oxide (GO-MNPs) in two reaction steps, and that such nanoparticles can be used as adsorbents for the removal of phthalate esters (PAEs) from water samples. The GO-MNPs were characterized by scanning electron microscopy, transmission electron microscopy, Fourier-transform infrared spectroscopy, zeta potential, and vibrating sample magnetometer. The impacts of contact time, sample pH, ionic strength and sample volume on the adsorption process were investigated. The maximum adsorption capacity for diethyl phthalate was calculated to be 8.71 mg g^?1 according to the Langmuir adsorption isotherm. The adsorption efficiency was tested by removal of PAEs. More than 99 % of the total quantity of PAEs (0.12 mg L^?1) in 500 mL real water samples can be removed when GO-MNPs (275–330 mg) were used as an adsorbent. In addition, other species (estriol and fluorene) containing benzene rings were also almost completely removed with the PAEs using GO-MNPs, indicating that GO-MNPs are suitable for the removal of the species containing π-electron system through π-π interactions.

A study of interaction of cationic dyes with anionic polyelectrolytes

The interactions of Acridine Orange with Sodium Alginate and Pinacyanol Chloride with Heparin have been investigated by spectrophotometric method. The polymers induce metachromasy in the dye as evidenced from the considerable blue shift in the absorption maxima of the corresponding dyes. The interaction constant and thermodynamic parameters of polymer–dye interactions have been determined. The effect of additives such as alcohols, and urea on the reversal of metachromasy has been studied. The data has been used to determine the stability of the metachromatic complex and the nature of binding. The thermodynamic parameters of interaction revealed that binding between Acridine Orange and Sodium Alginate involved only electrostatic forces while that between Pinacyanol Chloride involved both electrostatic and hydrophobic forces. The reversal studies using surfactants indicated the involvement of both electrostatic and hydrophobic forces in binding. Based on the results it can be concluded that Pinacyanol Chloride is more effective inducing metachromasy than Acridine Orange.     

Interaction of anionic dyes and cationic surfactants with ionic liquid character

The interactions of an imidazolium based ionic liquid (IL), namely 1-dodecyl-3-methylimidazolium chloride [C12 mim][Cl] with two sulfonated anionic dyes, azocarmine G and methyl orange, are studied spectrophotometrically in both acidic and basic media. ILs (with some surface active character) can interact with the above dyes and cause considerable shifts in their spectra. These interactions are then compared with some surfactant-dye interactions. Evolving factor analysis (EFA) and multivariate curve resolution-alternating least squares (MCR-ALS) are used for complete resolution of the measured spectrophotometric data. The concentration and spectral profiles of all species were calculated without any assumption of the chemical models. The spectral variation of dye solutions as a function of IL concentrations below and above the critical aggregation concentration (CAC) is analyzed using MCR-ALS as a soft-modeling technique. The ion pair formation constants between ILs and dyes were calculated using the obtained concentration profiles.     

Scalable sulfonate-coated cotton fibers as facile recyclable adsorbents for the highly efficient removal of cationic dyes

Adsorbents that exhibit a high adsorption capacity and facile recyclability are considered promising materials for dye wastewater remediation. In this work, a novel sulfonate-decorated cotton fiber was fabricated as a recyclable adsorbent for the highly efficient removal of cationic dyes. Herein, poly(sodium p-styrene sulfonate-co–N-methylol acrylamide) (P(SSNa-co-NMAM)) with SSNa units as adsorption sites and NMAM units as thermal-crosslinking points was synthesized for the modification of cotton fibers. As expected, the as-obtained P(SSNa-co-NMAM)-coated cotton fibers (PCFs) presented outstanding adsorption capacities toward cationic dyes, even in the simulated effluents. The processes of cationic dye absorbing onto the PCFs were well fitted by the Langmuir isotherm model and pseudo-second-order kinetics. The thermodynamic study revealed that the adsorption reaction of the cationic dyes onto PCF was spontaneous, and the efficiency of adsorption was more desirable at higher temperatures. The maximum adsorption capacities of PCF toward methylene blue (MEB), rhodamine B (RhB), and malachite green (MG) were 3976.10, 2879.80, and 3071.55 mg/g, respectively. The dye removal mechanism was ascribed predominantly to electrostatic interactions. Moreover, the adsorption capacity of the PCFs toward cationic dyes was slightly influenced by the pH of the solutions because of the sulfonate moieties, which exhibit stability under acidic and alkaline conditions. Furthermore, the recyclability and reusability of the as-prepared PCFs were satisfactory and good mechanical properties and thermal stability were observed compared to those of pristine cotton fibers. Given the aforementioned results, the as-obtained PCFs are highly promising as ideal adsorbents for the remediation of dye-contaminated wastewater.

Graphical abstract

     

Triphenylene-modified chitosan: novel high efficient sorbent for cationic and anionic dyes

The first example of triphenylene-modified chitosan 4 was prepared by reacting chitosan with triphenylene aldehyde derivative 3. Its structure and morphology was characterized by elemental analysis, ¹H NMR, FTIR, XRD, SEM and AFM image. The triphenylene units in Tp-chitosan 4 appended on the skeleton of chitosan and possessed orderly layered structure. Adsorption experiments of Tp-chitosan 4 indicated that it possessed excellent adsorption capacities for both cationic and anionic dyes [Orange G sodium salt, Brilliant ponceau 5R, Victoria blue B (VB), Crystal violet (CV), Neutral red (NR) and Methylene blue]. The highest adsorption capacities for CV, VB and NR were 5.612, 5.353 and 5.375 mmol/g, respectively. Adsorption kinetics and isotherms analysis showed that the adsorption processes obeyed pseudo second-order model and the Langmuir isotherm equation. The adsorption processes were exothermic and spontaneous. The best pH values for adsorption were pH = 6–8.     

Highly effective water adsorbents based on aluminum oxide

A method of preparation of a stable, high performance water adsorbent with the phase composition η-Al₂O₃ + γ-Al₂O₃ + χ-Al₂O₃ from thermally activated hydrargillite has been developed. The synthesis procedure does not involve a reprecipitation stage. The resulting adsorbent has a high specific surface area (400 m²/g) and a mean pore diameter of 3.5 nm or below. The static capacity of the adsorbent reaches 24.2 g H₂O per 100 g of sorbent, and its dynamic capacity is 8.2 g H₂O per 100 g of sorbent. Service life tests showed the stability of the adsorbent in multiple sorption-desorption cycles. The minimum dew point in drying is ?58.8°C.     

Planarity recognition of cationic dyes by anionic, crystalline bilayer aggregates

Steric selectivity in terms of molecular planarity of cationic dyes was investigated using anionic bilayer aggregates. Planar cationic dye (para-type stilbazolium) could be incorporated into the hydrophobic region of anionic crystalline bilayer aggregates, whereas structurally related, less planar dyes (ortho-type stilbazolium) could not be incorporated in spite of somewhat higher hydrophobicity resulting from lengthening of the N-alkyl group.     

Investigation of interactions between some anionic dyes and cationic surfactants by conductometric method

The interactions of cationic surfactants with anionic dyes were studied by conductometric method. Benzyltrimethylammonium chloride (BTMACl), benzyltriethylammonium chloride (BTEACl) and benzyltributylammonium chloride (BTBACl) were used as cationic surfactants and indigo carmine (IC) and amaranth (Amr) were chosen as anionic dyes. The specific conductance of dye–surfactant mixtures was measured at 25, 35 and 45 °C. A decrease in measured specific conductance values of dye–surfactant mixture was caused by the formation of non-conducting or less-conducting dye–surfactant complex. The equilibrium constants, K₁, the standard free energy changes, ΔG₁°$\mathrm{\Delta }{G}_1°$, the standard enthalpy changes, ΔH₁°$\mathrm{\Delta }{H}_1°$ and the standard entropy changes, ΔS₁°$\mathrm{\Delta }{S}_1°$ for the first association step of dye–surfactant complex formation were calculated by a theoretical model. The results showed that the equilibrium constants and the negative standard free energy change values for all systems decreased as temperature increased. Also these values decreased for all systems studied with increasing alkyl chains of surfactants due to the steric effect. When the equilibrium constant values, K₁, for the first association step of IC–surfactant and Amr–surfactant systems with the same surfactant were compared, the values of K₁ for IC–surfactant system were higher than that of Amr–surfactant system.     

Efficient adsorption of anionic dyes onto magnetic graphene oxide coated with polyethylenimine: Kinetic,isotherm, and thermodynamic studies

Research on Chemical Intermediates - The removal efficiency of two anionic dyes, namely direct red 81 (DR 81) and reactive blue 19 (RB 19), from aqueous solution was investigated through batch...     

A comparative adsorption study with different industrial wastes as adsorbents for the removal of cationic dyes from water

Four adsorbents have been prepared from industrial wastes obtained from the steel and fertilizer industries and investigated for their utility to remove cationic dyes. Studies have shown that the adsorbents prepared from blast furnace sludge, dust, and slag have poor porosity and low surface area, resulting in very low efficiency for the adsorption of dyes. On the other hand, carbonaceous adsorbent prepared from carbon slurry waste obtained from the fertilizer industry was found to show good porosity and appreciable surface area and consequently adsorbs dyes to an appreciable extent. The adsorption of two cationic dyes, viz., rhodamine B and Bismark Brown R on carbonaceous adsorbent conforms to Langmuir equation, is a first-order process and pore diffusion controlled. As the adsorption of dyes investigated was appreciable on carbonaceous adsorbent, its efficiency was evaluated by comparing the results with those obtained on a standard activated charcoal sample. It was found that prepared carbonaceous adsorbent exhibits dye removal efficiency that is about 80-90% of that observed with standard activated charcoal samples. Thus, it can be fruitfully used for the removal of dyes and is a suitable alternative to standard activated charcoal in view of its cheaper cost.     

Adsorption and kinetic studies of cationic and anionic dyes on pyrophyllite from aqueous solutions

The adsorption of cationic Methylene Blue (MB) and anionic Procion Crimson H-EXL (PC) dyes from aqueous medium on pyrophyllite was studied. Changes in the electrokinetics of pyrophyllite as a function of pH were investigated in the absence and presence of multivalent cations. The results show that pyrophyllite in water exhibits a negative surface charge within the range pH 2-12. Pyrophyllite is found to be a novel adsorbent for versatile removal of cationic and anionic dyes. The negative hydrophilic surface sites of pyrophyllite are responsible for the adsorption of cationic MB molecules. The adsorption of anionic PC dye is possible after a charge reversal by the addition of trivalent cation of Al. Nearly 2 min of contact time are found to be sufficient for the adsorption of both dyes to reach equilibrium. The experimental data follow a Langmuir isotherm with adsorption capacities of 70.42 and 71.43 mg dye per gram of pyrophyllite for MB and PC, respectively. For the adsorption of both MB and PC dyes, the pseudo-second-order chemical reaction kinetics provides the best correlation of the experimental data.     

Interaction of chromophores in dissimilar associates of cationic and anionic polymethine dyes in water

A strong interaction between chromophores of cationic and anionic components was found based on the analysis of electronic absorption spectra of aqueous solutions of mixtures of cationic indopolycarbocyanines with anionic cyanines. Strong dissimilar 1∶1 associates are formed. Association constants were estimated spectrophotometrically. The main factors determining the degree of interaction of chromophores were revealed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 950–955, May, 1997.     

Removal of anionic and cationic dyes from wastewater by adsorption using multiwall carbon nanotubes

This paper evaluated the efficiency and reusability of multiwall carbon nanotubes (MWNTs) on removal of cationic and anionic dyes under effect of pH, dose of MWNTs and concentration of dyes. The characterization of MWNTs is characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), Raman spectra and BET (Brunauer, Emmett and Teller) surface area. SEM and TEM analyses showed that MWNTs had size within nano scale range of 10–50 nm. The experimental results indicated that the efficiency of removal of MWNTs increase under condition of normal pH, at contact time 60 min with agitation speed 240 rpm and initial concentration of dyes 10 mg/l. Under these optimal conditions, the removal reached 98.7% and 97.2% for anionic dyes and cationic dyes, respectively. For economic use, MWNTs can be used more than one time where the same experiments with the already used MWNTs was repeated and it was found that the percent removal is almost the same.     

Click chemistry-induced selective adsorption of cationic and anionic dyes using functionalized cellulose methacrylate hydrogels

Cellulose - In the preparation of hydrogels for removing dye pollutants from wastewaters, cellulose, a natural polymer, has become a popular raw material of late. In an effort to develop adsorbents...