Understanding of the mechanism of crystal violet adsorption on modified halloysite: Hydrophobicity, performance, and interaction.

Halloysite was processed at 600 °C and then by acid leaching with HCl solutions of different concentrations, i.e. 0.5, 3 and 5 N (H600-xN; x = 0.5, 3 or 5). The resulting materials underwent chemical, textural, and laser diffraction analyses and were used in crystal violet (CV) adsorption. Bath experiments were conducted to evaluate the parameters influencing adsorption. A hydrophobicity study by adsorption of water/toluene and a spectroscopic investigation by FTIR and Raman were conducted, to understand the interaction mechanism. The affinity for CV is as follows: H600-0.5N (115 m2g-1) > H600-3N (434 m2g-1) > H600-5N (503 m2g-1) > H600-0N (61 m2g-1). The maximum adsorption of H600-0.5N would be explained by optimal hydrophilic and hydrophobic properties. Dealumination leads to the creation of more silanols responsible for hydrophilicity. Dehydroxylation at 600 °C combined with dealumination would induce a partial transformation of silanols into siloxanes which are responsible for organophilicity. The CV-H600-0.5N interaction implies two mechanisms: hydrophobic interactions and hydrogen bond. This study focused on hydrophobic interaction as a non-negligible component governing the interaction of organic contaminants with 1:1 clay minerals, while it was not sufficiently considered in the scientific literature.

Alginate-whey an effective and green adsorbent for crystal violet removal: Kinetic, thermodynamic and mechanism studies.

In this study, a novel biocomposite beads is developed by gelling sodium alginate (ALG) solutions in acid whey (Aw). The formation of alginate-whey biocomposite (ALG-Aw) was confirmed by FTIR analysis where the corresponding spectrum showed the presence of characteristic absorption bands of both ALG and Aw. SEM analysis showed the presence of lactic bacteria immobilized in the alginate matrix leading to the formation of new porous structure. The adsorption properties of adsorbents were evaluated in crystal violet dye (CV) removal from aqueous solutions using a batch adsorption technique. The results showed that the maximum adsorption occurred at pH 6 and for an adsorbent dose of 0.4 g/L. The kinetic of CV removal onto ALG-Aw adsorbent can be described well by the pseudo-second order equation. The equilibrium adsorption data of ALG-Aw followed well the Redlich-Peterson isotherm which is coherent with the calculated R2, χ2 and ARE values. Calculated thermodynamic parameters such as Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) shown that adsorption reaction is spontaneous and it is favored at low temperatures. Interactions of CV dye molecules with ALG-Aw composite beads were examined by FTIR and UV-visible DR spectroscopy.

Development and characterization of a new dolomite-based catalyst: application to the photocatalytic degradation of pentachlorophenol.

The development of new catalysts from abundant raw materials, generating attractive photocatalytic activity, constitutes a real challenge in the context of sustainable development concerns. In this setting, a dolomite was treated at 800 °C (D800) and then chemically modified by Ca(NO3)2 (CaD800) using a simple procedure. The resulting materials were characterized by X-ray diffraction, scanning electron microscopy, energy dispersive X-ray spectroscopy (EDS), solid state UV spectroscopy, and used as catalysts of pentachlorophenol (PCP) degradation in aqueous solutions under UV light irradiation. The treatment of dolomite at 800 °C enabled a full decarbonation of CaMg(CO3)2, with formation of CaO, Ca(OH)2, and MgO. Additional CaO was generated after chemical treatment as revealed by EDS analysis; the Ca/Mg ratio increased from 1.29 (D800) to 1.44 for CaD800. This CaO in aqueous medium hydrates by giving Ca(OH)2. CaD800 was found to be the best photocatalyst with a PCP degradation rate of 95% after only 1 h of treatment, for a CaD800/D800 degradation rate constant ratio of 1.58. In this regard, we investigated the Fourier transform infrared spectra of CaD800, PCP, and CaD800 loaded with PCP after degradation. We thus evidenced the involvement of Ca(OH)2 in the PCP degradation process. Catalytic activity was discussed through the contribution of OH radicals and electrodonation.

Removal of catechol from water by modified dolomite: performance, spectroscopy, and mechanism.

Dolomite was treated at 800 °C (D800), characterized, and used in the adsorptive removal of catechol (1,2-dihydroxybenzene) from aqueous solutions. The performances of the D800 sample, named dolomitic solid, were compared with those of the raw material. A bibliographic review shows that the data on the adsorption of phenolic compounds by dolomites are non-existent. Kinetic data, equilibrium isotherms, thermodynamic parameters, and pH influence were reported. Special attention was paid to the spectroscopic study, before and after adsorption. The purpose was to understand the mechanism of catechol uptake on dolomitic materials. Kinetics follows the pseudo-second order model. The Redlich-Peterson isotherm provides the best correlation of our isotherms. Affinity follows the sequence: D800 ≫ raw dolomite. The process is spontaneous at low temperatures and exothermic. After catechol adsorption, the shape of the band in the 3,600-3,000 cm-1 range and its red shift towards 3,429 cm-1 reflect a deep involvement of OH groups both of D800 and catechol, which confirm hydrogen bonding via their respective OH. On this basis, a schematic illustration was proposed. The understanding of the phenolic compound-dolomitic solid interactions constitutes a fundamental approach to developing the application of these materials in wastewater treatment.

Cu(II) adsorption by halloysites intercalated with sodium acetate.

Intercalated halloysites with sodium acetate at various contact time were prepared. The resulting materials were characterised by X-ray powder diffraction, Fourier transformed infrared spectroscopy, scanning electronic microscopy, and specific surface area evaluation. The modified halloysites were employed as Cu(II) adsorbents from aqueous solutions. Various parameters were studied through the batch method. Kinetic data, equilibrium isotherms, and thermodynamic parameters were evaluated by considering several models. The fraction of halloysite intercalated with sodium acetate remained low, up to 7 days, then linearly increased with contact time. Thirty days were required to achieve a ratio of 91%. For this sample, a proliferation of small tubes (nanotubes) was evidenced. The best results were achieved with the pseudo-second-order kinetic model associated with intraparticle diffusion and with the Redlich-Peterson isotherm, for the equilibrium data. The thermodynamic data show that adsorption would be spontaneous at low temperatures, of exothermic nature, resulting in an adsorbate-adsorbent system much more ordered. The insertion of CH(3)COONa into halloysite significantly affects the Cu(II) adsorption. The magnitude in enhancement of copper adsorption on solid phase thus depends on the content of the carboxylic functional groups, which increases with the insertion of CH(3)COONa into the halloysitic matrix. The involved mechanism is quite complex. It implies electrostatic considerations and a cationic exchange process. The most intercalated sample was found to be very effective as adsorbent of copper(II) from aqueous solutions.

TiO2-assisted degradation of a perfluorinated surfactant in aqueous solutions treated by gliding arc discharge.

The plasma-chemical degradation of Forafac 1110, a perfluorinated non-ionic surfactant, in aqueous solutions was investigated using TiO2 catalysts. The considered plasma was the gliding arc in humid air, which results from an electric discharge at atmospheric pressure and quasi-ambient temperature. Two titanium dioxide powders were used and their synergistic effects on the Forafac degradation were compared. The results were discussed through the evolution of the pH, the conductivity, the fluoride ions concentration released in solutions, the surfactant concentration remaining after treatment and the chemical oxygen demand (COD) measurement. The combination of the plasma-chemical treatment with heterogeneous catalysis through the use of TiO2 accelerated the Forafac degradation, since only 60 min was sufficient to remove 96% instead of 360 min needed in the absence of TiO2. The use of anatase and rutile under the trade-name of Rhodia TiO2 and Merck TiO2, respectively, led to different results, because Rhodia TiO2 has proven to be more efficient. It would seem that the crystalline phase as well as the crystallite size, explain the efficiency of anatase. The advantage of the plasma-catalysis is due to the fact that there is a significant production of the OH* radicals not only generated by the gliding arc discharge but also by TiO2.

Removal of pentachlorophenol from aqueous solutions by dolomitic sorbents.

The partial decomposition of dolomite carried out within the temperature range 600-1000 degrees C provides new sorbents, called dolomitic sorbents. Their surface properties and identification by X-ray diffraction are discussed. The lowest specific surface area value was found for the raw dolomite, while the highest value was achieved by the D-1000 sample. The adsorption equilibrium of pentachlorophenol from aqueous solutions on the examined sorbents was investigated at 30, 40, and 50 degrees C via a bath process. Langmuir, Freundlich, Langmuir-Freundlich, and Redlich-Petersen models were fitted to experimental equilibrium data, and their goodnesses of fit are compared. The adjustable parameters of Langmuir-Freundlich and Redlich-Petersen isotherms were estimated by nonlinear least-squares analysis. Langmuir and Freundlich models were found insufficient to explain the adsorption equilibrium, while Langmuir-Freundlich and Redlich-Petersen isotherms provide the best correlation of the pentachlorophenol adsorption onto dolomitic sorbents.

Adsorption of carbon dioxide by X zeolites exchanged with Ni2+ and Cr3+: isotherms and isosteric heat.

The adsorption of CO2, at intervals of 30 K from 303 K was carried out on M(n+)X zeolites (M(n+)=Ni2+ or Cr3+) exchanged at different degrees. The structural regularity of the zeolite lattice of NaX and the existence of well-defined cavities within which the adsorbate molecules are lodged suggest that it should be possible to use various isotherm equations. Several models were thus used to describe the experimental isotherms. The best fit of adsorption isotherm data is obtained with the Sips model. The Volmer model also describes satisfactorily the isotherms of CO2 adsorption by NaX, Ni(x)X, and Cr(x)X. Analysis of the isosteric heat reveals a character energetically heterogeneous for NaX and Ni(x)X samples exchanged at a higher degree of Ni2+ exchange and at low coverage. Specific interaction is also obtained between the adsorbate molecules and Cr(x)X exchanged at a lower degree. From these considerations, hypotheses will be advanced to describe the behavior of the adsorbed phase within zeolitic cavities.