M. Žunić

Synergic adsorption of Pb2+ and reactive dye--RB5 on two series of organomodified bentonites.

Two series of organobentonites (OBs) were synthesized from Na(+)-exchanged bentonite clay from Bogovina, Serbia. In the first series the starting material was modified using hexadecyltrimethylammonium (HDTMA(+)) ion in the amounts corresponding to 0.2, 0.5, 1.0 and 2.0 of the CEC value. The second series was obtained using quaternary alkyl ammonium cations (QAACs) with different alkyl chain lengths: hexadecyltrimethylammonium (HDTMA(+)), dodecyltrimethylammonium (DDTMA(+)) and tetramethylammonium (TMA(+)) ions. The synthesized OBs were characterized. The adsorption of anionic reactive dye Reactive Black 5 (RB5) and Pb(2+) from single component solutions and their bi-component solution was investigated for both series of OBs. The adsorptive properties of the OBs were correlated to the amount and type of incorporated QAACs. The correlation was tested using different mathematical models and best fits were found. Experimental results showed that simultaneous adsorption of RB5 and Pb(2+) exhibited synergic effect. The adsorption capacity for both RB5 and Pb(2+) was higher in their bi-component solution than in single-component solutions. These results indicate the creation of new adsorption sites during the simultaneous adsorption.

p-NITROPHENOL ELECTRO-OXIDATION ON A BTMA+-BENTONITE-MODIFIED ELECTRODE

Phenol and its derivatives are regarded as ‘priority pollutants’ and p-nitrophenol (p-NP), in particular, is of great interest due to its toxicity and frequent presence in waste waters and fresh waters. Straightforward, inexpensive methods to identify p-NP in water, however, is lacking. In the present study, an electrochemical technique using clay-modified electrodes to measure p-NP was investigated as a potentially promising method to fill that gap. A glassy carbon electrode (GCE) was modified with a thin layer of Na-enriched bentonite and a series of benzyltrimethylammonium (BTMA+)-bentonites (BTMA+-B) in order to confirm these materials as p-NP electrosensitive. A series of organobentonites was synthesized using different BTMA+/bentonite ratios. The materials obtained were characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, and a low-temperature nitrogen adsorptiondesorption method. A monolayer arrangement of BTMA+ within the interlamellar region of beidellite-rich smectite was confirmed. Deterioration of the textural properties was observed with increase of BTMA+ loading. The electro-oxidation of p-NP in an acidic medium on BTMA+-B-modified GCE was investigated. The cyclic voltammetry method with a three-electrode cell was used. The reference electrode was Ag/AgCl in 3 M KCl and a Pt foil was the counter electrode. For each electrochemical measurement, a different BTMA+ loading in BTMA+-B was used as the material for GCE coating and applied as the working electrode. The electrochemical activity of BTMA+-B-based electrodes increased with BTMA+ loading. The results confirmed that the organophylic character of the BTMA+-B-modified surface was the main influence on the electrochemical activity of the BTMA+-B-based GCE; the influence of textural properties was almost negligible. The increased electrode activity toward p-NP was achieved by the adsorption of p-NP on the electrode surface, the process that commonly precedes the electro-oxidation. The present study showed that synthesized materials could potentially be used in an electrochemical test for the presence of p-NP in water solutions.

Textural properties of poly(glycidyl methacrylate): acid-modified bentonite nanocomposites

The aim of this study was to obtain enhanced textural properties of macroporous crosslinked copolymer poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) by synthesizing nanocomposites with acid-modified bentonite. Nanocomposites were obtained by introducing various amounts of acid-modified bentonite (BA) into the reaction system. All samples were characterized by attenuated total reflectance infrared spectroscopy, scanning electron microscopy, transmission electron microscopy (TEM), mercury intrusion porosimetry, and low temperature physisorption of nitrogen. The FTIR and TEM analysis confirmed incorporation of BA into the copolymer structure and the successful formation of nanocomposites. TEM images confirmed formation of nanocomposites having both intercalated and exfoliated acid-modified bentonite in copolymer matrix. A significant increase of specific surface area, pore volume, and porosity of the nanocomposites in comparison to the copolymer were obtained. The difference between textural properties of nanocomposites with different amounts of incorporated acid-modified bentonite was less prominent.

Porous glycidyl methacrylate-bentonite composite

Crosslinked macroporous copolymer of glycidyl methacrylate and ethylene glycol dimethacrylate (CP) and copolymer composite with acid modified clay (CP-SA) were prepared by radical suspension copolymerization and functionalized by ring-opening reaction of the pendant epoxy groups with diethylene triamine (CP-deta and CP-SA-deta). Both SAmples were characterized by mercury porosimetry. The influence of pH, sorption time and initial 4-nitrophenol (4-NP) concentration on sorption efficiency of CP-deta and CP-SA-deta was studied in order to evaluate this material as wastewater sorbent. The isotherm data were best fitted with Langmuir model, while the sorption dynamics obeyed the pseudo-second-order kinetic model.

Modified bentonite as adsorbent and catalyst for purification of wastewaters containing dyes

Modification and characterization of bentonite from location Bogovina, Serbia was performed in order to obtain material applicable in wastewater purification. The <75μm bentonite fraction was used in organobentonite synthesis while the <2μm bentonite fraction, obtained by hydroseparation was used in pillaring procedure. Organo-modification of bentonite was performed with (1-hexadecyl)trimethylammonium bromide (HDTMA-Br). Pillared bentonite was obtained using standard procedure. Al3+ and Fe3+ ions were incorporated in pillars in 4:1 ratio and applied as catalyst in catalytic wet peroxide oxidation. Differences in structure of starting and modified bentonites were established by XRD analysis and nitrogen physisorption on -196 °C. The (001) smectite peak around 2θ = 6° shifts during the modification process. The Na-exchange process lowered d001 from 1.53 nm (2θ = 5.78°) for starting clay to 1.28 nm (2θ = 6.92°), but the clay retained its swelling properties. The pillaring process increased and fixed the basal spacing to 1.74 nm. Intercalation of HDTMA ions into smectite structure increased d001 to 2.00 nm for organobentonite. Specific surface area, SBET, was affected by particle size and type of modification. The samples with finer bentonite fraction had higher SBET due to increased smectite content. Na-exchanged bentonite samples had higher SBET value than starting clay samples of same granulation. Organomodification caused dramatic decrease in SBET value, while the pillaring process lead to an increase of SBET value. Adsorptive and catalytic purification of wastewaters containing dyes was tested using Acid Yellow 99 as a model dye. Na-exchanged bentonite had greater adsorption affinity for dye adsorption than raw bentonite owing to higher SBET. By organomodification this affinity was enhanced more than 70 times due to transition of bentonite surface from hydrophilic to organophilic. Al,Fe pillared bentonite was proven to be efficient in catalytic wet peroxide oxidation of Acid Yellow 99 dye at room temperature.

Modified Clays in Environmental Protection

Bentonite is cheap, natural raw material, whose usage is not detrimental to the environment. Bentonite clay is primarily composed of of smectite minerals, usually montmorillonite. Bentonite can be easily modified. Some of these modifications include pillaring and organomodification. Pillared clays (PILC) with incorporated mixed Al–Fe oxide pillars were used as Fenton-like catalysts in the catalytic oxidation of organic water pollutants in the presence of H2O2. The intercalation of quaternary alkyl ammonium cations resulted in the obtainment of organobentonites as adsorbents for the simultaneous removal of organic and inorganic pollutants. These sorbents are useful in the purification of multicomponent dye/toxic metal solutions and real waste waters. Organobentonites and PILCs were used as electrode materials in electroanalytic sensors and biosensors in environmental protection. Bentonite modification led to the synthesis of adsorbents for the removal of organic and toxic and radioactive inorganic pollutants, catalysts for the oxidation of water pollutants, sensors and biosensors, electrocatalysts.

Thermodynamics of the adsorption of different dyes onto bentonite modified with hexadecyltrimethylammonium cation

Removal of two different dyes: Acid Orange 10 (AO10) and Reactive Black 5 (RB5) from their aqueous solutions using organobentonite as adsorbent was investigated. The experiments were carried out at different temperatures (298, 313, 323, and 333 K) in order to obtain thermodynamic parameters for adsorbate/adsorbent system i.e., activation energy, Gibbs free energy, enthalpy and entropy. The results of thermodynamic studies indicated that the adsorption of both dyes onto organobentonite is an endothermic process, while the values for activation energies (76 kJ mol−1 for AO10 and 51 kJ mol−1 for RB5) indicated that chemisorption occurred.