Adsorption Capacity of Carbon-Silica Composites Towards Diclofenac in Poly(acrylic acid) Containing Systems: A Crucial Study on Common Wastewater Contaminants.

Diclofenac is one of the most popular over-the-counter non-steroidal anti-inflammatory drug and poly(acrylic acid) is a frequently used as thickener, filler or stabilizer. For these reasons, they are common organic contaminants in raw wastewater. The purpose of the presented studies was to compare the adsorption capacity of three carbon-silica composites - metal-free C/SiO2, iron-enriched C/Fe/SiO2 and manganese-enriched C/Mn/SiO2 towards diclofenac. The studies were carried out in single, and mixed systems in the presence of poly(acrylic acid) polymer. Adsorption, desorption and kinetics of the adsorption process were investigated. The concentration of diclofenac in the supernatants was determined using high-performance liquid chromatography. The solids were also characterized with an ASAP apparatus using low-temperature nitrogen desorption adsorption isotherms at liquid nitrogen temperature. In addition, potentiometric titrations and electrophoretic mobility measurements, as well as stability tests of the studied suspensions were carried out. The most efficient composite among investigated ones proved to be C/Fe/SiO2 removing diclofenac at the level of 46.68 mg/g for its initial concentration of 90 ppm. The results obtained clearly demonstrated that the carbon-silica composites are effective in separation of drugs from aqueous solutions and can be successfully used in the future for the removal of organic pollutants from water environment.

Green Synthesis and Efficient Adsorption: Na-X Zeolite vs. C/Mn/SiO2 Composite for Heavy Metals Removal.

The studies aimed to test the adsorption capacity of two silica-enriched porous materials, synthetic Na-X zeolite and Mn-containing carbon composite, towards Pb(II) and Zn(II) ions in single and mixed systems and in the presence of diclofenac (DCF) and (or) poly(acrylic acid) (PAA). The synthetic zeolite was characterized by a well-developed surface area of 728 m2/g and a pore diameter of 1.73 nm, while the carbon composite exhibited 268 m2/g and 7.37 nm, respectively. Na-X was found to be more efficient than the carbon composite (75-212 mg/g) in adsorbing heavy metal ions in both single and bimetallic systems (322-333 mg/g). In turn, the C/Mn/SiO2 composite was more effective in removing Pb(II) ions from the systems that simultaneously contained DCF or PAA (480 and 476 mg/g, respectively). The Na-X zeolite demonstrated the greatest stability in all the systems studied. The highest stability was observed in the DCF + Pb(II) mixture, in contrast to the carbon composites where the stability was much lower. To evaluate the possibility of regeneration of the solids, HCl proved to be the best desorbent for heavy metal ions (efficiency of 99%). In general, both adsorbents offer promising potential for solving environmental problems.

Fly Ash-Based Na-X Zeolite Application in Separation Process of Bovine Serum Albumin from Aqueous Solution in the Presence of Organic Substances with Anionic Character.

The main purpose of the investigations was to explore the protein adsorption on porous materials, as well as to identify the mechanisms of protein attachment without and with other common environmental contaminants, such as drugs, polymers or surfactants. This study applied the Na-X zeolite for the adsorption of bovine serum albumin (BSA) from solutions with various pH values. Electrophoretic mobility measurements and potentiometric titrations were conducted in systems containing both protein and/or PAA (poly(acrylic acid) polymer/DCF (diclofenac) drug/SDS (sodium dodecyl sulfate) surfactant to investigate the protein binding mechanisms in the complex adsorbate systems. In addition, aggregate size and stability measurements were performed in the investigated systems. Based on the research results, it was possible to conclude that the protein adsorbed most preferably on the zeolite surface at a pH value close to its isoelectric point (pI) (102.15 mg/g), and protein adsorption was the lowest in the solutions with strongly alkaline (29.61 mg/g) or acidic (77.45 mg/g) pH values. Thus, the examined zeolitic material can be considered an effective adsorbent for protein removal from an aqueous solution.

Novel carbon-based composites enriched with Fe and Mn as effective and eco-friendly adsorbents of heavy metals in multicomponent solutions.

With increasing demand for adsorbents highly effective in pollutant removal, carbon-based porous materials are becoming more and more popular. In this work, a new approach to the synthesis of such solids using an environmentally friendly, two-step preparation method is presented. A series of hybrid porous silica-containing carbon composites was synthesized, namely: metal free (C/SiO2), enriched with manganese (C/Mn/SiO2), as well as iron (C/Fe/SiO2). The effect of additives on the structure and morphology of the composites was evaluated using X-ray photoelectron spectroscopy (XPS), nitrogen adsorption/desorption and scanning electron microscope (SEM). The as-synthesized carbons were used as effective adsorbents for the simultaneous removal of heavy metals, including lead (Pb(II)) and zinc (Zn(II)) ions. In particular, it was determined that C/Mn/SiO2 sample demonstrated the highest adsorption capacity towards Pb(II) and Zn(II) ions. It was equal to 211.60 mg/g for Pb(II) and 74.95 mg/g for Zn(II). Zeta potential and surface charge density of the solids, with and without metals, were investigated to determine electrical double layer structure, whereas stability studies and aggregate size measurements were performed to estimate solid aggregation under selected conditions. It was established that solids with adsorbed metals formed suspensions with lower stability than those without ions. This, in turn, facilitates their separation from aqueous solutions.

Management of hazardous fly-ash energy waste in the adsorptive removal of diclofenac by the use of synthetic zeolitic materials.

Zeolite-carbon composites (Na-P1(C), Na-X(C)) and pure zeolites (Na-P1, Na-X) were synthesized from hazardous high-carbon fly ash waste (HC FA) via hydrothermal reaction with sodium hydroxide (NaOH). These solids were applied in the removal of diclofenac (DCF) from aqueous solution, with and without poly(acrylic acid) (PAA). The experiments included adsorption-desorption measurements, as well as electrokinetic and stability analyses. The obtained results showed that HC FA and Na-P1(C) had the greatest adsorption capacity towards DCF, i.e., 26.51 and 21.19 mg/g, respectively. PAA caused considerable decrease in the DCF adsorption due to the competition of both adsorbates of anionic character for active sites. For example, the adsorbed amount of DCF on Na-P1 without PAA was 14.11 mg/g, whereas the one measured with PAA was 5.08 mg/g. Most of prepared solids were effectively regenerated by the use of NaOH. Desorption degree reached even 73.65% in the single systems (with one adsorbate) and 97.24% in the mixed ones (with two adsorbates). Zeolitic materials formed suspensions of rather low stability, which underwent further deterioration in the organic molecules presence. All the results obtained in this study indicated that HC FA can be successfully managed in the removal of organic substances.

Comparison of Physicochemical Properties of Fly Ash Precursor, Na-P1(C) Zeolite-Carbon Composite and Na-P1 Zeolite-Adsorption Affinity to Divalent Pb and Zn Cations.

Considering the growing needs of environmental remediation, new effective solutions should be sought. Therefore, the adsorbed amounts of heavy metal ions, such as lead(II) and zinc(II), on the surface of high-carbon fly ash (HiC FA), zeolite--carbon composite (Na-P1(C)) and pure zeolite (Na-P1), were investigated. The applied solids were characterized using the following techniques: XRD, SEM-EDS, TEM, porosimetry, SLS, electrophoresis and potentiometric titration. The heavy metal concentration in the probes was determined by applying ICP-OES spectroscopy. Adsorption/desorption and electrokinetic measurements were performed in the systems containing one or two adsorbates. The obtained results indicated that Pb(II) ions are adsorbed in larger amounts on the investigated solid surface due to the molecular sieving effect. The largest adsorption capacity relative to lead(II) ions was observed for pure Na-P1 zeolite (407 mg/g). The simultaneous presence of Pb(II) + Zn(II) mixed adsorbates minimally affects the amount of adsorbed Pb(II) ions and causes a significant decrease of Zn(II) ion adsorption (in comparison with analogous systems containing single adsorbates). It was also shown that all solids can be efficiently regenerated using hydrochloric acid. Thus, the selected pure zeolite can be successfully applied in soil remediation or other purifying technologies as an effective Pb(II) adsorbent.

Carbon-Silica Composite as Adsorbent for Removal of Hazardous C.I. Basic Yellow 2 and C.I. Basic Blue 3 Dyes.

Treatment of wastewaters containing hazardous substances such as dyes from the textile, paper, plastic and food industries is of great importance. Efficient technique for the removal of highly toxic organic dyes is adsorption. In this paper, adsorptive properties of the carbon-silica composite (C/SiO2) were evaluated for the cationic dyes C.I. Basic Blue 3 (BB3) and C.I. Basic Yellow 2 (BY2). The sorption capacities were determined as a function of temperature (924.6-1295.9 mg/g for BB3 and 716.3-733.2 mg/g for BY2 at 20-60 °C) using the batch method, and the Langmuir, Freundlich and Temkin isotherm models were applied for the equilibrium data evaluation using linear and non-linear regression. The rate of dye adsorption from the 100 mg/L solution was very fast, after 5 min. of phase contact time 98% of BB3 and 86% of BY2 was removed by C/SiO2. Presence of the anionic (SDS), cationic (CTAB) and non-ionic (Triton X-100) surfactants in the amount of 0.25 g/L caused decrease in BB3 and BY2 uptake. The electrokinetic studies, including determination of the solid surface charge density and zeta potential of the composite suspensions in single and mixed adsorbate systems, were also performed. It was shown that presence of adsorption layers changes the structure of the electrical double layer formed on the solid surface, based on the evidence of changes in ionic composition of both surface layer and the slipping plane area. The greatest differences between suspension with and without adsorbates was obtained in the mixed dye + SDS systems; the main reason for this is the formation of dye-surfactant complexes in the solution and their adsorption at the interface.

Simultaneous Removal of Pb2+ and Zn2+ Heavy Metals Using Fly Ash Na-X Zeolite and Its Carbon Na-X(C) Composite.

Pure zeolite (Na-X) and a zeolite-carbon composite (Na-X(C)) were investigated as adsorbents of heavy metals-Pb2+ and Zn2+ from an aqueous solution. These materials were synthesized from fly ash-a waste from conventional hard coal combustion. Both solids were characterized using XRD, SEM-EDS, nitrogen adsorption/desorption, particle size and elemental composition analyses. The adsorption study was performed at pH 5 in the systems containing one or two adsorbates simultaneously. The obtained results showed that the pure zeolite was characterized by a more developed surface area (728 m2/g) than its carbon composite (272 m2/g), and the mean pore diameters were equal to 1.73 and 2.56 nm, respectively. The pure Na-X zeolite showed better adsorption properties towards heavy metals than its Na-X(C) composite, and Zn2+ adsorbed amounts were significantly higher than the Pb2+ ones (the highest experimental adsorption levels were: for Zn2+-656 and 600 mg/g, and for Pb2+-575 and 314 mg/g, on the Na-X and Na-X(C) surfaces, respectively). The zinc ions are exchanged with the cations inside the zeolite materials structure more effectively than lead ions with a considerably larger size. In the mixed systems, the competition between both heavy metals for access to the active sites on the adsorbent surface leads to the noticeable reduction in their adsorbed amounts. Moreover, the hydrochloric acid was a better desorbing agent for both heavy metals, especially Pb2+ one (desorption reached 78%), than sodium base (maximal desorption 25%).

Simultaneous adsorption of Cu(II) ions and poly(acrylic acid) on the hybrid carbon-mineral nanocomposites with metallic elements.

In order to propose a novel, effective adsorbent of Cu(II) ions, hybrid carbon-mineral nanocomposites with metallic elements (Mn/Fe in the case of B-6, Mn - B-8) were examined. A combination of mechanochemical and pyrolytic methods was used to obtain these bimodal micro-mesopore systems. First, mechanochemical mixing of phenol-formaldehyde resin and inorganic compounds in a ball mill was carried out. Then, the pyrolysis of the mixture under inert atmosphere at 800 °C was performed. The obtained composites were characterized using nitrogen adsorption/desorption, Fourier transform infrared spectroscopy, electron microscopes as well as X-ray diffraction, X-ray fluorescence and X-ray photoelectron spectroscopy. Adsorption, electrokinetic and aggregation studies were also performed, in the absence and presence of poly(acrylic acid) (PAA) - a macromolecular compound commonly used in industry and agriculture, which may be present in wastewater together with copper(II) ions. Under examined conditions (at pH 5 and 6), Cu(II) adsorbed amount was higher on the B-8 surface than on the B-6 one. At pH 6 for the initial Cu(II) concentration 100 ppm, 51.74% of the ions was adsorbed on B-8% and 46.68% - on B-6. Heavy metal adsorption contributes to stronger aggregation of nanocomposite particles. Thus, the presented bimodal solids, especially that containing Mn (called B-8), can be considered as adsorbents in heavy metal removal from aqueous solutions.