Synthesis of Composite Sorbents with Chitosan and Varied Silica Phases for the Adsorption of Anionic Dyes.

In this work, various types of silica materials were used for the synthesis of chitosan-silica composites. The composites were obtained using the chitosan (Ch) immobilization process from an aqueous solution on various silica phases, i.e., amorphous diatomite (ChAD), crystalline diatomite (ChCD), mesoporous silica MCM-41 (ChMCM), and mesoporous silica SBA-15 (ChSBA). Textural, structural, morphological, and surface properties of the materials were determined by using various measurement techniques, i.e., low-temperature adsorption/desorption isotherms of nitrogen, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), potentiometric titration, high-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The adsorption properties towards various anionic dyes, i.e., acid red 88 (AR88), acid orange 8 (AO8), and orange G (OG), were evaluated based on kinetic and equilibrium measurements. The ChSBA, ChAD, and ChMCM composites were characterized by relatively high adsorption capacities (am) for AR88, with values equal to 0.78, 0.71, and 0.69 mmol/g, respectively. These composites were also distinguished by the rapid AR88 adsorption rate, with the values of half-time parameter t0.5 equal to 0.35, 2.84, and 1.53 min, respectively. The adsorption equilibrium and kinetic data were analyzed by applying the generalized Langmuir isotherm and the multi-exponential equation (m-exp), respectively. An interaction mechanism between the dyes and the obtained materials was proposed.

Chitosan-Silica Composites for Adsorption Application in the Treatment of Water and Wastewater from Anionic Dyes.

A series of new types of composites (biopolymer-silica materials) are proposed as selective and effective adsorbents. A new procedure for the synthesis of chitosan-nanosilica composites (ChNS) and chitosan-silica gel composites (ChSG) using geometrical modification of silica and mechanosorption of chitosan is applied. The highest adsorption efficiency was achieved at pH = 2, hence the desirability of modifications aimed at stabilizing chitosan in such conditions. The amount of chitosan in the synthesis grew to 1.8 times the adsorption capacity for the nanosilica-supported materials and 1.6 times for the silica gel-based composites. The adsorption kinetics of anionic dyes (acid red AR88) was faster for ChNS than for ChSG, which results from a silica-type effect. The various structural, textural, and physicochemical aspects of the chitosan-silica adsorbents were analyzed via small-angle X-ray scattering, scanning electron microscopy, low-temperature gas (nitrogen) adsorption, and potentiometric titration, as well as their adsorption effectiveness towards selected dyes. This indicates the synergistic effect of the presence of dye-binding groups of the chitosan component, and the developed interfacial surface of the silica component in composites.

The Structure of Ordered Mesoporous Materials Synthesized from Aluminum Phyllosilicate Clay (Bentonite).

This paper reports the synthesis and structural analysis of mesoporous silica materials with the use of aluminum phyllosilicate clay (bentonite) as an alternative silica source. In the proposed synthesis, bentonite, as natural aluminosilicate, was used instead of commercially available and quite expensive tetraethyl orthosilicate (TEOS) silica source. The objective of the research study was to determine the effect of aluminum loading in the mesoporous silica body for ordering structure, porosity, and potential sorption capacity to thorium ions. The unique direction developed in this procedure is focused on preparing advanced materials from natural sources with their own desired functionality and general availability. The applied procedure based on the classic, one-step synthesis of SBA-15 silicates was modified by gradually increasing the bentonite amount with simultaneous reduction of the TEOS content. The structural and morphological characterization, as well as evaluation of the porous structure of the obtained materials, was performed using powder wide-angle X-ray diffraction (XRD), small-angle scattering (SAXS), transmission and scanning electron microscopy (TEM, SEM), low-temperature nitrogen adsorption-desorption methods and potentiometric titration. The new, cost-effective composites for the removal of Th(IV) ions are proposed. The synergistic effect of expanding the porous surface using bentonite as a silica precursor and the presence of thorium-binding groups (such as Al2O3) is indicated.

Mesoporous Carbons of Well-Organized Structure in the Removal of Dyes from Aqueous Solutions.

Mesoporous carbons with differentiated properties were synthesized by using the method of impregnation of mesoporous well-organized silicas. The obtained carbonaceous materials and microporous activated carbon were investigated by applying different methods in order to determine their structural, surface and adsorption properties towards selected dyes from aqueous solutions. In order to verify applicability of adsorbents for removing dyes the equilibrium and kinetic experimental data were measured and analyzed by applying various equations and models. The structural and acid-base properties of the investigated carbons were evaluated by Small-Angle X-ray Scattering (SAXS) technique, adsorption/desorption of nitrogen, potentiometric titration, and Transmission Electron Microscopy (TEM). The results of these techniques are complementary, indicating the type of porosity and structural ordering, e.g., the pore sizes determined from the SAXS data are in good agreement with those obtained from nitrogen sorption data. The SAXS and TEM data confirm the regularity of mesoporous carbon structure. The adsorption experiment, especially kinetic measurements, reveals the utility of mesoporous carbons in dye removing, taking into account not only the adsorption uptake but also the adsorption rate.

Physicochemical and Adsorption Characteristics of Divinylbenzene-co-Triethoxyvinylsilane Microspheres as Materials for the Removal of Organic Compounds.

In this work, organic-inorganic materials with spherical shape consisting of divinylbenzene (DVB) and triethoxyvinylsilane (TEVS) were synthesized and investigated by different complementary techniques. The obtained microspheres may be applied as sorbent systems for the purification of organic compounds from water. The hybrid microspheres combine the properties of the constituents depending on the morphologies and interfacial bonding. In this work, the influence of the molar ratio composition of crosslinked monomer (DVB) and silane coupling agent (TEVS) (DVB:TEVS molar ratios: 1:2, 1:1 and 2:1) on the morphology and quality of organic-inorganic materials have been examined. The materials were analysed using small angle X-ray scattering (SAXS) analysis, low-temperature nitrogen sorption, scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) to provide information on their structural and surface properties. Moreover, thermal analysis was performed to characterize the thermal stability of the studied materials and the adsorbent-adsorbate interactions, while adsorption kinetic studies proved the utility of the synthesized adsorbents for water and wastewater treatment.

Small AgNP in the Biopolymer Nanocomposite System.

In this work, ultra-small and stable silver nanoparticles (AgNP) on chitosan biopolymer (BP/AgP) were prepared by in situ reduction of the diamminesilver(I) complex ([Ag(NH3)2]+) to create a biostatic membrane system. The small AgNP (3 nm) as a stable source of silver ions, their crystal form, and homogeneous distribution in the whole solid membrane were confirmed by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and atomic force microscopy (AFM). The X-ray photoelectron spectroscopy (XPS) and Auger analysis were applied to investigate the elemental composition, concentration, and chemical state of surface atoms. It was found that ultra-small metallic nanoparticles might form a steady source of silver ions and enhance the biostatic properties of solid membranes. Ultra-small AgNP with disturbed electronic structure and plasmonic properties may generate interaction between amine groups of the biopolymer for improving the homogeneity of the nanometallic layer. In this work, the significant differences between the typical way (deposition of ex-situ-prepared AgNP) and the proposed in-situ synthesis approach were determined. The improved thermal stability (by thermogravimetry and differential scanning calorimetry (TG/DSC) analysis) for BP/AgP was observed and explained by the presence of the protective layer of a low-molecular silver phase. Finally, the antibacterial activity of the BP/AgP nanocomposite was tested using selected bacteria biofilms. The grafted membrane showed clear inhibition properties by destruction and multiple damages of bacteria cells. The possible mechanisms of biocidal activity were discussed, and the investigation of the AgNP influence on the bacteria body was illustrated by AFM measurements. The results obtained concluded that the biopolymer membrane properties were significantly improved by the integration with ultra-small Ag nanoparticles, which added value to its applications as a biostatic membrane system for filtration and separation issues.

Activated Carbon from Agricultural Wastes for Adsorption of Organic Pollutants.

Agricultural waste materials (strawberry seeds and pistachio shells) were used for preparation of activated carbons by two various methods. Chemical activation using acetic acid and physical activation with gaseous agents (carbon dioxide and water vapor) were chosen as mild and environmentally friendly methods. The effect of type of raw material, temperature, and activation agent on the porous structure characteristics of the materials was discussed applying various methods of analysis. The best obtained activated carbons were characterized by high values of specific surface area (555-685 m2/g). The Guinier analysis of small-angle X-ray scattering (SAXS) curves showed that a time of activation affects pore size. The samples activated using carbon dioxide were characterized mostly by the spherical morphology of pores. Adsorbents were utilized for removal of the model organic pollutants from the single- and multicomponent systems. The adsorption capacities for the 4-chloro-2-methyphenoxyacetic acid (MCPA) removal were equal to 1.43-1.56 mmol/g; however, for adsorbent from strawberry seeds it was much lower. Slight effect of crystal violet presence on the MCPA adsorption and inversely was noticed as a result of adsorption in different types of pores. For similar herbicides strong competition in capacity and adsorption rate was observed. For analysis of kinetic data various equations were used.

Silver Nanoparticles on Chitosan/Silica Nanofibers: Characterization and Antibacterial Activity.

A simple, low-cost, and reproducible method for creating materials with even silver nanoparticles (AgNP) dispersion was established. Chitosan nanofibers with silica phase (CS/silica) were synthesized by an electrospinning technique to obtain highly porous 3D nanofiber scaffolds. Silver nanoparticles in the form of a well-dispersed metallic phase were synthesized in an external preparation step and embedded in the CS/silica nanofibers by deposition for obtaining chitosan nanofibers with silica phase decorated by silver nanoparticles (Ag/CS/silica). The antibacterial activity of investigated materials was tested using Gram-positive and Gram-negative bacteria. The results were compared with the properties of the nanocomposite without silver nanoparticles and a colloidal solution of AgNP. The minimum inhibitory concentration (MIC) of obtained AgNP against Staphylococcus aureus (S. aureus) ATCC25923 and Escherichia coli (E. coli) ATCC25922 was determined. The physicochemical characterization of Ag/CS/silica nanofibers using various analytical techniques, as well as the applicability of these techniques in the characterization of this type of nanocomposite, is presented. The resulting Ag/CS/silica nanocomposites (Ag/CS/silica nanofibers) were characterized by small angle X-ray scattering (SAXS), X-ray diffraction (XRD), and atomic force microscopy (AFM). The morphology of the AgNP in solution, both initial and extracted from composite, the properties of composites, the size, and crystallinity of the nanoparticles, and the characteristics of the chitosan fibers were determined by electron microscopy (SEM and TEM).

Surface Properties of Al-Functionalized Mesoporous MCM-41 and the Melting Behavior of Water in Al-MCM-41 Nanopores.

We report an experimental investigation of structural and adhesive properties for Al-containing mesoporous MCM-41 and MCM-41 surfaces. In this work, highly ordered hexagonal mesoporous structures of aluminosilica with two different Si/Al molar ratios equal to 50 and 80 and silica samples were studied; Al was incorporated into the MCM-41 structures using the direct synthesis method, with CTAB as a surfactant. The incorporation of aluminum was evidenced simultaneously without any change in the hexagonal arrangement of cylindrical mesopores. The porous materials were examined by techniques such as low-temperature nitrogen sorption, energy-dispersive spectroscopy, and scanning and transmission electron microscopy. Surface properties were determined through X-ray photoelectron spectroscopy, potentiometric titration, and static contact angle measurements. It was shown that an increase in surface acidity leads to an increase in the wetting energy of the surface. To investigate the influence of acidity on the confinement effects, the melting behavior of water in Al-MCM-41 and MCM-41 with the same pore size was determined by using dielectric relaxation spectroscopy and differential scanning calorimetry methods. We found that the melting-point depression of water in pores is larger in the functionalized pores than in pure silica pores of the same pore diameter.

Evaluation of the Dye Extraction Using Designed Hydrogels for Further Applications towards Water Treatment.

In this work, novel chitosan-silica hydrogels were synthesized and investigated by various complementary techniques. The hydrogels were obtained via the immobilization of chitosan (Ch) on the surface of mesoporous cellular foams (MCFs). The latter silica materials were obtained by a sol-gel process, varying the composition of the reaction mixture (copolymer Pluronic 9400 or Pluronic 10500) and the ageing temperature conditions (80 °C or 100 °C). The role of the silica phase in the hydrogels was the formation of a scaffold for the biopolymeric chitosan component and providing chemical, mechanical, and thermal stability. In turn, the chitosan phase enabled the binding of anionic pollutions from aqueous solutions based on electrostatic interaction mechanisms and hydrogen bonds. To provide information on structural, morphological, and surface properties of the chitosan-silica hydrogels, analyses such as the low-temperature adsorption/desorption of nitrogen, small-angle X-ray scattering (SAXS), scanning electron microscopy (SEM), atomic force microscopy (AFM), and Fourier-transform infrared spectroscopy (FTIR) were performed. Moreover, the verification of the utility of the chitosan-silica hydrogels as adsorbents for water and wastewater treatment was carried out based on kinetic and equilibrium studies of the Acid Red 88 (AR88) adsorption. Adsorption data were analyzed by applying various equations and discussed in terms of the adsorption on heterogeneous solid-surfaces theory. The adsorption mechanism for the AR88 dye-chitosan-silica hydrogel systems was proposed.

Mesoporous Carbons and Highly Cross-Linking Polymers for Removal of Cationic Dyes from Aqueous Solutions-Studies on Adsorption Equilibrium and Kinetics.

This study presents the results of applying the methods of synthesizing mesoporous carbon and mesoporous polymer materials with an extended porous mesostructure as adsorbents for cationic dye molecules. Both types of adsorbents are synthetic materials. The aim of the presented research was the preparation, characterisation, and utilisation of obtained mesoporous adsorbents. The physicochemical properties, morphology, and porous structure characteristics of the obtained materials were determined using low-temperature nitrogen sorption isotherms, X-ray diffraction (XRD), small angle X-ray scattering (SAXS), and potentiometric titration measurements. The morphology and microstructure were imaged using scanning electron microscopy (SEM). The chemical characterisation of the surface chemistry of the adsorbents, which provides information about the surface-active groups, the elemental composition, and the electronic state of the elements, was carried out using X-ray photoelectron spectroscopy (XPS). The adsorption properties of the mesoporous materials were determined using equilibrium and kinetic adsorption experiments for three selected cationic dyes (derivatives of thiazine (methylene blue) and triarylmethane (malachite green and crystal violet)). The adsorption capacity was analysed to the nanostructural and surface properties of used materials. The Generalized Langmuir equation was applied for the analysis of adsorption isotherm data. The adsorption study showed that the carbon materials have a higher sorption capacity for both methylene blue and crystal violet, e.g., 0.88-1.01 mmol/g and 0.33-0.44 mmol/g, respectively, compared to the polymer materials (e.g., 0.038-0.044 mmol/g and 0.038-0.050 mmol/g, respectively). The kinetics of dyes adsorption was closely correlated with the structural properties of the adsorbents. The kinetic data were analysed using various equations: first-order (FOE), second-order (SOE), mixed 1,2-order (MOE), multi-exponential (m-exp), and fractal-like MOE (f-MOE).

Physicochemical, structural, and adsorption characteristics of DMSPS-co-DVB nanopolymers.

The aim of this work is the synthesis and characterization of the series of S,S'-thiodi-4,1-phenylene bis(thio-methacrylate)-co-divinylbenzene (DMSPS-co-DVB) nanomaterials. The series of new nanopolymers including three mixed systems with different ratios of DMSPS and DVB components, DMSPS-co-DVB = 1:1, DMSPS-co-DVB = 1:2, and DMSPS-co-DVB = 1:3, was synthesized in the polymerization reaction. The research task is to investigate the influence of the reaction mixture composition on morphological, textural, and structural properties of final nanosystems including size, shape, and agglomeration effect. The advanced biphasic nanomaterials enriched with thiol groups were successfully synthesized as potential sorbents for binding organic substances, heavy metals, or biomolecules. To determine the impact of the DMSPS monomer on the final properties of DMSPS-co-DVB nanocomposites, several techniques were applied to reveal the nano-dimensional structure (SAXS), texture (low-temperature nitrogen sorption), general morphology (SEM), acid-base properties (potentiometric titration), and surface chemistry and phase bonding effectiveness (FTIR/ATR spectroscopy). Finally, kinetic studies of aniline sorption on polymeric materials were performed.

Surface Properties of Synthesized Nanoporous Carbon and Silica Matrices.

In this work, we report the synthesis and characterization of ordered nanoporous carbon material (also called ordered mesoporous carbon material [OMC]) with a 4.6 nm pore size, and ordered silica porous matrix, SBA-15, with a 5.3 nm pore size. This work describes the surface properties of nanoporous molecular sieves, their wettability, and the melting behavior of D2O confined in the differently ordered porous materials with similar pore sizes. For this purpose, OMC and SBA-15 with highly ordered nanoporous structures are synthesized via impregnation of the silica matrix by applying a carbon precursor and by the sol-gel method, respectively. The porous structure of investigated systems is characterized by an N2 adsorption-desorption analysis at 77 K. To determine the electrochemical character of the surface of synthesized materials, potentiometric titration measurements are conducted; the obtained results for OMC shows a significant pHpzc shift toward the higher values of pH, relative to SBA-15. This suggests that investigated OMC has surface properties related to oxygen-based functional groups. To describe the surface properties of the materials, the contact angles of liquids penetrating the studied porous beds are also determined. The capillary rise method has confirmed the increased wettability of the silica walls relative to the carbon walls and an influence of the pore roughness on the fluid/wall interactions, which is much more pronounced for silica than for carbon mesopores. We have also studied the melting behavior of D2O confined in OMC and SBA-15 by applying the dielectric method. The results show that the depression of the melting temperature of D2O in the pores of OMC is about 15 K higher relative to the depression of the melting temperature in SBA-15 pores with a comparable 5 nm size. This is caused by the influence of adsorbate/adsorbent interactions of the studied matrices.