Tailoring Chitosan/LTA Zeolite Hybrid Aerogels for Anionic and Cationic Dye Adsorption.

Chitosan (CS) is largely employed in environmental applications as an adsorbent of anionic dyes, due to the presence in its chemical structure of amine groups that, if protonated, act as adsorbing sites for negatively charged molecules. Efficient adsorption of both cationic and anionic dyes is thus not achievable with a pristine chitosan adsorbent, but it requires the combination of two or more components. Here, we show that simultaneous adsorption of cationic and anionic dyes can be obtained by embedding Linde Type A (LTA) zeolite particles in a crosslinked CS-based aerogel. In order to optimize dye removal ability of the hybrid aerogel, we target the crosslinker concentration so that crosslinking is mainly activated during the thermal treatment after the fast freezing of the CS/LTA mixture. The adsorption of isotherms is obtained for different CS/LTA weight ratios and for different types of anionic and cationic dyes. Irrespective of the formulation, the Langmuir model was found to accurately describe the adsorption isotherms. The optimal tradeoff in the adsorption behavior was obtained with the CS/LTA aerogel (1:1 weight ratio), for which the maximum uptake of indigo carmine (anionic dye) and rhodamine 6G (cationic dye) is 103 and 43 mg g-1, respectively. The behavior observed for the adsorption capacity and energy cannot be rationalized as a pure superposition of the two components, but suggests that reciprocal steric effects, chemical heterogeneity, and molecular interactions between CS and LTA zeolite particles play an important role.

An insight on the role of PVP in the synthesis of monoclinic WO3 with efficiently photocatalytic activity.

Nanoparticles of monoclinic WO3 were synthesized by a facile method using Na2WO4 as raw material and PVP 70 000 (polyvinylpyrrolidone) as surfactant and template. The effect of PVP on the structure and photocatalytic activity of the synthesized WO3 was discussed in detail. The prepared samples were characterized by XRD, SEM, FT-IR, UV-vis, XPS, PL techniques, and the results show that the visible light is strongly absorbed by the obtained samples, whose particle size varies from 38 to 85 nm. The photocatalytic properties of the resulted samples were evaluated using RhB in water as a target substance, and results illustrate that 30 mg l-1 of RhB can be efficiently photodegraded by nano WO3 under visible light irradiation. Based on the results of XPS, PL and photocalysis experiments, the reason of such improved photocatalytic efficiency may be attributed to the reducing activity of PVP, which leads to the formation of oxygen vacancies beneficial for the capture of photoelectrons and the generation of superoxide radicals. Furthermore, the results show that the photocatalytic efficiency is greatly influenced by the morphology of the synthesized WO3 samples, and the WO3 with a block-shaped morphology is an ideal photocatalyst for the degradation of RhB under visible light irradiation.

Highly Cytocompatible Polylactic Acid Based Electrospun Microfibers Loaded with Silver Nanoparticles Generated onto Chestnut Shell Lignin for Targeted Antibacterial Activity and Antioxidant Action.

Electrospun (e-spun) fibers are generally regarded as powerful tools for cell growth in tissue regeneration applications, and the possibility of imparting functional properties to these materials represents an increasingly pursued goal. We report herein the preparation of hybrid materials in which an e-spun d,l-polylactic acid matrix, to which chitosan or crystalline nanocellulose was added to improve hydrophilicity, was loaded with different amounts of silver(0) nanoparticles (AgNP) generated onto chestnut shell lignin (CSL) (AgNP@CSL). A solvent-free mechanochemical method was used for efficient (85% of the theoretical value by XRD analysis) Ag(0) production from the reduction of AgNO3 by lignin. For comparison, e-spun fibers containing CSL alone were also prepared. SEM and TEM analyses confirmed the presence of AgNP@CSL (average size 30 nm) on the fibers. Different chemical assays indicated that the AgNP@CSL containing fibers exhibited marked antioxidant properties (EC50 1.6 ± 0.1 mg/mL, DPPH assay), although they were halved with respect to those of the CSL containing fibers, as expected because of the efficient silver ion reduction. All the fibers showed high cytocompatibility toward human mesenchymal stem cells (hMSCs) representative of the self-healing process, and their antibacterial properties were tested against the pathogens Escherichia coli (E. coli), Staphylococcus epidermidis, and Pseudomonas aeruginosa. Finally, competitive surface colonization as simulated by cocultures of hMSC and E. coli showed that AgNP@CSL loaded fibers offered the cells a targeted protection from infection, thus well balancing cytocompatibility and antibacterial properties.

Combining the Potent Reducing Properties of Pecan Nutshell with a Solvent-Free Mechanochemical Approach for Synthesizing High Ag0 Content-Silver Nanoparticles: An Eco-Friendly Route to an Efficient Multifunctional Photocatalytic, Antibacterial, and Antioxidant Material.

A straightforward, low-cost, and scalable solid-state mechanochemical protocol for the synthesis of silver nanoparticles (AgNP) based on the use of the highly reducing agri-food by-product pecan nutshell (PNS) is reported herein. Under optimized conditions (180 min, 800 rpm, PNS/AgNO3 ratio = 55/45 w/w), a complete reduction in silver ions was achieved, leading to a material containing ca. 36% w/w Ag0 (X-ray diffraction analysis). Dynamic light scattering and microscopic analysis showed a uniform size distribution (15-35 nm average diameter) of the spherical AgNP. The 2,2-Diphenyl-1-picrylhydrazyl (DPPH) assay revealed lower-although still absolutely high (EC50 = 5.8 ± 0.5 mg/mL)-antioxidant properties for PNS for the further incorporation of AgNP, supporting the efficient reduction of Ag+ ions by PNS phenolic compounds. Photocatalytic experiments indicated that AgNP-PNS (0.4 mg/mL) was able to induce the >90% degradation of methylene blue after 120 min visible light irradiation, with good recycling stability. Finally, AgNP-PNS demonstrated high biocompatibility and significantly light-enhanced growth inhibition properties against Pseudomonas aeruginosa and Streptococcus mutans at concentrations as low as 250 µg/mL, also eliciting an antibiofilm effect at 1000 µg/mL. Overall, the adopted approach allowed to reuse a cheap and abundant agri-food by-product and required no toxic or noxious chemicals, making AgNP-PNS a sustainable and easy-to-access multifunctional material.

Use of Zeolites in the Capture and Storage of Thermal Energy by Water Desorption-Adsorption Cycles.

In this work, four zeolite-bearing materials (three naturally occurring and one of synthetic origin) were considered for thermal energy capture and storage. Such materials can store thermal energy as heat of desorption of the water present therein, heat that is given back when water vapor is allowed to be re-adsorbed by zeolites. This study was carried out by determining the loss of water after different activation thermal treatments, the water adsorption kinetics and isotherm after an activation step of the zeolites, the intergranular and intragranular porosity, and the thermal conductivity of the zeolite-bearing materials. Moreover, the thermal stability of the framework of the zeolites of the four materials tested was investigated over a large number of thermal cycles. The results indicate that zeolite 13X was the most suitable material for thermal energy storage and suggest its use in the capture and storage of thermal energy that derives from thermal energy waste.

An unconventional method for the recovery of caustic soda from spent Al-rich pickling solutions.

This work presents an unconventional procedure for the recovery of spent Al-rich caustic soda solutions from the pickling of dies for the production of aluminium extrusions. Caustic soda was regenerated at roughly 70%, by precipitating aluminate, after addition of a silica source, in the form of zeolite A, a microporous material that is widely used in many technological sectors. It was shown that the process is reliable and can be repeated for several cycles, provided the concentration of the caustic soda solution is suitably restored. The by-product obtained, zeolite A, proved to be a high-grade material with performance as a cation exchanger and physical sorbent that is certainly comparable to that reported in literature (e.g., cation exchange capacity equal to 5.14 meq g(-1) vs. 5.48 meq g(-1) and water vapour adsorption capacity of 26.5% vs. 27.6% at 16 torr and 298 K). The economics of the process, although not examined yet, would appear generally favourable, considering that zeolite A is a valuable by-product which widely covers the costs for the recovery of the spent solutions. There are, therefore, significant prospects for the use of zeolite A, particularly as a builder in detergent formulation.

Chitosan/Zeolite Composite Aerogels for a Fast and Effective Removal of Both Anionic and Cationic Dyes from Water.

Organic dyes are extensively used in many industrial sectors, and their uncontrolled disposal into wastewaters raises serious concerns for environmental and human health. Due to the large variety of such pollutants, an effective remediation strategy should be characterized by a broad-spectrum efficacy. A promising strategy is represented by the combination of different adsorbent materials with complementary functionalities to develop composite materials that are expected to remove different contaminants. In the present work, a broad-spectrum adsorbent was developed by embedding zeolite 13X powder (ZX) in a chitosan (CS) aerogel (1:1 by weight). The CS-ZX composite adsorbent removes both anionic (indigo carmine, IC) and cationic (methylene blue, MB) dyes effectively, with a maximum uptake capacity of 221 mg/g and 108 mg/g, respectively. In addition, the adsorption kinetics are rather fast, with equilibrium conditions attained in less than 2 h. The composite exhibits good mechanical properties in both dry and wet state, which enables its handling for reusability purposes. In this regard, preliminary tests show that the full restoration of the IC removal ability over three adsorption-desorption cycles is achieved using a 0.1 M NaOH aqueous solution, while a 1 M NaCl aqueous solution allows one to preserve >60% of the MB removal ability.

Mechanically Coherent Zeolite 13X/Chitosan Aerogel Beads for Effective CO2 Capture.

The constant increase of CO2 concentration in the atmosphere is recognized worldwide to severely impact the environment and human health. Zeolites possess a high adsorption capacity for CO2 removal, but their powdery form prevents their use in many practical applications. When binding agents are used, a partial occlusion of the porosity can severely compromise the adsorption capacity. In this regard, a great challenge is producing compact composite adsorbents while maintaining a high specific surface area to preserve the pristine performance of zeolites. Here, this goal was achieved by preparing beads with a high content of zeolite 13X (up to 90 wt %) using a chitosan aerogel as the binding agent. A facile preparation procedure based on the freeze-drying of hydrogel beads obtained by phase inversion led to a peculiar microstructure in which a very fine polymeric framework firmly embeds the zeolite particles, providing mechanical coherence and strength (compressive strain >40% without bead fragmentation, deformation <20% under 1 kgf-load) and yet preserving the powder porosity. This allowed us to fully exploit the potential of the constituents, reaching a high specific surface area (561 m2 g-1) and excellent CO2 uptake capacity (4.23 mmol g-1) for the sample at 90% zeolite. The beads can also be reused after being fully regenerated by means of a pressure swing protocol at room temperature.

Fabrication of Green Diatomite/Chitosan-Based Hybrid Foams with Dye Sorption Capacity.

The latest tendency of the scientific community regards the development of different classes of green materials able to solve pollution problems caused by industrial and human activity. In this paper, chitosan and diatomite were used to produce a broad-spectrum hybrid adsorbent, either in powder or in monolithic form for environmental pollutant removal. Diatomite-chitosan-based powders and porous diatomite-chitosan hybrids were prepared and characterized by chemical-physical, thermal and morphological analysis. Moreover, their adsorbent capacity towards anionic dye (Indigo Carmine) was also evaluated. Obtained data showed that chitosan improves the adsorption capacity of both systems, increasing the uptake of dye in both diatomite-chitosan systems.

An insight into clustering of halogenated anesthetics molecules in metal-organic frameworks: Evidence of adsorbate self-association in micropores.

In order to better understand the adsorption of volatile halogenated anesthetics on metal organic frameworks (MOFs), sevoflurane vapor adsorption experiments were performed on commercial MOF-177 at different temperatures. Due to the surface homogeneity of such an adsorbent, arising from its almost unimodal pore size distribution and the absence of specific, coordinatively unsaturated adsorption active sites, sevoflurane adsorption isotherms exhibited a peculiar deviation from the Langmuirian behavior. Consequently, they show a "kink" at a specific pressure that increases with increasing equilibrium temperature. Successful modeling of such data by means of the Talu-Meunier equation confirmed clustering of adsorbate molecules inside adsorbent micropores, similarly to water vapor adsorption on activated carbon, which may play an important role when designing a system using MOFs as the potential adsorbents for capturing anesthetics.

Pozzolanic Activity of Zeolites: The Role of Si/Al Ratio.

A great challenge of research is the utilization of natural or synthetic zeolites, in place of natural pozzolans, for manufacturing blended cements. The difficulties of interpretation of the pozzolanic behavior of natural zeolite-rich materials and the role played by their nature and composition can be overcome by studying more simple systems, such as pure synthetic zeolites. This study aims at investigating the pozzolanic ability of isostructural zeolites with different framework compositions, such as three sodium zeolites of the faujasite (FAU) framework type: LSX, X, and Y. The pozzolanic activity has been estimated by thermogravimetry and X-ray diffraction analysis. The overall outcome of the investigation is that the zeolite structure affects its pozzolanic activity, as zeolites with similar framework densities exhibit distinct abilities to fix lime. Moreover, the framework composition is effective either from a kinetic point of view or on the total amount of fixed lime. Zeolite X appears to possess the best average features.

Surface modified natural zeolites (SMNZs) as nanocomposite versatile materials for health and environment.

The present research deals with the evaluation of a clinoptilolite-rich rock, occurring in the Nizný Hrabovec deposit (Slovakia), for high-value technological applications based on sorption and in vitro release of nonsteroidal anti-inflammatory drugs (i.e., ibuprofen sodium salt). This georesource was surface modified (SMNZ) using four cationic surfactants. Results demonstrate that ibuprofen sorption is very fast and SMZNs can sorb up to ˜26 mg/g of drug as a function of the type of counterion and morphology of surfactant, as well as the hydrophobicity and molecular structure of the drug. Maximum sorption capacities observed for all SMNZs are fully comparable to other adsorbent carriers usually used for removal of contaminants in wastewaters. Sorption of ibuprofen is controlled by a dual mechanism: external anionic exchange and partition into the hydrophobic portion of the patchy bilayer. A prompt drug release in simulated intestinal fluid (SIF) was also observed, making this natural material also suitable to provide rapid soothing effects in potential pharmacological applications. Comparing the results of this study with other recent investigations, a good technological performance of clinoptilolite-rich rock can be inferred despite the relatively low zeolite content (˜56 wt.%).

Use of a Metal Organic Framework for the Adsorptive Removal of Gaseous HCl: A New Approach for a Challenging Task.

In this work, the potentialities of the amino-functionalized, chromium-based MIL-101 metal organic framework (NH2-MIL-101) as a high capacity, fully regenerable hydrogen chloride adsorbent have been proved by a thorough adsorption thermodynamics investigation. The chosen adsorbent showed high gaseous HCl adsorption capacities and, to the best of our knowledge, it is the first example of a totally regenerable substrate for this kind of adsorbate, as evidenced by both experimental and modeling results. This paves the way to the implementation of greener, more energetically efficient pressure/temperature swing adsorption processes to purify biogas feeds for high-temperature fuel cells.