Layered double hydroxides (LDHs) play a fundamental role in the processes for the abatement of pollutants in water, with reference to heavy metal decontamination. The research on the topic is multiobjective target oriented, aiming at combining environmental remediation with the possibility of reusing a sorbent as many times as possible, turning it into a renewable resource. In this study, the antibacterial and catalytic properties of a ZnAl-SO4 LDH and its resulting product after being subjected to a Cr(VI) remediation process are compared. Both solid substrates have also been tested after undergoing a thermal annealing process. The sorbent (previously described and tested for remediation) has been investigated for its antibacterial activity in view of further surgery and drug delivery applications. Finally, its photocatalytic properties have been experimentally tested in the degradation of a model pollutant, i.e., Methyl Orange (MO), under solar-simulated light. Identifying the best recycling strategy for these materials requires an accurate knowledge of their physicochemical properties. The results show that both the antimicrobial activity and the photocatalytic performance may considerably improve after thermal annealing.
Owing to their structure, layered double hydroxides (LDHs) and allophane are nowadays considered as promising materials for application in different fields. The goal of this work is to compare the efficacy of allophane and ZnAl-SO4 LDH to remove, by adsorption, some cationic and anionic pollutants from industrial wastewater. Both compounds were synthesized via the co-precipitation route (direct method) followed by hydrothermal treatment, obtaining nanoscopic crystallites with a partially disordered turbostratic (ZnAl-SO4 LDH) or amorphous (allophane) structure. The characterization of the obtained compounds was performed by means of powder x-ray diffraction (PXRD), thermal gravimetry analysis (TGA), field emission scanning electron microscopy analysis (FESEM), and Fourier-transform infrared spectroscopy (FT-IR). The sorbents were tested using wastewater produced by a real metalworking plant and containing ionic species such as Cu(II), Fe(III) and Cr(VI), whose concentration was measured by means of inductively coupled plasma-optical emission spectrometry (ICP-OES). This investigation represents an alternative procedure with respect to standard protocols based on customarily made and artificially lab-produced wastewaters. Both sorbents and their combination proved to be efficient in Cr(VI) removal, irrespective of the presence of cations like Cu(II) and Fe(III). A synergistic effect was detected for Cu(II) adsorption in a mixed allophane/LDH sorbent, leading to a Cu(II) removal rate of 89.5%.
The performance of an innovative material based on expanded graphite, Grafysorber® G+ (Directa Plus), has been tested through laboratory, tank, and confinement tests for oil removal in case of an oil spill and water treatment. In addition to the ability to retain oil, the possibility of reusing this material after regeneration via squeezing was also evaluated. As a comparison, the same experimental tests were conducted using polypropylene flakes (PP), the material currently most used to deal with spill accidents. Oils with different chemical and physical properties were used, namely kerosene, diesel, and crude oil. From the laboratory tests, the capacity of Grafysorber® G+ to retain oil was found to be directly proportional to the viscosity of the latter, with adsorption values ranging from 76.8 g/g for diesel to 50.8 g/g for kerosene, confirming the potential of the innovative material compared to the PP. Cyclical use tests have confirmed certain reusability of the material, even if its adsorbent capacity decreases significantly after the first cycle and continues to decrease in subsequent cycles, but a less marked manner. Finally, some considerations based on the adsorption capacities were found to suggest that the adoption of the new material is also economically preferable, resulting in savings of 20 to 40% per kg of hydrocarbon treated.
An experimental study of hydrogen sulfide adsorption on a fixed bed for biogas purification is proposed. The adsorbent investigated was powdered hematite, synthesized by a wet-chemical precipitation method and further activated with copper (II) oxide, used both as produced and after pelletization with polyvinyl alcohol as a binder. The pelletization procedure aims at optimizing the mechanical properties of the pellet without reducing the specific surface area. The active substrate has been characterized in its chemical composition and physical properties by X-ray Diffraction (XRD), Field Emission Scanning Electron Microscopy (FE-SEM), thermogravimetric analysis (TGA) and N2 physisorption/desorption for the determination of surface area. Both powders and pellets have been tested as sorbents for biogas purification in a fixed bed of a steady-state adsorption column and the relevant breakthrough curves were determined for different operating conditions. The performance was critically analyzed and compared with that typical of other commercial sorbents based on zinc oxide or relying upon specific compounds supported on a chemically inert matrix (SulfaTreat®). The technique proposed may represent a cost-effective and sustainable alternative to commercial sorbents in conventional desulphurization processes.
A sample of rhyolitic obsidian (OS) was used as raw material for zeolite synthesis by long (4 days) and fast (2 h)-aging hydrothermal processes. Zeolite synthesis was also performed by a fast (2 h) sonication method. The products were analysed by X-ray diffraction (XRD) and scanning electron microscopy (SEM) both immediately after and 3 years after their formation in order to determine the stability of synthetic materials according to the method used. The results confirm zeolitization of obsidian both by long-aging conventional hydrothermal heating and fast hydrothermal process. However, the data highlight the efficiency of direct ultrasound energy in achieving more stable zeolite crystals over time. These results carried out using a natural source, follow those already obtained using wastes and pure sources as raw materials thus providing a definitive validation of the different mechanisms controlling zeolite formation according to the process used. Moreover, the results confirm the effectiveness of ultrasonic energy in the formation of zeolites that are more stable over time. Due to the chemical composition of the obsidian precursor, all synthetic zeolites show good magnetic properties (i.e., saturation magnetization), in view to potential magnetic separation.
A low-energy, magnetically-driven milling technique for the synthesis of silver nanoparticles is proposed, where the grinding medium and the metal precursor consisting of silver spheres have the same shape and size, belonging to a millimetric scale. The process is carried out at room temperature in aqueous solvent, where different types of capping agents have been dissolved to damp particle agglomeration. The particle diameters, determined by dynamic light scattering and transmission electron microscopy, have been compared with those typical of conventional wet-chemical bottom-up synthesis processes. The use of milling spheres and metal precursor of the same initial shape and size allows to overcome some drawbacks and limitations distinctive of conventional bead-milling equipment, generally requiring complex operations of separation and recovery of milling media. The milling bead/nanoparticle diameter ratio obtained by this approach is lower than that typical of most previous wet bead milling techniques. The method described here represents a simple, one-pot, cost-effective, and eco-friendly process for the synthesis of metal nanoparticles starting from a bulky solid.
The performances of an innovative material based on graphene multilayers in a 3D structure similar to expanded graphite, Grafysorber® G+ (Directa Plus), have been tested via in field applications on a real contaminated site. Several experimental tests were performed using Grafysorber® inside adsorbent devices (booms and pillows) to treat waters polluted by oil. The experimental campaign was carried out with the aim of comparing the performances of Grafysorber® with those of polypropylene (PP), which is the material used worldwide in case of water oil spill clean-up activities. The results achieved have confirmed a considerably higher selective adsorption capacity of Grafysorber® compared to PP, and configure the new material as a promising alternative to standard materials in enhancing oil spill remediation by selective adsorption.
Copper nanoparticles have been synthesized in ethylene glycol (EG) using copper sulphate as a precursor and vanadium sulfate as an atypical reductant being active at room temperature. We have described a technique for a relatively simple preparation of such a reagent, which has been electrolytically produced without using standard procedures requiring an inert atmosphere and a mercury cathode. Several stabilizing agents have been tested and cationic capping agents have been discarded owing to the formation of complex compounds with copper ions leading to insoluble phases contaminating the metallic nanoparticles. The elemental copper nanoparticles, stabilized with polyvinylpyrrolidone (PVP) and sodium dodecyl sulphate (SDS), have been characterized for composition by energy dispersive X-ray spectroscopy (EDS), and for size by dynamic light scattering (DLS), and transmission electron microscopy (TEM), giving a size distribution in the range of 40-50 nm for both stabilizing agents. From a methodological point of view, the process described here may represent an alternative to other wet-chemical techniques for metal nanoparticle synthesis in non-aqueous media based on conventional organic or inorganic reductants.
