Aerogels are a class of lightweight, nanoporous, and nanostructured materials with diverse chemical compositions and a huge potential for applications in a broad spectrum of fields. This has led the IUPAC to include them in the top ten emerging technologies in chemistry for 2022. This review provides an overview of aerogel-based adsorbents that have been used for the removal and recovery of uranium from aqueous environments, as well as an insight into the physicochemical parameters affecting the adsorption efficiency and mechanism. Uranium removal is of particular interest regarding uranium analysis and recovery, to cover the present and future uranium needs for nuclear power energy production. Among the methods used, such as ion exchange, precipitation, and solvent extraction, adsorption-based technologies are very attractive due to their easy and low-cost implementation, as well as the wide spectrum of adsorbents available. Aerogel-based adsorbents present an extraordinary sorption capacity for hexavalent uranium that can be as high as 8.8 mol kg^–1 (2088 g kg^–1). The adsorption data generally follow the Langmuir isotherm model, and the kinetic data are in most cases better described by the pseudo-second-order kinetic model. An evaluation of the thermodynamic data reveals that the adsorption is generally an endothermic, entropy-driven process (ΔH⁰, ΔS⁰ > 0). Spectroscopic studies (e.g., FTIR and XPS) indicate that the adsorption is based on the formation of inner-sphere complexes between surface active moieties and the uranyl cation. Regeneration and uranium recovery by acidification and complexation using carbonate or chelating ligands (e.g., EDTA) have been found to be successful. The application of aerogel-based adsorbents to uranium removal from industrial processes and uranium-contaminated waste waters was also successful, assuming that these materials could be very attractive as adsorbents in water treatment and uranium recovery technologies. However, the selectivity of the studied materials towards hexavalent uranium is limited, suggesting further developments of aerogel materials that could be modified by surface derivatization with chelating agents (e.g., salophen and iminodiacetate) presenting high selectivity for uranyl moieties.

Aerogels have been defined as solid colloidal or polymeric networks of nanoparticles that are expanded throughout their entire volume by a gas. They have high surface areas, low thermal conductivities, low dielectric constants, and high acoustic attenuation, all of which are very attractive properties for applications that range from thermal and acoustic insulation to dielectrics to drug delivery. However, one of the most important impediments to that potential has been that most efforts have been concentrated on monolithic aerogels, which are prone to defects and their production requires long and costly processing. An alternative approach is to consider manufacturing aerogels in particulate form. Recognizing that need, the European Commission funded “NanoHybrids”, a 3.5 years project under the Horizon 2020 framework with 12 industrial and academic partners aiming at aerogel particles from bio- and synthetic polymers. Biopolymer aerogels in particulate form have been reviewed recently. This mini-review focuses on the emerging field of particulate aerogels from synthetic polymers. That category includes mostly polyurea aerogels, but also some isolated cases of polyimide and phenolic resin aerogels. Particulate aerogels covered include powders, micro granules and spherical millimeter-size beads. For the benefit of the reader, in addition to the literature, some new results from our laboratory concerning polyurea particle aerogels are also included.

Zinc oxide (ZnO) possesses exceptional potential to be utilized in water and wastewater treatment applications, either as a photocatalyst or in membrane incorporation. In the present study, ZnO nanoparticles were synthesized using the precipitation method. The Taguchi approach with the L_32b orthogonal array was utilized in order to optimize the experimental conditions for the synthesis of the nanoparticles and to ensure that relatively smaller-sized particles were obtained. The design was characterized by ten factors, where nine of them possessed four levels, while one had two levels. This study’s design factors were the type of Zn precursor, the concentration of the Zn precursor, the type of precipitating agent, the precipitation agent’s concentration, the type of utilized solvent, the pH value of the solvent, the temperature used during the synthetic procedure, the calcination temperature, the time of stirring during synthesis, as well as the stirring speed. The influences of those factors on the selected response parameters (the average crystallite size, degree of crystallinity, energy band gap (E_g), and photodegradation constant (k)) were then evaluated. XRD analysis and the calculated E_g values indicated that the hexagonal wurtzite structure was the only crystalline phase present in the produced samples. The photocatalytic efficiency of all ZnO nanoparticles was examined in the degradation of rhodamine B under UV light irradiation. The optimal conditions were achieved using zinc acetate dihydrate as the Zn precursor at a concentration equal to 0.3 M, sodium hydroxide as the precipitating agent (1.5 M), methanol as the solvent (the pH value of the solvent was equal to 13), a temperature during the synthetic procedure of 70 °C, 600 °C as calcination temperature, a 90 min stirring time, and 700 rpm as the stirring speed. The optimized ZnO sample was synthesized based on the aforementioned conditions and thoroughly characterized. The acquired results confirmed the prediction of the Taguchi approach, and the most enhanced k-value was observed.

The removal of polyvalent metal ions Eu(III) and Th(IV) from aqueous solutions using polyurea-crosslinked calcium alginate (X-alginate) aerogels has been investigated by batch-type experiments under ambient conditions and pH 3. The material presents relatively high sorption capacity for Eu(III) (550 g kg⁻¹) and Th(IV) (211 g kg⁻¹). The lower sorption capacity for Th(IV) compared to Eu(III) is attributed to the net charge of the dominant species in solution under the given experimental conditions, which is Eu³⁺ for Eu(III), and Th(OH)₂²⁺ and Th(OH)₃⁺ for Th(IV). Generally, the sorption is an endothermic and entropy-driven process, and it follows the Langmuir isotherm model. According to the FTIR spectra, sorption occurs via formation of inner-sphere complexes between the surface functional groups and the f-metal cationic species. The presence of europium and thorium in the adsorbent material was confirmed and quantified with EDS analysis. To the best of our knowledge, this is the first report of an aerogel material used as an adsorbent for Eu(III). Compared to other materials used for the sorption of the specific ions, which are mostly carbon-based, X-alginate aerogels show by far the highest sorption capacity. Regarding Th(IV) uptake, X-alginate aerogels show the highest capacity per volume (27.9 g L⁻¹) among the aerogels reported in the literature. Both Eu(III) and Th(IV) could be recovered from the beads by 65% and 70%, respectively. Furthermore, Th(VI) could also be quantitatively removed from wastewater, while Eu(III) could be removed by 20%. The above, along with their stability in aqueous environments, make X-alginate aerogels attractive candidates for water treatment and metal recovery applications.

The purpose of this work was to investigate the effect of multifunctionality on material properties of synthetic polymer aerogels. For this purpose, we present the synthesis and characterization of monolithic dendritic-type urethane-acrylate monomers based on an aliphatic/flexible (Desmodur N3300), or an aromatic/rigid (Desmodur RE) triisocyanate core. The terminal acrylate groups (three at the tip of each of the three branches, nine in total) were polymerized with 2,2′-azobis(isobutyronitrile) (AIBN) via free radical chemistry. The resulting wet-gels were dried with supercritical fluid (SCF) CO₂. Aerogels were characterized with ATR-FTIR and solid-state ¹³C NMR. The porous network was probed with N₂-sorption and scanning electron microscopy (SEM). The thermal stability of aerogels was studied with thermogravimetric analysis (TGA). Most aerogels were macroporous materials (porosity > 80%), with high thermal stability (up to 300 °C). Aerogels were softer at low monomer concentrations and more rigid at higher concentrations. The material properties were compared with those of analogous aerogels bearing only one acrylate moiety at the tip of each branch and the same cores, and with those of analogous aerogels bearing norbornene instead of acrylate moieties. The nine-terminal acrylate-based monomers of this study caused rapid decrease of the solubility of the growing polymer and made possible aerogels with much smaller particles and much higher surface areas. For the first time, aliphatic/flexible triisocyanate-based materials could be made with similar properties in terms of particle size and surface areas to their aromatic/rigid analogues. Finally, it was found that with monomers with a high number of crosslinkable groups, material properties are determined by multifunctionality and thus aerogels based on 9-acrylate- and 9-norbornene-terminated monomers were similar. Materials with aromatic cores are carbonizable with satisfactory yields (20–30% w/w) to mostly microporous materials (BET surface areas: 640–740 m² g⁻¹; micropore surface areas: 360–430 m² g⁻¹).

Polyurea-crosslinked Ca-alginate (X-Ca-alginate) aerogel beads (diameter: 3.3 mm) were evaluated as adsorbents of metal ions, organic solvents, and oils. They were prepared via reaction of an aromatic triisocyanate (Desmodur RE) with pre-formed Ca-alginate wet gels and consisted of 54% polyurea and 2% calcium. X-Ca-alginate aerogels are hydrophobic nanoporous materials (90% v/v porosity), with a high BET surface area (459 m²/g⁻¹), and adsorb Pb^II not only from ultrapure water (29 mg/g⁻¹) but also from seawater (13 mg/g⁻¹) with high selectivity. The adsorption mechanism involves replacement of Ca^II by Pb^II ions coordinated to the carboxylate groups of the alginate backbone. After treatment with a Na₂EDTA solution, the beads can be reused, without significant loss of activity for at least two times. X-Ca-alginate aerogels can also uptake organic solvents and oil from seawater; the volume of the adsorbate can be as high as the total pore volume of the aerogel (6.0 mL/g⁻¹), and the absorption is complete within seconds. X-Ca alginate aerogels are suitable for the decontamination of aquatic environments from a broader range of inorganic and organic pollutants.