Carbon Nanostructures-Silica Aerogel Composites for Adsorption of Organic Pollutants.

Silica aerogels are a class of materials that can be tailored in terms of their final properties and surface chemistry. They can be synthesized with specific features to be used as adsorbents, resulting in improved performance for wastewater pollutants' removal. The purpose of this research was to investigate the effect of amino functionalization and the addition of carbon nanostructures to silica aerogels made from methyltrimethoxysilane (MTMS) on their removal capacities for various contaminants in aqueous solutions. The MTMS-based aerogels successfully removed various organic compounds and drugs, achieving adsorption capacities of 170 mg⋅g-1 for toluene and 200 mg⋅g-1 for xylene. For initial concentrations up to 50 mg⋅L-1, removals greater than 71% were obtained for amoxicillin, and superior to 96% for naproxen. The addition of a co-precursor containing amine groups and/or carbon nanomaterials was proven to be a valuable tool in the development of new adsorbents by altering the aerogels' properties and enhancing their adsorption capacities. Therefore, this work demonstrates the potential of these materials as an alternative to industrial sorbents due to their high and fast removal efficiency, less than 60 min for the organic compounds, towards different types of pollutants.

Synthesis of Highly Luminescent Silica-Coated Upconversion Nanoparticles from Lanthanide Oxides or Nitrates Using Co-Precipitation and Sol-Gel Methods.

Upconversion nanoparticles (UCNPs) are under consideration for their use as bioimaging probes with enhanced optical performance for real time follow-up under non-invasive conditions. Photostable and core-shell NaYF4:Yb3+, Er3+-SiO2 UCNPs obtained by a novel and simple co-precipitation method from lanthanide nitrates or oxides were herein synthesized for the first time. The sol-gel Stöber method followed by oven or supercritical gel drying was used to confer biocompatible surface properties to UCNPs by the formation of an ultrathin silica coating. Upconversion (UC) spectra were studied to evaluate the fluorescence of UCNPs upon red/near infrared (NIR) irradiation. ζ-potential measurements, TEM analyses, XRD patterns and long-term physicochemical stability were also assessed and confirmed that the UCNPs co-precipitation synthesis is a shape- and phase-controlling approach. The bio- and hemocompatibility of the UCNPs formulation with the highest fluorescence intensity was evaluated with murine fibroblasts and human blood, respectively, and provided excellent results that endorse the efficacy of the silica gel coating. The herein synthesized UCNPs can be regarded as efficient fluorescent probes for bioimaging purposes with the high luminescence, physicochemical stability and biocompatibility required for biomedical applications.

Aerogel Composites Produced from Silica and Recycled Rubber Sols for Thermal Insulation.

Hydrophobic rubber-silica aerogel panels (21.5 × 21.5 × 1.6 cm3) were fabricated from silica and rubber sols and reinforced with several fiber types (recycled tire textile fibers, polyester blanket, silica felt, glass wool). A recycled rubber sol was prepared using peracetic acid and incorporated for the first time in TEOS-based sol-gel chemistry. The composites exhibited good thermal stability up to 400 °C and very low thermal conductivity, in the superinsulation range when using polyester fibers (16.4 ± 1.0 mW·m-1·K-1), and of 20-30 mW·m-1·K-1 for the remaining fibers. They could also endure cyclic compression loads with near full recovery, thus showing very promising properties for insulation of buildings.

Silica-Based Aerogel Composites Reinforced with Reticulated Polyurethane Foams: Thermal and Mechanical Properties.

In this work, silica aerogel composites reinforced with reticulated polyurethane (PU) foams have been manufactured having densities in the range from 117 to 266 kg/m3 and porosities between 85.7 and 92.3%. Two different drying processes were employed (ambient pressure drying and supercritical drying) and a surface modification step was applied to some of the silica formulations. These composites, together with the reference PU foam and the monolithic silica aerogels, were fully characterized in terms of their textural properties, mechanical properties and thermal conductivities. The surface modification with hexamethyldisilazane (HMDZ) proved to improve the cohesion between the reticulated foam and the silica aerogels, giving rise to a continuous network of aerogel reinforced by a polyurethane porous structure. The samples dried under supercritical conditions showed the best interaction between matrixes as well as mechanical and insulating properties. These samples present better mechanical properties than the monolithic aerogels having a higher elastic modulus (from 130 to 450 kPa), a really exceptional flexibility and resilience, and the capacity of being deformed without breaking. Moreover, these silica aerogel-polyurethane foam (Sil-PU) composites showed an excellent insulating capacity, reaching thermal conductivities as low as 14 mW/(m·K).

Amine Modification of Silica Aerogels/Xerogels for Removal of Relevant Environmental Pollutants.

Serious environmental and health problems arise from the everyday release of industrial wastewater effluents. A wide range of pollutants, such as volatile organic compounds, heavy metals or textile dyes, may be efficiently removed by silica materials advanced solutions such as aerogels. This option is related to their exceptional characteristics that favors the adsorption of different contaminants. The aerogels performance can be selectively tuned by an appropriate chemical or physical modification of the aerogel's surface. Therefore, the introduction of amine groups enhances the affinity between different organic and inorganic contaminants and the silica aerogels. In this work, different case studies are reported to investigate and better understand the role of these functional groups in the adsorption process, since the properties of the synthesized aerogels were significantly affected, regarding their microstructure and surface area. In general, an improvement of the removal efficiency after functionalization of aerogels with amine groups was found, with removal efficiencies higher than 90% for lead and Rubi Levafix CA. To explain the adsorption mechanism, both Langmuir and Freundlich models were applied; chemisorption is most likely the sorption type taking place in the studied cases.

Influence of Structure-Directing Additives on the Properties of Poly(methylsilsesquioxane) Aerogel-Like Materials.

The effect of glycerol (GLY) and poly(ethylene glycol) (PEG) additives on the properties of silica aerogel-like monoliths obtained from methyltrimethoxysilane (MTMS) precursor was assessed. The tested molar ratios of additive/precursor were from 0 to 0.1 and the lowest bulk densities were obtained with a ratio of 0.025. When a washing step was performed in the sample containing the optimum PEG ratio, the bulk density could be reduced even further. The analysis of the material's microstructure allowed us to conclude that GLY, if added in an optimum amount, originates a narrower pore size distribution with a higher volume of mesopores and specific surface area. The PEG additive played a binder effect, leading to the filling of micropores and the appearance of large pores (macropores), which caused a reduction in the specific surface area. The reduction of the bulk density and the microstructural changes in the aerogels induced by adding a small amount of these additives confirm the possibility of fine control of properties of these lightweight materials. The achieved high porosity (97%) and low thermal conductivity (~35 mW·m-1·K-1) makes them suitable to be used as thermal insulators.

Electrochemical determination of copper ions in spirit drinks using carbon paste electrode modified with biochar.

This work describes for first time the use of biochar as electrode modifier in combination with differential pulse adsorptive stripping voltammetric (DPAdSV) techniques for preconcentration and determination of copper (II) ions in spirit drinks samples (Cachaça, Vodka, Gin and Tequila). Using the best set of the experimental conditions a linear response for copper ions in the concentration range of 1.5 × 10(-6) to 3.1 × 10(-5) mol L(-1) with a Limit of Detection (LOD) of 4.0 × 10(-7) mol L(-1). The repeatability of the proposed sensor using the same electrode surface was measured as 3.6% and 6.6% using different electrodes. The effect of foreign species on the voltammetric response was also evaluated. Determination of copper ions content in different samples of spirit drinks samples was also realized adopting inductively coupled plasma optical emission spectroscopy (ICP-OES) and the results achieved are in agreement at a 95% of confidence level.