Synthesis of silica aerogel films in liquid molds.

By virtue of their low density and thermal conductivity, aerogels constitute attractive thermal insulators. Of those, aerogel films are best suited for thermal insulation in microsystems. Processes for the synthesis of aerogel films with thicknesses smaller than 2 µm or thicker than 1 mm are well established. However, for microsystems films in the range of a few microns and up to several hundred microns would be beneficial. To circumvent the present limitations, we describe a liquid mold made of two immiscible liquids, used here to produce aerogel films thicker than 2 µm in a single molding step. Following gelation and aging, the gels were removed from the liquids and dried using supercritical carbon dioxide. In contrast to spin/dip coating, liquid molding avoids solvent evaporation from the gel's outer surface during gelation and aging, films are free-standing and have smooth surfaces. The choice of liquids determines the aerogel film thickness. As a proof of concept, 130 µm thick homogeneous and high porosity (>90%) silica aerogel films were synthesized in a liquid mold with fluorine oil and octanol. The resemblance of the liquid mold approach to the float glass technique offers the prospect of mass production of large sheets of aerogel films.

Application of Poly(caffeic acid) for the Extraction of Critical Rare Earth Elements.

Poly(caffeic acid) was synthesized and utilized for the extraction and determination of rare earth elements (REEs), thorium, and uranium. Oxidative polymerization of caffeic acid, a low-cost plant-based material, in the presence of ethylenediamine produced a granular, air-stable, and cross-linked polymer. The polymer is highly oxygenated and together with the amino group from ethylenediamine efficiently coordinates and preconcentrates these critical elements from aqueous media. Extraction was dependent on solution pH, amount of sorbent, and extraction time, while the concentration and flow rate of the desorption solution governed the recovery efficiency. Removal and recovery efficiencies greater than 98 and 90%, respectively, and low levels of detection ranging from 0.1 to 2.9 ng/L were achieved. Determination of these strategic elements in the presence of potentially interfering ions as well as in complex matrices such as well water and produced water samples also was demonstrated. The capacity of poly(caffeic acid) was determined with lanthanum as a representative REE to be 161.7 mg/g, establishing the promise of poly(caffeic acid) for larger-scale extractions in addition to the ability to screen sources for the presence of REEs.

Using small angle x-ray scattering to examine the aggregation mechanism in silica nanoparticle-based ambigels for improved optical clarity.

Silica-based aerogels are a promising low-cost solution for improving the insulation efficiency of single-pane windows and reducing the energy consumption required for space heating and cooling. Two key material properties required are high porosity and small pore sizes, which lead to low thermal conductivity and high optical transparency, respectively. However, porosity and pore size are generally directly linked, where high porosity materials also have large pore sizes. This is unfavorable as large pores scatter light, resulting in reduced transmittance in the visible regime. In this work, we utilized preformed silica colloids to explore methods for reducing pore size while maintaining high porosity. The use of preformed colloids allows us to isolate the effect of solution conditions on porous gel network formation by eliminating simultaneous nanoparticle growth and aggregation found when using typical sol-gel molecular-based silica precursors. Specifically, we used in situ synchrotron-based small-angle x-ray scattering during gel formation to better understand how pH, concentration, and colloid size affect particle aggregation and pore structure. Ex situ characterization of dried gels demonstrates that peak pore widths can be reduced from 15 to 13 nm, accompanied by a narrowing of the overall pore size distribution, while maintaining porosities of 70%-80%. Optical transparency is found to increase with decreasing pore sizes while low thermal conductivities ranging from 95 +/- 13 mW/m K are maintained. Mechanical performance was found to depend primarily on effective density and did not show a significant dependence on solution conditions. Overall, our results provide insights into methods to preserve high porosity in nanoparticle-based aerogels while improving optical transparency.

Transparent silica aerogel slabs synthesized from nanoparticle colloidal suspensions at near ambient conditions on omniphobic liquid substrates.

This paper presents a novel sol-gel method to synthesize large and thick silica aerogel monoliths at near ambient conditions using a commercial aqueous solution of colloidal silica nanoparticles as building blocks. To achieve slabs with high visible transmittance and low thermal conductivity, the method combines the strategies of (i) synthesizing gels on an omniphobic perfluorocarbon liquid substrate, (ii) aging at temperatures above room temperature, and (iii) performing solvent exchange with a low-surface-tension organic solvent prior to ambient drying. The omniphobic liquid substrates were used to prevent cracking and ensure an optically-smooth surface, while nanoparticle building blocks were small (<10 nm) to limit volumetric light scattering. Gels were aged at temperatures between 25 and 80 °C for up to 21 days to make them stronger and stiffer and to reduce shrinkage and cracking during ambient drying. Ambient drying was achieved by first exchanging water in the gel pores for octane, followed by drying in an octane-rich atmosphere to decrease capillary forces. The synthesized nanoparticle-based silica aerogel monoliths had thicknesses up to 5 mm, diameters up to 10 cm, porosities exceeding 80%, and thermal conductivities as low as 0.08 W m-1 K-1. Notably, the slabs featured visible transmittance exceeding 75% even for slabs as thick as 5 mm. The as-synthesized aerogel monoliths were exposed to TMCS vapor to induce hydrophobic properties resulting in a water contact angle of 140° that prevented water infiltration into the pores and protected the aerogels from water damage. This simple synthesis route conducted at near ambient conditions produces hydrophobic aerogel monoliths with promising optically transparent and thermally insulating properties that can be adhered to glass panes for window insulation and solar-thermal energy conversion applications.

Controlling Thermal Conductivity in Mesoporous Silica Films Using Pore Size and Nanoscale Architecture.

This work investigates the effect of wall thickness on the thermal conductivity of mesoporous silica materials made from different precursors. Sol-gel- and nanoparticle-based mesoporous silica films were synthesized by evaporation-induced self-assembly using either tetraethyl orthosilicate or premade silica nanoparticles. Since wall thickness and pore size are correlated, a variety of polymer templates were used to achieve pore sizes ranging from 3-23 nm for sol-gel-based materials and 10-70 nm for nanoparticle-based materials. We found that the type of nanoscale precursor determines how changing the wall thickness affects the resulting thermal conductivity. The data indicate that the thermal conductivity of sol-gel-derived porous silica decreased with decreasing wall thickness, while for nanoparticle-based mesoporous silica, the wall thickness had little effect on the thermal conductivity. This work expands our understanding of heat transfer at the nanoscale and opens opportunities for tailoring the thermal conductivity of nanostructured materials by means other than porosity and composition.

Artificial phototropism for omnidirectional tracking and harvesting of light.

Many living organisms track light sources and halt their movement when alignment is achieved. This phenomenon, known as phototropism, occurs, for example, when plants self-orient to face the sun throughout the day. Although many artificial smart materials exhibit non-directional, nastic behaviour in response to an external stimulus, no synthetic material can intrinsically detect and accurately track the direction of the stimulus, that is, exhibit tropistic behaviour. Here we report an artificial phototropic system based on nanostructured stimuli-responsive polymers that can aim and align to the incident light direction in the three-dimensions over a broad temperature range. Such adaptive reconfiguration is realized through a built-in feedback loop rooted in the photothermal and mechanical properties of the material. This system is termed a sunflower-like biomimetic omnidirectional tracker (SunBOT). We show that an array of SunBOTs can, in principle, be used in solar vapour generation devices, as it achieves up to a 400% solar energy-harvesting enhancement over non-tropistic materials at oblique illumination angles. The principle behind our SunBOTs is universal and can be extended to many responsive materials and a broad range of stimuli.

Toward tunable adsorption properties, structure, and crystallinity of titania obtained by block copolymer and scaffold-assisted templating.

Nanostructured titania and composite titania materials were synthesized for the first time by a one-pot strategy in an aqueous solution containing Pluronic P123 block copolymer and suitable precursors. The strategy can be considered as more facile, environmentally friendly, and less expensive as compared to the existing ones that require use of organic solvents. In the case of composites, silica and alumina particles were used as a structure protecting scaffold and composite components. This synthesis strategy allowed tuning of adsorption and structural properties of the resulting materials; namely, the specific surface area was varied from 84 to 250 m(2) g(-1), total pore volume from 0.11 to 0.46 cm(3) g(-1), and the pore width from 5.6 to 11.2 nm. All samples studied but one showed exclusively anatase phase, and the composites obtained with silica scaffold showed tunable degree of crystallinity. The proposed approach to tailoring the surface and structure properties of titania is especially important for the development of high performance materials for photocatalysis, lithium-based batteries, and dye-sensitized solar cells.

Microwave-assisted synthesis of porous carbon-titania and highly crystalline titania nanostructures.

Porous carbon-titania and highly crystalline titania nanostructured materials were obtained through a microwave-assisted one-pot synthesis. Resorcinol and formaldehyde were used as carbon precursors, triblock copolymer Pluronic F127 as a stabilizing agent, and titanium isopropoxide as a titania precursor. This microwave-assisted one-pot synthesis involved formation of carbon spheres according to the recently modified Stöber method followed by hydrolysis and condensation of titania precursor. This method afforded carbon-titania composite materials containing anatase phase with specific surface areas as high as 390 m(2) g(-1). The pure nanostructured titania, obtained after removal of carbon through calcination of the composite material in air, was shown to be the anatase phase with considerably higher degree of crystallinity and the specific surface area as high as 130 m(2) g(-1). The resulting titania, because of its high surface area, well-developed porosity, and high crystallinity, is of great interest for catalysis, water treatment, lithium batteries, and other energy-related applications.

Carbon-gold core-shell structures: formation of shells consisting of gold nanoparticles.

Carbon spheres were obtained via the Stöber method using phenolic resin followed by carbonization. Spherical carbon-gold core-shell particles were fabricated by deposition of gold nanoparticles on the modified surface of carbon spheres.