Phenolic aerogels containing oxygen and other polymeric aerogels containing both oxygen and nitrogen (polybenzoxazine and a polyamide‐polyimide‐polyurea co‐polymer) are converted to carbon aerogels (800 °C/Ar), and are etched with CO2 (1000 °C). Etching opens closed pores and increases micropore volumes and size. Heteroatoms are retained in the etched samples. All carbon aerogels are evaluated as CO2 absorbers in terms of their capacity and selectivity toward CH4, H2, and N2. CO2 adsorption capacity is linked to microporosity. In most cases, monolayer coverage of micropore walls is enough to explain CO2 uptake quantitatively. The interaction of CO2 with micropore walls is evaluated via isosteric heats of adsorption, and is stronger with carbons containing only oxygen heteroatoms. The adsorption capacity of those carbons (5–6 mmol g−1) is on par with the best carbon and polymeric CO2 adsorbers known in the literature, with one exception however: etched carbon aerogels from low‐density resorcinol‐formaldehyde aerogels show a very high CO2 uptake (14.8 ± 3.9 mmol g−1 at 273 K, 1 bar) attributed to a pore‐filling process that proceeds beyond monolayer coverage, whereas surface phenoxides engage in a thermally neutral carbonate forming reaction (surface‐O– + CO2 → surface‐O–(CO)–O–) that continues until micropores are filled.

We report the carbothermal synthesis of sturdy, highly porous (>85%) SiC and Si 3 N 4 monolithic aerogels from compressed polyurea-cross-linked silica xerogel powders. The high porosity in those articles was created via reaction of core silica nanoparticles with their carbonized polymer coating toward the new ceramic framework and CO that escaped. Sol−gel silica powder was obtained by disrupting gelation of a silica sol with vigorous agitation. The grains of the powder were about 50 μm in size and irregular in shape and consisted of 3D assemblies of silica nanoparticles as in any typical silica gel. The individual elementary silica nanoparticles within the grains of the powder were coated conformally with a nanothin layer of carbonizable polyurea derived from the reaction of an aromatic triisocyanate (TIPM: triisocyanatophenyl methane) with the innate −OH, deliberately added −NH 2 groups, and adsorbed water on the surface of silica nanoparticles. The wet-gel powder was dried at ambient temperature under vacuum. The resulting free-flowing silica/polyurea xerogel powder was vibrationsettled in suitable dies and was compressed to convenient shapes (discs, cylinders, donut-like objects), which in turn were converted to same-shape SiC or Si 3 N 4 artifacts by pyrolysis at 1500 °C under Ar or N 2 , respectively. The overall synthesis was time-, energy-, and materials-efficient: (a) solvent exchanges within grains of powder took seconds, (b) drying did not require high-pressure vessels and supercritical fluids, and (c) due to the xerogel compactness, the utilization of the carbonizable polymer was at almost the stoichiometric ratio. Chemical and materials characterization of all intermediates and final products included solid-state 13 C and 29 Si NMR, XRD, SEM, N 2 -sorption, and Hg intrusion porosimetry. Analysis for residual carbon was carried out with TGA. The final ceramic objects were chemically pure, sturdy, with compressive moduli at 37 ± 7 and 59 ± 7 MPa for SiC and Si 3 N 4 , respectively, and thermal conductivities (using the laser flash method) at 0.16 3 ± 0.010 and 0.070 ± 0.001 W m −1 K −1 , respectively. The synthetic methodology of this report can be extended to other sol−gel derived oxide networks and is not limited to ceramic aerogels. A work in progress includes metallic Fe(0) aerogels.

Polymeric aerogels (PA-xx) were synthesized via room-temperature reaction of an aromatic triisocyanate (tris(4-isocyanatophenyl) methane) with pyromellitic acid. Using solid-state CPMAS C andN NMR, it was found that the skeletal framework of PA-xx was a statistical copolymer of polyamide, polyurea, polyimide, and of the primary condensation product of the two reactants, a carbamic-anhydride adduct. Stepwise pyrolytic decomposition of those components yielded carbon aerogels with both open and closed microporosity. The open micropore surface area increased from <15 m g in PA-xx to 340 m g in the carbons. Next, reactive etching at 1,000 °C with CO opened access to the closed pores and the micropore area increased by almost 4× to 1150 m g (out of 1750 m g of a total BET surface area). At 0 °C, etched carbon aerogels demonstrated a good balance of adsorption capacity for CO (up to 4.9 mmol g), and selectivity toward other gases (via Henry's law). The selectivity for CO versus H (up to 928:1) is suitable for precombustion fuel purification. Relevant to postcombustion CO capture and sequestration (CCS), the selectivity for CO versus N was in the 17:1 to 31:1 range. In addition to typical factors involved in gas sorption (kinetic diameters, quadrupole moments and polarizabilities of the adsorbates), it is also suggested that CO is preferentially engaged by surface pyridinic and pyridonic N on carbon (identified with XPS) in an energy-neutral surface reaction. Relatively high uptake of CH (2.16 mmol g at 0 °C/1 bar) was attributed to its low polarizability, and that finding paves the way for further studies on adsorption of higher (i.e., more polarizable) hydrocarbons. Overall, high CO selectivities, in combination with attractive CO adsorption capacities, low monomer cost, and the innate physicochemical stability of carbon render the materials of this study reasonable candidates for further practical consideration.

Morphology is a qualitative property of nanostructured matter and is articulated by visual inspection of micrographs. For deterministic procedures that relate nanomorphology to synthetic conditions, it is necessary to express nano- and microstructures numerically. Selecting polyurea aerogels as a model system with demonstrated potential for rich nanomorphology and guided by a statistical design-of-experiments model, we prepared a large array of materials (208) with identical chemical composition but quite different nanostructures. By reflecting on SEM imaging, it was realized that our first preverbal impression about a nanostructure is related to its openness and texture; the former is quantified by porosity (Π), and the latter is oftentimes related to hydrophobicity, which, in turn, is quantified by the contact angle (θ) of water droplets resting on the material. Herewith, the θ-to-Π ratio is referred to as the K-index, and it was noticed that all polyurea samples of this study could be put in eight K-index groups with separate nanomorphologies ranging from caterpillar-like assemblies of nanoparticles, to thin nanofibers, to cocoon-like structures, to large bald microspheres. A first validation of the K-index as a morphology descriptor was based on compressing samples to different strains: it was observed that as the porosity decreases, the water-contact angle decreases proportionally, and thereby the K-index remains constant. The predictive power of the K-index was demonstrated with 20 polyurea aerogels prepared in 8 binary solvent systems. Subsequently, several material properties were correlated to nanomorphology through the K-index and that, in turn, provided insight about the root cause of the diversity of the nanostructure in polyurea aerogels. Finally, using response surface methodology, K-indexes and other material properties of practical interest were correlated to the monomer, water, and catalyst concentrations as well as the three Hansen solubility parameters of the sol. That enabled the synthesis of materials with up to six prescribed properties at a time, including nanomorphology, bulk density, BET surface area, elastic modulus, ultimate compressive strength, and thermal conductivity.

A family of ambient-dried polybenzoxazine aerogels is prepared with a facile and scalable process as a high-performance polymeric aerogel with strong and robust thermomechanical properties at elevated temperatures. Those materials are inherently flame-retardant and superhydrophobic over the entire bulk density range (0.24–0.46 g cm–3). In addition, they are mechanically strong with strengths (e.g., 1 MPa at 0.24 g cm–3 at room temperature) higher than those of other high-performance aerogels of similar density, including polyimide and polyamide (Kevlar-like) aerogels as well as polymer-cross-linked X-silica and X-vanadia aerogels, at a significantly lower cost. Furthermore, unlike most other glassy polymeric materials, the maximum strength of the synthesized aerogels occurs at service temperatures slightly higher than room temperature (about 50 °C), which eliminates the possibility of any drop in strength with respect to the room temperature strength up to 150 °C at all densities. At higher temperatures (up to 250 °C), the overall performance of those aerogels is also stable and robust without any significant drop in Young’s modulus or strength levels, which makes them suitable for various industrial applications including high-performance structural and thermal protection applications as an alternative to the significantly more expensive polyimides.