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Despite the growing use of organic or mixed solvents in zeolite processing, most studies focus only on aqueous suspension systems. We investigated the colloidal characteristics of submicron-sized zeolite NaA in mixed ethanol-water solvents. The effects of the mixing ratio of solvents and various additives on the dispersion of the zeolite powders were studied. The zeolite NaA particles were destabilized in solvent mixtures at a high ethanol-to-water ratio, a reduction in the zeta potential was observed, and the destabilization was rationalized by the Derjaguin, Landau, Verwey, Overbeek (DLVO) theory. An improved stabilization of the zeolite NaA suspensions was achieved in ethanol-rich solvent mixtures using nonionic low molecular weight organic additives, but not with their ionic counterparts such as anionic, cationic surfactants or inorganic acids or bases. Polyethylene glycol (PEG)-400 was found to be a good dispersant for the submicron-sized zeolite NaA particles in the ethanol-water mixtures, which was attributed to its interaction with the zeolite surface, leading to an increased zeta potential. The PEG-stabilized zeolite suspensions led to low suspension viscosities as well as uniform and consistent spin-coated films.

Carbon dioxide must be removed from biogas or natural gas to obtain compressed or liquefied methane, and adsorption-driven isolation of CO2 could be improved by developing new adsorbents. Zeolite adsorbents can select CO2 over CH4, and the adsorption of CH4 on zeolite |Na12-xKx|-A is significantly lower for samples with a high K+ content, i.e., x > 2. Nevertheless, we show, using 1H NMR experiments, that these zeolites adsorb CH4 after long equilibration times. Pulsed-field gradient NMR experiments indicated that in large crystals of zeolites |Na12-xKx|-A, the long-time diffusion coefficients of CH4 did not vary with x, and the upper limit of the mean-square displacement was about 1.5 μm, irrespective of the diffusion time. Also for zeolite |Na12|-A samples of three different particle sizes (∼0.44, ∼2.9, and ∼10.6 μm), the upper limit of the mean-square displacement of CH4 was 1.5 μm and largely independent of the diffusion time. This similarity provided further evidence for an intracrystalline diffusion restriction for CH4 within the medium- and large-sized zeolite A crystals and possibly of clustering and close contact among the small zeolite A crystals. The upper limit of the long-time diffusion coefficient of adsorbed CH4 was (at 1 atm and 298 K) about 10-10 m2/s irrespective of the size of the zeolite particle or the studied content of K+ in zeolites |Na12-xKx|-A and |Na12|-A. The T1 relaxation time for adsorbed CH4 on zeolites |Na12-xKx|-A with x > 2 was smaller than for those with x < 2, indicating that the short-time diffusion of CH4 was hindered.

Adsorbents with high capacity and selectivity for adsorption of CO2 are currently being investigated for applications in adsorption-driven separation of CO2 from flue gas. An adsorbent with a particularly high CO2-over-N2 selectivity and high capacity was tested here. Zeolite ZK-4 (Si:Al ∼ 1.3:1), which had the same structure as zeolite A (LTA), showed a high CO2 capacity of 4.85 mmol/g (273 K, 101 kPa) in its Na(+) form. When approximately 26 at. % of the extraframework cations were exchanged for K(+) (NaK-ZK-4), the material still adsorbed a large amount of CO2 (4.35 mmol/g, 273 K, 101 kPa), but the N2 uptake became negligible (0.03 mmol/g, 273 K, 101 kPa). The majority of the CO2 was physisorbed on zeolite ZK-4 as quantified by consecutive volumetric adsorption measurements. The rate of physisorption of CO2 was fast, even for the highly selective sample. The molecular details of the sorption of CO2 were revealed as well. Computer modeling (Monte Carlo, molecular dynamics simulations, and quantum chemical calculations) allowed us to partly predict the behavior of fully K(+) exchanged zeolite K-ZK-4 upon adsorption of CO2 and N2 for Si:Al ratios up to 4:1. Zeolite K-ZK-4 with Si:Al ratios below 2.5:1 restricted the diffusion of CO2 and N2 across the cages. These simulations could not probe the delicate details of the molecular sieving of CO2 over N2. Still, this study indicates that zeolites NaK-ZK-4 and K-ZK-4 could be appealing adsorbents with high CO2 uptake (∼4 mmol/g, 101 kPa, 273 K) and a kinetically enhanced CO2-over-N2 selectivity.

We studied equilibrium adsorption and uptake kinetics and identified molecular species that formed during sorption of carbon dioxide on amine-modified silica. Bicontinuous silicas (AMS-6 and MCM-48) were postsynthetically modified with (3-aminopropyl)triethoxysilane or (3-aminopropyl)methyldiethoxysilane, and amine-modified AMS-6 adsorbed more CO(2) than did amine-modified MCM-48. By in situ FTIR spectroscopy, we showed that the amine groups reacted with CO(2) and formed ammonium carbamate ion pairs as well as carbamic acids under both dry and moist conditions. The carbamic acid was stabilized by hydrogen bonds, and ammonium carbamate ion pairs formed preferably on sorbents with high densities of amine groups. Under dry conditions, silylpropylcarbamate formed, slowly, by condensing carbamic acid and silanol groups. The ratio of ammonium carbamate ion pairs to silylpropylcarbamate was higher for samples with high amine contents than samples with low amine contents. Bicarbonates or carbonates did not form under dry or moist conditions. The uptake of CO(2) was enhanced in the presence of water, which was rationalized by the observed release of additional amine groups under these conditions and related formation of ammonium carbamate ion pairs. Distinct evidence for a fourth and irreversibly formed moiety was observed under sorption of CO(2) under dry conditions. Significant amounts of physisorbed, linear CO(2) were detected at relatively high partial pressures of CO(2), such that they could adsorb only after the reactive amine groups were consumed. authorCount :7

Mesoporous silica particles (Davisil) were functionalized with aminopropyltriethoxysilane (APTES) in a fractional factorial design with 19 different synthesis and uptake experiments. The number of amino groups and the uptake of CO(2) were optimized in a 2(V)(5-1) design. Most important to functionalization was the amount of water present during synthesis, the reaction time, and pretreating the silica with a mineral acid; certain two-way interactions were shown to be statistically significant as well. Modifications performed at 110 or 80 °C showed no significant differences concerning amine content or uptake of CO(2). Properly choosing center points for the discrete variables is problematic and is somewhat related to the lack of fit with respect to CO(2) uptake; the regression was good. Solid-state (29)Si NMR showed that the APTES was mainly fully condensed. Specific surface areas did not correlate with the number of n-propylamine groups on the silica, which is indicative of differential levels of heterogeneity in the coverage of propylamines. The uptake of CO(2) and N(2) was measured from -20 to 70 °C and from 0 to 1 bar and parametrized by the Freundlich isotherm. Amine-modified silica adsorbed significant amounts of CO(2), especially at the low partial pressure, which is important for CO(2) capture from flue gas. At such pressures, samples with a high density of amine (4 amines/nm(2)) showed a much higher uptake of CO(2) than did those with densities of ∼2-3 amines/nm(2), reflecting differential tendencies to form propylammonium-propylcarbamate ion pairs; these require close proximity among amine groups to form. Water affected the uptake of carbon dioxide in different ways. Certain samples took up more moist CO(2) gas than dry CO(2), and others took up less moist CO(2) than dry CO(2), which is indicative of differential tendencies toward water adsorption. We conclude that experimental design is a time-efficient approach to the functionalization of silica with propylamine groups.

Adsorption-mediated CO(2) separation can reduce the cost of carbon capture and storage. The reduction in cost requires adsorbents with high capacities for CO(2) sorption and high CO(2)-over-N(2) selectivity. Amine-modified sorbents are promising candidates for carbon capture. To investigate the details of CO(2) adsorption in such materials, we studied mesocaged (cubic, Pm3n symmetry) silica adsorbents with tethered propylamines using Fourier transform infrared (FTIR) spectroscopy and volumetric uptake experiments. The degree of heterogeneity in these coatings was varied by either cosynthesizing or postsynthetically introducing the propylamine modification. In situ FTIR spectroscopy revealed the presence of both physisorbed and chemisorbed CO(2) in the materials. We present direct molecular evidence for physisorption using FTIR spectroscopy in mesoporous silica sorbents modified with propylamines. Physisorption reduced the CO(2)-over-N(2) selectivity in amine-rich sorbents. Samples with homogeneous coatings showed typical CO(2) adsorption trends and large quantities of IR-observable physisorbed CO(2). The uptake of CO(2) in mesocaged materials with heterogeneous propylamine coatings was higher at high temperatures than at low temperatures. At higher temperatures and low pressures, the postsynthetically modified materials adsorbed more CO(2) than did the extracted ones, even though the surface area after modification was clearly reduced and the coverage of primary amine groups was lower. The principal mode of CO(2) uptake in postsynthetically modified mesoporous silica was chemisorption. The chemisorbed moieties were present mainly as carbamate-ammonium ion pairs, resulting from the quantitative transformation of primary amine groups during CO(2) adsorption as established by NIR spectroscopy. The heterogeneity in the coatings promoted the formation of these ion pairs. The average propylamine-propylamine distance must be small to allow the formation of carbamate-propylammonium ion pairs.

The transport of oligomeric molecules in silica spheres with cylindrical mesopores has been quantified and related to the structural features of the spherical particles and the interactions at the solid-liquid interface. An emulsion-solvent evaporation method was used to produce silica spheres having cylindrical mesopores with an average pore diameter of 6.5 nm. The transport of dextran molecules (fluorescently tagged) with molecular weights of 3000 and 10,000 g/mol was quantified using confocal laser scanning microscopy (CLSM). The intraparticle concentration profiles in the dextran-containing spheres were flat at all times, suggesting that the release is not isotropic and not limited by diffusion. The release of dextran into the solution is characterized by an initial burst, followed by long-term sustained release. The release follows a logarithmic time dependency, which was rationalized by coupling concentration-dependent effective diffusion constants with adsorption/desorption.

The purpose of this work is to study the kinetics of self-assembly in the formation mechanism of anionic templated mesoporous solids (AMS-n) during the first few seconds of the synthesis as well as to demonstrate the use of alternating ion current (AIC) conductivity measurements to follow the self-assembly in complex hybrid systems. The formation of different AMS-n caged-type mesostructures through the delayed addition of the silica source is demonstrated and explained in terms of the interaction between the co-structure-directing agent (CSDA) and the oppositely charged surfactant headgroup regions. Our findings, supported by transmission electron microscopy, 29Si magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy, dynamic light scattering (DLS) measurements, and powder X-ray diffraction suggest that the interaction of the CSDA with the surfactant headgroup occurs within seconds after its addition to the synthesis gel leading to interaction between the polymerizing CSDAs and the oppositely charged micelle and to an increase in the micelle-CSDA aggregate size. Both DLS and AIC measurements agree that this process occurs within the first 1000 s after addition of the CSDA to the synthesis gel at room temperature. In addition to the mechanistic study it was found that the intermediate materials are comprised of a three-layer entity. Time-dependent 29Si MAS NMR studies reveal that an organo-silica layer forms around the micelles prior to a condensed outer inorganic shell of silica.

Coarsening of surfactant-stabilized oil-in-water emulsions (C12E5−decane−D2O) induced by a fast temperature drop from their microemulsion phase is studied by 1H stimulated-echo-type pulsed-field-gradient spin−echo (PGSE) NMR spectroscopy. The data obtained on a small amount of hexamethyldisilane dissolved in the oil phase display two distinct diffusion coefficients. The slower diffusion is interpreted in terms of large droplets containing the oil that had been expelled from the original microemulsion droplets. The faster diffusion belongs to smaller microemulsion droplets that coexist with the large oil droplets. The results show that the investigated emulsions exhibit regular Ostwald ripening. Both the actual amounts of the expelled oil and the obtained coarsening rates agree well with theoretical estimates. As a consequence of fast surfactant exchange among the different droplets, the diffusion of the surfactant molecules is described by a single diffusion coefficient.

Growth of C12E8 micelles with increasing temperature. A convection-compensated PGSE NMR study