Incompatible Liquids in Confined Conditions

In applications involving organic vapour, the performance of high surface area carbons is often challenged by water vapour in the atmosphere. Small angle neutron scattering (SANS), through its ability to distinguish between different components by means of contrast variation, is ideally suited to investigating the behaviour of adsorbed layers in simultaneous contact with a mixed vapour phase. Even at high relative humidity (RH), water alone forms a discontinuous film composed of clusters on the surface of the oxidized microporous carbon used for these studies. When toluene is also present, all the available carbon surface is wetted. Toluene and water adsorb as a single phase already at RH 11.5%, and the concentration of water present in the adsorbed phase is as high as 2.9 wt.%, far above its solubility in bulk toluene (0.033 wt.% at 25 deg C). At RH 87% the concentration of water in the adsorbed phase is four times higher, approximately 12 wt.%. The recently proposed mechanism of anchoring of the water by the aromatic molecules may provide an explanation for this phenomenon

TiO2-doped resorcinol–formaldehyde (RF) polymer and carbon gels with photocatalytic activity

Resorcinol-formaldehyde (RF) polymer gels offer a relatively easy and versatile route for incorporating metals into a carbon aerogel matrix. The hybrid materials thus obtained are ideal candidates for applications involving enhanced adsorption or catalysis. This paper presents a detailed study of Ti-doped RF and carbon aerogels. The metal was introduced into the system at three different stages of the preparation process: during polymerization, by impregnation of the RF gel, or by impregnation of the carbon gel. The structure and morphology of the samples are compared using low temperature N2 adsorption, SEM, and small and wide angle X-Ray scattering (SAXS/WAXS) methods. The TiO2-doped carbon aerogels display photocatalytic activity in breaking down aromatic compounds

MOLYBDENUM DOPED CARBON AEROGELS WITH CATALYTIC POTENTIAL

Mo-doped carbon aerogels were obtained in the polycondensation reaction of aqueous resorcinol and formaldehyde by adding Mo-salt at two different stages of the synthesis: i) to the initial sol; ii) by incipient wetting impregnation of the supercritically dried polymer gel. Molybdenum added during the polymerization yielded a more compact gel structure with practically no mesoporosity. With post-impregnation, by contrast, mesopores of diameter 3-15 nm were generated. Carbonization appreciably enhanced the microporous character of both samples, but in the mesopore range their pore size distribution was conserved. The Mocontent of the samples was also different: Mo was lost during the solvent exchange before the supercritical drying (i.e., the Mo failed to bind chemically to the polymer matrix). The residual Mo congregated into 25-60 nm bulk clusters of α-Mo2C. In the other carbon aerogel, finely dispersed α-Mo2C and η-Mo3C2 crystals formed, of size 8-20 nm. On the surface of both carbons the Mo formed oxides. In the model test reaction (acetic acid hydroconversion) the catalytic activity of both carbon aerogels was enhanced by molybdenum. The more open pore structure, higher concentration and finer Mo distribution, as well as its chemical form, may all be responsible for the greater conversion and higher value products obtained with the post-impregnated sample

Graphene derivatives in responsive hydrogels: Effect of concentration and surface chemistry

Reduced graphene oxide (RGO) containing composite hydrogels, based on poly(N-isopropylacrylamide) (PNIPA) were prepared by two different methods: (i) by incorporating RGO directly into the polymer matrix; (ii) applying a post-synthesis reduction of the graphene-oxide (GO) already incorporated into the polymer. The samples were compared by various microscopic (small angle neutron scattering, differential scanning calorimetry, 1H NMR spectroscopy, thermogravimetry) and macroscopic (kinetic and equilibrium swelling properties and mechanical testing) techniques. Results from microscopic and macroscopic measurements show that the dispersity of the nanoparticles as well as their interaction with the polymer chains are influenced by their surface chemistry. Incorporation of nanoparticles limits the shrinkage and slows down the kinetics of the thermal response. Both thermogravimetric and solid-state NMR measurements confirmed strong polymer – nanoparticle interaction when hydrophilic GO was used in the synthesis. In these cases, the slow thermal response may be explained by the decrease of the free volume inside the nanocomposite matrix caused by a hypernodal structure. Our results imply that both the chemistry and the concentration of incorporated graphene derivatives are promising in tuning the thermal responsivity of PNIPA

Topological dynamics of micelles formed by geometrically varied surfactants

The molecular architecture of sugar-based surfactants strongly affects their self-assembled structure, i.e., the type of micelles they form, which in turn controls both the dynamics and rheological properties of the system. Here, we report the segmental and mesoscopic structure and dynamics of a series of C16 maltosides with differences in the anomeric configuration and degree of tail unsaturation. Neutron spin-echo measurements showed that the segmental dynamics can be modeled as a one-dimensional array of segments where the dynamics increase with inefficient monomer packing. The network dynamics as characterized by dynamic light scattering show different relaxation modes that can be associated with the micelle structure. Hindered dynamics are observed for arrested networks of worm-like micelles, connected to their shear-thinning rheology, while nonentangled diffusing rods relate to Newtonian rheological behavior. While the design of novel surfactants with controlled properties poses a challenge for synthetic chemistry, we demonstrate how simple variations in the monomer structure can significantly influence the behavior of surfactantsThe authors thank the Swedish Research Council Formas (Grant 2015-666) for funding J.L. The research was performed with financial support from the Vinnova─Swedish Governmental Agency for Innovation Systems within the NextBioForm Competence Centre. The authors also thank the Institut Laue-Langevin, France, for the awarded beamtime (Proposal No. 9-10-1652). NSE data is openly available at doi: 10.5291/ILL-DATA.9-10-1652S

Neutron spin echo monitoring of segmental-like diffusion of water confined in the cores of carbon nanotubes

An unexpected formal similarity to the segmental dynamics of entangled polymers is found for the subdiffusional behavior of water axially confined inside single-wall carbon nanotubes of average diameter d = 1.4 nm

Role of water molecules in the decomposition of HKUST-1: Evidence from adsorption, thermoanalytical, X-ray and neutron scattering measurements

HKUST-1 is a strictly microporous crystalline metal organic framework with pore sizes of 5, 11, and 13.5 Å. Detailed gas adsorption measurements show that its adsorption capacity for water at 20 °C is higher than that for nitrogen at-196 °C, and far exceeds that for methane at 0 °C. Extended exposure to water vapour at high relative humidity, or consecutive adsorption-desorption cycling of water vapour, destroys both the MOF crystal structure and its adsorption capacity, after a reduced number (< 5) of cycles. Destruction proceeds through mesoporous defects that open within the crystal structure, as attested both by the development of hysteresis in the adsorption isotherms and by changes in the small angle X-ray scattering pattern. In the pristine crystal, the structure of the water in the micropores closely resembles that of bulk liquid water. Small angle neutron scattering demonstrates that water is adsorbed preferentially over methane, and that the size of the spherical cavities occupied by the adsorbed water molecules in the intact crystal is consistent with the known pore size structure in this system