On the Formation of Nanobubbles in Vycor Porous Glass during the Desorption of Halogenated Hydrocarbons.

Vycor porous glass has long served as a model mesoporous material. During the physical adsorption of halogenated hydrocarbon vapours, such as dibromomethane, the adsorption isotherm exhibits an hysteresis loop; a gradual ascent is observed at higher pressures during adsorption, and a sharp drop is observed at lower pressures during desorption. For fully wetting fluids, an early hypothesis attributed the hysteresis to mechanistic differences between capillary condensation (adsorption) and evaporation (desorption) processes occurring in the wide bodies and narrow necks, respectively, of 'ink-bottle' pores. This was later recognized as oversimplified when the role of network percolation was included. For the first time, we present in-situ small angle x-ray scattering measurements on the hysteresis effect which indicate nanobubble formation during desorption, and support an extended picture of network percolation. The desorption pattern can indeed result from network percolation; but this can sometimes be initiated by a local cavitation process without pore blocking, which is preceded by the temporary, heterogeneous formation of nanobubbles involving a change in wetting states. The capacity of the system to sustain such metastable states is governed by the steepness of the desorption boundary.

Alginate fibers as photocatalyst immobilizing agents applied in hybrid photocatalytic/ultrafiltration water treatment processes.

Ca alginate polymer fibers were developed to effectively disperse and stabilize an efficient photocatalyst such as AEROXIDE(®) TiO(2) P25 in their matrix. The biopolymer/TiO(2) fibers were prepared and tested either in the hydrogel non-porous form or in the highly porous aerogel form prepared by sc-CO(2) drying. Batch photocatalytic experiments showed that the porous, Ca alginate/TiO(2) fibers, exhibited high efficiency for the removal of methyl orange (MO) from polluted water. In addition, their high porosity and surface area led to high MO degradation rate which was faster than that observed not only for their non-porous analogs but also of the bulk P25 TiO(2) powder. Specifically, 90% removal for 20 µM MO was achieved within 220 min for the porous sc-CO(2) dried fibers while for their non-porous analogs at 325 min. The corresponding value (at 60 µM MO) for the porous sc-CO(2) dried fibers was 140 min over 240 min for the AEROXIDE(®) TiO(2) P25 as documented in the literature. Furthermore the composite alginate/photocatalyst porous fibers were combined with TiO(2) membranes in a continuous flow, hybrid photocatalytic/ultrafiltration water treatment process that led to a three fold enhancement of the MO removal efficiency at 400 ml of 20 µM MO total treated volume and to dilution rather than condensation in the membrane retentate as commonly observed in filtration processes. Furthermore the permeability of the photocatalytic membrane was enhanced in the presence of the fibers by almost 20%. This performance is achieved with 26 cm(2) and 31 cm(2) of membrane and stabilized photocatalyst surfaces respectively and in this context there is plenty of room for the up-scaling of both membranes and fibers and the achievement of much higher water yields since the methods applied for the development of the involved materials (CVD and dry-wet phase inversion in a spinning set-up) are easily up-scalable and are not expected to add significant cost to the proposed water treatment process.