Highly efficient recycling of a "sandwich" type polyoxometalate oxidation catalyst using solvent resistant nanofiltration.

A "sandwich" type polyoxometalate catalyst ([MeN(n-C8H17)3]12[WZn3(ZnW9O34)2]) was very efficiently recycled by nanofiltration with almost quantitative retention, using an alpha-alumina supported mesoporous gamma-alumina membrane.

Factors influencing the transport of short-chain alcohols through mesoporous gamma-alumina membranes.

The pressure-driven transport of water, ethanol, and 1-propanol through supported gamma-alumina membranes with different pore diameters is reported. Water and alcohols had similar permeabilities when they were transported through gamma-alumina membranes with average pore diameters of 4.4 and 6.0 nm, and the permeability coefficient was found to be proportional to the square of pore size, in accordance with a viscous flow mechanism. For transport through membranes with an average diameter of 3.2 nm, the behavior of water was in accordance with the viscous flow mechanism, but the permeability of the membrane for ethanol and 1-propanol was much smaller than expected and could not be explained in terms of viscous flow. Although the low permeability of the membrane with 3.2 nm pores for ethanol and 1-propanol was partly due to the presence of small amounts of water in the alcohols, the permeability coefficients were still substantially smaller when water was absent. This intrinsic difference between water and alcohol may be due to differences in molecular size, chemisorption of alcohols on the oxide pore wall, which would lead to a reduction of the effective pore size, and/or a certain degree of translational ordering of the alcohol molecules inside the membrane pores, which leads to an effectively higher viscosity and, therefore, to a higher transport resistance.

Si-supported mesoporous and microporous oxide interconnects as electrophoretic gates for application in microfluidic devices.

Microfluidic analysis systems are becoming an important technology in the field of analytical chemistry. An expanding area is concerned with the control of fluids and species in microchannels by means of an electric field. This paper discusses a new class of Si-compatible porous oxide interconnects for gateable transport of ions. The integration of such thin oxide films in microfluidics devices has been hampered in the past by the compatibility of oxides with silicon technology. A general fabrication method is given for the manufacture of silicon microsieve support structures by micromachining, on which a thin oxide layer is deposited by the spin-coating method. The deposition method was used for constructing gamma-alumina, MCM-48 silica, and amorphous titania films on the support structures, from both water-based and solvent-based oxide sols. The final structures can be applied as microporous and mesoporous interconnecting walls between two microchannels. It is demonstrated that the oxide interconnects can be operated as ion-selective electrophoretic gates. The interconnects suppress Fick diffusion of both charged and uncharged species, so that they can be utilized as ionic gates with complete external control over the transport rates of anionic and cationic species, thus realizing the possibility for implementation of these Si-compatible oxide interconnects in microchip analyses for use as dosing valves or sensors.

Effect of trace amounts of water on organic solvent transport through gamma-alumina membranes with varying pore sizes.

The transport behavior of toluene and n-hexane in gamma-alumina membranes with different pore diameters was studied. It was shown that the permeability of water-lean hexane and toluene is in agreement with Darcy's law down to membrane pore diameters of 3.5 nm. The presence of molar water fractions of 5-8 x 10(-4) in these solvents led to a permeability decrease of the gamma-alumina layer by a factor of 2-4 depending on pore size. In general, a lower permeability was found for hexane than for toluene. Moreover, in the presence of water a minimum applied pressure of 0.5-1.5 bar was required to induce net liquid flow through the membrane. These phenomena were interpreted in terms of capillary condensation of water in membrane pores with a size below a certain critical diameter. This is thought to lead to substantial blocking of these pores for transport, so that the effective tortuosity of the membrane for transport of hydrophobic solvents increases.