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In this work, an acetylacetonate-modified equimolar SiO2–ZrO2 composite-derived membrane with molecular sieving properties was successfully fabricated. The sol-gel method was successfully employed to chemically modify zirconium tetrabutoxide prior to co-hydrolysis and -condensation with tetraethoxysilane, the resulting sol then used to fabricate a gas separation layer. An acetylacetonate-modified SiO2–ZrO2-derived membrane prepared at 300 °C showed H2 permeance of 9.9 × 10 −7 mol m−2 s−1 Pa−1 with a H2/SF6 permeance ratio of 7,600, which was a significant improvement over pure SiO2–ZrO2-derived membranes (H2 permeance: 1.4 × 10 −6 mol m−2 s−1 Pa−1, H2/SF6 permeance ratio: 11). Heat-treatment of an acac−-modified SiO2–ZrO2-derived membrane prepared at temperatures that ranged from 250 °C (H2 permeance: 4.5 × 10−8 mol m−2 s−1 Pa−1, H2/CH4: 100, CO2/CH4: 60, H2/SF6: >18,000 at 50 °C) to 550 °C resulted in an improved H2 permeance of 3.4 × 10−6 mol m−2 s−1 Pa−1 with reduced permeance ratios (H2/CH4: 3, H2/SF6: 9) at 50 °C. A membrane prepared by heat-treating a 250 °C-fired membrane at 300 °C showed the best trade-off with H2 permeance-H2/SF6 permeance ratios above the trade-off line compared with membranes prepared at other temperatures.

Bis(triethoxysilyl)propane (BTESP) is a bridged-type organoalkoxysilane with a Si-C3H6-Si bond. It was utilized for membrane fabrication via a sol-gel method to achieve high permselectivity for large molecules. Membrane fabrication parameters such as the acid molar ratio (AR) in the sol and calcination temperature were evaluated for their effect on the network pore size and on gas permeation properties, as evaluated by the molecular size dependence (0.26–0.55 nm) and temperature dependence (50–200 °C) of gas permeance. BTESP membranes with different ARs (10−1, 100, and 10) showed H2/N2 and H2/CF4 selectivities of 20–30 and 640–32,000, respectively. As AR was increased, each gas permeance also increased, but H2 selectivity that corresponds to network pore size was decreased. FT-IR analysis indicated that the density of the Si-OH groups (Si-OH/Si-O-Si) of unfired gels was decreased with a higher AR, so that condensation of the Si-OH groups during the calcination process formed a dense network structure in the case of BTESP membranes with a low AR (10−1). Calcination temperature also affected the network structure of BTESP membranes. BTESP membranes calcined at different temperatures (350, 450, and 600 °C) showed H2/N2 and H2/CF4 selectivities of 10–30 and 410–32,000, respectively. A BTESP membrane calcined at high temperature (600 °C) showed loose networks since the linking units derived from BTESP were decomposed at temperatures above 500 °C, which resulted in the formation of methyl groups. In conclusion, the AR in a sol is suitable for tuning small pore sizes, while calcination temperature as a membrane fabrication parameter offers the advantage of controllability for loose network structures.

The mechanisms involved in pressure driven gas permeation through a micropore on vitreous SiO2 membranes were examined molecular dynamics (MD) simulation. Virtual amorphous SiO2 membranes were prepared by the melt-quench method utilizing modified Born-Mayer-Huggins (BMH) pair potential and Stillinger-Weber (SW) three-body interactions. A dual control plane non-equilibrium MD (DCP-NEMD) technique was employed to simulate gas permeation phenomena under a constant upstream pressure, in which the permeating molecules were modeled as Lennard-Jones particles. The dependencies of the permeance of helium and CO2 molecules on temperature and pore size were examined. For cylindrical pores about 8 and 6 Å in diameter, the calculated temperature dependencies for the permeance of helium molecules were similar to the tendencies predicted by the normal Knudsen permeation mechanism, while in the case of CO2 permeation, a temperature dependency larger than helium and a significant deviation from the Knudsen mechanism were observed. The deviation was more obvious for the smaller 6 Å pore model. A simple gas permeation model that takes the effect of the pore wall potential field into consideration satisfactorily explained the permeation properties of CO2 in the high temperature region. The permeation mechanism was also examined from the viewpoint of the lateral potential and density distribution in a micropore. The values for the potential within micropores, predicted from the observed temperature dependencies of the gas permeation rate and using the simple gas permeation model, were in good agreement with the depth of the potential field resulting from the given potential parameters. The findings also indicate that the density (pressure) difference in a micropore between the pore entrance and exit, which could be enhanced by an attractive pore wall potential, might be the true driving force for permeation, particularly in the high temperature region.

The mechanisms involved in pressure driven gas permeation through a micropore on vitreous SiO2 membranes were examined molecular dynamics (MD) simulation. Virtual amorphous SiO2 membranes were prepared by the melt-quench method utilizing modified Born-Mayer-Huggins (BMH) pair potential and Stillinger-Weber (SW) three-body interactions. A dual control plane non-equilibrium MD (DCP-NEMD) technique was employed to simulate gas permeation phenomena under a constant upstream pressure, in which the permeating molecules were modeled as Lennard-Jones particles. The dependencies of the permeance of helium and CO2 molecules on temperature and pore size were examined. For cylindrical pores about 8 and 6 Å in diameter, the calculated temperature dependencies for the permeance of helium molecules were similar to the tendencies predicted by the normal Knudsen permeation mechanism, while in the case of CO2 permeation, a temperature dependency larger than helium and a significant deviation from the Knudsen mechanism were observed. The deviation was more obvious for the smaller 6 Å pore model. A simple gas permeation model that takes the effect of the pore wall potential field into consideration satisfactorily explained the permeation properties of CO2 in the high temperature region. The permeation mechanism was also examined from the viewpoint of the lateral potential and density distribution in a micropore. The values for the potential within micropores, predicted from the observed temperature dependencies of the gas permeation rate and using the simple gas permeation model, were in good agreement with the depth of the potential field resulting from the given potential parameters. The findings also indicate that the density (pressure) difference in a micropore between the pore entrance and exit, which could be enhanced by an attractive pore wall potential, might be the true driving force for permeation, particularly in the high temperature region.

type:text, Porous titanium oxide membranes with pore sizes in the range of 2.5-22 nm were prepared by a sol-gel procedure, and were applied for decomposition of methanol and ethanol as model volatile organic compounds (VOCs) in a photocatalytic membrane reactor, where oxidation reaction occurs both on the surface and inside the porous TiO2 membrane while reactants are permeating via one-pass flow. Methanol was completely photo-oxidized by black-light irradiation to CO2 when methanol at a concentration of 100 ppm was used at a feed flow rate of 500 × 10-6 m3/min, but the conversion decreased when the MeOH concentration in the feed was increased. Pt-modification was carried out by photo-deposition, and led to a decrease in pore diameter. Using Pt-modified membranes, a nearly complete oxidation of methanol up to 10,000 ppm at a feed flow rate of 500 × 10-6 m3/min was observed. Thus, such membranes would be effective for purifying a permeate stream after one-pass permeation through the TiO2 membranes. The decomposition of ethanol is also discussed.

Porous titanium oxide membranes with pore sizes in the range of 2.5-22 nm were prepared by a sol-gel procedure, and were applied for decomposition of methanol and ethanol as model volatile organic compounds (VOCs) in a photocatalytic membrane reactor, where oxidation reaction occurs both on the surface and inside the porous TiO2 membrane while reactants are permeating via one-pass flow. Methanol was completely photo-oxidized by black-light irradiation to CO2 when methanol at a concentration of 100 ppm was used at a feed flow rate of 500 × 10-6 m3/min, but the conversion decreased when the MeOH concentration in the feed was increased. Pt-modification was carried out by photo-deposition, and led to a decrease in pore diameter. Using Pt-modified membranes, a nearly complete oxidation of methanol up to 10,000 ppm at a feed flow rate of 500 × 10-6 m3/min was observed. Thus, such membranes would be effective for purifying a permeate stream after one-pass permeation through the TiO2 membranes. The decomposition of ethanol is also discussed.

Porous titanium oxide membranes with pore sizes in the range of 2.5-22 nm were prepared by a sol-gel procedure, and were applied for decomposition of methanol and ethanol as model volatile organic compounds (VOCs) in a photocatalytic membrane reactor, where oxidation reaction occurs both on the surface and inside the porous TiO2 membrane while reactants are permeating via one-pass flow. Methanol was completely photo-oxidized by black-light irradiation to CO2 when methanol at a concentration of 100 ppm was used at a feed flow rate of 500 × 10-6 m3/min, but the conversion decreased when the MeOH concentration in the feed was increased. Pt-modification was carried out by photo-deposition, and led to a decrease in pore diameter. Using Pt-modified membranes, a nearly complete oxidation of methanol up to 10,000 ppm at a feed flow rate of 500 × 10-6 m3/min was observed. Thus, such membranes would be effective for purifying a permeate stream after one-pass permeation through the TiO2 membranes. The decomposition of ethanol is also discussed.

The mechanisms involved in pressure driven gas permeation through a micropore on vitreous SiO2 membranes were examined molecular dynamics (MD) simulation. Virtual amorphous SiO2 membranes were prepared by the melt-quench method utilizing modified Born-Mayer-Huggins (BMH) pair potential and Stillinger-Weber (SW) three-body interactions. A dual control plane non-equilibrium MD (DCP-NEMD) technique was employed to simulate gas permeation phenomena under a constant upstream pressure, in which the permeating molecules were modeled as Lennard-Jones particles. The dependencies of the permeance of helium and CO2 molecules on temperature and pore size were examined. For cylindrical pores about 8 and 6 Å in diameter, the calculated temperature dependencies for the permeance of helium molecules were similar to the tendencies predicted by the normal Knudsen permeation mechanism, while in the case of CO2 permeation, a temperature dependency larger than helium and a significant deviation from the Knudsen mechanism were observed. The deviation was more obvious for the smaller 6 Å pore model. A simple gas permeation model that takes the effect of the pore wall potential field into consideration satisfactorily explained the permeation properties of CO2 in the high temperature region. The permeation mechanism was also examined from the viewpoint of the lateral potential and density distribution in a micropore. The values for the potential within micropores, predicted from the observed temperature dependencies of the gas permeation rate and using the simple gas permeation model, were in good agreement with the depth of the potential field resulting from the given potential parameters. The findings also indicate that the density (pressure) difference in a micropore between the pore entrance and exit, which could be enhanced by an attractive pore wall potential, might be the true driving force for permeation, particularly in the high temperature region.

Porous titanium oxide membranes with pore sizes in the range of 2.5-22 nm were prepared by a sol-gel procedure, and were applied for decomposition of methanol and ethanol as model volatile organic compounds (VOCs) in a photocatalytic membrane reactor, where oxidation reaction occurs both on the surface and inside the porous TiO2 membrane while reactants are permeating via one-pass flow. Methanol was completely photo-oxidized by black-light irradiation to CO2 when methanol at a concentration of 100 ppm was used at a feed flow rate of 500 × 10-6 m3/min, but the conversion decreased when the MeOH concentration in the feed was increased. Pt-modification was carried out by photo-deposition, and led to a decrease in pore diameter. Using Pt-modified membranes, a nearly complete oxidation of methanol up to 10,000 ppm at a feed flow rate of 500 × 10-6 m3/min was observed. Thus, such membranes would be effective for purifying a permeate stream after one-pass permeation through the TiO2 membranes. The decomposition of ethanol is also discussed.