Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
Abstract View references (60)Here we show the long term performance at high temperatures of a multi-tube module containing 8 membranes in 4 parallel lines with a total of 545 cm 2 area. The membranes were prepared via thin film dip coating of cobalt oxide silica (CoO xSi) sol-gel on tubular alumina supports. A preliminary study found that the sol-gel containing 20 mol% cobalt oxide formed the best microporous structure with the highest surface area and pore volume. All resulting membranes delivered permeances of ∼1 × 10 -7 mol m -2 s -1 Pa -1 at 500 °C, indicating a high repeatability for the membrane fabrication process. The permselectivities of helium (He) and hydrogen (H 2) over carbon dioxide (CO 2) and nitrogen (N 2) increased from 10-20 at 100 °C to values close to 1000 at 500 °C. Additionally, the apparent energies of activation (E act) for the smaller kinetic diameter gases He and H 2 at 12.2 and 19.5 kJ mol -1 were high and contrary to the negative values for larger gases N 2 and CO 2 at -1.8 and -7.4 kJ mol -1. These remarkable results were attributed to the molecular sieving mechanism of the microporous silica which was enhanced by the embedding of cobalt oxide into the matrix, delivering structural control with an average pore size of 3 Å. The E act for H 2 permeance was higher than that of He, indicating that the cobalt oxide played an important role in H 2 transport. Two membrane lines performed exceptionally well for binary gas mixture processing with H 2 purity reaching values close to 100% in the permeate stream for argon (Ar) concentrations of up to 80% in the retentate stream. A major finding here is that the binary gas selectivity was independent of temperature, contrary to the permselectivity observed for single gas permeance. Further, the H 2 flow rate was greatly affected by the concentration of Ar in the mixture, while the temperature dependency played only a marginal role. In particular, competitive adsorption in the percolative pathways containing pore constrictions or bottlenecks of the anisotropic CoO xSi matrix allowed Ar to impede H 2 diffusion. Finally, the CoO xSi membranes proved thermally stable and robust for 2000 h of testing for various thermal cycles up to 500 °C. © The Royal Society of Chemistry 2012.
Energy & Environmental Science

hal-01683199
https://hal.univ-antilles.fr/hal-01683199
DOI : 10.1039/c2ee03247c

Éditeur(s) : HAL CCSD Nature Publishing Group
Résumé : International audience
Abstract The functionality or oxidation state of cobalt within a silica matrix can be tailored through the use of cationic surfactants and their halide counter ions during the sol-gel synthesis. Simply by adding surfactant we could significantly increase the amount of cobalt existing as Co3O4 within the silica from 44% to 77%, without varying the cobalt precursor concentration. However, once the surfactant to cobalt ratio exceeded 1, further addition resulted in an inhibitory mechanism whereby the altered pyrolysis of the surfactant decreased Co3O4 production. These findings have significant implications for the production of cobalt/silica composites where maximizing the functional Co3O4 phase remains the goal for a broad range of catalytic, sensing and materials applications.
ISSN: 2045-2322

hal-01683204
https://hal.univ-antilles.fr/hal-01683204
DOI : 10.1038/srep02449

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
This work shows the preparation and separation performance assessment of carbon membranes derived from phenolic resin by a vacuum-assisted method and carbonisation in an inert atmosphere. The vacuum time played an important role in tailoring the structure of the membranes. For instance, pore volumes and surface areas increased from 0.81 and 834 to 2.2 cm3g−1and 1910 m2g−1, respectively, as the vacuum time exposure increased from 0 to 1200 s. The significant structural changes correlated very well with water permeation, as fluxes increased by 91% as the vacuum time increased from 0 to 1200 s reaching up to 169 L m−2h−1at 5 bar. Molecular weight cut-off tests showed no rejection for the smaller glucose and sucrose molecules, though this increased to ~ 80% and full rejection for 36 kDa and 400 kDa polyvinyl pyrrolidine. Interestingly, FTIR spectra showed that the peaks of C–H stretching vibration (2800–3200 cm−1) and C–O stretching (1030 cm−1) became more pronounced as a function of increasing vacuum time, strongly suggesting that the use of vacuum further assisted in the polycondensation of phenolic oligomers. Based on these outcomes, a cluster to cluster model is proposed, whereby vacuum application promoted crosslinking reactions of the phenolic resin, creating microporous regions within the clusters, and mesoporous regions between the clusters. © 2016 Elsevier B.V
ISSN: 0376-7388

hal-01683220
https://hal.univ-antilles.fr/hal-01683220
DOI : 10.1016/j.memsci.2016.11.002

Éditeur(s) : HAL CCSD MDPI
Résumé : International audience
This work investigates the structural formation and analyses of titania membranes (TM) prepared using different vacuum exposure times for molecular weight (MW) cut-off performance and oil/water separation. Titania membranes were synthesized via a sol-gel method and coated on macroporous alumina tubes followed by exposure to a vacuum between 30 and 1200 s and then calcined at 400 °C. X-ray diffraction and nitrogen adsorption analyses showed that the crystallite size and particle size of titania increased as a function of vacuum time. All the TM membranes were mesoporous with an average pore diameter of ~3.6 nm with an anatase crystal morphology. Water, glucose, sucrose, and polyvinylpyrrolidone with 40 and 360 kDa (PVP-40 kDa and PVP-360 kDa) were used as feed solutions for MW cut-off and hexadecane solution for oil filtration investigation. The TM membranes were not able to separate glucose and sucrose, thus indicating the membrane pore sizes are larger than the kinetic diameter of sucrose of 0.9 nm, irrespective of vacuum exposure time. They also showed only moderate rejection (20%) of the smaller PVP-40 kDa, however, all the membranes were able to obtain an excellent rejection of near 100% for the larger PVP-360 kDa molecule. Furthermore, the TM membranes were tested for the separation of oil emulsions with a high concentration of oil (3000 ppm), reaching high oil rejections of more than 90% of oil. In general, the water fluxes increased with the vacuum exposure time indicating a pore structural tailoring effect. It is therefore proposed that a mechanism of pore size tailoring was formed by an interconnected network of Ti-O-Ti nanoparticles with inter-particle voids, which increased as TiO2 nanoparticle size increased as a function of vacuum exposure time, and thus reduced the water transport resistance through the TM membranes. © 2016 by the authors.
ISSN: 1996-1944

hal-01683214
https://hal.univ-antilles.fr/hal-01683214
DOI : 10.3390/ma9110938

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Abstract View references (35)La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) hollow fibres were prepared by a phase inversion/sintering method using polyetherimide as a binder. In order to overcome surface exchange kinetics limitation, LSCF hollow fibres were coated with ∼200nm palladium (Pd) nanoparticles. The O2 flux of best performing membranes increased by up to 350% in comparison to unmodified LSCF hollow fibres. Optimal enhancement was achieved with a single Pd coating. Additional coatings resulted in reduced O2 fluxes, thus counter acting the beneficial spill-over effect of the catalyst. Long term stability testing in atmospheric air at 850°C showed that a LSCF membrane modified with a single Pd coating continually outperformed a pure LSCF hollow fibre for over 400h, though the level of enhancement was reduced over time. A dramatic reduction in performance of more than 45% occurred within the first 24h of testing, which was attributed to the coalescence and aggregation of Pd catalyst particles to ∼1000nm size at the LSCF grain boundaries. This greatly reduced the available area for the oxygen species to spill-over onto the LSCF surface and thus reduced the overall O2 flux. © 2011 Elsevier B.V.
ISSN: 0376-7388

hal-01683196
https://hal.univ-antilles.fr/hal-01683196
DOI : 10.1016/j.memsci.2011.07.008

Éditeur(s) : HAL CCSD MDPI
Résumé : International audience
AbstractThis review provides a global overview of microporous silica based membranes for desalination via pervaporation with a focus on membrane synthesis and processing, transport mechanisms and current state of the art membrane performance. Most importantly, the recent development and novel concepts for improving the hydro-stability and separating performance of silica membranes for desalination are critically examined. Research into silica based membranes for desalination has focussed on three primary methods for improving the hydro-stability. These include incorporating carbon templates into the microporous silica both as surfactants and hybrid organic-inorganic structures and incorporation of metal oxide nanoparticles into the silica matrix. The literature examined identified that only metal oxide silica membranes have demonstrated high salt rejections under a variety of feed concentrations, reasonable fluxes and unaltered performance over long-term operation. As this is an embryonic field of research several target areas for researchers were discussed including further improvement of the membrane materials, but also regarding the necessity of integrating waste or solar heat sources into the final process design to ensure cost competitiveness with conventional reverse osmosis processes. © 2012 by the authors.
ISSN: 2073-4441

hal-01683200
https://hal.univ-antilles.fr/hal-01683200
DOI : 10.3390/w4030629

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Abstract This work shows the preparation, characterisation and testing of TiO2 membranes dip-coated on commercial α-Al2O3 tubes for desalination. TiO2 thin films (∼400 nm) were synthesised from titanium propoxide and exposed to a gentle thermal treatment to control particle and pore sizes (dp ∼ 4 nm). The TiO2 membranes were tested for brackish (0.3 wt%), sea water (3.5 wt%) and brine concentrations (7.5 and 10 wt%) up to 75°C in a pervaporation setup. Water fluxes as high as 10.5 kg m-2 h-1 were achieved for brackish concentrations, whilst values of up to 4.0 and 6.0 kg m-2 h-1 were measured for the highest brine concentration (10 wt%). Concentration and temperature polarisation both affected the water fluxes, particularly for brine solutions, though the latter was more dominant. Salt rejection remained very high at ∼99% for all tested conditions, thus demonstrating the feasibility of mesoporous inorganic TiO2 structures for desalination and brine processing. The TiO2 membranes proved to be stable for long term (>350 h) testing even under thermal cycling conditions. © 2015 Elsevier B.V. All rights reserved.
ISSN: 1383-5866

hal-01683212
https://hal.univ-antilles.fr/hal-01683212
DOI : 10.1016/j.seppur.2015.04.028

Éditeur(s) : HAL CCSD RSC Publishing
Résumé : International audience
Abstract View references (36)The size or alkyl chain length of cationic surfactants can be used to tailor both the pore morphology and the functionality or oxidation state of cobalt in silica materials. This work shows for the first time that these two mechanisms are interconnected. Cobalt oxide silica materials, with the same cobalt loading (Co:Si = 1:4), were prepared using an acid catalysed sol-gel method where the cobalt/surfactant ratio was systematically varied. The alkyl chain length of the cationic surfactant was also varied from 2 to 12 by using tetraethyl (C2-AB) ammonium bromide, and triethyl hexyl (C6-AB) and dodecyl trimethyl (C12-AB) ammonium bromides as the templating agents. Initial addition of C2-AB, C6-AB or C12-AB enhanced the oxidation of cobalt to cobalt (ii,iii) oxide in the xerogels. However, as more surfactant is added the enhancement effect is reversed and the cobalt (ii,iii) oxide content of the sample begins to decline. The point at which this transition occurs is a function of the alkyl chain length of the surfactant, with a longer chain indicating an earlier transition. Pore morphology was influenced in a similar fashion with the longer alkyl chain C12-AB surfactant undergoing an earlier transition (i.e. at lower concentrations) towards mesoporosity, than either of the smaller C2-AB and C6-AB surfactants. In both mechanisms it was the increased propensity of the C12-AB surfactant to aggregate (given its larger size and lower solubility) that was the controlling factor. This journal is © the Partner Organisations 2014.
EISSN: 2046-2069

hal-01683205
https://hal.univ-antilles.fr/hal-01683205
DOI : 10.1039/c4ra05934d