Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Well-dispersed iron oxide nanoparticles supported onto graphene oxide sheets (i.e. GO-Fe3O4 nanocomposite) were synthesised and used as heterogeneous Fenton-like catalyst for the degradation of Acid Orange 7 dye (AO7). The reaction was systematically investigated under various experimental conditions such as nanocomposite dosage, pH, temperature, oxidant and dye concentrations. Best results showed a fast 80% degradation in ∼20 min, whilst ∼98% of AO7 was successfully removed after 180 min of reaction time. The degradation kinetics of AO7 was most influenced by pH and temperature, and can be described by a pseudo-first-order reaction following the Langmuir-Hinshelwood mechanism. Analysis of the spent nanocomposite suggested that the phase of iron oxide nanoparticles remained unchanged whilst minor pore volume losses occurred via carbon deposition and/or re-stacking of GO sheets. © 2014 Elsevier Ltd.
ISSN: 2213-3437

hal-01683206
https://hal.univ-antilles.fr/hal-01683206
DOI : 10.1016/j.jece.2014.08.001

Éditeur(s) : HAL CCSD MDPI AG, Basel, Switzerland
Résumé : International audience
Abstract View references (46)This work shows the preparation of silica membranes by a two-step sol-gel method using tetraethyl orthosilicate in ethanolic solution by employing nitric acid and ammonia as co-catalysts. The sols prepared in pH 6 resulted in the lowest concentration of silanol (Si-OH) species to improve hydrostability and the optimized conditions for film coating. The membrane was tested to desalinate 0.3-15 wt % synthetic sodium chloride (NaCl) solutions at a feed temperature of 22 °C followed by long term membrane performance of up to 250 h in 3.5 wt % NaCl solution. Results show that the water flux (and salt rejection) decrease with increasing salt concentration delivering an average value of 9.5 kg m-2 h-1 (99.6%) and 1.55 kg m-2 h-1 (89.2%) from the 0.3 and 15 wt % saline feed solutions, respectively. Furthermore, the permeate salt concentration was measured to be less than 600 ppm for testing conditions up to 5 wt % saline feed solutions, achieving below the recommended standard for potable water. Long term stability shows that the membrane performance in water flux was stable for up to 150 h, and slightly reduced from thereon, possibly due to the blockage of large hydrated ions in the micropore constrictions of the silica matrix. However, the integrity of the silica matrix was not affected by the long term testing as excellent salt rejection of >99% was maintained for over 250 h. © 2013 by the authors; licensee MDPI, Basel, Switzerland.
ISSN: 2077-0375

hal-01683203
https://hal.univ-antilles.fr/hal-01683203
DOI : 10.3390/membranes3030136

Éditeur(s) : HAL CCSD
Résumé : International audience
In this work, a series of zinc partially substituted magnetite nanoparticles (Fe3-xZnxO4, 0 ≤ x ≤ 0.4), were synthesised through a facile precipitation-oxidation method. The partial substitution of zinc into the magnetite (Fe3O4) structure was confirmed by the collective findings of nitrogen sorption, XRD and TG-DTG analysis. It was found that the partial substitution of zinc slightly changed the textural properties of the resultant Fe3-xZnxO4 nanoparticles. From the XRD analysis, there was no visible formation of secondary phase or impurity peaks in the nanoparticles. These findings indicated the partial substitution of zinc into the Fe3O4 crystal structure with a good dispersion within the Fe3O4 matrix. © 2016 Author(s).
1st International Conference on Advanced Science,
Penang, Malaysia

hal-01683217
https://hal.univ-antilles.fr/hal-01683217

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Here we show that copper substitution in perovskite-type barium strontium cobalt copper oxide (BSCC) membranes confers extremely high oxygen fluxes well beyond the state of art, reaching 27.5 ml cm−2 min−1at 950 °C. A key feature of BSCC is the formation of a mixed matrix catalyst-perovskite membrane caused by the segregation of copper, leading to the formation of an intergranular network of copper-rich oxide between perovskite grains. BSCC membranes delivered pressure normalised oxygen flux (i.e. permeance) of up to 86 times higher, above pressure difference of 18 kPa, as compared to best perovskite membrane, BBSC, due to the catalytic effect of segregated copper oxide. Unlike conventional dual-phase membranes which contain ion and electron conducting phases, this work shows for the first time perovskite-type membranes consisting of a mixed matrix of oxygen ion/electron conducting (perovskite) and catalytic (copper oxide) phases, thus paving the way to the development of high performance membranes for oxygen separation from air for clean energy applications. © 2016 Elsevier B.V.
ISSN: 0376-7388

hal-01683219
https://hal.univ-antilles.fr/hal-01683219
DOI : 10.1016/j.memsci.2016.12.035

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 Elsevier
Résumé : International audience
Porous thin films considered for applications like separation, sensing and microelectronic have to sustain mechanical stresses during their integration process or in working conditions. Thanks to recent progress in processing methods, it is now possible to precisely control the porosity and combine ordered mesopores with randomly-distributed macropores to achieve hierarchically porous materials. The mechanical properties of thin films containing different types of porosity (ordered meso, random macro and hierarchical) have been investigated by means of nanoindentation. In particular a method recently proposed by Li and Vlassak (H. Li, J.J. Vlassak, Journal of Materials Research 24 (2009) 1114-1126) is applied to account for the substrate effect. Residual indent impressions were imaged by Atomic Force Microscopy (AFM) to provide some insights in the mechanical behavior of the films. In addition, experimental indentation moduli are compared to theoretical predictions obtained via Finite Element (FE) analysis. The different porous structures have been modeled by FE to obtain the effective elastic properties from which the indentation modulus can be inferred. Finally, the experimental-model differences are discussed. © 2010 Elsevier Inc. All rights reserved.
ISSN: 1387-1811

hal-01683194
https://hal.univ-antilles.fr/hal-01683194
DOI : 10.1016/j.micromeso.2010.09.004

Éditeur(s) : HAL CCSD
Résumé : International audience
Abstract View references (38)This work presents a facile, scalable method for the fabrication of graphene oxide-iron oxide (GO-Fe3O4) nanocomposites produced by co-precipitation of iron ions onto the GO surfaces in basic aqueous media. FTIR and XRD characterisation suggests that Fe3O4 was chemically anchored to the GO sheets, possibly via the carboxyl and hydroxyl groups. Small GO loadings of 0.5 and 1 wt% were not sufficient to alter the Fe3O4 structures. However, increasing the GO loading to 5 and 10 wt% resulted in significant loss in pore volume, thus suggesting the lamellar GO sheets decorated with Fe3O4 were assembling into GO-Fe3O4 nanocomposite stacks. It was found that the GO-Fe3O4 nanocomposites had an enhanced catalytic activity in the heterogeneous Fenton-like oxidation of Acid Orange 7 (AO7) compared to pure GO flat sheets and Fe3O4 nanoparticles. Interestingly, the GO-Fe3O4 nanocomposite with 5 wt% loading ratio exhibited the best catalytic activity with 76% degradation of AO7 dye observed within 90 min of reaction. This was attributed to the synergistic effect of GO by enriching the adsorbed AO7 molecules onto the nanocomposite to be further oxidised in the vicinities of active sites. This finding suggests the promising employment of GO-Fe3O4 nanocomposites in removing organic dyes from polluted water by heterogeneous Fenton-like reaction. © 2014 by American Scientific Publishers.
SCIENCE OF ADVANCED MATERIALS

hal-01683207
https://hal.univ-antilles.fr/hal-01683207
DOI : 10.1166/sam.2014.1812

Éditeur(s) : HAL CCSD
Résumé : International audience
Euromembrane Conference 2012
London, United Kingdom

hal-01683198
https://hal.univ-antilles.fr/hal-01683198
DOI : 10.1016/j.proeng.2012.08.470

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 Royal Society of Chemistry
Résumé : International audience
Owing to the electron donor-acceptor properties of GO, the active sites (≡Fe2+) of Fe3O4 are not oxidised (≡Fe3+) in the heterogeneous Fenton-like reaction. GO plays a sacrificial role via the oxidation of (C=C) carbon domains, and transferring electrons to Fe3O4. Therefore, GO-Fe3O4 confers superior catalytic efficiency, recyclability and longevity, otherwise not available in Fe3O4. © The Royal Society of Chemistry 2015.
ISSN: 1359-7345

hal-01683211
https://hal.univ-antilles.fr/hal-01683211
DOI : 10.1039/c5cc02292d

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
ISSN: 1387-1811

hal-01680610
https://hal.univ-antilles.fr/hal-01680610
DOI : 10.1016/j.micromeso.2009.06.012

Éditeur(s) : HAL CCSD EDP Sciences
Résumé : International audience
Understanding mechanisms in DSSCs is fundamental for their improvement; this includes the nanocrystalline semiconducting layer behaviour. Different mesoporous TiO2 layers are fabricated and analyzed for possible use in DSSC solar cells. The preparations included the addition of P123 triblock copolymer as structuring agent to the synthesized anatase sol. This preparation was also mixed with Degussa P25 TiO2 nanoparticles in one case and polystyrene latex in another. Mesoporous mixed TiO2-SiO2 thin layers were also analyzed. The diverse morphologies and features are studied by microscopic techniques and by means of spectral quantum efficiency of a photoelectrochemical cell (PEC) that uses as photoelectrode the unsensitized porous TiO2 layer. Contact angle measurements are also performed. We have found that a very high specific area due to very small nanocrystals and small pores can hinder electrolyte penetration in the pores formed by TiO2 nanograins, affecting photoelectrodes efficiency. © EDP Sciences, 2015.
ISSN: 1286-0042

hal-01683213
https://hal.univ-antilles.fr/hal-01683213
DOI : 10.1051/epjap/2015150221

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Carbonised template silica membranes were synthesised and investigated for water desalination for brackish (0.3wt%), sea water (3.5wt%) and brine (7.5wt%) NaCl solutions at temperatures range from 22 to 60°C. The membranes were prepared by a two-step base catalysed sol-gel method using tetraethyl orthosilicate TEOS as the silica precursor and triblock copolymer of Pluronic® P123 as the templating agent. The P123 silica membranes calcined under vacuum only produced high quality membranes by the interlayer-free method. The membranes were stable during testing of up to 250h under different thermal and salt concentration solutions, always delivering very high salt rejections >99.5%. It was found that by increasing the template concentration in the silica matrix from 5 to 50wt%, salt concentration polarisation was greatly reduced. As such, high water fluxes were measured up to 8.5kgm-2h-1 for brackish water and 6.6kgm-2h-1 for brine water. © 2014 Elsevier B.V.
ISSN: 0376-7388

hal-01683210
https://hal.univ-antilles.fr/hal-01683210
DOI : 10.1016/j.memsci.2014.10.026

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Mesoporous cobalt oxide silica matrices and membranes were successfully prepared using a dual acid-base catalysed sol-gel and interlayer-free approach for desalination applications. The effects of cobalt addition (0-35 mol%) on the structure-property relationship of the silica materials and membrane performance were systematically studied as a function of feed salt concentration (0.3-7.5 wt.% NaCl) and temperature (22-60 °C). As cobalt concentration increases beyond 5 mol%, the concentration of tricobalt tetroxide and proportion of silica mesopores were found to increase within the matrices. Silica membranes with high amount of tricobalt tetroxide (35 mol%) were found to be highly mesoporous with water fluxes of 20, 11.3 and 7.7 kg m-2 h-1 for the 0.3, 3.5 and 7.5 wt.% solutions at 60 °C, respectively, with >99.7% salt rejection at all times. This is attributed to the high pore volume (mesopores formation) and structural robustness of the silica network provided by the presence of tricobalt tetroxide. Even higher performance was achieved for low tricobalt tetroxide (mol%) silica membranes with water fluxes of 47.6 (0.3 wt.%) and 31.5 (3.5 wt.%) kg m-2 h-1 at 60 °C, respectively, though with reduced salt rejections of 90%. © 2015 Elsevier B.V.
ISSN: 0011-9164

hal-01683209
https://hal.univ-antilles.fr/hal-01683209
DOI : 10.1016/j.desal.2015.02.034

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A versatile sol-gel route has been developed for the preparation of hierarchical porous silica membrane material with highly dispersed platinum nanoparticles (Pt-NPs). The outstanding feature of the "one pot" synthesis developed in this work lies in the successful preparation of a stable complex suspension made of silica sol, multi-scale porogens and Pt nanoparticles. The multi-scale porogens were based on non-ionic triblock copolymers and aqueous latex suspension to create mesopores and macropores, respectively, with finely tuned pore size and organization. For further functionalization of the membranes, Pt nanoparticles of about 4 nm in diameter were prepared by irradiating with microwaves (MW) the Pt precursors added in the starting suspension. This original path is suggested to enable a pre-organization of Pt nanoparticles in the ordered mesoporous structure. The suspensions were then deposited as thin films on either dense or macroporous supports, and further thermally treated at 450°C to remove the porogen units. Hierarchical porous layers composed of micropores (<2 nm), ordered mesopores (∼4 nm) and macropores (∼70 nm) with or without Pt were prepared and characterized. The resulting membranes are foreseen to exhibit great potential as multifunctional membranes for gas separation coupled with catalytic reaction. © The Royal Society of Chemistry 2008.
ISSN: 0959-9428

hal-01680586
https://hal.univ-antilles.fr/hal-01680586
DOI : 10.1039/b807029f

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 Nature Publishing Group
Résumé : International audience
Abstract View references (45)Graphene oxide-iron oxide (GO-Fe3O4) nanocomposites were synthesised by co-precipitating iron salts onto GO sheets in basic solution. The results showed that formation of two distinct structures was dependent upon the GO loading. The first structure corresponds to a low GO loading up to 10wt%, associated with the beneficial intercalation of GO within Fe3O4nanoparticles and resulting in higher surface area up to 409m2g-1. High GO loading beyond 10 wt% led to the aggregation of Fe3O4 nanoparticles and the undesirable stacking of GO sheets. The presence of strong interfacial interactions (Fe-O-C bonds) between both components at low GO loading lead to 20% higher degradation of Acid Orange 7 than the Fe3O4 nanoparticles in heterogeneous Fenton-like reaction. This behaviour was attributed to synergistic structural and functional effect of the combined GO and Fe3O4 nanoparticles.
ISSN: 2045-2322

hal-01683208
https://hal.univ-antilles.fr/hal-01683208
DOI : 10.1038/srep04594

Éditeur(s) : HAL CCSD Royal Society of Chemistry
Résumé : International audience
A series of graphene oxide (GO) and zinc partially substituted magnetite GO-Fe1-xZnxOy (0 ≤ x ≤ 0.285) catalysts were synthesised through a precipitation-oxidation method. The rate constants for the degradation of acid orange seven (AO7) proceeded at a significant faster rate under UV-irradiation (up to 670%) than the conventional heterogeneous Fenton-like reaction. The resultant catalysts were mesoporous, so there was no mass transfer limitation for AO7 to access active sites in the catalysts. Further, maximum increases of rate constant up to 220% occurred as the zinc molar concentration increased from x = 0 to x = 0.159. GO enhanced to incorporation of zinc into the combined metal oxide, whilst zinc limited crystal growth, thus forming smaller crystallite sizes. These features proved to be essential for the improved catalytic activity of the resultant catalysts. The optimised zinc molar value at x = 0.159 delivered the best catalytic activity. © The Royal Society of Chemistry 2016.
ISSN: 2046-2069

hal-01683215
https://hal.univ-antilles.fr/hal-01683215
DOI : 10.1039/c6ra04068c

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