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 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
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 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 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
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 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 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

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

Éditeur(s) : HAL CCSD Elsevier
Résumé : International audience
Abstract View references (38)Silicalite-1 (S-1) and ZSM-5 membranes prepared by secondary growth on tubular ceramic supports were tested using a pervaporation set up for the desalination of aqueous solutions containing NaCl in concentrations corresponding to brackish (0.3-1wt%), sea (3.5wt%) and brine (7.5-15wt%) water. ZSM-5 membranes delivered higher water fluxes when compared with S-1 membranes due to enhanced hydrophilicity of the Al-rich zeolite structure leading to fluxes as high as 11.5kgm -2h -1 for 0.3wt% NaCl feed solutions at 75°C. At higher salt concentration the water flux decreased alongside with the salt rejection rate, however the hydrophilic ZMS-5 membrane became more susceptible to performance loss, particularly at high temperatures. Detailed stability experiments carried out for up to 560h showed the dissolution of both S-1 and ZSM-5 top layers. This was attributed to the combined effects of ion exchange and water dissolution mechanisms. Interesting though, the MFI structure zeolite was still observed on the XRD patterns whilst EDX depth profile showed the presence of silica up to 30μm depth into the support. These results suggest the formation/infiltration of a compact amorphous phase in the substrate, derived from the aggregation of the dissolved silicate species and possibly together with the arrangement of MFI nano-slabs during the desalination tests. Despite generating lower water fluxes, the S-1 membrane exhibited relatively high robustness under the long term testing conditions which included temperature cycling, delivering salt rejections from initial >99% to <80% at the end of the testing period (560h). © 2012 Elsevier B.V.
ISSN: 0376-7388

hal-01683201
https://hal.univ-antilles.fr/hal-01683201
DOI : 10.1016/j.memsci.2012.05.074