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 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 ACS American Chemical Society - Publications
Résumé : International audience
ABSTRACT: In this paper, the structural, optical and thermal properties of n-type (100),p-type (100) and (111) mesoporous silicon (MePSi) are reported. The mesoporous silicon wasprepared by an electrochemical process from bulk silicon wafer. Depending on the etchingdepth, analyses show that the porosity of p-type (111) increased by 32 to 40% compared to p(100) which, in turn, increased by 22 to 48% compared to n-type (100). The structuremorphology and the abundance of Si-Ox and Si-Hy also depended heavily on the type andcrystal orientation of MePSi. The thermal properties of the MePSi layers such as thermalconductivity (κ), volumetric heat capacity (ρCp) and thermal contact resistance (Rth) weredetermined using the pulsed photothermal method. The thermal conductivity of bulk silicondropped sharply after etching, decreasing by more than twenty-fold in the case of n-type (100)and by over forty-five fold for p-type (100) and (111). According to the percolation modeldepending on both porosity and phonon confinement, the drop in thermal conductivity wasmainly due to the nanostructure formation after etching. Thermal investigations showed thatthe volumetric heat capacity (ρCp) followed the barycentric model which depends mainly onthe porosity. The thermal contact resistances of MePSi layers were estimated to be in therange of 1x10-8 to 1x10-7 K⋅m2⋅W-1.
The Journal of Physical Chemistry C

hal-01495490
https://hal.archives-ouvertes.fr/hal-01495490
DOI : 10.1021/acs.jpcc.6b13101

Éditeur(s) : HAL CCSD Wiley
Résumé : International audience
In order to progress in the understanding of mechanical stress generation, the mesoporosity of the cell wall and its changes during maturation of poplar (Populus deltoides x P. nigra) tension wood (TW) and opposite wood (OW) were measured by nitrogen adsorption–desorption. Variations in the thickness of the gelatinous layer (G-layer) were also measured to clarify whether the mesoporosity change simultaneously with the deposition of the G-layer in TW. Results show that mesoporous structures of TW and OW were very similar in early development stages before the deposition of G-layers. With the formation of the S2 layer in OW and the G-layer in TW, the mesopore volume decreased steeply before lignification. However, in TW only, the decrease in mesopore volume occurred together with the pore shape change and a progressive increase in pore size. The different patterns observed in TW revealed that pores from G-layers appear with a different shape compared to those of the compound middle lamella, and their size increases duringthe maturation process until stabilising in mature wood. This observation strongly supports the hypothesis of the swelling of the G-layer matrix during maturation as the origin of maturation stress in poplar tension wood.
ISSN: 0028-646X

hal-01081834
https://hal.archives-ouvertes.fr/hal-01081834
https://hal.archives-ouvertes.fr/hal-01081834/document
https://hal.archives-ouvertes.fr/hal-01081834/file/Chang_al_Mesoporosity_changes_New-Phyto._2015.pdf
DOI : 10.1111/nph.13126

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
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 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
Résumé : International audience
A key element of the biomechanical design of trees is their ability to generate largemechanical stresses in wood at the stem periphery. This function is necessary for the tree tocontrol the orientation of its axes, and therefore to grow in height, maintain its branches at anoptimal angle or achieve adaptive reorientations (Fournier et al., 2013). This “maturationstress” appears in wood fibres during their cellular maturation when their secondary cell wallis thickening. In hardwoods, the stress asymmetry is generated by the formation of specificfibres with a very high tensile growth stress on the upper side of the inclined axis. Theresulting tension wood has microstructural features highly different from the normal wood.Tension wood in almost all temperate species has a specific gelatinous cell wall layer, calledG-layer, that is not lignified and highly mesoporous (Chang et al., 2015). It has been shownrecently, at the macroscopic scale, that cellulose tension appears during maturation and issynchronous with the development of this specific layer (Clair et al., 2011). Tropical species,like simarouba, are able to generate lignified tension wood fibres. The mechanisms of stressgeneration in tension wood fibres are not yet well known. The aim of our study is tounderstand these mechanisms and to know the spatial and temporal kinetics of the differentcell wall layers stiffening during maturation, in parallel with tensile stress generation.Contact-Resonance Atomic Force Microscopy, CR-AFM, was used here to address thisquestion on embedded samples (Arnould and Arinero, 2015) using dual resonance frequencytracking (DRFT, Rodriguez et al., 2007). Change in the contact modulus between, and within,each layer of the cell wall has been measured on several radial lines of developing fibres atdifferent steps. In order to understand the obtained results, and to estimate the sensitivity ofthe AFM indentation-like technique to the different cell wall components stiffness, an elasticanisotropic indentation model was used (Vlassak et al., 2003; Jäger et al., 2011). Finally,these mechanical measurements have been compared to topochemical data obtained on thesame fibres.
8th Plant Biomechanics International Conference
Nagoya, Japan

hal-01436113
https://hal.archives-ouvertes.fr/hal-01436113

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 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 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