Serge Kaliaguine

Publications of Serge Kaliaguine

• One-step-impregnation hard templating synthesis of high-surface-area nanostructured mixed metal oxides (NiFe2O4, CuFe2O4 and Cu/CeO2).

  Authors: Hoang Yen, Yongbeom Seo, Rémy Guillet-Nicolas, Serge Kaliaguine, Freddy Kleitz

  Chemical communications (Cambridge, England). 08/2011; 47(37):10473-5.

  We report here on an efficient one-step-impregnation method to synthesize crystalline mesoporous bimetal oxides (e.g. NiFe(2)O(4), CuFe(2)O(4), Cu/CeO(2)) using mesoporous silicas as hard templatesWe report here on an efficient one-step-impregnation method to synthesize crystalline mesoporous bimetal oxides (e.g. NiFe(2)O(4), CuFe(2)O(4), Cu/CeO(2)) using mesoporous silicas as hard templates under optimized mixing conditions. This new procedure enables a true replication of the mesostructure with high yield and phase purity, while retaining particle morphology of the template.

• Cross-linked sulfonated poly(ether ether ketone) by using diamino-organosilicon for proton exchange fuel cells.

  Authors: Marie J Kayser, Marc X Reinholdt, Serge Kaliaguine

  The journal of physical chemistry. B. 03/2011; 115(12):2916-23.

  Fuel cells are at the battlefront to find alternate sources of energy to the highly polluting, economically and environmentally constraining fossil fuels. This work uses an organosilicon moleculeFuel cells are at the battlefront to find alternate sources of energy to the highly polluting, economically and environmentally constraining fossil fuels. This work uses an organosilicon molecule presenting two amine functions, bis(3-aminopropyl)-tetramethyldisiloxane (APTMDS) with the aim of preparing cross-linked sulfonated poly(ether ether ketone) (SPEEK) based membranes. The hybrid membranes obtained at varying APTMDS loadings are characterized for their acid, proton conductivity, water uptake, and swelling properties. APTMDS may be considered as an extreme case of silica nanoparticle and is therefore most advantageously distributed within the polymeric matrix. The two amine groups can interact, via electrostatic interactions, with the sulfonic acid groups of SPEEK, resulting in a double anchoring of the molecule. The addition of a small amount of APTMDS is enhancing the mechanical and hydrolytic properties of the membranes and allows some unfolding of the polymer chains, rendering some acid sites accessible to water molecules and thus available for proton transport.

• Proton exchange membranes for application in fuel cells: grafted silica/SPEEK nanocomposite elaboration and characterization.

  Authors: Marc X Reinholdt, Serge Kaliaguine

  Langmuir : the ACS journal of surfaces and colloids. 07/2010; 26(13):11184-95.

  Hydrogen technologies and especially fuel cells are key components in the battle to find alternate sources of energy to the highly polluting and economically constraining fossil fuels in an aim toHydrogen technologies and especially fuel cells are key components in the battle to find alternate sources of energy to the highly polluting and economically constraining fossil fuels in an aim to preserve the environment. The present paper shows the synthesis of surface functionalized silica nanoparticles, which are used to prepare grafted silica/SPEEK nanocomposite membranes. The nanoparticles are grafted either with hexadecylsilyl or aminopropyldimethylsilyl moieties or both. The synthesized particles are analyzed using XRD, NMR, TEM, and DLS to collect information on the nature of the particles and the functional groups, on the particle sizes, and on the hydrophilic/hydrophobic character. The composite membranes prepared using the synthesized particles and two SPEEK polymers with sulfonation degrees of 69.4% and 85.0% are characterized for their proton conductivity and water uptake properties. The corresponding curves are very similar for the composites prepared with both polymers and the nanoparticles bearing the two functional groups. The composites prepared with the nanoparticles bearing solely the aminopropyldimethylsilyl moiety exhibit lower conductivity and water uptake, possibly due to higher interaction of the polymer sulfonic acid sites with the amine groups. The composites prepared with the nanoparticles bearing solely the hexadecylsilyl moiety were not further investigated because of very high particles segregation. A study of the proton conductivity as a function of temperature was performed on selected membranes and showed that nanocomposites made with nanoparticles bearing both functional moieties have a higher conductivity at higher temperatures.

• Amine grafted silica/SPEEK nanocomposites as proton exchange membranes.

  Authors: Marie J Kayser, Marc X Reinholdt, Serge Kaliaguine

  The journal of physical chemistry. B. 07/2010; 114(25):8387-95.

  This work presents the elaboration of porous silica nanospheres, eventually amine functionalized, which are used as the inorganic filler in mixed matrix silica/SPEEK membranes. The surface of theThis work presents the elaboration of porous silica nanospheres, eventually amine functionalized, which are used as the inorganic filler in mixed matrix silica/SPEEK membranes. The surface of the silica nanoparticles is modified by grafting (3-aminopropyl)dimethylethoxysilane (APDMS). The two sets of nanocomposite membranes obtained at varying silica loadings are characterized for their proton conductivity and water uptake properties. At higher degrees of sulfonation, some cross-linking due to the interaction of the amine groups of the silica with the sulfonic acid groups of the SPEEK polymer is attested by the water uptake reduction between the composites made with amine grafted or pristine silica particles. However, even in these conditions the proton conductivity of the mixed matrix membrane is not essentially different in the two sets of nanocomposites. This indicates that the inorganic filler effect on proton conductivity is related to changes in the microstructure of the water channels in the polymer lattice.

• Mesostructured silica SBA-16 with tailored intrawall porosity part 2: Diffusion

  Authors: Oliver C. Gobin, Qinglin Huang, Hoang Vinh-Thang, Freddy Kleitz, Mladen Eic, Serge Kaliaguine

  Journal of Physical Chemistry C. 01/2007; 111(7):3059-3065.

  In this Part 2 of the present work, the diffusivities of n-heptane, cumene, and mesitylene in the SBA-16 silica samples described in Part I have been measured by the zero length column (ZLC) method.In this Part 2 of the present work, the diffusivities of n-heptane, cumene, and mesitylene in the SBA-16 silica samples described in Part I have been measured by the zero length column (ZLC) method. A comparison is made between the diffusivities and diffusion apparent activation energies in these materials and in a series of SBA-15 samples of similar pore size and pore volume. The latter series was discussed in a previous work. Clear differences are indeed observed and rationalized in terms of differences in the pore structure of the two series of solids.

• Structural and diffusion characterizations of steam-stable mesostructured zeolitic UL-ZSM-5 materials.

  Authors: Hoang Vinh-Thang, Qinglin Huang, Adrian Ungureanu, Mladen Eić, Do Trong On, Serge Kaliaguine

  Langmuir : the ACS journal of surfaces and colloids. 06/2006; 22(10):4777-86.

  A series of mesoporous UL-ZSM-5 materials (Si/Al = 50) with different micro- and mesoporosity as well as crystallinity was prepared following the procedure proposed in one of our recent studiesA series of mesoporous UL-ZSM-5 materials (Si/Al = 50) with different micro- and mesoporosity as well as crystallinity was prepared following the procedure proposed in one of our recent studies (Trong-On, D.; Kaliaguine, S. Angew. Chem. Int. Ed. 2001, 40, 3248-3251. Trong-On, D.; Kaliaguine, S. U.S. Patent 6,669,924, B1, 2003). These materials have zeolitic structure in the form of nanoparticles intergrown in the walls of the amorphous wormhole-like aluminosilicate mesopores of Al-Meso-50, which was used as a precursor in the synthesis. The structure, crystallinity, and textural properties of the synthesized materials, as well as a reference ZSM-5 zeolite sample, were determined by X-ray diffraction (XRD), transmission electron microscopy (TEM)/scanning electron microscoy (SEM) analyses, Fourier transform infrared spectroscopy (FTIR), 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR), and nitrogen adsorption/desorption techniques. The acid properties were examined by FTIR of adsorbed pyridine. UL-ZSM-5 materials were shown to be highly hydrothermally stable. The diffusion of two C7 hydrocarbons, i.e., n-heptane and toluene, in four UL-ZSM-5 materials with different microporosities, related acidities, and crystallinities were investigated using the zero-length column (ZLC) method. Furthermore, the wormhole-like mesostructured aluminosilicate precursor (Al-Meso-50) and a reference MFI zeolite sample were also investigated using the same technique. A theoretical model considering a combination of mesopore diffusion (with surface slip in the main channels) with an activated, mainly surface diffusion mechanism in the intrawall biporous structure, was proposed and employed to interpret the experimental ZLC results. A classical Knudsen type of diffusion was replaced by an activated surface slip type of diffusion mechanism in the mesopores. The transport of n-heptane in UL-ZSM-5 materials was found to be mainly controlled by mesopore diffusion in the main-channel structure, while that of toluene was dominated by the intrawall diffusion process. Diffusion activation energies of n-heptane are about 2 times higher in comparison to toluene, which has a larger kinetic diameter. The main mesopore channel structure seems to appreciably contribute to the overall mass transport. Furthermore, the effect of hydrothermal treatment (20% steam at 800 degrees C for 24 h) on the diffusion of these two sorbates on UL-ZSM-5 materials was also evaluated.

• Intercalation/Exfoliation mechanism of hybrid formation in polypropylene/lamellar mesostructured silica nanocomposites.

  Authors: Christophe Danumah, Suprakas Sinha Ray, Serge Kaliaguine, Mosto Bousmina

  Journal of nanoscience and nanotechnology. 03/2006; 6(2):523-9.

  Understanding the optimal processing conditions for the fabrication of polymer nanocomposites is of fundamental importance in designing materials with balance of properties. To understand theseUnderstanding the optimal processing conditions for the fabrication of polymer nanocomposites is of fundamental importance in designing materials with balance of properties. To understand these conditions in the case of maleic anhydride grafted polypropylene (PP-g-MA)/layered mesostructured silica (LMS) nanocomposites, the effect of temperature, shear rate, and residence time during processing on the structure of the nanocomposites were studied. The results showed that the combination of temperature, residence time, and mechanical shears have strong effect on the structure of the nanocomposites, rather than just interfacial interactions between the polymer matrix and silicate layers. However, interfacial interactions between the polymer matrix and silicate layers primarily play an important role to the intercalation of polymer chains into the silicate galleries. On the basis of our experimental results, a first explanation of the formulation mechanism of PP-g-MA/LMS nanocomposites is proposed. Finally, a general concept of processing conditions for manufacturing of polymer nanocomposites by melt-compounding process in a batch-mixer is described.

• Adsorption of C7 hydrocarbons on biporous SBA-15 mesoporous silica.

  Authors: Hoang Vinh-Thang, Qinglin Huang, Mladen Eić, Do Trong On, Serge Kaliaguine

  Langmuir : the ACS journal of surfaces and colloids. 06/2005; 21(11):5094-101.

  In our recent studies (Vinh-Thang, H.; Huang, Q.; Eic, M.; Trong-On, D.; Kaliaguine, S. Langmuir 2005, 21, 2051-2057; Vinh-Thang, H.; Huang, Q.; Eic, M.; Trong-On, D.; Kaliaguine, S. Stud. Surf. Sci.In our recent studies (Vinh-Thang, H.; Huang, Q.; Eic, M.; Trong-On, D.; Kaliaguine, S. Langmuir 2005, 21, 2051-2057; Vinh-Thang, H.; Huang, Q.; Eic, M.; Trong-On, D.; Kaliaguine, S. Stud. Surf. Sci. Catal. 2005, in press), a series of synthesized SBA-15 materials were characterized using nitrogen adsorption/desorption isotherms at 77 K and SEM images. In the present paper, four of them (MMS-1-RT, MMS-1-60, MMS-1-80, and MMS-5-80) were further investigated with regard to their equilibrium characteristics using n-heptane and toluene as sorbates by the standard gravimetric technique. SBA-15 materials proved to have a broad pore size distribution within the micropore/small-mesopore range in the walls of their main mesoporous channels. The adsorption capacities for toluene were found to be higher than for n-heptane. The isosteric heats of adsorption, estimated by the Clausius-Clapeyron equation, are also higher for toluene compared to n-heptane. They were found to depend on framework microporosity of the relevant SBA-15 samples. The isosteric heats of adsorption for all sorbates decrease with increased loading and approach the heats of evaporation of the respective sorbate. The adsorption capacities of SBA-15 samples are significantly higher than those of silicalite, i.e., the MFI zeolite silica analogue. In contrast to that, the isosteric heats of adsorption in the mesopore channels of SBA-15 were found to be much smaller. This result also suggests that SBA-15 can potentially be a good candidate for separation of C(7) hydrocarbons.

• Structure and diffusion characterization of SBA-15 materials.

  Authors: Vinh-Thang Hoang, Qinglin Huang, Mladen Eić, Trong-On Do, Serge Kaliaguine

  Langmuir : the ACS journal of surfaces and colloids. 04/2005; 21(5):2051-7.

  In situ formation of the micro- and mesoporous structures of SBA-15 materials was investigated. It was found that the structure is significantly different from that for cylindrical or hexagonalIn situ formation of the micro- and mesoporous structures of SBA-15 materials was investigated. It was found that the structure is significantly different from that for cylindrical or hexagonal pores, which suggests that the SBA-15 is more complex than an array of hexagonally ordered channels. Nitrogen adsorption isotherms at 77 K provided evidence that large (primary) mesopores are accompanied by a certain amount of significantly smaller pores with a broad distribution in the micropore/small-mesopore range within the mesoporous walls of main channels. It was found that the microporosity can be controlled by the time of heating as well as the synthesis temperature. The diffusion properties of n-heptane as a probe molecule in four selected SBA-15 samples with different micropore volumes were studied by the standard zero length column technique and related to their structural characteristics. The results have shown that the diffusion process involving n-heptane at a low concentration level takes place inside the walls of main mesoporous channels and depends on the relative content of micropores. In the samples that have a relatively high content of micropores, n-heptane diffusivities are relatively low, their activation energies are high, and the process is similar to diffusion in typical microporous adsorbents, like zeolites. As the micropore content is decreased, diffusion becomes more and more controlled by secondary mesopores of the intrawall pore structure, rendering diffusion faster and activation energies lower.

• Zeolite nanoclusters coated onto the mesopore walls of SBA-15.

  Authors: Trong-On Do, Andrei Nossov, Marie-Anne Springuel-Huet, Celine Schneider, Jeremy L Bretherton, Colin A Fyfe, Serge Kaliaguine

  Journal of the American Chemical Society. 12/2004; 126(44):14324-5.

  Ultrahigh-field 27Al MAS and MQMAS NMR and 129Xe NMR were used to characterize the zeolite-coated SBA-15 materials. This study shows evidence that zeolite nanoclusters are coated on the mesoporeUltrahigh-field 27Al MAS and MQMAS NMR and 129Xe NMR were used to characterize the zeolite-coated SBA-15 materials. This study shows evidence that zeolite nanoclusters are coated on the mesopore surface of SBA-15. These techniques are useful for the detection of zeolite nanoclusters and different aluminum environments in zeolite/aluminosilicate composites, which are difficult or even impossible to detect by conventional techniques.

• Zeolite-coated mesostructured cellular silica foams.

  Authors: Do Trong On, Serge Kaliaguine

  Journal of the American Chemical Society. 02/2003; 125(3):618-9.

  ZSM-5- and NaY-coated MCF materials as new acid catalysts for conversion of bulky molecules were prepared by the coating procedure using diluted clear zeolite gel solutions. The resulting materialsZSM-5- and NaY-coated MCF materials as new acid catalysts for conversion of bulky molecules were prepared by the coating procedure using diluted clear zeolite gel solutions. The resulting materials have high acidity and improved steam stability as compared to that of the corresponding MCF aluminosilica. This could be due to the zeolitic nature and relative hydrophobicity of the mesopore surface.

• Periodic mesoporous organosilica from micellar oligomer template solution.

  Authors: Safia Hamoudi, Serge Kaliaguine

  Chemical communications (Cambridge, England). 10/2002;

  Periodic mesoporous organosilica (PMO) with two-dimensional hexagonal symmetry was synthesised using a bridged silsesquioxane (CH3O)3Si-CH2-CH2-Si(CH3O)3 as precursor and polyoxyethylene non-ionicPeriodic mesoporous organosilica (PMO) with two-dimensional hexagonal symmetry was synthesised using a bridged silsesquioxane (CH3O)3Si-CH2-CH2-Si(CH3O)3 as precursor and polyoxyethylene non-ionic surfactant (Brij-56) as template. The hybrid material was characterised by X-ray diffraction, N2 adsorption, TEM, and solid-state 29Si MAS NMR spectroscopy.

• Ultrastable and highly acidic, zeolite-coated mesoporous aluminosilicates.

  Authors: Do Trong On, Serge Kaliaguine

  Angewandte Chemie (International ed. in English). 04/2002; 41(6):1036-40.

• Zeolite containing catalytic membranes as interphase contactors

  Authors: Shanqiang Wu, Jean-Emile Gallot, Mosto Bousmina, Christian Bouchard, Serge Kaliaguine

  Catalysis Today.

  A composite membrane (TS-1/PDMS) was used as a catalytic interphase contactor in the two-phase reaction of n-hexane oxyfunctionalization by hydrogen peroxide. An experimental study allowed toA composite membrane (TS-1/PDMS) was used as a catalytic interphase contactor in the two-phase reaction of n-hexane oxyfunctionalization by hydrogen peroxide. An experimental study allowed to establish the effects of the main membrane parameters (thickness, loading, chemical modifications . . .) on the performances of the membrane reactor. A simple mathematical model of the catalytic phase contactor was derived and shown to represent quantitatively the observed experimental trends.

• Inverse gas chromatography studies of alkali cation exchanged X-zeolites

  Authors: Jinhai Xie, Mosto Bousmina, Guoying Xu, Serge Kaliaguine

  Journal of Molecular Catalysis A: Chemical.

  The base strength of alkali cation exchanged X-zeolites was investigated using the IGC technique. The results show that IGC can give information about the acid–base interaction with polar probeThe base strength of alkali cation exchanged X-zeolites was investigated using the IGC technique. The results show that IGC can give information about the acid–base interaction with polar probe molecules. The specific interaction (Isp, mJ/m2) between zeolites and benzene, toluene, chloroform can be correlated to the strength of acid–base interaction.

• Mesostructured silica SBA-16 with tailored intrawall porosity part 1: Synthesis and characterization

  Authors: Oliver C. Gobin, Ying Wan, Dongyuan Zhao, Freddy Kleitz, Serge Kaliaguine

  JOURNAL OF PHYSICAL CHEMISTRY C. 111(7):3053-3058.

  Mesostructured silica materials of SBA-16 type were synthesized under varying conditions affecting the pore size distribution. The alpha(s)-plot method allows us to identify two populations ofMesostructured silica materials of SBA-16 type were synthesized under varying conditions affecting the pore size distribution. The alpha(s)-plot method allows us to identify two populations of intrawall pores and measure their respective specific volumes. A semiquantitative treatment of these data yields an estimate for the intrawall pore radius. These results are discussed and related to the behavior of the long polar chains of the F127 surfactant in the synthesis gel.

• Proton exchange membranes based on sulfonated poly(phthalazinone ether ketone)s/aminated polymer blends

  Authors: Yan Gao, Gilles Robertson, Michael Guiver, Xigao Jian, Serguei Mikhailenko, Serge Kaliaguine

  Acid–base blend proton exchange membrane films were prepared from sulfonated poly(phthalazinone ether ketone)s (SPPEK)s, either polymerized from sulfonated monomer (M-SPPEK) or post-sulfonatedAcid–base blend proton exchange membrane films were prepared from sulfonated poly(phthalazinone ether ketone)s (SPPEK)s, either polymerized from sulfonated monomer (M-SPPEK) or post-sulfonated (P-SPPEK), and three kinds of aminated polysulfones, namely: Udel® PSf aminated ortho to ether linkage (ortho-O-APSf), PSf phenylmethylene aminated ortho to the sulfone linkage (ortho-S-PMAPSf), or 6F polysulfone aminated ortho to the sulfone linkage (ortho-S-6F-APSf). Films were prepared by casting mixed N,N-dimethylacetamide (DMAc) solutions of (SPPEK)s in ammonium or sodium salt form and aminated polysulfones, followed by treatment of the blend membrane films in aqueous sulfuric acid. The blend membrane films showed slightly lower thermal stabilities than SPPEKs. M-SPPEK-based blend membrane films showed an obvious decrease in proton conductivity compared with their parent sulfonated polymer, whereas the P-SPPEK-based blend membrane films showed similar proton conductivities to their parent sulfonated polymer from room temperature to about 80 °C. All blend membrane films showed increased swelling stability. Keywords: Sulfonated poly(arylene ether ketone); Proton exchange membrane; Acid-base blend; Sulfonated polyphthalazinone; Aminated polysulfone; Poly(phthalazinone ether ketone)s; Blend membrane; Aminated polymer; Ionomer; Fuel cell

• Properties of PEMs based on cross-linked sulfonated poly(ether ether ketone)

  Authors: Serguei Mikhailenko, Gilles Robertson, Michael Guiver, Serge Kaliaguine

  PEMs prepared from sulfonated poly(ether ether ketone) and cross-linked with simple polyols (ethylene glycol and glycerol), exhibited enhanced strength, stability in hot water and high protonPEMs prepared from sulfonated poly(ether ether ketone) and cross-linked with simple polyols (ethylene glycol and glycerol), exhibited enhanced strength, stability in hot water and high proton conductivity. The properties and chemical structure of the cross-linked membranes were studied using TGA, 1H NMR and FTIR. These data suggest that ethylene glycol and glycerol molecules do not link neighbouring main chains via sulfonic acid functions, but rather form alcohol–ether oligomers, bonded to –SO3– group and generating an interpenetrating network which interacts with the main chains. The thermal stability of cross-linked membranes is inferior to that of non-cross-linked ones. It is shown that splitting off of the sulfonic acid groups occurring above 200 °C is accompanied by main chain degradation in both initial and cross-linked membranes. The fact that the degradation temperature exceeds 200 °C suggests that this could be a promising and effective approach to cross-linking sulfonated membranes for FC application. Keywords: Sulfonated poly(ether ether ketone); Proton exchange membrane; Cross-linking; Proton conductivity

• 1-Butanol etherification over sulfonated mesostructured silica and organo-silica

  Authors: Bineta Sow, Safia Hamoudi, M. Hassan Zahedi-Niaki, Serge Kaliaguine

  Microporous and Mesoporous Materials. 79(1-3):129-136.

  A new series of sulfonated mesoporous silica and organosilica was synthesized and their catalytic activity was investigated in 1-butanol dehydration reaction. The reaction was carried out in liquidA new series of sulfonated mesoporous silica and organosilica was synthesized and their catalytic activity was investigated in 1-butanol dehydration reaction. The reaction was carried out in liquid phase inside a batch reactor equipped with a diamond FTIR probe for continuous concentration monitoring of 1-butanol and reaction products namely dibutyl ether (DBE) and water. Good catalytic activity and high conversion from 1-butanol to DBE was observed for all catalysts which include sulfonic acid functionalized SBA-15 (SAF-SBA-15), arenesulfonic acid functionalized SBA-15 (ArSAF-SBA-15) and arenesulfonic acid functionalized mesostructured ethane silica (ArSAF-MES). ArSAF-MES showed the highest 1-butanol conversion ([approximate]80%) at 473 K compared to all other catalysts tested. A kinetic model was adopted for this reaction that describes the strong competition effect between water and alcohol molecules for -SO3H active sites. The higher catalytic activity of ArSAF-MES is associated with the more hydrophobic nature of -SO3H environment in this material.