Synthesis and characterization of high surface area TiO2/SiO2 mesostructured nanocomposite

Recently titania synthesis was reported using various structuration procedures, leading to the production of solid presenting high surface area but exhibiting moderate thermal stability. The study presents the synthesis of TiO₂/SiO₂ nanocomposites, a solid that can advantageously replace bulk titania samples as catalyst support. The silica host support used for the synthesis of the nanocomposite is a SBA-15 type silica, having a well-defined 2D hexagonal pore structure and a large pore size. The control of the impregnation media is important to obtain dispersed titania crystals into the porosity, the best results have been obtained using an impregnation in an excess of solvent. After calcination at low temperature (400 °C), nanocomposites having titania nanodomains (～2–3 nm) located inside the pores and no external aggregates visible are obtained. This nanocomposite exhibits high specific surface area (close to that of the silica host support, even with a titania loading of 55 wt.%) and a narrow pore size distribution. Surprisingly, the increase in calcination temperature up to 800 °C does not allow to detect the anatase to rutile transition. Even at 800 °C, the hexagonal mesoporous structure of the silica support is maintained, and the anatase crystal domain size is evaluated at ～10 nm, a size close to that of the silica host support porosity (8.4 nm). Comparison of their physical properties with the results presented in literature for bulk samples evidenced that these TiO₂/SiO₂ solids are promising in term of thermal stability.     

Synthesis of highly active nanostructured PtRu electrocatalyst with three-dimensional mesoporous silica template

Nanostructured PtRu material has been successively synthesized via chemical co-reduction of hexachloroplatinic acid and ruthenium trichloride using three-dimensional (3D) hexagonal mesoporous SBA-12 silica as a solid template, and has been studied as an electrocatalyst toward methanol electro-oxidation. The ordered nanostructure of the PtRu particles has been disclosed by transmission electron micrographs and is characterized by regular pores of ca. 3.0 ± 0.3 nm in diameter separated by walls of ca. 3.0 ± 0.3 nm thick. X-ray diffraction and energy dispersive X-ray spectroscope studies indicate that the PtRu material comprises of complicated phases rather than a single alloy phase of Pt and Ru. The specific electrochemical surface area of the nanostructured powder measured using both CO and underpotential deposited Cu stripping techniques is 74–78 m² g^–1, higher than that of unsupported precious metal catalysts prepared using standard techniques. The combination of high surface area and periodic nanostructure of the templated PtRu makes it an interesting promising fuel cell electrocatalyst. This has been demonstrated by the high activity of the templated PtRu towards the methanol electrooxidation. Therefore the solid template route based on 3D mesoporous silica with controlled pore size and high pore interconnectivity provides an interesting alternative to produce promising high-surface-area electrode materials.     

Investigation of Mg modified mesoporous silicas and their CO2 adsorption capacities

CO₂ adsorption properties on Mg modified silica mesoporous materials were investigated. By using the methods of co-condensation, dispersion and ion-exchange, Mg²⁺ was introduced into SBA-15 and MCM-41, and transformed into MgO in the calcination process. The basic MgO can provide active sites to enhance the acidic CO₂ adsorption capacity. To improve the amount and the dispersion state of the loading MgO, the optimized modification conditions were also investigated. The XRD and TEM characteristic results, as well as the CO₂ adsorption performance showed that the CO₂ adsorption capacity not only depended on the pore structures of MCM-41 and SBA-15, but also on the improvement of the dispersion state of MgO by modification. Among various Mg modified silica mesoporous materials, the CO₂ adsorption capacity increased from 0.42 mmol g⁻¹ of pure silica SBA-15 to 1.35 mmol g⁻¹ of Mg–Al–SBA-15-I1 by the ion-exchange method enhanced with Al³⁺ synergism. Moreover, it also increased from 0.67 mmol g⁻¹ of pure silica MCM-41 to 1.32 mmol g⁻¹ of Mg–EDA–MCM-41-D10 by the dispersion method enhanced with the incorporation of ethane diamine. The stability test by 10 CO₂ adsorption/desorption cycles showed Mg–urea–MCM-41-D10 possessed quite good recyclability.     

CO oxidation catalyzed by Ag/SBA-15 catalysts: Influence of the hydrothermal treatment

Four types of SBA-15 were prepared with different times and temperatures of treatment in order to obtain a range of micropore sizes. CO oxidation was used as a probe reaction in order to evaluate the nature of the active species when SBA-15s were doped with ca 10% Ag deposited from an AgNO₃ solution and calcined or reduced at 350 °C. The texture (TEM, nitrogen physisorption), structure (XRD) and reducibility (TPR) of the various catalysts (Ag/SBA-15) were studied and compared to those of a catalyst prepared by deposition of silver on fumed silica as a reference. These catalysts differ initially by the nature of silica and by pore sizes. In CO oxidation, pre-reduced catalysts are more active than pre-oxidised ones. This has to do with two phenomena, i.e. sintering, which produces large inactive silver particles, and formation of active silver species in the form of small Ag₂O particles.     

A comparison of lipase and trypsin encapsulated in mesoporous materials with varying pore sizes and pH conditions

Immobilized enzymes have an advantage over enzymes free in solution in that they are easily recovered after completed reaction. In addition, immobilization often gives enhanced stability. Entrapment of an enzyme in the pores of a mesoporous material is an attractive procedure since the enzyme is immobilized without any covalent bonding to a support which may be detrimental to the catalytic performance. The objective of this work is to compare the encapsulation and catalytic performance of lipase from Mucor miehei and trypsin from bovine pancreas, two hydrolases with rather dissimilar properties and structures. We also demonstrate the importance of the pore dimensions and the pH for proper function of the encapsulated enzyme. Mesoporous silica particles (SBA-15) with three different pore sizes (50 Å, 60 Å and 89 Å) were synthesized and hexagonal structures with narrow pore size distributions were confirmed with TEM, SAXS and N₂-adsorption. Lipase and trypsin were encapsulated separately in the silica particles and the results indicate distinct differences between the two enzymes, both in loading capacity and catalytic activity. For trypsin the encapsulation rate and the loading capacity were large with a maximum reached at pH 7.6. The largest product yield was obtained with the particles with 60 Å pores, however, the yield was significantly lower than with free trypsin. For lipase optimal encapsulation rate and loading capacity were reached with the particles with 89 Å pores at pH 6.0 but were low compared to trypsin. However, the catalytic activity of the encapsulated lipase was more than twice as large as for free lipase, which can be explained by an interfacial activation of lipase at the silica surface.     

Unusual phase behavior of decane-dodecane mixtures confined in SBA-15:Size effect on binary phase diagram

Phase behavior of normal decane-dodecane(n-C₁₀H₂₂-C₁₂H₂₆,C₁₀-C₁₂) system confined in SBA-15（Santa Barbara Amorphous,pore diameters 3.8,7.8,and 17.2 nm） has been studied by using differential scanning calorimetry.It has been found solid-liquid phase diagram of the C₁₀-C₁₂/SBA-15 system is composed of a straight line（3.8 nm）,a curve（7.8 nm） and a loop line （17.2 nm）.The growth of the phase diagram clearly shows the size effect on phase behavior of binary alkanes.Phase behavior has been compared among the systems C₁₀H₂₂-C₁₂H₂₆/SBA-15,C₁₂H₂₆-C₁₄H₃₀/SBA-15 and C₁₄H₃₀-C₁₆H₃₄/SBA-15.     

Effect of the order of Ni and Ce addition in SBA-15 on the activity in dry reforming of methane

Dry reforming of methane has been carried out on SBA-15 catalysts containing 5 wt% Ni and 6 wt% Ce. The effect of the order of Ni and Ce impregnation on the catalytic activity has been studied. Both metals were added using the “two-solvent” method that favors metal dispersion inside the pores. Characterizations by XRD (low and high angles), N₂ sorption, SEM and TEM of the materials after metal addition and calcination indicate good preservation of the porosities and high NiO and CeO₂ dispersion inside the porous channels. Reduction was carried out before the catalytic tests and followed by TPR measurements. The most active reduced catalyst was the Ni–Ce/SBA-15 sample prepared by impregnating cerium first, then nickel. All catalysts were highly active and selective towards H₂ and CO at atmospheric pressure. Full CH₄ conversion was obtained below 650 °C. The higher performances compared to those reported in the literature for mesoporous silica with supported Ni and Ce catalysts are discussed.     

Encapsulation of a chiral MnIII(salen) complex in ordered mesoporous silicas: an approach towards heterogenizing asymmetric epoxidation catalysts for non-functionalized alkenes

Two immobilized chiral Mn^III(salen) complexes covalently anchored on modified MCM-41 (50 Å) and SBA-15 (75 Å) were prepared using 3-aminopropyltriethoxysilane as a reactive surface modifier to afford comparable or even higher enantioselectivity than homogeneous catalysts for the enantioselective epoxidation of a series of smaller to bulkier alkenes. The catalyst immobilized in silica with larger pore diameters was found to be more active. Compared to homogeneous catalysts, the heterogenized catalysts are more stable and can be recycled four times with retention of enantioselectivity.     

Oxidation of carbon black,propene and toluene on highly reducible Co/SBA-15 catalysts

Different cobalt loadings (3, 6, 12, 24 wt%) were impregnated using the double-solvent technique on SBA-15 calcined at 500 °C presenting a high specific surface area. The impregnated solids were stabilized at 450 °C in the air. The impregnation of cobalt led to the incorporation of cobalt oxide nanoparticles in the mesoporosity of the SBA-15. The cobalt nanoparticles were easily reducible compared to similar solids prepared by different methods. The presence of these nanoparticles enhanced significantly the reactivity of the catalysts in the considered reaction. The addition of more than 12 wt% of cobalt did not enhance the catalytic reactivity due to the deposition of cobalt oxide species on the surface of the support. The cobalt-impregnated solids are efficient in decreasing the oxidation temperature of different probe molecules and are totally selective towards the formation of CO₂ and H₂O.     

Synthesis, characterization and catalytic behavior of functionalized mesoporous SBA-15 with various organo-silanes

Mesoporous silica SBA-15 has been synthesized and functionalized by one-step synthesis method to widen their various application possibilities. In this study, phenyltrimethoxysilane (PTMS), 3-mercaptopropyltrimethoxysilane (MPTMS) and trimethoxypropylsilane (TMPS) were used as silane precursors for the functionalization, and after treated with HCl solution, their catalytic activities were evaluated in the lactic acid-methanol esterification. The presence of anchoring of functional groups on SBA-15 was proved by XRD, FT-IR, BET surface area and pore size distributions. Good catalytic activity was observed especially for SBA-15-SO(3)H-MPTMS, and the catalytic activity order was determined as follows: SBA-15-SO(3)H-MPTMS>SBA-15-TMPS>SBA-15-PTMS, which is directly associated with the surface area, pore size and pore volume. As compared with homogeneous catalyst, SBA-15-SO(3)H-MPTMS heterogeneous catalyst shows remarkable performance, such as separation, recovery and reusability.     

Encapsulation hemoglobin in ordered mesoporous silicas: Influence factors for immobilization and bioelectrochemistry

The encapsulation of hemoglobin (Hb) on the mesoporous silicas SBA-15 and Au-doped SBA-15 (Au-SBA-15) has been studied as a model protein adsorption system. The influences of solution pH, structure of mesoporous silicas and gold nanoparticles incorporation on Hb immobilization are investigated in detail. The spectral characteristics of Hb/SBA-15 and Hb/Au-SBA-15 nanoconjugate show an absorption curve quite similar to that of native Hb, indicating that Hb retains its higher-order structure in the mesopores of SBA-15. Direct electrochemistry of Hb is obtained when Hb is adsorpted by mesoporous silicas SBA-15 or Au-SBA-15. Moreover, Hb/Au-SBA-15 exerts enhancing electron transfer ability because of the Au incorporation. Additionally, the Hb/Au-SBA-15 displays good electrocatalytic reduction of hydrogen peroxide with a detection limit of 1.0 μM, about 3 times as low as that for the Hb/SBA-15. The Hb/Au-SBA-15 exhibits higher peroxidase-like activity with the apparent Michaelis–Menton constant (K_m) of 2.87 mM, significantly lower than the 7.78 mM value for the Hb/SBA-15.     

Oxygen reduction activity dependence on the mesoporous structure of imprinted carbon supports

Two mesoporous carbons (with 15 (CIC-15) and 26 nm (CIC-26) diameter pores) were synthesized using a silica colloid imprinting method, loaded with 10 wt.% Pt, and then evaluated (against Vulcan^? carbon (VC)) as oxygen reduction (ORR) catalysts for use in proton exchange membrane fuel cells. Both Pt/CICs reproducibly out-performed Pt/VC, with Pt/CIC-15 demonstrating higher ORR activity than Pt/CIC-26, despite its smaller pore size and lower surface area. Transmission electron tomography showed that the Pt nanoparticles (4–5 nm diameter) are fully deposited throughout the pores of the CICs and that the pore distribution in CIC-26 is partially ordered, while CIC-15 shows no ordering of its pores. Importantly, using the powerful imaging capabilities of transmission electron tomography, a first-time correlation is demonstrated between the ORR activity and the wall thickness of the carbon support materials. Pt/CIC-15 has significantly thicker walls, giving a lower measured electronic resistance, a lower ORR Tafel slope, and thus better performance overall compared to Pt/CIC-26.     

Monolithic bed structure for capillary liquid chromatography

Monolithic stationary phases show promise for LC as a result of their good permeability, ease of preparation and broad selectivity. Inorganic silica monoliths have been extensively studied and applied for separation of small molecules. The presence of a large number of through pores and small skeletal structure allows the chromatographic efficiencies of silica monoliths to be comparable to columns packed with 5 μm silica particles, at much lower back pressure. In comparison, organic polymeric monoliths have been mostly used for separation of bio-molecules; however, recently, applications are expanding to small molecules as well. Organic monoliths with high surface areas and fused morphology rather than conventional globular morphology have shown good performance for small molecule separations. Factors such as domain size, through-pore size and mesopore size of the monolithic structures have been found to govern the efficiency of monolithic columns. The structure and performance of monolithic columns are reviewed in comparison to particle packed columns. Studying and characterizing the bed structures of organic monolithic columns can provide great insights into their performance, and aid in structure-directed synthesis of new and improved monoliths.     

Synthesis and characterization of surface modified SBA-15 silica materials and their application in chromatography

Hexagonally ordered SBA-15 mesoporous silica spheres with large uniform pore diameters are obtained using the triblock copolymer, Pluronic P123, as template with a cosurfactant cetyltrimethylammonium bromide (CTAB) and the cosolvent ethanol in acidic media. A series of surface modified SBA-15 silica materials is prepared in the present work using mono- and trifunctional alkyl chains of various lengths which improves the hydrothermal and mechanical stability. Several techniques, such as element analysis, nitrogen sorption analysis, small angle X-ray diffraction, scanning electron microscopy (SEM), FTIR, solid-state (29)Si and (13)C NMR spectroscopy are employed to characterize the SBA-15 materials before and after surface modification with the organic components. Nitrogen sorption analysis is performed to calculate specific surface area, pore volume and pore size distribution. By surface modification with organic groups, the mesoporous SBA-15 silica spheres are potential materials for stationary phases in HPLC separation of small aromatic molecules and biomolecules. The HPLC performance of the present SBA-15 samples is therefore tested by means of a suitable test mixture.     

Quantum-dots containing Fe/SBA-15 silica as “green” catalysts for the selective photocatalytic oxidation of alcohol (methanol,under visible light)

Fe/SBA-15 catalysts containing iron oxide nanoparticles confined inside silica pores (replicated, internal, poorly crystalline) and grown outside silica grains (external, mainly crystalline hematite) in different proportions are prepared using a single silica support. Fe-species are deposited by the two-solvent technique with two iron salts precursors (Fe(NO₃)₃·9H₂O, FeCl₃·6H₂O) and two solvents (cyclohexane, hexane) for 11 wt% of iron. Calcination is performed in reproducible conditions (700 °C, 2 °C/min, thin bed, in air). SAXS measurements are used to show that the 2D hexagonal structure of the used silica is maintained after Fe-loading and calcination. Ar sorption measurements show that the pores are partially plugged. The oxidation of pure methanol is used as a test reaction to compare photocatalytic properties. H₂O₂ and visible light both activate the reaction. More active catalysts are formed with hexane associated with FeCl₃·6H₂O than with Fe(NO₃)₃·9H₂O. A reversed situation is observed with cyclohexane. Iron leaching (after 1 h 30 of test, up to 3 mg of Fe by mL) is important. These results are expected to be of interest in the exploration of size and shape “nanocatalysis” and to provide a further understanding for the reactions that take place when porous silicas are used as supports.     

Mesoporous materials incorporating a zinc(II) complex: Synthesis and direct luminescence quantum yield determination

New luminescent inorganic–organic hybrid materials incorporating the luminescent zinc(II) complex ZnL₂ (λ_em = 457 nm and Φ_em = 4.4% reference values for ZnL₂; HL = chelating ligand resulting from the reaction between salicylaldehyde and 3-aminopropyltriethoxysilane), covalently bonded to different types of mesoporous silica hosts (namely MCM-41, MCM-48 and SBA-15), were prepared via both the methods of grafting post-synthesis (GPS) and one-pot synthesis (OPS). The products obtained, which form the GPS [(GPS)(Zn/MCM-41), (GPS)(Zn/MCM-48), (GPS)(Zn/SBA-15)] and the OPS [(OPS)(Zn/MCM-41), (OPS)(Zn/MCM-48), (OPS)(Zn/SBA-15)] series, contain the ZnL₂ guest covalently bonded to the silica framework through silicon–oxygen bonds formed when the silane group is placed at the periphery of the Zn(II) coordination sphere. GPS and OPS materials were characterized by powder X-ray diffraction, N₂ adsorption/desorption, thermogravimetric analysis (TGA) and UV/vis spectroscopy. For the new mesoporous materials the emission quantum yield (EQY) was measured by means of an integrating sphere combined with a spectrofluorimeter. The ZnL₂ loading (measured by the ZnL₂/SiO₂ ratio calculated from TGA data) for MCM-41 appears to be independent of the synthesis procedure, whereas, for both MCM-48 and SBA-15, the ZnL₂/SiO₂ ratio of the materials obtained via OPS is about four times higher than products obtained from GPS. The ZnL₂ loaded GPS and OPS series show λ_em maxima at about 485 and 455 nm, respectively. Moreover, with reference to EQY (GPS)(Zn/SBA-15) and (OPS)(Zn/SBA-15), although featuring ZnL₂/SiO₂ ratios of 0.13 and 0.45, respectively, they showed similar EQY values: 2% and 5%. On the contrary, (GPS)(Zn/MCM-41) and (OPS)(Zn/MCM-41) which give similar ZnL₂/SiO₂ ratios (0.09 and 0.14) exhibit very different EQY, i.e. 2% and 22%, respectively.     

Assessment of the intrinsic interactions of mesoporous silica with carbon dioxide

Three mesoporous silica, SBA-16, SBA-15 and MCM-41, with different structures and porosities were synthesized via a hydrothermal method and their interactions with carbon dioxide (CO₂) were investigated through thermal programmed desorption (TPD) and differential scanning calorimetry. TPD measurements provided precise assessments of the intrinsic affinity towards CO₂, without the influence of moisture. All silica materials were found to exhibit intrinsic affinity towards carbon dioxide, but the surface basicity, expressed in terms of retained CO₂ amount, is markedly influenced by increases in pore size and framework structures. SBA-15 displayed the highest CRC values, explained in terms of larger pore size, lower numbers of acidic out-of plane Si–OH and higher numbers of much less acidic in-plane silanols. These findings provide valuable information for a better understanding of the role of the silica structure in the intrinsic basicity, prior to further modifications for improving the affinity towards CO₂ or merely for catalysis purposes involving CO₂ as reagents, intermediates or products.     

Catalytic upgrading of lignin derived bio-oil model compound using mesoporous solid catalysts

The catalytic upgrading of a lignin-derived bio-oil model compound, the hydrodeoxygenation of guaiacol, was performed using mesoporous solid catalysts. Platinum supported on silica and mesoporous silica (SBA-15 and KIT-6) were used as catalysts. The level of platinum incorporation and aluminum grafting did not alter the physical properties of the supports, such as surface area and pore size distribution. On the other hand, these treatments drastically affected the catalytic activities. A catalyst with platinum alone converted guaiacol to oxygenate compounds. In contrast, a series of catalysts with both platinum incorporation and aluminum grafting enhanced hydrodeoxygenation by converting guaiacol into hydrocarbons (cyclohexane and benzene). A comparison of the catalyst supports revealed the ordered mesoporous silica, SBA-15 and KIT-6, with high surface area, to have a higher hydrocarbon yield than conventional silica.     

Preparation of mesocellular carbon foam and its application for lithium/oxygen battery

A mesocellular carbon foam (MCF-C) was prepared by nanocasting technology using mesocellular foam (MCF) silica hard template. The obtained carbon sample exhibits bimodal mesopores with narrow pore size distribution, centered at 4.3 and 30.4 nm. The MCF-C was evaluated as positive electrode in lithium/oxygen battery. It showed a higher discharge capacity, about 40% increased capacity compared to several commercial carbon black. The enhanced performance is probably ascribed to their large pore volumes and ultra-large mesoporous structures, which allow more lithium oxide deposit during discharge process.     

High capacity organic monoliths for the simultaneous application to biopolymer chromatography and the separation of small molecules

A method for controlling the mesoporous structure of monolithic organic copolymers is presented by systematic variation in polymerisation time, employing poly(p-methylstyrene-co-1,2-(p-vinylphenyl)ethane) (MS/BVPE) as a representative styrene system. Decreasing the time of polymerisation introduces a considerable fraction of mesopores (up to 20% of the total pore volume), while keeping the support permeability reasonable high (～1.3 × 10^?14 m²). Monolith structures, prepared in such a manner, enable efficient (typically around 70,000 plates/m) and fast separation of low-molecular-weight compounds, whereas their performance towards biopolymers is comparable to column supports, fabricated according to typically used protocols (polymerisation time >12 h and thus monomer conversion >98%). The polymerisation time is hence a valuable tool to tailor the fraction of support flow-channels, macropores as well as mesopores, which is shown dramatically to influence the chromatographic separation characteristics of the respective column. This way, the preferred applicability of organic (styrene) monolithic copolymers can be extended to the separation of small molecules beyond biopolymer chromatography.