Synthesis and characterization of the SBA-15/carbon cryogel nanocomposites

The ordered mesoporous silica SBA-15 materials were synthesized using Pluronic P123 (non-ionic triblock copolymer, EO₂₀PO₇₀O₂₀), under acidic conditions. SBA-15/carbon cryogel composites were obtained by sol–gel polycondensation of resorcinol and formaldehyde followed by freeze drying, and subsequent pyrolysis, in the presence of different amounts of SBA-15. For comparison purpose, SBA-15/carbon composite was also prepared using sucrose as carbon source. These materials were characterized by room temperature nitrogen adsorption–desorption measurement, X-ray diffraction, scanning electron microscopy (SEM) and Fourier transform infrared (FT-IR) spectroscopy. It was revealed that the samples have amorphous structure, high specific surface area (350–520 m² g^?1) and developed meso- as well as microporosity. The porosity of structure depends on the carbon source and Si/C ratio which can be easily controlled by varying concentration of starting solution.     

Novel synthesis of mesoporous hydroxyapatite using carbon nanorods as a hard-template

A novel hard-template synthesis approach for the fabrication of mesoporous hydroxyapatite (HAP) is described herein. Carbon nanorods, synthesised using mesoporous silica (SBA-15) and an acidified sucrose solution, are used as a hard template, after which, they are utilised to synthesise mesoporous HAP. Transmission electron microscopy (TEM), X-ray diffraction (XRD) energy-dispersive X-ray spectroscopy (EDX) and nitrogen adsorption/Brunauer–Emmett–Teller (BET), are all employed to characterise the synthesised materials. We demonstrate that this approach allows for the successful fabrication of single phase HAP with surface area 242.20±2.27 m² g⁻¹ and average pore diameter 3.5 nm and 18.9 nm. This work proposes for the first time a bespoke innovative procedure that employs carbon nanorods as a template for the synthesis of mesoporous HAP via a hard templating protocol.     

Facile heterogenization of homogeneous ferrocene catalyst on SBA-15 and its hydroxylation activity

Hexagonally ordered mesoporous silica SBA-15 was synthesized with amino propyl groups by direct co-condensation method using triblock co-polymer (P123) as a template, tetra ethyl orthosilicate as a silica source under conventional SBA-15 synthesis conditions. Amino propyl trimethoxy silane was utilized for introducing SBA-15 with propyl amine anchoring moiety. Ferrocene was anchored to SBA-15 post-synthetically by the condensation of amine group from propylamine SBA-15 with the carbonyl group of ferrocenecarboxaldehyde. The structural ordering and the textural properties of propyl amine functionalized SBA-15 (SBA-15-NH₂) and further ferrocene tethered SBA-15 (SBA-15-N = ferrocene) were characterized by low angle XRD and nitrogen gas adsorption techniques. The attached organic moieties were identified by mid-infrared (MIR) and near-infrared (NIR) spectroscopy. The ferrocene functionalized SBA-15 is highly active towards the hydroxylation of benzene to phenol. The catalyst was reused without significant loss in activity.     

Synthesis and characterization of mesoporous carbon through inexpensive mesoporous silica as template

Mesoporous silica materials have been synthesized through sol–gel reaction using inexpensive sodium silicate as source of silica and low cost hydroxy carboxylic acid compounds as templates/pore forming agents. The material measured surface area of 1014 m²/g, pore diameter of 65 Å and pore volume of 1.4 cc/g when parameters like time and temperature of synthesis along with mole ratio of TA/SiO₂ were optimized. Here TA stands for tartaric acid. Carbonization of sucrose inside the pores of above silica material at 900 °C followed by removal of silica framework using aqueous ethanoic solution of NaOH gave rise to mesoporous carbon material. The resulting materials were characterized by N₂-sorption, FTIR spectroscopy, X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, thermal analysis and cyclic voltammetry. Three dimensional interconnecting wormhole channel arrangement of mesoporous silica template leads to mesoporous carbon replica with surface area of 1200 m²/g. X-ray photoelectron spectroscopic study (XPS) of the mesoporous carbon material shows the concentration of carbon atom in the range of 97–98% with 1–2% oxygen and negligible amount of silica. The electrochemical double layer capacitance behavior of carbon material with the specific capacitance value of 88.0 F/g at the scan rate of 1 mV/s appears to be promising.     

Influence of carbon precursor on porosity,surface composition and catalytic behaviour of CMK-3 in oxidative dehydrogenation of propane to propene

Ordered mesoporous CMK-3 carbon replicas were synthesized by infiltration of mesopores present in a SBA-15 silica template with two different carbon precursors, i.e. sucrose and poly(furfuryl alcohol). The obtained composites were carbonized under an inert gas atmosphere at 550, 650, 750 and 850?°C, and the template was etched with a HF solution. The final carbon replicas were analyzed by various physicochemical techniques, including low-temperature N₂ adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, scanning and transmission electron microscopy, and tested as catalysts in the oxidative dehydrogenation of propane (ODP) at 450?°C. Both series of materials differed strongly with respect to their porosity, but showed very similar surface composition determined by XPS. Higher porosity of CMK-3 prepared using the sucrose precursor influenced propane conversion and selectivity to propene. Furthermore, oxygen containing groups (e.g. carbonyl-type) were found to be less sensitive to the type of carbon precursor than to the ODP reaction conditions.     

In situ hydrothermally synthesized mesoporous LaCoO3/SBA-15 catalysts: High activity for the complete oxidation of toluene and ethyl acetate

Mesoporous yLaCoO₃/SBA-15 (y = 10–50 wt%) catalysts were prepared and characterized for the combustion of toluene and ethyl acetate (EA). The results show that well-ordered mesoporous LaCoO₃/SBA-15 catalysts of high surface areas (338–567 m²/g) could be fabricated by a facile in situ method of hydrothermal treatment. The particles of perovskite-type LaCoO₃ were highly dispersed on the walls of pore channels. The ordered mesoporous structure and high dispersion of LaCoO₃ are beneficial to the adsorption and activation of toluene and EA molecules. We found that in terms of specific activity, the in situ fabricated 35LaCoO₃/SBA-15 and 40LaCoO₃/SBA-15 is, respectively, superior to 35LaCoO₃/SBA-15_imp (generated by incipient wetness impregnation method) and bulk LaCoO₃ (prepared by sol–gel method) in catalytic performance. Based on the above results, we conclude that the excellent performance can be attributed to the good dispersion of highly reducible LaCoO₃ species in yLaCoO₃/SBA-15.     

Epoxidation of propene on vanadium species supported on silica supports of different structure

Silica supports such as mesoporous materials (SBA-3, SBA-15 and MCM-41), silicalite and amorphous silica were used for accommodation of vanadium species introduced on the support surface by means of impregnation, with vanadium concentration from 1 to 7 wt.%. Catalysts were characterised by means of XRD, low temperature adsorption/desorption of nitrogen, DR UV–vis and Raman spectra and also H₂-TPR measurements. Isolated vanadium species dispersed in the channels of mesoporous SBA-3 with pores diameter related to micropores range, seems to be the most active for propene epoxidation.     

Mesoporous silicas containing carboxylic acid: Preparation,thermal degradation,and catalytic performance

The calcination and thermal degradation behaviors of surfactants in mesoporous silicas SBA-15 and MCM-41 were investigated by FT-IR, ¹³C CP/MAS NMR, TG/DTA, and GPC. It was found that carboxylic acid-containing products were generated as active components in the mesopores of SBA-15 and MCM-41 from the triblock copolymer (PEO)₂₀(PPO)₇₀(PEO)₂₀ and cetyltrimethylammonium bromide (CTAB), respectively; the latter materials were used as templates. The carboxylic acid-containing mesoporous silica obtained showed a catalytic activity for hydrolysis of sucrose. The acidity was evaluated by means of NaOH titration. The acidity sensitively depended on both the calcination temperature and the atmosphere; the maximum appeared at 150 °C in air for SBA-15 where the highest activity was observed. However, the product in MCM-41 showed a lower catalytic activity than that in SBA-15. The SBA-15 product was easily leached from the mesopores of SBA-15 into the solution, but the degree of leaching for MCM-41 was considerably smaller than that for SBA-15.     

SBA-15-supported ionic liquid compounds containing silver salts: Novel mesoporous π-complexing sorbents for separating polyunsaturated fatty acid methyl esters

Novel π-complexing sorbents were prepared by covalently immobilizing ionic liquids (ILs) onto mesoporous SBA-15 using a one-pot sol–gel process followed by coating these SBA-15-supported IL compounds with silver salts. The mesoporous π-complexing sorbents were characterized by small angle X-ray scattering (SAXS), FTIR, TEM, SEM, nitrogen adsorption desorption isotherm, NMR, and nitrogen elemental analysis. Two advantages were obtained using these novel mesoporous π-complexing sorbents versus the traditional π-complexing sorbents formed by directly anchoring silver salts onto silica gel. (1) Higher extraction capacities were found. The extraction capacity for the polyunsaturated fatty acid methyl ester (PUFAME), methyl all-cis-5,8,11,14,17-eicosapentaenoate (20:5 or EPA), was 195 mg/g sorbent using the mesoporous AgBF₄/SBA-15 · IL · PF₆ sorbent. The capacity decreased to 121 mg/g sorbent with microporous complexing sorbent AgBF₄/SiO₂ · IL · PF₆. (2) Better reusability was also achieved. The supported IL phase immobilized and retained silver salt on SBA-15 due to the interaction between the ionic liquid’s imidazolium cations and silver ions. Eight successive sorption runs with the AgBF₄/SBA-15 · IL · PF₆ sorbent showed a satisfactory reusability. The traditional π-complexing sorbent has a silver salt directly anchored on silica without the supported ionic liquid phase. Higher silver leaching into organic solution occurred from the AgBF₄/SBA-15 sorbent determined by ICP-AES. The combined percentage (wt%) of the omega-3 PUFAMEs: 20:5 and methyl all-cis-4,7,10,13,16,19-docosahexaenoate (22:6 or DHA) stripped from the AgBF₄/SBA-15 · IL · PF₆ by 1-hexene was significantly enriched from 18% in the original cod liver oil to 90.5%.     

Preparation of hollow submicrocapsules with a mesoporous carbon shell

The preparation of carbon submicrocapsules with size up to 800 nm and a mesoporous shell by hard silica templating is reported. Washing and template synthesis conditions were varied to promote porosity and avoid deformation of the microcapsules. The silica template synthesis conditions analyzed were: silica nucleus formation time (0.25–6 h), octadecyltrimethoxysilane/tetraethylorthosilicate volume ratio for silica shell formation (0.2–0.6) and silica shell formation time (1–24 h). The samples were characterized by 77 K nitrogen adsorption/desorption, mercury porosimetry and electron microscopy. Under all the washing conditions tested the carbon submicrocapsules were deformed due to the large size of the hollow core and the thickness of the shell. Changes in the silica template synthesis conditions did not result in substantial improvement of the strength of the microcapsules. The synthesis of a silica template with a double shell allowed us to obtain thick shell carbon submicrocapsules without significant deflation and with higher porosity. The characterization of these microcapsules showed that they have a BET surface area of 1541 m²/g and a pore size distribution with peaks centered at 0.75, 0.86, 1.0 nm in the micropore range and 3.5 nm in the mesopore range. The pore volume in the 2–80 nm range was 1.7 cm³/g.     

Control of amine functionality distribution in polyvinylamine/SBA-15 hybrid catalysts for Knoevenagel condensation

Poly(N-vinylformamide) was deposited on the surface of highly ordered hexagonal mesoporous silica SBA-15 by in situ polymerization. Acid-catalyzed hydrolysis followed by neutralization with NaOH (pH = 7.0–10.0) allowed obtaining the poly(vinylamine)/SBA-15 hybrid materials with various distributions of N-containing species, which were determined by XPS and DRIFT spectroscopy. The changes in the form of deposited polymer as well as its interaction with the silica support were discussed. The poly(vinylamine)/SBA-15 materials were tested as catalysts of Knoevenagel condensation of benzaldehyde with ethyl cyanoacetate, ethyl acetoacetate and diethyl malonate. It was found that the sample neutralized at pH = 9.0 showed the best catalytic performance, which was attributed to a high content of accessible NH₂ groups.     

Synthesis of mesoporous materials SBA-15 and CMK-3 from fly ash and their application for CO2 adsorption

A supernatant solution of silicate species extracted from coal fly ash in a power plant by alkali fusion was used in acidic condition to prepare a mesoporous silica SBA-15. The SBA-15 was used as a template for the synthesis of a mesoporous carbon CMK-3 using sucrose as a carbon source. Characterization of the produced mesoporous materials by XRD, N₂ adsorption-desorption, SEM, and TEM confirmed the formation of well-ordered hexagonal mesostructures. Textural properties were found close to those prepared by pure chemicals. SBA-15 after polyethyleneimine impregnation and CMK-3 were tested for carbon dioxide adsorption, successfully demonstrating the possibility of recycling the industrial waste product in a power plant into a useful adsorbent.     

Colloidal templating synthesis and adsorption characteristics of microporous–mesoporous carbons from Kraft lignin

Microporous–mesoporous carbons were synthesized via colloidal silica templating using Kraft lignin as a carbon precursor, which is a waste byproduct from paper industry. A unique feature of these carbons are uniform spherical mesopores achieved after dissolving colloidal silica used as a hard template, while micropores were created by post-synthesis CO₂ activation. The resulting activated lignin-based carbons possessed high specific surface area (up to 2000 m²/g) and microporosity and mesoporosity easily tunable by adjusting activation conditions and optimizing the amount and particle size of the colloidal silica used. The total pore volumes of activated carbons obtained by using 20 and 13 nm silica colloids as a hard template exceeded 1 and 2 cm³/g, respectively.     

Sulfonic acid functionalized mesoporous SBA-15 for selective synthesis of 4-phenyl-1,3-dioxane

Mesoporous SBA-15 silica has been functionalized with propylsulfonic acid groups post-synthetically using 3-mercaptopropyltrimethoxysilane as sulfur source. The materials before and after functionalization have been characterized by BET surface area and pore size distribution by BJH method, powder X-ray diffraction and temperature programmed desorption (TPD) of NH₃. The resultant mesoporous material (solid acid catalyst) exhibited hexagonal mesoscopic ordering, which possess 1.3 meq H⁺ g⁻¹ SiO₂ exchange capacity, 96 Å mesopore size diameter, and 660 m² g⁻¹surface area. Sulfonic acid groups anchored to SBA-15 silica pore surfaces are thermally stable up to 653 K, hydrothermally robust in boiling water and resistant to leaching in organic and aqueous solvents under mild conditions. XRD results indicate that there is no change in the structure after anchoring SBA-15 with SO₃H group. SBA-15-SO₃H catalyst has been found to be highly active and selective for the Prins condensation of styrene with formaldehyde. Both the conversion of styrene and the selectivity to 4-phenyl-1,3-dioxane are nearly 100%. Presence of more number of acid sites in SBA-15-SO₃H catalyst helps in achieving high yields. Furthermore, the conversion and the selectivity to 4-phenyl-1,3-dioxane are found to be consistent in four repeated cycles.     

Effects of Fe addition on the structure and catalytic performance of mesoporous Mn/Al–SBA-15 catalysts for the reduction of NO with ammonia

Mesoporous Al–SBA-15 has been synthesized by a hydrothermal method and used as a support for Mn/Al–SBA-15, Fe/Al–SBA-15, and Mn–Fe/Al–SBA-15 catalysts. XRD, N₂ sorption, XPS, H₂-TPR and activity tests have been used to assess the properties of catalysts. The Mn–Fe/Al–SBA-15 catalyst exhibited a higher SCR activity than Mn/Al–SBA-15 or Fe/Al–SBA-15 due to a synergistic effect between Mn and Fe. After the addition of Fe, the binding energy of Mn 2p_3/2 on Mn–Fe/Al–SBA-15(573) decreased by about 0.4 eV and the Mn^4 +/Mn^3 + ratio decreased to 1.10. The appropriate Mn^4 +/Mn^3 + ratio may have a great effect on the reduction of NO over Mn–Fe/Al–SBA-15(573) catalyst.     

Novel low-κ polyimide/mesoporous silica composite films: Preparation,microstructure, and properties

A series of novel low-dielectric constant (low-κ) polyimide (PI) composite films containing the SBA-15 or the SBA-16-type mesoporous silica were successfully prepared via in situ polymerization and following thermal imidization. Their morphologies, dielectric constants, and thermal and dynamic mechanical properties were investigated. It is found that the dielectric constants of the composite films can be reduced from 3.34 of the pure PI to 2.73 and 2.61 by incorporating 3 wt% SBA-15 and 7 wt% SBA-16, respectively. The reduction of the dielectric constant is attributed to the incorporation of the air voids (κ = 1) stored within the mesoporous silica materials, the air volume existing in the gaps on the interfaces between the mesoporous silica and the PI matrix, and the free volume created by introducing large-sized domains. The PI/mesoporous silica composite films prepared in this study also present stable dielectric constants across the wide frequency range and a good phase interconnection. The improvement of the thermal stability and dynamic mechanical properties of the PI film is achieved by incorporation of the mesoporous silica materials. The enhanced interfacial interaction between the surface-treated mesoporous silica and the PI matrix has led to the minimization of the deterioration of the mechanical properties. The incorporation of the mesoporous silica materials is a promising approach to prepare the low-κ PI films.     

Composites of V2O3–ordered mesoporous carbon as anode materials for lithium-ion batteries

The composites of V₂O₃–ordered mesoporous carbon (V₂O₃–OMC) were synthesized and used as anode materials for Li-ion intercalation. These materials exhibited large reversible capacity, high rate performance and excellent cycling stability. For instance, a reversible capacity of V₂O₃–OMC composites was 536 mA h g⁻¹ after 180 cycles at a current density of 0.1 A g⁻¹. The high electrochemical performance of the V₂O₃–OMC composites is attributed to the anchoring of nanoparticles on mesoporous carbon for improving the electrochemical active of V₂O₃ particles for energy storage applications in high performance lithium-ion batteries.     

Production of high-quality biodiesel fuels from various vegetable oils over Ti-incorporated SBA-15 mesoporous silica

Ti-incorporated SBA-15 mesoporous silica (shortly termed Ti-SBA-15) was a highly efficient and recyclable solid acid to synthesize high-quality biodiesel fuel (BDF) derived from various vegetable oils at moderate reaction condition, in comparison to siliceous SBA-15 and commercial TiO₂ catalysts with different anatase sizes, where the catalytically active sites mainly related to the tetrahedral-coordinated Ti(IV) species with weak Lewis acid nature. The TOF values of Ti-SBA-15 catalysts were around 18–166 h^− 1, an order of magnitude larger than those of commercial TiO₂ catalysts. A high-quality BDF containing more than 98.4 mass% of fatty acid methyl ester (FAME), which met with international fuel standard, was obtained over 3Ti-SBA-15 catalyst at 200 °C using a methanol/oil ratio of 108. Most importantly, the 3Ti-SBA-15 catalyst showed extremely high water and free fatty acid (FFA) tolerance levels, which were several ten times better than homogeneous and heterogeneous catalysts in conventional BDF production technology.     

Hollow micro-mesoporous carbon polyhedra produced by selective removal of skeletal scaffolds

An approach has been demonstrated for fabricating hollow micro-mesoporous carbon polyhedra by selective removal of the skeletal scaffolds of polyurethane (PU) foam in monolithic mesostructured resin/PU composites. Hollow micro-mesoporous carbon polyhedra with an irregular shape molded from the cellular cavities of PU foam were synthesized by using phenolic resol as a precursor, triblock copolymer Pluronic F127 as a template, PU foam as a skeletal scaffold and triethyl phosphate as a reaction agent. By a reaction with triethyl phosphate, the PU foam in resin/PU composites can be degraded, simultaneously leading to the disassembly of the monolithic structure into separated polyhedral particles. The method can also be used for synthesizing hollow micro-mesoporous carbon–silica polyhedra, using tetraethyl orthosilicate as a silica source. Moreover, after etching the silica away, hollow micro-mesoporous carbon polyhedra with an ordered hexagonal mesostructure (space group p6mm), large particle sizes of 65–500 μm, a large surface area of 1384 m² g^?1, a uniform pore size of 3.2 nm and a high pore volume of 1.15 cm³ g^?1 as well as a high mesoporosity of 81% can be obtained, which exhibits excellent adsorption performance toward methylene blue compared with the active carbon having a similar surface area.     

Highly mesoporous LaNiO3/NiO composite with high specific surface area as a battery-type electrode

This study reports the fabrication and characterization of mesoporous LaNiO₃/NiO composite with a very high specific surface area for a battery-type electrode. The mesoporous LaNiO₃/NiO composite was synthesized via a sol–gel method by using silica gel as a template, the colloidal silica gel was obtained by the hydrolysis and polymerization of tetraethoxysilane in the presence of La and Ni salts. We investigated the structure and the electrochemical properties of mesoporous LaNiO₃/NiO composite in detail. The mesoporous composite sample showed a specific surface area of 372 m² g⁻¹ with 92.7% mesoporous area and displayed remarkable electrochemical performance as a battery-type electrode material for supercapacitor. The specific capacity values were found to be 237.2 mAh g⁻¹ at a current density of 1 A g⁻¹ and 128.6 mAh g⁻¹ at a high current density of 20 A g⁻¹ in 1 M KOH aqueous electrolyte. More importantly, this mesoporous composite also showed an excellent cycling performance with the retention of 92.6% specific capacitance after 60,000 charging and discharging cycles.