Synthesis of polyaniline/mesoporous carbon nanocomposites and their application for CO<Subscript>2</Subscript> sorption

Ordered mesoporous carbons (OMC), were synthesized by nanocasting using ordered mesoporous silica as hard templates. Ordered mesoporous carbons CMK-1 and CMK-3 were prepared from MCM-48 and SBA-15 materials with pore diameters of 3.4 nm and 4.2 nm, respectively. Mesoporous carbons can be effectively modified for CO₂ adsorption with amine functional groups due to their high affinity for CO₂. Polyaniline (PANI)/mesoporous carbon nanocomposites were synthesized from in-situ polymerization by dissolving OMC in aniline monomer. The polymerization of aniline molecules inside the mesochannels of mesoporous carbons has been performed by ammonium persulfate. The nanocomposition, morphology, and structure of the nanocomposite were investigated by nitrogen adsorption-desorption isotherms, Fourier Transform Infrared (FT–IR), X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) and thermo gravimetric analysis (TGA). CO₂ uptake capacity of the mesoporous carbon materials was obtained by a gravimetric adsorption apparatus for the pressure range from 1 to 5 bar and in the temperature range of 298 to 348 K. CMK-3/PANI exhibited higher CO₂ capture capacity than CMK-1/PANI owing to its larger pore size that accommodates more amine groups inside the pore structure, and the mesoporosity also can facilitate dispersion of PANI molecules inside the pore channels. Moreover, the mechanism of CO₂ adsorption involving amine groups is investigated. The results show that at elevated temperature, PANI/mesoporous carbon nanocomposites have a negligible CO₂ adsorption capacity due to weak chemical interactions with the carbon nanocomposite surface.     

Synthesis of chloropropylamine grafted mesoporous MCM-41, MCM-48 and SBA-15 from rice husk ash: their application to CO<Subscript>2</Subscript> chemisorption

Mesoporous siliceous MCM-41, MCM-48 and SBA-15 were synthesized using Rice Husk Ash (RHA) as the silica source. Their defective –OH sites were then grafted with 3-chloropropyl amine hydrochloride (3-CPA) and characterized by X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and BET techniques. Those results portrayed their resemblance with that synthesized from conventional silica sources. 3-CPA grafted mesoporous silicas were tested for CO₂ chemisorption over fixed bed reactor at different temperatures. The maximum adsorption of 1.7 mmol/g of CO₂ was observed on 3-CPA grafted SBA-15 (SBA-15/CPA) at 25°C. The chemisorbed CO₂ on amine grafted mesoporous silica was stabilized by weak hydrogen bonds formed during the nucleophilic attack between lone pair of electrons in amine groups and quadrupolar CO₂ with more degree of positive charge to form carbamates. The rapid steep slope which arises due to CO₂ adsorption illustrated a minimal mass transfer effect and extreme fast kinetics. Performance tests such as reproducibility, stability and selectivity towards CO₂ adsorption were also carried out over 3-CPA grafted mesoporous silica and the results were in line with that of well established CO₂ sorbent.     

Phase transition of mesoporous SiO<Subscript>2</Subscript> impregnated with an organic templating agent by post-synthetic microwave heating

Mesoporous silica SBA-15 samples were subjected to microwave heating for 10–40 min at 393 and 443 K after dry-impregnation with TPAOH (tetrapropylammonium hydroxide) to prepare a mesoporous material with zeolytically ordered pore walls. Physicochemical properties of the materials prepared were characterized by XRD, N₂ adsorption at 77 K, SEM, TEM, UV–vis and FT-IR spectroscopies. These investigations revealed that selective transformation of amorphous pore walls of SBA-15 to crystalline zeolytic phase is difficult to be achieved and a mixed phase of mesoporous silica/zeolite composite material was obtained, instead. Microwave heating time, temperature, TPAOH concentration, and hydrothermal stability of the mesoporous host materials tested (MCM-41, HMS, and SBA-15) were important factors to maintain the mesopore structure of the host materials during the post-synthetic microwave heating treatment.     

Highly ordered mesoporous CoFe<Subscript>2</Subscript>O<Subscript>4</Subscript> and CuFe<Subscript>2</Subscript>O<Subscript>4</Subscript> with crystalline walls

The highly ordered mesoporous CoFe₂O₄ and CuFe₂O₄ with crystalline walls can be synthesized by hard template with using mesoporous silica SBA-15 as hard template and using ferric nitrate, cobalt nitrate, and copper nitrate as metal precursors. These new mesoporous materials above have high surface areas, narrow pore size distribution, and large pore volumes, which are believed to be valuable for the potential application in the field of sensors, catalysis, message recording, magnetics, and biology. This work provides a method to fabricate the highly ordered mesoporous materials composed of multi-metal oxides with crystalline walls. The development of such versatile approach is of great significance in practical application. It can be envisaged that this established method is significantly expandable to the controlled synthesis of the mesoporous functional materials with diverse compositions.     

Development of silica‐gel‐supported polyethylenimine sorbents for CO2 capture from flue gas

In order to reduce the sorbent preparation cost and improve its volume‐based sorption capacity, the use of an inexpensive and commercially available silica gel was explored as a support to prepare a solid polyethylenimine sorbent (PEI/SG) for CO₂ capture from flue gas. The effects of the pore volume and particle size of the silica gels, molecular weight of polyethylenimine and amount of polyethylenimine loaded, sorption temperature and moisture in the flue gas on the CO₂ sorption capacity of PEI/SG were examined. The sorption performance of the developed PEI/SG was evaluated by using a thermogravimetric analyzer and a fixed‐bed flow sorption system in comparison with the SBA‐15‐supported polyethylenimine sorbent (PEI/SBA‐15). The best PEI/SG sorbent showed a mass‐based CO₂ sorption capacity of 138 mg‐CO₂/g‐sorbent, which is almost the same as that of PEI/SBA‐15. In addition, the PEI/SG gave a high volume‐based sorption capacity of 83 mg‐CO₂/cm³‐sorbent, which is higher than that of PEI/SBA‐15 by a factor of 2.6. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2495–2502, 2012     

Simplified synthesis of K<Subscript>2</Subscript>CO<Subscript>3</Subscript>-promoted hydrotalcite based on hydroxide-form precursors: Effect of Mg/Al/K<Subscript>2</Subscript>CO<Subscript>3</Subscript> ratio on high-temperature CO<Subscript>2</Subscript> sorption capacity

Hydrotalcite was synthesized from hydroxide-form precursors to prepare a novel high-temperature CO₂ sorbent, and the effect of Mg/Al ratio on CO₂ sorption was studied. To enhance the CO₂ sorption capacity of the sorbent, K₂CO₃ was coprecipitated during the synthetic reaction. X-ray diffraction analysis indicated that the prepared samples had a well-defined crystalline hydrotalcite structure, and confirmed that K₂CO₃ was successfully coprecipitated in the samples. The morphology of the hydrotalcite was confirmed by scanning electron microscopy, and N₂ adsorption analysis was used to estimate its surface area and pore volume. In addition, thermogravimetric analysis was used to measure its CO₂ sorption capacity, and the results revealed that the Mg: Al: K₂CO₃ ratio used in the preparation has an optimum value for maximum CO₂ sorption capacity.     

Amine modified mesocellular siliceous foam (MCF) as a sorbent for CO2

Adsorption is considered a promising method for carbon capture. CO₂ adsorbents take a variety of forms - but one approach is to fill mesoporous substrates with a polymeric CO₂ selective sorbent. SBA-15 and mesocellular siliceous foam (MCF) are high pore volume, high surface area ordered mesoporous materials for which modification with amine should result in high capacity, highly selective adsorbents. SBA-15 and MCF were separately loaded with approximately one pore volume equivalent of linear polyethyleneimine (PEI) (M_w = 2500) or branched PEI (M_n = 1200). CO₂ adsorption/desorption isotherms under dry CO₂ were obtained at 75, 105 and 115 °C. The CO₂ adsorption/desorption kinetics were improved with temperature, though the CO₂ capacities generally decreased. The adsorption capacity for MCF loaded with branched PEI at 105 and 115 °C were 151 and 133 mg/g adsorbent, respectively (in 50% CO₂/Ar, 20 min adsorption time). These are significantly higher than the adsorption capacity observed for SBA-15 loaded with branched PEI under same conditions, which were 107 and 83 mg/g adsorbent, respectively. Thus the results indicate that, on a unit mass basis, amine modified MCF's are potentially better adsorbents than amine modified SBA-15 for CO₂ capture at modestly elevated temperature in a vacuum swing adsorption process.     

Mixed-amine Modified SBA-15 as Novel Adsorbent of CO2 Separation for Biogas Upgrading

A novel adsorbent of CO₂ from biogas was prepared by synthesizing and modifying the mesoporous molecular silica of SBA-15 with methyl-diethyl-amine (MDEA) and piperazine (PZ). The adsorbent showed good performance in separating CO₂ from biogas. The loaded amines did not change the ordered structure of SBA-15, but enhanced its adsorption of CO₂. The adsorbents were characterized by X-ray powder diffraction (XRD) and N₂ adsorption/desorption. With the increase in MDEA loading, the surface area, pore size, and pore volume of the MDEA-loaded SBA-15 decreased. The modification of amines enlarged the difference between the equilibrium adsorption of CO₂ and CH₄. Quantitatively evaluated on the basis of the breakthrough curves, the separation factors between CO₂ and CH₄, was increased more than seven fold due to the MDEA modification. With mixed-amine (MDEA + PZ) modification, the separation factors between CO₂ and CH₄ was further improved. In addition, not only the adsorbent was regenerable by purging with the purified gas, but also the adsorption performance is stable in adsorption cycles. Effect of moisture on adsorption of CO₂ is investigated and the results show the increase in the adsorption performance.     

Synthesis of Ni(II)-3,5-dichloro-2-hydroxybenzenesulfonyl chloride supported SBA-15 and its application as a nanoreactor catalyst for the synthesis of diaryl sulfides via reaction of aryl halides with thiourea or S<Subscript>8</Subscript>

In the present work, SBA-15 mesoporous grafted with 3-(trimethoxysilyl)-1-propanethiol as a linker and subsequently reacted by 3, 5-dichloro-2-hydroxybenzenesulfonyl chloride. Then to obtain the new catalyst Ni(II) was supported on functionalized SBA-15 by using Ni(NO₃)₂ as Ni(II) source. The Ni/SBA-15 catalyst was characterized with SEM, EDS, ICP, XRD, TGA, FT-IR and N₂ sorption–desorption analysis. The key advantages of this heterogeneous catalyst are inexpensive, short reaction times, excellent yields, recovery and reusability.     

Characterization of Pt/SBA-15 prepared by the deposition–precipitation method

Mesoporous silica SBA-15 was prepared and loaded with Pt using the deposition–precipitation method (DP). The Pt loaded material was characterized by N₂ sorption, and X-ray diffraction (XRD) at low scattering angles as well as XRD at wide angles, in order to monitor the impact of the metal deposition pathway on the mesoporous texture. After DP the material contains ordered mesoporous silica as well as a fraction appearing as non-ordered amorphous silica. This is most likely caused by the hydrothermal treatment involved in the DP. The material was also characterized using NIR and ²⁹Si MAS NMR spectroscopy. The NIR results of the calcined materials indicate that the silanol groups of SBA-15 may act as anchoring groups for the metallic Pt particles. The NMR spectroscopy data shows that the Pt/SBA-15 sample prepared by the DP method posseses a better short-range regularity of SBA-15 walls as compared to the parent SBA-15. This is suggested to be caused by dissolution and possible re-precipitation of siliceous species.     

Desulfurization of fuels by means of a nanoporous carbon adsorbent

Mesoporous carbon, CMK-3, was prepared using hexagonal Al-SBA-15 mesoporous silica, instead of SBA-15, as a template. The synthesized materials were examined via X-ray diffraction and N₂-adsorption. The mesoporous carbon was studied for its adsorption of dibenzothiophene (DBT) from petroleum fuels. The performance of this adsorbent was compared with SBA-15 and Al-SBA-15, through which CMK-3 showed higher sulfur adsorption capabilities due to a larger mesopore volume and a higher specific surface area. The uptake capacity for DBT followed the order CMK-3 > Al-SBA-15 > SBA-15. The results confirmed the importance of the adsorbent pore size and its surface chemistry for the adsorption of DBT from liquid phase.Langmuir and Freundlich isotherm models were used to fit equilibrium data for CMK-3. The equilibrium data were best represented by the Langmuir isotherm. Kinetic studies were carried out and showed the sorption kinetics of dibenzothiophene was best described by a pseudo-second-order kinetic model.     

Morphological control of mesoporous silica SBA-15 synthesized at low temperature without additives

Fiber-like or rod-like mesoporous SBA-15 silicas with different lengths and diameter of macrostructures and pore diameter could be synthesized by the self-assembly of silica-surfactant (commonly used Pluronic P123 (EO₂₀-PO₇₀EO₂₀) as a structure-directing agent) through careful control of the synthetic temperature and stirring time without any additives. X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM), and nitrogen adsorption–desorption isotherms are used to characterize these mesoporous silica materials. Compared with those reports on conventional SBA-15, our work is focused on one-step synthesis and the morphological control of ordered mesoporous silica synthesized at low temperature under low concentration of P123 (0.67 wt%) without the addition of inorganic salts, where pre-hydrolyzed silica species may favor the self-assembly of silica-polymer hybrid micelles. Moreover, the pore diameter of fiber-like SBA-15 synthesized at 40 °C is slightly smaller than that of conventional SBA-15, revealing that the average micellar radius of P123 micelles in this low concentration of P123 solution was almost same as that for the conventional synthesis of SBA-15.     

Functionalized Mesoporous SBA-15 with CeF<Subscript>3</Subscript>: Eu<Superscript>3+</Superscript> Nanoparticle by Three Different Methods: Synthesis,Characterization, and Photoluminescence

Luminescence functionalization of the ordered mesoporous SBA-15 silica is realized by depositing a CeF₃: Eu³⁺ phosphor layer on its surface (denoted as CeF₃: Eu³⁺/SBA-15/IS, CeF₃: Eu³⁺/SBA-15/SI and CeF₃: Eu³⁺/SBA-15/SS) using three different methods, which are reaction in situ (I-S), solution impregnation (S-I) and solid phase grinding synthesis (S-S), respectively. The structure, morphology, porosity, and optical properties of the materials are well characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, N₂ adsorption, and photoluminescence spectra. These materials all have high surface area, uniformity in the mesostructure and crystallinity. As expected, the pore volume, surface area, and pore size of SBA-15 decrease in sequence after deposition of the CeF₃: Eu³⁺ nanophosphors. Furthermore, the efficient energy transfer in mesoporous material mainly occurs between the Ce³⁺ and the central Eu³⁺ ion. They show the characteristic emission of Ce³⁺ 5d → 4f (200–320 nm) and Eu^{3+ 5}D₀ → ⁷F _J (J = 1–4, with ⁵D₀ → ⁷F₁ orange emission at 588 nm as the strongest one) transitions, respectively. In addition, for comparison, the mesoporous material CeF₃: Eu³⁺/SBA-15/SS exhibits the characteristic emission of Eu³⁺ ion under UV irradiation with higher luminescence intensity than the other materials.     

Simultaneous control of rod length and pore diameter of SBA-15 for PPL loading

Mesoporous silica materials are attractive materials for immobilizing enzymes because of their well-ordered structures, large surface area are pore volume. Diffusion of large enzyme molecules such as porcine pancreatic lipase (PPL) through the lengthy channels of MPS takes place too slowly. Therefore, the squat of the enzyme at the pore mouth entrance, actually makes the rest of the channel useless. In this study, to overcome this problem, synthesis parameters of SBA-15 were changed, since along with pore diameter increasing, the mesochannel length becomes shorter. The main point to obtain a well-ordered 2D hexagonal pore structure was the pre-hydrolysis of tetraethyl orthosilicate (TEOS) before the addition of 1,3,5-trimethyl benzene as a micelle swelling agent. Due to the strong effect of zirconium in changing the morphology of SBA-15 particles, we modified SBA-15 in the presence of a small amount of ZrOCl₂ in the synthesis solution under acidic conditions. As a result, mesochannel length of SBA-15-Zr was shortened from 600 to <200 nm. The morphology of mesoporous silica was also changed from rod-like to platelet, because of the accelerating effect of Zr(IV) on the self-assembly rate of P123 and TEOS condensation. Characteristic results conducted by low angle XRD, high resolution transmission electron microscopy and nitrogen adsorption, confirmed tuning effect of Zr(IV) in SBA-15. Furthermore, it was shown that the number of pore entrances increases with decreasing the length of SBA-15 mesochannels, leading to obvious improvement of enzyme uptake. PPL has been successfully immobilized in the mesoporous channels of SBA-15-Zr. The total amount of lipase adsorbed on the mesoporous SBA-15-Zr was measured by thermal gravimetric analysis. The largest PPL adsorption capacity was 784 mg/g belonging to the SBA-15-Zr with the length of 150 nm and the mean pore size diameter of 9.22 nm.     

Mesoporous-molecular-sieve-supported Polymer Sorbents for Removing H2S from Hydrogen Gas Streams

A series of sorbents with a linear polyethylenimine (PEI) supported on the mesoporous molecular sieves, including MCM-41, MCM-48 and SBA-15, have been prepared and used to remove H₂S from a model gas containing 0.40 v% of H₂S and 20 v% H₂ in N₂ gas. The sorption was conducted in a fixed-bed system at a temperature range of 22–75 °C, a GHSV range of 337–1,011 h^?1 and atmospheric pressure. The effects of the operating temperature, GHSV, the amount of PEI loading and the different molecular sieve supports were studied. A reduction in the temperature and GHSV improves the sorption performance of the supported PEI sorbents. A synergetic effect of the SBA?15 support and PEI on the H₂S sorption performance was observed. Loading 50 wt% PEI on SBA-15 gave the best breakthrough capacity, while loading 65 wt% PEI on SBA-15 had the highest saturation capacity. The mesoporous molecular sieve with large pore size and three-dimensional channel structure favors increasing the kinetic capacity of the supported PEI sorbent. In addition, the developed sorbents can be regenerated easily at mild conditions (temperature range of 75–100 °C) and have excellent regenerability and stability. The results indicate that the mesoporous-molecular-sieve-supported polymer sorbents are promising for removing H₂S from hydrogen gas streams.     

Direct synthesis of nano titania on highly-ordered mesoporous SBA-15 framework for enhancing adsorption and photocatalytic activity

This paper reports the synthesis of TiO₂-containing mesoporous catalysts for effectively enhancing the adsorption and photocatalytic activity. The factors that affect the photocatalytic activity of catalyst composites, including types of silica support, TiO₂ content, calcination temperature, and catalyst mass, were examined in this study. The samples were characterized by X-ray diffraction, field-emission scanning electron microscopy, transmission electron microscopy, thermogravimetric analysis, and surface area analysis. The experimental results showed that incorporating TiO₂ nanoparticles into silica gel or SBA-15 frameworks could enhance the photodegradation rate more effectively than pure TiO₂. The TiO₂/SBA-15 sample displayed much higher adsorption and photocatalytic activity levels than did TiO₂/silica-gel. The pore volume and pore size of TiO₂/SBA-15 were as high as 1.317 cm³/g and 7.51 nm, respectively, which exceeded those of TiO₂/silica-gel (0.437 cm³/g and 3.68 nm, respectively). The rate constants of photocatalysis were determined. The photodegradation rate of the catalyst increased with decreasing TiO₂ content and increasing calcination temperature. The proposed method of preparing mesoporous photocatalysts is simple and suitable for mass production.     

Selective removal of sulfur compounds in city-gas by adsorbents

Silver nitrate impregnated on beta zeolite (BEA), mesoporous silica MCM-41 and SBA-15 (AgNO₃/BEA, AgNO₃/MCM-41, AgNO₃/SBA-15) were prepared to remove sulfur compounds selectively in city-gas, which contains tetrahydrothiophene and tert-butylmercaptane. Sulfur adsorption capacity was determined when the sulfur concentration of effluent gas in breakthrough test reached 0.1 ppm, which is acceptable sulfur concentration for hydrogen production in a reformer for fuel cells. As the AgNO₃ concentration in AgNO₃/BEA, AgNO₃/MCM-41, and AgNO₃/SBA-15 increased, their sulfur adsorption capacities also increased. Although microporous zeolite BEA has smaller pore volume and lower surface area than those of mesoporous silica MCM-41 and SBA-15, the sulfur adsorption capacity of AgNO₃/BEA was higher than those of AgNO₃/MCM-41 and AgNO₃/SBA-15. Adsorbed sulfur molecules per impregnated silver nitrate and the shape change of breakthrough curves depending on the adsorption temperature showed that not only chemisorption but also physisorption was involved in sulfur compounds adsorption on AgNO₃ impregnated adsorbent. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Synthesis,analysis and characterization of ordered mesoporous TiO2/SBA-15 matrix: Effect of calcination temperature

Mesoporous TiO₂/SBA-15 matrix was prepared by the sol–gel synthesis of TiO₂ in previously prepared SBA-15 particles. Nonionic surfactant was used as liquid template and Na₂SiO₄ as SiO₂ precursor for the synthesis of mesoporous silica SBA-15 with high specific surface area. Different calcination temperature was used for the synthesis and analysis of TiO₂/SBA-15 matrix. The synthesized titania/silica composites were characterized by X-ray diffraction, FTIR, TEM, UV–vis spectroscopy, etc. TEM micrographs showed titania is successfully embedded in SBA-15 channel. Different calcination temperature indicates different size of particle formation and different photocatalytic properties. The activity test indicated that TiO₂/SBA-15 composite prepared by this method had better photocatalytic performance than pure TiO₂. The preparation method and the textural characteristics of mesoporous materials have great influence for the photocatalytic activity.     

Influence of Drying Conditions on Amine-Functionalized SBA-15 as Adsorbent of CO2

Adsorption of pure CO₂ on amine-functionalized SBA-15 mesoporous silica materials has been studied. Adsorbent materials were prepared by grafting the silica surface with aminopropyl (AP), ethylene-diamine (ED) and diethylene-triamine (DT) organosilane molecules. Materials so obtained were dried under air atmosphere at 110 °C and at room temperature. CO₂ adsorption isotherms were carried out at 45 °C, showing that grafted materials are very efficient for CO₂ removal at atmospheric pressure when samples are dried at 20 º C. However, when the drying step is carried out at 110 °C in air, CO₂ adsorption capacity is low. DRIFTS analysis has shown that amino groups can undergo oxidation to oxime or imine species during drying. Adsorption capacity of the materials was found to be unchanged after some consecutive adsorption?Cdesorption cycles, being the regeneration step performed at 110 °C under vacuum.     

Comparison of amine-functionalized mesoporous silica particles for ibuprofen delivery

We have prepared three different types of amine-functionalized silica particles: i) mesoporous silica (MESO1); ii) nonporous core-mesoporous shell silica (MESO2); iii) SBA-15 particles. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and nitrogen sorption experiment were used to study the morphology of the synthesized particles. To investigate the drug loading and subsequent release of the particles, ibuprofen was used as a model drug for oral delivery. Loading capacity of the particles in this work was found to be higher than that in the previous studies, and followed the order of MESO1>MESO2>SBA-15 particles. Release experiments showed the similar release rate for MESO1 and MESO2 particles from which only <40% of ibuprofen was released after 5 h. From SBA-15 particles, however, more than 80% of ibuprofen was released in 5 h at pH 4 and 7.4. Ibuprofen release from SBA-15 was slowest at pH 2 (～pH of stomach body) and fastest at pH 7.4 (～pH of proximal intestine). Difference in release rates was ascribed to the different morphology and pore structure of the carrier particles.