Adsorption of l-histidine over mesoporous carbon molecular sieves

Mesoporous carbon, CMK-3, was prepared by large pore hexagonal mesoporous silica SBA-15. The structural order and textural properties of all the materials were studied by XRD, HRTEM, and nitrogen adsorption. Adsorption of l-histidine (His) over various porous adsorbents such as CMK-3, SBA-15, and activated carbon was studied from solutions with different pH. His adsorption was observed to be pH dependent with maximum adsorption near the isoelectric point of the amino acid. CMK-3 showed a larger amount of His adsorption as compared to SBA-15 and the conventional adsorbent, namely activated carbon. CMK-3 registers the total adsorption capacity of ca. 1350 μmol g⁻¹ which is ca. 12 times higher than the adsorption capacity of SBA-15. This large difference could be mainly due to the stronger hydrophobic interaction between the non-polar side chains of amino acids and the hydrophobic surface of the mesoporous carbon as compared to mesoporous silica. The influence of ionic strengths on the adsorption of His was also studied and the results are discussed. Nitrogen adsorption of CMK-3 after His adsorption confirmed that His molecules are tightly packed inside the mesopores.     

A simplified route to the synthesis of CMK-3 replica based on precipitation polycondensation of furfuryl alcohol in SBA-15 pore system

A novel method of synthesis of mesoporous, polymer-derived CMK-3 carbon replica was proposed. Instead of a multi-stage, time-consuming and toxic solvent involving procedure, the direct, acid-catalyzed precipitation polycondensation of furfuryl alcohol to poly(furfuryl alcohol) (PFA), as the carbon precursor, in the pore system of SBA-15 silica was used. The optimal PFA/SBA-15 mass ratio resulting in the complete pore filling was found. The final carbon material was obtained by carbonization of the formed composite and subsequent removal of silica by treatment with HF. Low-temperature sorption of nitrogen, powder X-ray diffraction and transmission electron microscopy confirmed the formation of well-ordered, hexagonal carbon mesostructure. The produced CMK-3 exhibited the presence of oxygen-containing surface groups, recognized as mainly carbonyl and carboxyl species by X-ray photoelectron spectroscopy and temperature-programmed desorption. The presence ofthese groups caused the mesoporous carbon to be catalytically active in the oxidative dehydrogenation of ethylbenzene to styrene.     

Effect of Filler Treatment on the Release Properties of Coating on Urea Granules

Polyurethane composite coatings on urea granules were prepared by SBA-15 mesoporous silica (in as-synthesized and calcined forms) as a pseudo-crosslinker without any other chain extenders. The calcination of mesoporous silica leaded to reduction of hydroxyl groups and increase of mesopores. The composite coating containing calcined SBA-15 showed enhanced controlled release properties compared with the other two coatings. At the loading content of 1 wt%, the initial release rate and release duration of urea coated by polyurethane/calcined SBA-15 composite were 0.08% and 83 d, respectively. It is shown that the calcination played an important role in controlling the properties of composite coating.     

An overview of ordered mesoporous material SBA-15: synthesis,functionalization and application in oxidation reactions

Ordered mesoporous materials are attracting wide concern because of their applications in the field of catalysis, adsorption, separations, drug delivery systems and gas sensors owing of their extremely high surface area combined with well-defined pore structures with narrow pore size distributions. Various mesoporous materials such as MCM-41, MCM-48, SBA-15 and SBA-16 have been reported in past two decades. Synthesis of mesoporous materials involves the concept of aggregation of surfactants as structure directing agents under acidic or basic conditions. The dimensions of these mesopores can be obtained by type of surfactant, auxiliary chemicals and synthesis conditions. At present, SBA-15 has attracted more attention among different mesoporous silica structures due to their desirable properties such as thick pore wall and hexagonal mesopores (4–12 nm), high surface area, ease of synthesis and functionalization and high thermal and mechanical stability. In last few years, great effort has been made on the development of various methods for the synthesis of mesoporous materials as support for oxidation reactions. The aim of this review article is to focus mainly on mesoporous SBA-15 together with its application as support for various oxidation reactions.     

α-Amylase immobilization capacities of mesoporous silicas with different morphologies and surface properties

α-Amylase was encapsulated in several mesoporous materials (folded sheet mesoporous silica (FSM), cubic mesoporous silica (KIT-6), and two-dimensional hexagonal mesoporous silica (SBA-15)) that differed morphologically in terms of particle shape, pore size, and pore structure. The encapsulation capacity and thermal stability of encapsulated α-amylase were examined. The amount of α-amylase encapsulated increased with increasing pore size in the following order: SBA-15 < KIT-6 < FSM. Nitrogen adsorption experiments were performed before and after α-amylase encapsulation in mesoporous silicas with pore sizes larger than the size of α-amylase, confirming that α-amylase was encapsulated in the pores. Among mesoporous silicas with similar pore sizes, FSM was found to have the highest capacity for α-amylase encapsulation both per weight and per surface area of silica. Furthermore, α-amylase encapsulated in FSM demonstrated high thermal stability at 90 °C relative to the thermal stability of free α-amylase or free α-amylase encapsulated in other mesoporous silicas. Zeta potential measurements showed that the FSM surface had an isoelectric point that was lower than that of other mesoporous silicas, and hydrophilicity measurements showed that its surface was more hydrophilic. The surface properties of FSM contributed to the high thermal stability of the α-amylase encapsulated within the pores.     

调控表面活性剂浓度制备单分散SBA-15介孔材料

采用溶胶-凝胶水热法,调控反应参数和反应工艺制备SBA-15介孔材料。通过扫描电镜、透射电镜、X射线衍射以及氮气吸附-脱附分析表征表明,在一定范围,随着表面活性剂浓度增加,介孔材料SBA-15形貌出现由球形、陀螺形到米粒状的变化,介观有序度提高。在反应物料P123与Si物质的量比为0.012时,介孔材料的物性常数如晶面间距、比表面积、孔体积和最可几孔径较小。采用静态陈化-水热法研究不同表面活性剂浓度对介孔材料形貌演变的影响,为有效调控SBA-15介孔材料形貌提供必要依据。     

Controlling the textural parameters of mesoporous carbon materials

The mesoporous carbon materials prepared by inorganic templating technique using mesoporous silica, SBA-15 as a template and sucrose as a carbon source, have been systematically investigated as a function of sucrose to mesoporous silica composition, with a special focus on controlling the mesoporous structure, surface morphology and the textural parameters such as specific surface area, specific pore volume and pore size distribution. All the materials have been unambiguously characterized by XRD, N₂ adsorption–desorption isotherms, high-resolution transmission electron microscopy, high-resolution field emission scanning electron microscopy, and Raman spectroscopy. It has been found that the porous structure, morphology and the textural parameters of the mesoporous carbons materials, CMK-3-x where x represent the sucrose to silica weight ratio, can be easily controlled by the simple adjustment of concentration of sucrose molecules. It has also been found that the specific surface area of the mesoporous carbon materials systematically increases with decreasing the sucrose to silica weight ratio. Moreover, the specific pore volume of the materials increases from 0.57 to 1.31 cm³/g with decreasing the sucrose to silica weight ratio from 5 to 1.25 and then decreases to 1.23 cm³/g for CMK-3-0.8. HRTEM and HR-FESEM also show a highly ordered pore structure and better surface morphology for CMK-3-1.25 as compared to other materials prepared in this study. Thus, it can be concluded that the sucrose to silica weight ratio of 1.25 is the best condition to prepare well ordered mesoporous carbon materials with good textural parameters, pore structure and narrow pore size distribution.     

A biomimetic mesoporous silica–polymer composite scaffold for bone tissue engineering

A biomimetic organic–inorganic composite system comprising of microspheres fabricated from combination of a biodegradable polymer poly(lactide-co-glycolide) (PLGA) and bioactive mesoporous silica (SBA-15) has been developed through sintering technique for bone regeneration applications. The morphological and structural properties of the SBA-15/PLGA composite scaffold were evaluated using electron microscopy and fourier transform infrared spectroscopy and the results showed spherical morphology and composite nature. The presence of mesopores in the silica was confirmed through nitrogen adsorption–desorption isotherms. The surface area and pore size of mesoporous silica were found to be 792 m² g^?1 and 3.7 nm, respectively. The thermal characteristics of the SBA-15/PLGA composites studied using thermogravimetry analysis shows a weight loss of around 80% with the degradation occurring at 324?°C. The prepared scaffold is also found to support the adhesion and proliferation of osteoblast cells. The expression of specific bone markers is significantly enhanced in the SBA-15/PLGA composite scaffold when compared with the pristine polymeric scaffold indicating the positive effect of mesoporous silica. Hence, these SBA-15/PLGA composite scaffolds can be explored further for bone regeneration applications.     

A mesoporous Pt-SBA-15 nano architecture with catalytic functions on oxidation of CO

Among many kinds of noble metal catalysts, platinum is the most efficient and widely used as automotive exhaust catalysts for treatment to remove poison gases. Due to the regular pore system and controllable pore size, mesoporous silica has been acknowledged as supports of adsorption, separation, catalysts for the extremely large surface areas and shape selective properties. SBA-15 supported Pt particles are prepared by a facile method and characterized by X-ray diffraction, Transmission Electron Microscopy and N₂ isotherms techniques. Results indicate that the Pt precursor is introduced into the mesoporous successfully and all of the particles are confined in SBA-15 with monodispersed form and uniform size. The catalytic activity of Pt-SBA-15 on oxidation of carbon monoxide are also investigated and the result indicate that the catalysts possess high catalytic activity, catalytic efficiency and stability on oxidation of CO.     

Pd/SBA-15 nanocomposite: Synthesis, structure and catalytic properties in Heck reactions

Pd nanoparticles supported in mesoporous silica SBA-15 (or Pd/SBA-15 nanocomposites) were prepared by ion-exchange with cationic Pd precursor in an alkaline solution on an uncalcined silica. The high Pd loading in these nanocomposites can be achieved up to 5.21 wt.% by adjusting the pH value of the solution. The surface area and the pore volume decrease with increasing Pd loading. The Pd nanoparticles equal to or smaller than 6 nm in size in the nanocomposites are distributed in the channels of the mesoporous SBA-15. The Pd/SBA-15 nanocomposites exhibit excellent catalytic activities and high reuse ability in air for the Heck carbon-carbon coupling reactions.     

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.     

Pore structure and graphitic surface nature of ordered mesoporous carbons probed by low-pressure nitrogen adsorption

Ordered mesoporous carbons (OMCs) were produced by pyrolysis of sucrose adsorbed in two different silica matrices (MCM-48 and SBA-15), followed by dissolution of the matrix in hydrofluoric acid. Subsequently, some of these OMCs were heat-treated at temperatures of up to 1600 °C. The OMC pore structure was studied by low-pressure nitrogen adsorption. Information on the graphitic order of the surface of the mesopore walls was also obtained from the nitrogen adsorption data. These results were correlated to the order of the graphene layers at the outer surface, which was studied by X-ray photoelectron spectroscopy (XPS).

The OMCs were predominantly mesoporous, but they also contained micropores. For OMCs produced in an SBA-15 matrix, the micropore volume decreased upon heating. After heating to 1600 °C, nearly all micropores had disappeared. Furthermore, upon heating the width of the mesopores increased from 35 to 50 Å. All these changes can be explained by a shrinking of the OMC framework upon heating. A different behavior was found for OMCs derived from MCM-48. Upon heating these materials at increasingly high temperatures, the width of the mesopores first decreased, and for temperatures above 1100 °C it increased again. For all OMCs studied the graphitic order of the mesopores and the order of the graphene layers at the outer surface increased upon heating. For a given temperature, the graphitic surface order of OMCs derived from SBA-15 and MCM-48 was similar.     

Mesoporous silica supported cobalt oxide catalysts for catalytic removal of benzene

Two types of mesoporous silica SBA-15 with different pore diameter were synthesized with an ageing temperature of 373 K and an ageing temperature of 308 K, respectively; in addition, mesoporous silica with amorphous structure was synthesized by adding organosiloxane as part of the silica source during the synthesis procedure. Mesoporous silica and conventional alumina supported cobalt oxide catalysts were prepared by incipient wetness impregnation method. These materials were characterized by FT-IR, nitrogen adsorption–desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and Temperature programmed reduction (TPR) techniques, and the activity of the supported cobalt oxide catalysts for deep oxidation of benzene were evaluated in a fixed-bed reactor. It seems that the pore diameter of the silica increase with the elevation of the ageing temperature. Mesoporous silica supported cobalt oxide catalysts are more active than conventional alumina supported ones. Cobalt oxide can be relatively better dispersed on the surface of mesoporous silica which has larger pore diameter and surface areas. Meanwhile, more silanol groups exist on the surface of amorphous silica, which could induce a strong interaction with the supported cobalt oxide species, leading to poor activity for benzene oxidation.     

Trypsin immobilization on mesoporous silica with or without thiol functionalization

The effects of pore size, structure, and surface functionalization of mesoporous silica on the catalytic activity of the supported enzyme, trypsin, were investigated. For this purpose, SBA-15 with 1-dimensional pore arrangement and cubic Ia3d mesoporous silica with 3-dimensional pores were prepared and tested as a support. Materials with varying pore diameters in the range 5–10 nm were synthesized using a non-ionic block copolymer by controlling the synthesis temperature. Thiol-group was introduced to the porous materials via siloxypropane tethering either by post synthesis grafting or by direct synthesis. These materials were characterized using XRD, SEM, TEM, N₂ adsorption, and elemental analysis. Trypsin-supported on the solids prepared was active and stable for hydrolysis of N-α-benzoyl-DL-arginine-4-nitroanilide (BAPNA). Without applying thiol-functionalization, cubic Ia3d mesoporous silica with ca. 5.4 nm average pore diameter was found to be superior to SBA-15 for trypsin immobilization and showed a better catalytic performance. However, enzyme immobilized on the 5% thiol-functionalized SBA-15 prepared by directly synthesis was found to be the most promising and was also found recyclable.     

New mesoporous carbon materials synthesized by a templating procedure

The new porous carbon materials were obtained by templating procedure using mesoporous silica (SBA-15) as template. The ordered mesoporous silica materials were synthesized by using Pluronic P123 (non-ionic triblock copolymer, EO₂₀PO₇₀O₂₀). SBA-15/cryogel carbon composites were obtained by sol–gel polycondenzation of resorcinol and formaldehyde in the presence of different amount of SBA-15. The polycondenzation was followed by freeze drying and subsequent pyrolysis. One set of SBA-15/sucrose carbon composites was prepared by using sucrose as carbon source. The silica template was eliminated by dissolving in hydrofluoric acid (HF) to recover the carbon material. The obtained carbon replicas were characterized by nitrogen adsorption–desorption measurements, X-ray diffraction and scanning electron microscopy (SEM). It was revealed that the samples have high specific surface (533–771 m² g^?1), developed meso- and micro-porosity and amorphous structure. Porous structure of carbon replicas was found to be a function of the carbon source, properties of SBA-15 and silica/carbon ratio. Room temperature adsorption of nitrogen and adsorption of phenol from aqueous solutions were investigated.     

有序介孔氮化碳的制备及其催化Knoevenagel缩合反应

以四氯化碳和乙二胺为前驱体,介孔氧化硅SBA-15为硬模板剂,采用纳米浇铸法合成系列不同碳氮比的介孔类石墨相氮化碳材料CN-SBA15。通过N2吸附-脱附、XRD、TEM、FT-IR和XPS等对CN-SBA15进行表征,并考察其在苯甲醛和丙二腈Knoevenagel缩合反应中的催化性能。结果表明,CN-SBA15的比表面和孔体积与前驱体的比例有直接关系,很好地反向复制了原SBA-15的有序结构。CN-SBA15含有大量的N杂环结构,在Knoevenagel缩合反应中显示出较高的催化活性、重复使用性和底物普适性。     

Trypsin immobilization on mesoporous silica with or without thiol functionalization

The effects of pore size, structure, and surface functionalization of mesoporous silica on the catalytic activity of the supported enzyme, trypsin, were investigated. For this purpose, SBA-15 with 1-dimensional pore arrangement and cubic Ia3d mesoporous silica with 3-dimensional pores were prepared and tested as a support. Materials with varying pore diameters in the range 5–10 nm were synthesized using a non-ionic block copolymer by controlling the synthesis temperature. Thiol-group was introduced to the porous materials via siloxypropane tethering either by post synthesis grafting or by direct synthesis. These materials were characterized using XRD, SEM, TEM, N₂ adsorption, and elemental analysis. Trypsin-supported on the solids prepared was active and stable for hydrolysis of N-α-benzoyl-DL-arginine-4-nitroanilide (BAPNA). Without applying thiol-functionalization, cubic Ia3d mesoporous silica with ca. 5.4 nm average pore diameter was found to be superior to SBA-15 for trypsin immobilization and showed a better catalytic performance. However, enzyme immobilized on the 5% thiol-functionalized SBA-15 prepared by directly synthesis was found to be the most promising and was also found recyclable.     

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.     

Structure and catalytic properties of Pd encapsulated in mesoporous silica SBA-15 fabricated by two-solvent strategy

The two-solvent method was employed to prepare Pd encapsulated in mesoporous silica (Pd/SBA-15). A 3.01 wt% Pd loading was achieved without the loss of pore ordering. Highly dispersed and uniform palladium nanoparticles could be detected using transmission electron microscopy confirming also the absence of large particles outside the mesopore silica. The catalytic activities of the Pd/SBA-15 nanocomposites were investigated in Heck coupling reactions with activated and non-activated aryl substrates. The Pd/SBA-15 nanocomposite exhibits excellent catalytic activities and reuse ability in air for the Heck carbon–carbon coupling reactions.     

Synthesis of mesoporous silica from bottom ash and its application for CO<Subscript>2</Subscript> sorption

A supernatant solution of silicate species extracted from bottom ash in a power plant was used to prepare a mesoporous silica by the synthesis protocol of SBA-15. XRD, N₂ adsorption-desorption, and TEM confirmed a disordered mesopore structure. The pore volume and average pore size of the product were significantly larger than SBA-15 prepared using pure chemicals, and complementary textural mesoporosity was detected. When the mesoporous silica was tested for carbon dioxide sorption after polyethyleneimine (PEI) impregnation, substantially higher CO₂ sorption capacity (169 mg CO₂/g-sorbent) was achieved than that of PEI-impregnated pure SBA-15 under the same test conditions. High CO₂ sorption capacity was maintained when the gas composition was changed to 15% CO₂, and the hybrid material exhibited satisfactory performances during the 10 recycle runs.