Highly Sensitive Fluorescence Probe Based on Functional SBA-15 for Selective Detection of Hg<Superscript>2+</Superscript>

An inorganic–organic hybrid fluorescence chemosensor (DA/SBA-15) was prepared by covalent immobilization of a dansylamide derivative into the channels of mesoporous silica material SBA-15 via (3-aminopropyl)triethoxysilane (APTES) groups. The primary hexagonally ordered mesoporous structure of SBA-15 was preserved after the grafting procedure. Fluorescence characterization shows that the obtained inorganic–organic hybrid composite is highly selective and sensitive to Hg²⁺ detection, suggesting the possibility for real-time qualitative or quantitative detection of Hg²⁺ and the convenience for potential application in toxicology and environmental science.     

Inorganic–organic hybrid materials based on functionalized silica and carbon: A comprehensive understanding toward the structural property and catalytic activity difference over mesoporous silica and carbon supports

Inorganic–organic hybrid materials based on functionalized silica and carbon were synthesized by anchoring molybdovanadophosphoric acid (H₅[PMo₁₀V₂O₄₀] · 32.5H₂O) onto amine-functionalized SBA-15, ethane-bridged SBA-15 and mesoporous carbon, respectively. Small angle X-ray diffraction, N₂ sorption analysis, HRTEM, SEM, FT-IR, CP-MAS NMR were used to diagnose the mesoporous structure of inorganic–organic hybrid materials. The structural integrity of molybdovanadophosphoric acid has been found to be retained after immobilization over mesoporous materials. These inorganic–organic hybrid materials were tested in the environmentally friendly oxidation of 2-methylnaphthalene (2MN) with 30% aqueous hydrogen peroxide. Molybdovanadophosphoric acid containing mesoporous organosilica hybrid material (ethane-bridged SBA-15) exhibited higher catalytic activities in the oxidation of 2MN to give a clean product 2-methy-1,4-naphthoquinone (menadione vitamin K3 precursor), because of the improved hydrophobicity of the material. The correlation between structural properties and catalytic activities of these hybrid materials has been well addressed in our present studies.     

Recovery of nitrate from water streams using amine-grafted and magnetized SBA-15

Mesoporous silica SBA-15 was modified using amine-grafting and magnetization to enhance its nitrate adsorption capacity and to render the spent silica particles recoverable from the working solution after use. Such modifications result in an outstanding adsorbent for recovering nitrate from water streams by adding high adsorption ability and easy handling to the intrinsic properties of SBA-15. When the molar ratio of SBA-15 to 3-aminopropyltriethoxysilane (APTES) is 10 : 3 during amine-grafting, the resulting SBA-15G-4 sample exhibits the highest nitrate adsorption capacity (44.9 mg/g) among the tested materials. The other sample, 67-SBA-15MG, which was magnetized with iron nitrate content of 67 wt% of SBA-15, exhibits sufficient magnetic force for recovery from the working solution, while maintaining ～81% of nitrate adsorption capacity of the corresponding amine-grafted SBA-15G-5. Furthermore, the 67-SBA-15MG material retains its adsorption capacity and magnetic strength after ten adsorption/desorption cycles, indicating excellent characteristics as a magnetically recyclable adsorbent for recovering nitrate.     

介孔SBA-15有机化修饰对PMMA杂化材料力学性能的影响

采用硅烷偶联剂对SBA-15进行了有机化修饰(即:SBA-15-G),利用在位分散聚合法制备了SBA-15/PMMA和SBA-15-G/PMMA杂化材料,研究了SBA-15和SBA-15-G在PMMA基体中的介观有序性和分散性以及对杂化材料的力学性能的影响规律。结果表明有机化修饰使SBA-15孔容、孔径和比表面积减小,表面亲油性提高;SBA-15和SBA-15-G在基体中仍保持长程有序结构;有机化修饰改善了SBA-15在基体中的分散性和与基体的界面结合,显著增强了杂化材料的力学性能。当SBA-15-G为4%时,杂化材料的拉伸强度和模量分别提高了45%和40.4%,当SBA-15-G为2%时冲击强度达到最大,比基体提高了36.6%。,     

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.     

Novel composite polymer electrolyte comprising poly(ethylene oxide) and triblock copolymer/mesostructured silica hybrid used for lithium polymer battery

Ordered mesoporous materials, due to its potential applications in catalysis, separation technologies, and nano-science have attracted much attention in the past few years. In this work, a novel PEO-based composite polymer electrolyte by using organic-inorganic hybrid EO₂₀PO₇₀EO₂₀ @ mesoporous silica (P123 @ SBA-15) as the filler has been developed. The interactions between P123 @ SBA-15 hybrid and PEO chains are studied by X-ray diffraction (XRD), differential scanning calorimeter (DSC), and FT-IR techniques. The effects of P123 @ SBA-15 on the electrochemical properties of the PEO-based electrolyte, such as ionic conductivity, lithium ion transference number are studied by electrochemical ac impedance spectroscopy and steady-state current method. The experiment results show that P123 @ SBA-15 can enhance the ionic conductivity and increase the lithium ion transference number of PEO-based electrolyte, which are induced by the special topology structure of P123 in P123 @ SBA-15 hybrid, at the same time. The excellent lithium transport properties and broad electrochemical stability window suggesting that PEO-LiClO₄/P123 @ SBA-15 composite polymer electrolyte can be used as candidate electrolyte materials for lithium polymer batteries.     

Towards superior permeability and antifouling performance of sulfonated polyethersulfone ultrafiltration membranes modified with sulfopropyl methacrylate functionalized SBA-15

A non-solvent induced phase separation (NIPS) process was used to fabricate a series of sulfonated polyethersulfone (SPES) membranes blending with different concentrations of SBA-15-g-PSPA with the applications in the ultrafiltration (UF) process. SBA-15 was modified with 3-methacrylate-propyltrimethoxysilane (MPS) to form SBA-15-g-MPS. It was further modified with the charge tailorable polymer chains by reacting with 3-sulfopropyl methacrylate potassium salt. The nanoparticles were uniformly dispersed and finger-like channels were developed within the membrane. The adding of surface modified SBA-15-g-PSPA nanoparticles has significantly improved membrane water permeability, hydrophilicity, and antifouling properties. The pure water fluxes of the composite SPES membranes were significantly higher than the pristine SPES membrane. For the membrane containing 5% (mass) of SBA-15-g-PSPA (MSSPA5), the pure water flux was increased dramatically to 402.15 L·m^-2·h^-1, which is ~1.5 times that of MSSPA0 (268.0 L·m^-2·h^-1). The high flux rate was achieved with 3% (mass) of SBA-15 nanoparticles with retained high rejection ratio 98% for natural organic matter. The results indicate that the fashioned composite membrane comprising SBA-15-g-PSPA nanoparticles have a promising future in ultrafiltration applications.     

Luminescent Organic–Inorganic Hybrids of Functionalized Mesoporous Silica SBA-15 by Thio-Salicylidene Schiff Base

Novel organic–inorganic mesoporous luminescent hybrid material N,N′-bis(salicylidene)-thiocarbohydrazide (BSTC-SBA-15) has been obtained by co-condensation of tetraethyl orthosilicate and the organosilane in the presence of Pluronic P123 surfactant as a template. N,N′-bis(salicylidene)-thiocarbohydrazide (BSTC) grafted to the coupling agent 3-(triethoxysilyl)-propyl isocyanate (TESPIC) was used as the precursor for the preparation of mesoporous materials. In addition, for comparison, SBA-15 doped with organic ligand BSTC was also synthesized, denoted as BSTC/SBA-15. This organic–inorganic hybrid material was well-characterized by X-ray diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy (HRTEM), and photoluminescence spectra, which reveals that they all have high surface area, uniformity in the mesostructure. The resulting materials (BSTC-SBA-15 and BSTC/SBA-15) exhibit regular uniform microstructures, and no phase separation happened for the organic and the inorganic compounds was covalently linked through Si–O bonds via a self-assemble process. Furthermore, the two materials have different luminescence range: BSTC/SBA-15 presents the strong dominant green luminescence, while BSTC-functionalized material BSTC-SBA-15 shows the dominant blue emission.     

Rapid synthesis of La–Ce–silica mesoporous SBA-15-type material via microwave technique

La–Ce–silica mesoporous SBA-15-type material has been rapidly synthesized using microwave technique and characterized by XRD, FT-IR, DRS, and low temperature N₂ adsorption–desorption measurement. The results show the La and Ce were successfully incorporated into the framework of SBA-15 molecular sieve and the synthesized material not only retains the hexagonal order and physical properties of purely siliceous SBA-15 but also possesses high surface area and narrow pore-size distribution. Further, the obtained material La–Ce–SBA-15 was used as catalyst support to load active metal Pt for CO oxidation reaction. The results of experiment indicate that the catalytic activity of Pt/La–Ce–SBA-15 is higher than that of the Pt/SBA-15 and Pt/La/Ce/SBA-15.     

介孔分子筛SBA-15的研究进展

自从介孔分子筛SBA - 15首次合成出来 ,成为众多研究领域的一个研究热点。文章综述了介孔分子筛SBA -15的合成及机理 ,影响孔径尺寸的因素及研究应用进展 ,介孔分子筛SBA - 15在催化、吸附和分离及纳米材料等领域具有广泛的应用前景。     

Hydrothermal stability and catalytic activity of mesoporous aluminum-containing SBA-15

Mesoporous silica structure SBA-15 and Al-containing SBA-15 (AlSBA) were synthesized and tested their activity in catalytic cracking of waste fatty acid mixture (palm oil based) in a fixed-bed micro-reactor. The catalytic activity of AlSBA was improved and more selective towards gasoline fraction present in the organic liquid product (OLP) as compared to mesoporous siliceous material SBA-15. Even though the hydrothermal stability of AlSBA was poorer but the sample with Si/Al ratio of 20 was found to be comparable with SBA-15. The hydrothermal stability of AlSBA was higher than AlMCM-41 with similar cracking activity and thus AlSBA is a more potential cracking catalyst.     

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.     

介孔材料SBA-15的改性及其应用研究进展

文章综述了介孔材料SBA-15的改性方法,包括有机功能化改性、杂原子改性和负载活性组分。在此基础上评述了改性SBA-15的应用研究进展,重点介绍了其在催化和吸附领域的应用进展。通过改性引入杂原子或有机官能团或负载活性组分,根据催化反应或吸附分离等性能要求可以有目的地进行功能化调控,可大大拓展其应用范围。     

In-vitro drug release kinetics studies of mesoporous SBA-15-azathioprine composite

The mesoporous silica (or SBA-15) was loaded with azathioprine drug. Azathioprine drug was incorporated into mesoporous silica by post impregnation method to reduce its toxic effects by controlling the drug release property. The synthesized pure SBA-15 and SBA-15-azathioprine composite were characterized by UV–visible spectrophotometry, thermo-gravimetric analysis, small and large angle powder X-ray diffraction, field emission scanning electron microscopy, high resolution transmission electron microscopy, Fourier transform infrared spectroscopy and nitrogen adsorption–desorption analysis. The successful inclusion of azathioprine drug in host material SBA-15 was confirmed by the reduced surface area (114 m²/g) and pore diameter (6.5 nm) of the organic–inorganic composite material. The drug entrapment efficiency of 90.67 % and loading efficiency of 72.67 % was achieved. The azathioprine drug release process from the mesoporous silica to simulated gastric, intestinal and body fluid were examined and the controlled release effect of the azathioprine drug in all fluids were studied. The Korsmeyer–Peppas model fits well the drug release data with the non-Fickian diffusion model and zero order kinetics for produced mesoporous silica. The controlled drug release enhanced the bioavailability and reduces its repeated administration. Hence, the composite drug can reduce the toxicity and side effects of the azathioprine.     

Grafting of lignin onto nanostructured silica SBA-15: preparation and characterization

The slow decline in oil reserves with mounting oil prices is pushing industry to find more sustainable sources for industrial manufacturing. Lignin is the second most abundant natural renewable biopolymer that is underutilized and has many functional groups (–OH, phenolics) that make the biopolymer a convenient substrate for materials manufacturing by the industry. The present study thus describes grafting of lignin onto nanostructured silica SBA-15 (Santa Barbara amorphous 15) by first silylating lignin with triethoxychlorosilane followed by treatment of silylated lignin with SBA-15. The resulting nanocomposite denoted as LIG–SBA-15-G was then characterized by powder X-ray diffraction, infra-red (FTIR), ³¹P nuclear magnetic resonance (³¹P NMR), N₂ adsorption (BET), scanning and transmission electron micrographs (SEM and TEM) and thermogravimetric analysis (TGA). X-ray data showed that LIG–SBA-15-G exhibited hexagonal structure closely similar to that observed for the SBA-15 host. FTIR of LIG–SBA-15-G showed characteristic absorption bands from lignin and attenuated Si–OH band due to its conversion to Si–O–Si ether bonds. Whereas, ³¹P NMR revealed that the majority of hydroxyl groups in lignin were replaced by Si–O–LIG ether bonds in LIG–SBA-15-G. SEM images of LIG–SBA-15-G displayed little changes in the macroscopic structure as compared to SBA-15. TEM images showed some disordered area in LIG–SBA-15-G and the grafted lignin appeared as black film on the silica surface. Using BET analysis the surface area of LIG–SBA-15-G was found to be 560 m² g^?1. Finally, TGA showed that LIG–SBA-15-G was more thermally stable than lignin and contained 13 % w/w lignin. Understanding the physicochemical and structural properties of the resulting lignin-nanosilica hybrid material should help engineer a robust and sustainable biomaterial suitable for various application, e.g. removal of contaminants from contaminated water.     

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.     

Characterization and catalytic performance of poly(4-vinylpyridine) supported on mesoporous carbon: comparison with poly(4-vinylpyridine) supported on mesoporous silica

In this study, the synthesis of poly(4-vinylpyridine) (P4VP) supported on mesoporous carbon (CMK-3) by in situ polymerization of 4-vinylpyridine in the presence of CMK-3 has been investigated. The structural properties of the P4VP/CMK-3 were investigated by FT-IR, XRD, BET, TGA, SEM and TEM techniques. The catalytic activity of this new heterogeneous basic catalyst was tested for Knoevenagel reaction. Excellent yields at room temperature in aqueous media and solvent-free conditions were obtained. The catalytic activity of this purely organic hybrid catalyst was compared with P4VP/SBA-15 to clarify the advantages of mesoporous carbon on mesoporous silica as support. The results showed that the stability of P4VP/CMK-3 was excellent and could be reused 10 times without much loss of activity in Knoevenagel reaction. Surprisingly, the composite prepared by mesoporous carbon showed much higher activity than that of P4VP/SBA-15. This unique result opens new perspectives for application of mesoporous carbons as structurally defined hydrophobic catalyst support in catalytic reactions.     

Influence of antistatic agent encapsulated into functionalized mesoporous silica on antistatic properties of polystyrene

Small molecular surfactant (SMS) such as HDC-193 was encapsulated into mesoporous silica SBA-15 and 3-aminopropyltriethoxysilane-modified SBA-15 (mSBA-5) to develop new controlled release SMS system. The diffusion process of HDC-193 from mesoporous silica with different structures and diameters was investigated. Both situations of large pore and organic modification promoted the adsorption and thus a larger load of SMS in mesoporous silica. The results of molecular dynamics simulations and washing durability experiments showed that the lifetime of HDC-193 encapsulated into mSBA-15 in polystyrene blends is five times longer than that of HDC-193/polystyrene. This suggests an efficient strategy for designing permanent antistatic agents.     

介孔分子筛SBA-15的改性研究进展

从金属改性、酸改性和氧化物改性三方面综述了介孔分子筛SBA-15的改性研究进展,重点介绍了SBA-15表面功能化后引入金属改性的方法。评述了金属纳米粒子的制备对改性的SBA-15催化剂催化性能的影响。     

Effects of mesoporous SBA-15 contents on the properties of polystyrene composites via in-situ emulsion polymerization

Different loading of mesoporous molecular sieve SBA-15 was used to prepare polystyrene (PS)/SBA-15 composite materials via in-situ emulsion polymerization. The influence of SBA-15 silica on the styrene emulsion polymerization was studied regarding to the monomer conversion, particle size and particle size distribution, stability and viscosity of the resulting emulsion. The structure and properties of the composites were investigated by infrared spectroscopy (IR), X-ray diffraction (XRD), scanning electron microscopy (SEM) and gel permeation chromatography (GPC). In addition, the glass transition temperature (T_g), thermal mechanical property and thermal stability of the composite film were measured by differential scanning calorimeter (DSC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA), respectively. The results indicated that the composite emulsion showed high monomer conversion, thick viscosity, low coagulum, uniform particle size and broad size distribution. Molecular weight of the polymer decreased with the increase of mesoporous silica. SBA-15 silica was dispersed evenly in PS matrix at a loading of 5 %. The PS/SBA-15 composite material containing 10 % silica maintained a certain ordered structure. DMA results demonstrated that PS/SBA-15 composite exhibited greater storage modulus and high T_g compared to pure PS. The improved thermal stability and T_g of the composite were also confirmed by the TGA and DSC.