新型磺酸基功能化的介孔MCM-41分子筛的合成及其性能研究

利用糠醇的聚合和碳化对介孔分子筛Al-MCM-41进行表面处理后,直接加浓硫酸磺化制备了一系列新型的磺酸基功能化的介孔MCM-41分子筛催化剂,并用氮气吸附-脱附(BET)、X-射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)和吡啶-程序升温脱附(吡啶-TPD)等方法对其进行了结构表征,以乙酸与乙醇的酯化反应为模...     

Template method synthesis of mesoporous carbon spheres and its applications as supercapacitors

Mesoporous carbon spheres (MCS) have been fabricated from structured mesoporous silica sphere using chemical vapor deposition (CVD) with ethylene as a carbon feedstock. The mesoporous carbon spheres have a high specific surface area of 666.8 m²/g and good electrochemical properties. The mechanism of formation mesoporous carbon spheres (carbon spheres) is investigated. The important thing is a surfactant hexadecyl trimethyl ammonium bromide (CTAB), which accelerates the process of carbon deposition. An additional advantage of this surfactant is an increase the yield of product. These mesoporous carbon spheres, which have good electrochemical properties is suitable for supercapacitors.     

利用甲基纤维素辅助合成介孔二氧化硅微球

通过调节硅酸四乙酯（TEOS）和嵌段聚合物F127（EO₁₀₆PO₇₀EO₁₀₆）体系的pH值调控TEOS水解的速度,并利用甲基纤维素（MC）在水热条件下形成网格状液晶微滴结构的特点,一步诱导硅胶初级粒子聚沉制备微米级介孔氧化硅微球。研究了溶胶 凝胶的温度、pH值对成球性和孔结构的影响,通过氮吸附（BET）,X射线衍射（XRD）、透射电子显微镜（TEM）、扫描电子显微镜（SEM）、马尔文激光粒度分析（Malven）等手段分析表征了介孔氧化硅微球的形貌和孔结构,实验结果表明通过向TEOS和F127体系中加入MC,在pH＝1、80℃条件下一步水热晶化可以合成直径在4～6 μm、比表面积为450 m²·g^-1、孔径为4.2 nm的介孔氧化硅微球。     

Synthesis of monodispersed mesoporous spheres of submicron size amorphous silica

A technique has been developed for synthesis of submicron monodispersed mesoporous spheres of amorphous silica from an alcohol-water-ammonia mixture by means of tetraethoxysilane hydrolysis in the presence of hexadecyltrimethylammonium bromide. The mechanism of sphere formation from aggregates of close-packed surfactant cylindrical micelles coated by silica has been proposed. The specific surface area in the synthesized spheres is higher than 800 m²/g, whereas the pore volume and average diameter are equal to 0.63 cm³/g and 3 nm, respectively. The average size of particles is shown to decrease twice after the temperature of the synthesis is increased twice. According to the data of atomic force spectroscopy and dynamic light scattering, the average diameter of mesoporous spheres can be controllably varied in the range 300–1500 nm with a root-mean-square deviation of no more than 6%.     

Control of ordered structure and morphology of cubic mesoporous silica SBA-1 via direct synthesis of thiol-functionalization

Well-ordered cubic mesoporous silicas SBA-1 functionalized with thiol groups have been synthesized via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strongly acidic conditions. Various synthesis parameters such as HCl concentration, synthesis temperature, and time for hydrothermal treatment were systematically investigated as a function of MPTMS contents. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), solid-state ¹³C and ²⁹Si NMR spectroscopy, thermogravimetric analysis (TGA), scanning electron microscopy (SEM), and nitrogen sorption measurements. Direct evidence of the presence of chemically attached thiol moieties was provided by solid-state ²⁹Si and ¹³C NMR spectroscopy. A high degree of structural ordering was still retained when MPTMS loading was incorporated up to 20 mol% in the synthesis mixture. Increasing the synthesis temperature and the time for the hydrothermal treatment not only increased the degree of framework cross-linking, but also did not lead to the undesirable phase transformation as often observed in the conventional synthesis of pure silica SBA-1. SEM results reveal that the morphology of thiol-functionalized SBA-1 depends on the HCl concentration used in the synthesis. The sample prepared with a low acid concentration exhibits a highly isotropic morphology with more facets than that of pure silica SBA-1, whereas it changes to a spherical shape as the acid concentration is increased. The maximum content of the attached thiol group (–SH) in the mesoporous framework is 2.39 mmol/g. The thiol-functionalized SBA-1 mesoporous materials are efficient Hg²⁺ adsorbents.     

Morphology controlling of micrometer-sized mesoporous silica spheres assisted by polymers of polyethylene glycol and methyl cellulose

Based on the PEG (polyethylene glycol)’s function of bridging flocculation and the MC (methyl cellulose)’s function of formation of liquid crystal in aqueous solution, the morphology of micrometer-sized mesoporous silica spheres with good dispersivity were synthesized by adding the mixture of PEG and MC into the aqueous solution containing F127 and TEOS. It was found that only when PEG was added, the micrometer sized spheres could be synthesized, the spheres possess meso-pores from 2.5 nm to 3.0 nm, and the specific surface area was from 744 m²/g to 861 m²/g by changing the amount of PEG, but the dispersibility of microspheres needs to be improved. Only when MC was added, the dispersibility of resultant spheres was good, but the out surface of spheres was not smooth. Then, when suitable amount of PEG and MC were simultaneously added, the spheres with good dispersibility and smooth out surface were obtained.     

含磺酸基的介孔分子筛SO3H-SBA-15催化合成油酸丁酯

采用水热法直接合成了含磺酸基的介孔分子筛SO3H-SBA-15.以油酸与正丁醇为原料催化合成油酸丁酯,进行了不同催化剂的对比实验以及反应条件包括催化剂用量、反应温度、反应时间、酸醇摩尔比的考察.得到最佳反应条件为：催化剂质量分数为10%,反应温度120 ℃,反应时间3 h,酸醇摩尔比1∶2.     

Silica foams with ultra-large specific surface area structured by hollow mesoporous silica spheres

Ceramic foams with multi-scale pores and large specific surface area have received extensive attention due to their unique structure and superior properties. Considering that there are still challenges to synthesize porous ceramics with large specific surface area, a novel ceramic foam material with ultra-large specific surface area has been prepared using hollow silica mesoporous spheres (HMSSs) as building block in this work. These building blocks were made weakly hydrophobic in order to produce HMSS particle stabilized foams. The foams exhibit a uniform primary macropore structure, which is composed of a three dimensional HMSS-assembled network, via HMSS-stabilized foams. The influence of sintering temperature on the microstructure and properties of HMSS foams is investigated. The HMSS foams exhibit highest specific surface area of 1733 m²/g, attributed to the radial mesopores in HMSS shell, when sintered at between 500°C and 800°C. This specific surface area is much higher than that of existing ceramic materials. The uniform pore structure and ultra-large specific surface area make it a promising lightweight material in potential application fields, including catalyst, adsorption, fire-resistant thermal insulation, and load and control release system.     

Synthesis of porous carbon and silica spheres using PEO-PF polymer blends

In this paper, we performed a physical mixture of PEO and PF polymers (i.e. a polymer blend) as an organic template for synthesizing PF-PEO-silica homogeneous composites in a dilute silicate solution at pH = 4.0–5.0. The PF-PEO-silica composites exhibit spherical morphology, in micrometer dimension, and the sphere size is dependent on the pH value of the solution. After undergoing calcination to remove the organic part of the PF-PEO-silica composites with and without the hydrothermal treatment, porous silica spheres of different pore sizes were obtained. Due to the existence of the carbonizing PF polymer in the PF-PEO-silica composite, porous carbon spheres can be conveniently obtained from pyrolysis of the PF-PEO-silica composites under a N₂ atmosphere and HF-etching procedures. TEM images demonstrate that the mesostructures of the mesoporous silica and porous carbons are disordered.     

Synthesis of a sulfonic acid functionalized acidic ionic liquid modified silica catalyst and applications in the hydrolysis of cellulose

A sulfonic acid functionalized acidic ionic liquid modified silica catalyst was prepared in 68% overall yield from 3-chloropropyl silica by a simple two step method involving nucleophilic substitution of chlorine with imidazole, then condensation with 1,3-propanesultone and acidification using HCl. This silica supported acid catalyst was shown to be effective in the hydrolysis of cellulose (DP ∼ 450) dissolved in 1-n-butyl-3-methylimidazolium chloride at 70 °C, producing glucose and total reducing sugars in 26 and 67% yields respectively.     

Sulfonic acid-functionalized mesoporous silica catalyst with different morphology for biodiesel production

Sulfonic acid functionalized mesoporous silica based solid acid catalysts with different morphology were designed and fabricated. The synthesized materials were characterized by various physicochemical and spectroscopic techniques like scanning electron microscope-energy dispersive X-ray spectroscopy, Fourier transform infrared spectroscopy, Brunauer–Emmett–Teller surface area, thermogravimetric analysis and n-butylamine acidity. The shape of catalysts particles plays an important role in its activity. The sulfonic acid functionalized mesoporous silica catalysts of spherical shape and the cube shape were assessed for catalytic activity in biodiesel production. The catalytic biodiesel production reaction over the catalysts were studied by esterification of free fatty acid, oleic acid with methanol. The effect of various reaction parameters such as catalyst concentration, acid/alcohol molar ratio, catalyst amount, reaction temperature and reaction time on catalytic activity were investigated to optimize the conditions for maximum conversion. It was sulfonated cubic shape mesoporous silica which exhibited better activity as compared to the spherical shape silica catalysts. Additionally, the catalyst was regenerated and reused up to three cycles without any significant loss in activity. The present catalysts exhibit superior performance in biodiesel production and it can be used for the several biodiesel feedstock’s that are rich in free fatty acids.     

二氧化硅空心球的制备及研究

在乙醇/水的混合溶液中,采用聚乙烯吡咯烷酮（PVP）为分散剂,偶氮二异丁腈（AIBN）为引发剂,通过分散聚合法制备出聚苯乙烯（PS）微球。然后以微球为模板,PS粒子作为核,SiO_2作为壳,在600℃时经过热分解得到SiO_2空心球。通过热分析仪、扫描电子显微镜对制得的空心球进行了表征和分析,并讨论其影响因素。     

Synthesis and electronic property of platinum nanowire and nanoparticle in mesoporous silica template

Platinum nanowires and nanoparticles were selectively synthesized in mesoporous silicas FSM-16 and HMM-1. The nanowires are 3 nm in diameter and several hundred nm to μm in length with high crystallinity. Pt nanowires and nanoparticles can be isolated by dissolving silica matrix with HF. The Pt wires extracted from organosilica HMM-1 have a nanonecklace structure, while the wires from siliceous FSM-16 have a nanorod structure. The extracted Pt nanoparticles (3 nm in size) on HOPG show the Coulomb staircase phenomena in STM/STS analysis. The mechanism for formation of the Pt nanowires is based on the migration of Pt ions in the mesoporous channels.     

Characterization of acidic property of sulfo-group functionalized microporous and mesoporous silica by adsorption microcalorimetry

Sulfo-group functionalized microporous and mesoporous silica based-on a MCM-41 framework which showed solid acid property were synthesized and characterized by adsorption microcalorimetry. Both the sulfo-functionalized microporous and mesoporous silica (Micro-SO₃H and Meso-SO₃H) were prepared by the oxidation of thiol group (–SH) included mesoporous silica which was obtained through the hydrolysis and co-condensation of tetramethoxysilane (TMOS) and mercaptopropyl trimethoxysilane (MPTMS). The samples have an ordered two-dimensional hexagonal pore array similar to that of MCM-41 as depicted from the XRD patterns. Nitrogen adsorption also shows that both microporous and mesoporous silica have pore characteristics similar to MCM-41, i.e. high surface area and high pore volume. However, pore regularity, surface area and pore volume decreased as the MPTMS loading increased. Solid-state ²⁹Si NMR indicated that the sulfo groups were successfully incorporated into both microporous and mesoporous silica frameworks. This sulfo-functionalized porous silica have high NH₃ uptakes and high differential heats of NH₃ adsorption, suggesting the presence of strong acidic sulfo groups on the silica surface. Acid catalyses of the samples were characterized by the isomerization reaction of but-1-ene to cis, trans-but-2-ene.     

Biodegradability of mesoporous silica nanoparticles

Biodegradability significantly impacts the bioapplication of mesoporous silica nanoparticles (MSN). In recent years, immense efforts have been made to understand and tailor the biodegradability of MSN. In this mini review, we overview the recent reports on the biodegradation of MSN, with a focus on the correlation between biodegradation and physicochemical properties including specific surface area, morphology, pore size, particle diameter and condensation degree of silicon-oxygen network. In addition, strategies for improving the biodegradability of MSN such as metal ions and organic species doping are also introduced.     

Preparation of mesoporous silica fiber matrix for VOC removal

A novel method for the preparation of the mesoporous silica fiber matrix was introduced for a removal of volatile organic compounds (VOCs). Paper making technology was applied to make a sheet of mesoporous silica fiber matrix. Reinforcing the mesoporous silica fiber with the ceramic fibers (50 wt.%) increased the mechanical strength of the matrix. Mesoporous silica fibers using TMOS (tetramethoxysilane) as a silica source and CTAC (cetyltrimethyl-ammoniumchloride) as a surfactant were drawn by the spinning method. The spinning process increased both the crystallinity and the fraction of mesopores (1.9 nm) of the fiber. As the spinning rate was increased both the crystallinity and the specific area of the mesoporous silica fiber increased, but the diameter of fiber decreased. We could control the size and morphology of mesoporous silica fiber matrix by changing the shape of substrates. This leads to easy fabrication of honeycomb-structured adsorbent which can be used for the VOC removal.     

Synthesis of hexagonal and cubic mesoporous silica using power plant bottom ash

An alkali fusion method was adopted to extract silicate species from coal bottom ash in a power plant and the supernatant solution was used for the synthesis of MCM-41, SBA-15, and SBA-16 mesoporous silica materials. The minor impurities present in the bottom ash were not found to be detrimental to the successful formation of mesoporous silica phases. Additional silica from sodium metasilicate was introduced to improve the textural properties for SBA-15 and SBA-16. According to SEM analyses, particle morphology of the samples gradually approaches those prepared using pure chemical as the amount of external silica source increases. XRD analyses confirmed well-ordered mesostructures in all of these silica materials. N₂ adsorption–desorption isotherms of MCM-41 prepared using bottom ash showed a type IV isotherm with a region of steep increase due to capillary condensation, whilst SBA-15 and SBA-16 showed type IV isotherm with H1 and H2 hysteresis loops, respectively. ²⁷Al MAS NMR analysis of MCM-41 synthesized from the supernatant solution reveals that the extracted Al species from bottom ash were tetrahedrally incorporated in the framework. TEM clearly showed the uniform pore structure of the materials prepared using the industrial waste.     

Voltammetric response of ferrocene-grafted mesoporous silica

The electrochemical behavior of ferrocene moieties immobilized by covalent grafting on ordered mesoporous silica samples has been studied by cyclic voltammetry in aqueous medium using carbon paste electrodes modified with these solids. The functionalized silica samples were obtained using (3-(ferrocenylamide)propyl)triethoxysilane as the grafting agent. The results have been discussed in relation to the ferrocene content in the materials and compared to those obtained with non-ordered ferrocene-grafted silica gels. Well-defined voltammetric signals have been observed in spite of the insulating character of the mesoporous silica matrix and they were found to increase as a function of the ferrocene groups content in the material. They displayed a better stability upon continuous cycling potentials in comparison to those recorded with amorphous gels, suggesting a beneficial effect of the long-range structural order on the electron transfer processes in such confined media.     

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.     

丙烯腈催化剂用硅溶胶的制备及其性能研究

采用常压粒子增长工艺合成丙烯腈催化剂载体专用硅溶胶,研究了硅溶胶的粒径、pH、稳定剂对丙烯腈催化剂性能的影响。结果表明:当硅溶胶粒径分布集中、平均粒径23～25nm、pH9.0～9.5、适量加入氢氧化钠和氨水混合溶液作为稳定剂和加入少量助剂时,丙烯腈单程收率接近80%。