Synthesis and hydrophobic adsorption properties of microporous/mesoporous hybrid materials

Hybrid materials of silicalite-1 (Sil-1)-coated SBA-15 particles (MSs) have been successfully synthesized by crystallization process under hydrothermal conditions. These MSs materials were characterized by X-ray diffraction, nitrogen adsorption/desorption and TEM techniques, which illustrated that the silicalite-1-coated SBA-15 particles were successfully prepared and had large pore volume and hierarchical pore size distribution. Further experimental studies indicated that longer crystallization time under basic condition caused the mesostructure of SBA-15 materials to collapse destructively and higher calcination temperature tended to disrupt the long-range mesoscopic order while they had little influence on the phase of microcrystalline silicalite-1 zeolite. The resultant MSs materials were investigated by estimating dynamic adsorption capacity under dry and wet conditions to evaluate their adsorptive and hydrophobic properties. The hydrophobicity index (HI) value followed the sequence of silicalite-1>MSs>SBA-15, which revealed that the SBA-15 particles coated with the silicalite-1 seeds enhanced the surface hydrophobicity, and also were consistent with FTIR results. Our studies show that MSs materials combined the advantages of the ordered mesoporous material (high adsorptive capacity, large pore volume) and silicalite-1 zeolite (super-hydrophobic property, high hydrothermal stability), and the presence of micropores directly led to an increase in the dynamic adsorption capacity of benzene under dry and wet conditions.     

Preparation and photocatalytic activity of highly ordered mesoporous TiO2–SBA-15

TiO₂–SBA-15 complex materials with highly ordered mesostructures have been prepared by a one-step hydrothermal synthesis method of titanium tetraisopropoxide (TTIP) and tetraethoxysilane (TEOS) in an acidic solution using surfactant P123 (EO₂₀PO₇₀EO₂₀) as structure-directing reagent. The prepared materials were characterized by transmission electron microscopy (TEM), small-angle X-ray diffraction patterns (SAXRD), Fourier transformed infrared spectroscopy (FT-IR) and N₂ adsorption–desorption experiments. The resulting TiO₂–SBA-15 complex materials showed highly ordered mesoporous structure with uniform pore sizes of 5.95 and 8.24 nm, high specific surface areas S_BET of 689 m² g^? 1 and 347 m² g^? 1 at different hydrothermal temperatures (100 °C and 130 °C). The photocatalytic activity of these TiO₂–SBA-15 mesoporous materials has been studied by 4-chlorophenol decomposition under UV light irradiation. The TiO₂–SBA-15 mesoporous materials prepared at the TiO₂:SiO₂ mass ratios of 25:75, 40:60 and 50:50 showed higher photocatalytic activity than that prepared at the TiO₂:SiO₂ mass ratio of 75:25.     

高氮含量的有序氮氧化物介孔材料的研究

通过使用氨气作氮源,氮化介孔氧化硅和含铝氧化硅(SBA-15和Al-MCM-41)的前驱体(含模板剂),成功制备出高氮含量的有序氮氧化物介孔材料。主要氮化条件为:1273～1323K,8～24h.采用 CNH元素分析、红外光谱、Si固体核磁共振谱(MASNMR)、N₂吸附-脱附分析、小角XRD和高分辨透射电镜(HRTEM)进行表征,分析结果表明经过高温长时间氮化制备出的高氮含量(～21wt％)的氮氧化硅和含铝氮氧化硅介孔材料仍然具有高达700～900m²g^-1的比表面积、窄的孔径分布和良好的有序性.     

改性SBA-15介孔孔道内甲基丙烯酸甲酯的反向原子转移自由基聚合的溶液聚合

分别使用硅烷偶联剂KH-151、KH-560、KH-570对介孔材料SBA-15进行改性,以改性前后的介孔材料作为"微反应器",在其内部进行了甲基丙烯酸甲酯(MMA)的反向原子转移自由基聚合(RATRP)。通过X射线衍射、氮气吸附-脱附测试、热重分析、差示扫描量热、凝胶渗透色谱、傅里叶变换红外光谱等手段对所得产物进行了测试表征。结果表明,MMA在改性前后的SBA-15内部聚合成功;聚合后的复合材料仍然保持其SBA-15的母体结构,但比表面积、孔径、孔体积均有所下降;孔道内所得的PMMA较常规RATRP聚合所得的PMMA相对分子质量有所增加,相对分子质量分布变宽,初始热分解温度升高,玻璃化转变温度升高;改性后介孔材料对反应液有更好的吸附能力且对孔道内的MMA的RATRP溶液聚合有更强的孔道限制作用。     

Synthesis of nano titania particles embedded in mesoporous SBA-15: characterization and photocatalytic activity

Supported nanocrystalline titanium dioxide (TiO2) has been prepared by a post-synthesis step via Ti-alkoxide hydrolysis through the use of mesoporous SBA-15 silica. TiO2/SBA-15 composites with various TiO2 loading have been prepared and characterized by X-ray diffraction, nitrogen adsorption, Fourier transform infrared spectroscopy and diffusive reflective UV-vis spectroscopy. The addition of mesoporous SBA-15 prevents the anatase to rutile phase transformation and the growth of crystal grain. TiO2 did not block the SBA-15 pores, and their surface was fully accessible for nitrogen adsorption. Calcination in air of the composites up to 800 degrees C did not change the nanocrystal phase and slightly increased the domain size from 5.0 to 7.5 nm, indicating that the anatase TiO2 grains in the mesostructures have a relatively high thermal stability and proper pore diameter allows controlling the size of obtained titania particles. The TiO2/SBA-15 composites prepared by this study showed much higher photodegradation ability for methylene blue (MB) than commercial pure TiO2 nanoparticles P-25. Experimental results indicate that the photocatalytic activity of titania/silica mixed materials depends on the adsorption ability of composite and the photocatalytic activity of the titania, and there is an optimal ratio of Ti:Si, too high or low Ti:Si ratio will lower the photodegradation ability of the composites.     

One-step preparation of FeCo nanoparticles in a SBA-16 matrix as catalysts for carbon nanotubes growth

Nanocomposites containing FeCo alloy nanoparticles dispersed in a highly ordered 3D cubic Im3m mesoporous silica (SBA-16) matrix were prepared by a novel, single-step templated-assisted sol-gel technique. Two different approaches were used in the synthesis of nanocomposites; a pure SBA-16 sample was also prepared for comparison. Low-angle X-ray diffraction, transmission electron microscopy and N2 physisorption at 77 K show that after metal loading, calcination at 500 degrees C and reduction in H2 flux at 800 degrees C the nanocomposites retain the cubic mesoporous structure with pore size not very different from the pure matrix. X-ray absorption fine structure (EXAFS) analysis at Fe and Co K-edges demonstrates that the FeCo nanoparticles have the typical bcc structure. The final nanocomposites were tested as catalysts for the production of carbon nanotubes by catalytic chemical vapour deposition and high-resolution TEM shows that good quality multi-walled carbon nanotubes are obtained.     

Enhanced dehydrogenation of nanoscale MgH2 confined by ordered mesoporous silica

Nanoscale MgH₂ was synthesized through loading di-n-butylmagnesium (MgBu₂) solution into the pores of ordered mesoporous silicas (SBA-15) with a pore diameter in a range of 5–10 nm, followed by freeze drying and hydrogenation treatment. The MgBu₂ inside the pore channels of SBA-15 decomposed into MgH₂ upon hydrogenation at 493 K under 6 MPa hydrogen. The nanoconfined MgH₂ exhibited greatly decreased desorption temperature of 540 K, a reduction of 146 K in comparison with that of commercial MgH₂, or 65 K reduction relative to that of MgH₂ obtained from MgBu₂ without confinement. Moreover, lower desorption temperature for the MgH₂ supported by SBA-15 with smaller pore diameter. The improvement on the dehydrogenation properties of MgH₂ was attributed to the nanosizing effect induced by the nanoconfinement of mesoporous silica.     

以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征

利用嵌段共聚物P123和F127分别在强酸性条件下合成了两种结构不同的介孔氧化硅材料:一维直孔道六方相的SBA-15和三维立方相的SBA-16,并通过XRD、N₂吸附-脱附、HTEM等手段对材料进行了研究。结果表明:商品化的嵌段共聚物作为结构导向剂合成的介孔氧化硅材料SBA-15和SBA-16孔道规整有序,比表面积分别达到765m²·g^-1和930m²·g^-1,相应的最可几孔径分别为6.46nm和3.92nm,这有利于介孔材料向经济实用方向发展。     

基于短孔道Zr-Ce-SBA-15固定胃蛋白酶的活性生物催化剂

在不外加无机酸的条件下, 通过水热合成法制备了短孔道六方板状有序介孔材料Zr-Ce-SBA-15 (ZCS). 以ZCS和传统SBA-15为载体对胃蛋白酶进行固定, 并利用N-(2-氨乙基)-3-氨丙基三甲氧基硅烷(AAPTS)对酶固定化材料进行功能化, 以缩小开口孔径从而减少酶泄漏. 采用小角X射线衍射、扫描电镜、透射电镜、氮气吸附和红外光谱对样品进行结构表征. 结果表明, 胃蛋白酶成功固定到介孔孔道中, AAPTS嫁接到材料中且没有破坏介孔结构. 固定化实验表明相比于SBA-15, ZCS对胃蛋白酶具有较快的吸附速度和较强的固定化能力(最大负载量为257.9 mg/g), 短孔道材料能有效地促进分子的扩散传递. 催化活性测定以牛血红蛋白为探针物, 与游离酶相比, 固定酶对牛血红蛋白保持着稳定的活性.     

表面高氨基官能化介孔SBA－15分子筛的制备

文章报道了一种利用甲苯二异氰酸酯（TDI）作桥连分子制备高氨基官能化介孔SBA－15分子筛的方法。首先,SBA－15表面的Si－OH与TD1分子中的一个－NCO基反应,然后,TD1分子中另一端未参与反应的－NCO基与乙二胺分子中的一个－NH2基反应,如此,－NH2被成功地嫁接到介孔SBA－15分子筛表面,用XRD、N2－吸脱附、FTIR和^29Si MA SNMR表征,结果表明,一NH2被成功引入到SBA－15分子筛表面,且材料具有良好的介孔结构。     

采用不同钛源合成介孔钛硅催化材料的研究

利用聚氧乙烯-聚氧丙烯-聚氧乙烯三嵌段共聚物(P123)作为结构导向剂,用氯化钾调控材料的形貌,以1,3,5-三甲苯(TMB)为分子筛的扩孔剂,钛酸正丁酯和四氯化钛作为不同的钛源,原位一步法合成出Ti-SBA-15分子筛。在高温煅烧除去模板剂之后,利用X射线衍射、紫外-可见漫反射光谱、红外光谱、扫描电镜以及N2吸附-脱附曲线对合成的介孔材料进行表征。结果表明:合成的介孔钛硅材料具有有序的孔道结构,钛在SBA-15的孔道内,钛在硅中的分散好。以钛酸丁酯为钛源合成的Ti-SBA-15呈规则的球形,平均直径为3.0μm;四氯化钛为钛源合成的Ti-SBA-15没有规则的形状,大小也不均一。     

镧(Ⅲ)对SBA-15分子筛改性研究

借助水热法，利用三嵌段共聚物聚(1，2—亚乙基二醇)—嵌段—聚(丙二醇)—嵌段—聚(1，2—亚乙基二醇)为模板剂，正硅酸四乙酯为硅源，强酸性条件下制备了分子筛SBA—15．分别以水及水 乙醇为介质采用LaCl3溶液与煅烧的主体材料SBA—15分子筛固—液相交换法，制备了La—(SBA—15)复合材料．利用化学分析、粉末XRD、N2吸附技术、IR评价了制备方法的有效性及对SBA—15分子筛孔结构的影响．结果表明，镧已并入SBA—15分子筛中，SBA—15内表面上的硅羟基团是镧进入的主要位置，部分客体在分子筛孔道内．制得的材料La—(SBA—15)保持高度有序的介孔二维六角结构，不改变载体SBA—15的介SLSL道结构．此外，考察了La—(SBA—15)产物的发光现象。     

镧(Ⅲ)对SBA-15分子筛改性研究

借助水热法,利用三嵌段共聚物聚(1,2-亚乙基二醇)-嵌段-聚(丙二醇)-嵌段-聚(1,2-亚乙基二醇)为模板剂,正硅酸四乙酯为硅源,强酸性条件下制备了分子筛SBA-15.分别以水及水+乙醇为介质采用LaCl₃溶液与煅烧的主体材料SBA-15分子筛固-液相交换法,制备了La-(SBA-15)复合材料.利用化学分析、粉末XRD、N₂吸附技术、IR评价了制备方法的有效性及对SBA-15分子筛孔结构的影响.结果表明,镧已并入SBA-15分子筛中,SBA-15内表面上的硅羟基团是镧进入的主要位置,部分客体在分子筛孔道内.制得的材料La-(SBA-15)保持高度有序的介孔二维六角结构,不改变载体SBA-15的介孔孔道结构.此外,考察了La-(SBA-15)产物的发光现象.     

High-resolution electron microscopy study of mesoporous dichalcogenides and their hydrogen storage properties

In this work, we report a detailed investigation on the surface topology of ordered mesoporous WS(2) nanoarrays nanocast from the silica SBA-15 template. Using a high-resolution scanning electron microscopy (HRSEM) technique, we acquire distinguishably clear images of the WS(2) surface. A large number of small nanorods are found to be evenly distributed among the nanowire arrays, supporting their ordered mesostructures. Based on these observations, tunnel-like connecting pores are proposed to have a similar distribution in the mother mesoporous silica SBA-15 template. Interestingly, we observe the atomic crystal lattices of the layered WS(2) on the HRSEM image. To the best of our knowledge, this is the first time that atomic crystal lattices have been directly observed using a SEM technique. In addition, both materials show good adsorption-desorption capabilities with hydrogen, and the maximum amount of hydrogen that can be taken up is 0.34 wt% for mesoporous WS(2) and 0.52 wt% for mesoporous MoS(2) at a pressure of 10 bar, indicating that both are potential hydrogen storage materials.     

Adsorption myoglobin over mesoporous silica molecular sieves: Pore size effect and pore-filling model

The present work describes the adsorption of myoglobin over mesoporous materials with different pore diameters (SBA-15 and MCM-41) from buffered solutions. The Langmuir-type adsorption of myoglobin occurs with monolayer coverage on the inner surface of the mesoporous channels. These adsorbents were thoroughly characterized by X-ray diffraction, nitrogen adsorption/desorption and FT-IR spectroscopy before and after the myoglobin adsorption. The amount of myoglobin adsorbed significantly depends on the specific pore volume and/or the pore diameter of the mesoporous silica adsorbents. These experimental results were analyzed using pore-filling models, suggesting that myoglobin molecules are well-packed in the SBA-15 pores. FT-IR spectra before and after the adsorption confirm the structural stability of the adsorbed myoglobin.     

Synthesis and characterization of imidazole-functionalized SBA-15 as an adsorbent of hexavalent chromium

Mesoporous SBA-15 was functionalized with imidazole groups by a facile two-step post-grafting method. The resultant material has been characterized by powder X-ray diffraction, N₂ adsorption/desorption measurements, FT-IR, NMR and elemental analysis to confirm the ordered mesoporous structure and the functionalization of the imidazole groups and employed as an adsorbent of Cr(VI) from aqueous solutions at room temperature. It was showed that the imidazole group can be introduced into the mesoporous channel by the postsynthesis route with high content under controlled reaction conditions. The imidazole-functionalized material exhibits high adsorption capacity of 113 mg/g for Cr(VI) and fast adsorption rate of less than 1 h in aqueous solutions. Equilibrium data were well fitted to the Langmuir adsorption isotherms.     

Preparation of conductive transparent adhesive films from carbon nanomaterials and polar acrylate

Electrically conductive optically clear adhesives (ECOCAs) were prepared using a nanostructured carbon material (CMK-3(150)) as a conductive filler. The mesoporous carbon material, CMK-3(150), was synthesized using an ordered mesoporous silica template to produce inverse replica ordered mesoporous carbon material with an approximately 10 nm pore diameter. An adhesive solution of acrylic monomers containing polar acrylate, CMK-3(150), and thermal initiator was reacted at 80 degrees C to prepare the ECOCA composite which had appropriate viscosity for further processing. The adhesive composite was adhered to various surfaces including ITO films upon thermal processing at 60 degrees C to afford a highly transparent and adhesive film. Tensile strength of the ECOCA films was increased with the contents of conductive filler up to 4 wt%. The percolation concentration of the CMK-3(150) in the composite was approximately 7 wt%, which is much less than those of typical conductive fillers. The optimum content of CMK-3(150) to assure optical clarity, tensile strength, and high conductivity was 2-3 wt%.     

Characterization and application of Ti-containing mesoporous silica for dye removal with synergistic effect of coupled adsorption and photocatalytic oxidation

Highly ordered mesoporous silica, Santa Barbara Amorphous-15 (SBA-15), and titanium-substituted mesoporous silica (TiSBA-15) materials were successfully synthesized, characterized, and evaluated. The textual and structural properties of the prepared materials with various titanium contents were characterized by inductively coupled plasma-mass spectrometer (ICP-MS), powder X-ray diffraction (XRD) patterns, nitrogen physisorption isotherms, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). A limited content of titanium could be effectively substituted into the framework of SBA-15 without provoking structure change. The adsorptive performance was examined by methylene blue (MB) adsorbed on prepared materials. The isotherm models were analyzed to describe the adsorption behavior of prepared materials. The adsorption isotherms were well-fitted with Langmuir and Freundlich models in the simulation of the adsorption behavior of dyes. The SBA-15 and TiSBA-15 materials were found to be effective adsorbents for MB from aqueous solutions. The photodegradation of MB and total organic carbon (TOC) analysis on solid composites were used to evaluate the catalytical performance of Ti-containing mesoporous silica. The synergistic effect of adsorptive and photocatalytical ability of prepared TiSBA-15 was identified. The regeneration and cyclic performance were also proved. These results revealed that TiSBA-15 could be one effective alternative material for dye removal.     

Highly efficient tungsten-substituted mesoporous SBA-15 catalysts for 1-butene metathesis

Tungsten-substituted mesoporous SBA-15 materials have been synthesized by using a direct co-condensation sol–gel method. These resultant materials have been characterized by X-ray diffraction (XRD), nitrogen adsorption, transmission electron microscopy (TEM), ²⁹Si MAS NMR and UV–Visible spectroscopy. Results of these analysis indicated that these materials had high surface area, uniform hexagonal channels and thick framework walls which were similar to that of SBA-15 and the tungsten species were highly dispersed in the silica-based framework structure. The tungsten-substituted mesoporous SBA-15 materials were used as catalysts for 1-butene metathesis for the first time, and they showed excellent catalytic performance. Such outstanding catalytic performance should be attributed to the proper content of tungsten species and its high dispersion.     

Synthesis and characterization of ordered mesoporous silicon carbide with high specific surface area

Ordered mesoporous silicon carbide with a high specific surface area was prepared using poly(methlysilylene)ethynylene by utilizing mesoporous silica SBA-15 as a template which was etched off after pyrolysis in an argon atmosphere. The obtained sample is mainly composed of randomly oriented β-SiC crystallites, and it exhibits an ordered mesoporous structure, a high surface area of 511 m²/g, a large pore volume of 0.61 cm³/g, and narrow pore-size distributions of 4 nm. The rough surface and high order of the material that result from the strong interconnections of the SiC products are the main reasons for such high surface areas. The mesoporous ceramics have stability even after re-treatment at 900 °C for 2 h under an air atmosphere.