MCM-48介孔材料相转化合成的形成机制

利用水热合成的方法,使用新型的表面活性剂十六烷基三甲基对苯磺酸盐作为模板剂合成了高质量的MCM-48介孔分子筛,并用X-射线衍射(XRD)、扫描电镜(SEM)、高分辨透射电镜(HRTEM)以及N₂吸附-脱附进行了表征。合成过程的研究表明该合成体系经历了三相,起始相为具有六方对称性的MCM-41,随着加热时间的延长,生成了具有立方对称性的MCM-48,进一步延长加热时间则生成了层状相MCM-50。三相转变发生的核心驱动力来自于表面活性剂有效堆积参数g因子的改变。另外,XRD、傅立叶变换的红外光谱(FT-IR)以及固体魔角自旋核磁共振(²⁹Si MAS NMR)的表征结果证明：随着晶化时间的延长,相转变的同时伴随着介孔材料的孔壁逐渐由原子无序的非晶态向原子有序的晶态结构转变。最终形成的原子有序层状介孔分子筛可以作为扩孔型微孔分子筛合成的有效前驱体。     

Anionic surfactant-templated mesoporous silica (AMS) nano-spheres with radially oriented mesopores

Mesoporous silica nano-spheres with pore size larger than 3 nm were synthesized using an anionic surfactant as the template. These nano-spheres possess centrosymmetric radial mesopores (emanating from the spherical center to the exterior surface) and form stable suspension. The spherical size and mesostructure can be finely tuned by changing the pH value of the synthetic system in the range of 8.8 to 6.4. In addition, when the pH value was decreased to 5.8, instead of spheres, anisotropic morphologies such as elliptical, peanutlike and trifurcate particles were obtained, exhibiting core/shell structure due to the different orientations of the mesopores in the core and the shell of the particles. It is proposed that the evolution of the morphologies and mesostructures of the products templated by anionic surfactants strongly depend on the pH value of the synthetic system.     

MCM-48介孔材料相转化合成的形成机制

利用水热合成的方法,使用新型的表面活性剂十六烷基三甲基对苯磺酸盐作为模板剂合成了高质量的MCM-48介孔分子筛,并用X-射线衍射(XRD)、扫描电镜(SEM)、高分辨透射电镜(HRTEM)以及N₂吸附-脱附进行了表征。合成过程的研究表明该合成体系经历了三相,起始相为具有六方对称性的MCM-41,随着加热时间的延长,生成了具有立方对称性的MCM-48,进一步延长加热时间则生成了层状相MCM-50。三相转变发生的核心驱动力来自于表面活性剂有效堆积参数g因子的改变,随着反应时间的延长,由于对甲基苯磺酸根离子（Tos^-）的流失,表面活性剂极性头所占的有效面积（a₀）明显减小,g值变大。另外,XRD、傅立叶变换的红外光谱(FT-IR)以及固体魔角自旋核磁共振(²⁹Si MAS NMR)的表征结果证明：随着晶化时间的延长,相转变的同时伴随着介孔材料的孔壁逐渐由原子无序的非晶态向原子有序的晶态结构转变。最终形成的原子有序层状介孔分子筛可以作为扩孔型微孔分子筛合成的有效前驱体。     

Construction of a hierarchical architecture in a wormhole-like mesostructure for enhanced mass transport

A unique hierarchical architecture is successfully constructed in a wormhole-like mesopore structure via a multiple nanocasting route. This novel type of hierarchical porous carbon (HPC) consists of three-dimensional ordered macropores (ca. 150 nm) with interconnecting pore windows, and the walls of these macropores are rich in wormhole-like mesopores (ca. 2.7 nm) and large spherical mesopores (ca. 10 nm), as well as a significant microporosity, presenting a macro-meso-microporous structure with a three-dimensional interconnectivity. Such a hierarchically porous structure may provide fine diffusion pathways for reaction species, which is demonstrated by the experimental result of an enhanced performance in a supercapacitor. For example, with the introduction of a hierarchical porous structure for fast transport and effective access of ions, the as-prepared HPC exhibits a specific capacitance as high as 247 F g(-1), whereas traditional wormhole-like mesoporous carbon has only a specific capacitance of 176 F g(-1).     

Comparisons between surfactant-templated mesoporous and conventional sol-gel-derived CaO-B2O3-SiO2 glasses: Compositional, textural and in vitro bioactive properties

Compositional, textural and in vitro bioactive comparisons between surfactant-templated mesoporous (MCBS) and conventional sol-gel-derived CaO-B₂O₃-SiO₂ (CBS) glasses are studied in this paper. CBS glasses are heterogeneous in composition. Due to the heterogeneity, melting boron oxide that formed during the heat treatment will fill in the pores that should have been generated by decomposition of calcium species. So, unlike other conventional sol-gel-derived bioactive glasses that have disordered and widely distributed mesopores, the CBS glasses are almost nonporous. MCBS glasses are more homogeneous in composition than CBS glasses, mainly ascribed to the effect of the surfactant. MCBS glasses of different compositions possess wormhole-like mesoporous structure and have similar pore size. In vitro bioactive tests show that wormhole-like MCBS glasses are more bioactive than CBS glasses, due to their high porosity.     

Preparation of Hierarchical Mesoporous Silica Nanoparticles through a Single‐Templating Approach

Silicas with hierarchical porous architectures attracted much attention, due to their potential applications in catalysis and separation. Generally, they were prepared through dual‐ or triple‐templating approaches. Herein, mesoporous silica nanoparticles with rod‐like pore channels inside and lamellar mesopores on the surfaces were prepared using the self‐assemblies of a chiral low‐molecular‐weight amphiphile as templates through a single‐templating approach. The formation of the lamellar mesopores was studied by taking field‐emission scanning electron microscopy and transmission electron microscopy images after different reaction times. The lamellar pores were proposed to be formed by merging rod‐like micelles during the sol‐gel process. Moreover, helical nanofibers with rod‐like pore channels inside and lamellar mesopores on the surfaces were prepared with the addition of n‐octanol as a co‐structure‐directing agent.     

Synthesis of mesoporous TiO2 with colloidal gas aphrons,colloidal liquid aphrons,and colloidal emulsion aphrons for dye-sensitized solar cells

High surface area mesoporous titanium dioxide (TiO₂) particles have been prepared by three different kinds of colloidal aphrons: colloidal gas aphrons, colloidal liquid aphrons, and colloidal emulsion aphrons (CEAs). The precipitate of amorphous TiO₂ was prepared by hydrolysis, condensation, and polycondensation reaction of the precursor. The reaction took place under the effect of coulombic repulsion and electrostatic layers of multilayer surfactant molecules. TiO₂ particles with various sizes were prepared with different molar ratio of titanium ion to surfactants, which were sodium lauryl sulfate (SDS), cetyltrimetyhlammonium bromide, triblock copolymer Pluronic P123, and triblock copolymer Pluronic F127. The synthesized samples were characterized by X-ray diffraction, Brunauer-Emmett-Teller analysis, N₂ adsorption/desorption, and transmission electron microscopy. The mesoporous TiO₂ prepared by CEAs method showed a high specific surface area of 224 m²/g with the total pore volume of 0.7751 cm³/g by using SDS as the membrane phase surfactant due to electrostatic attraction favors of anionic surfactant. The solar conversion efficiency of the cell made from TiO₂ increases with the combination of increased surface area and total pore volume for higher amount of dye wetting and loading.     

Hierarchical control of porous silica by pH adjustment: Alkyl polyamines as surfactants for bimodal silica synthesis and its carbon replica

Bimodal macro-mesoporous silica networks have been prepared in a simple one-pot synthesis using an inexpensive tetramine surfactant and tetraethoxysilane as a silica precursor. These novel materials show high pore volumes and templated mesopores (average pore size 3.0 nm) embedded in 20 nm thick walls forming interparticle large meso/macropores. The judicious control of the pH during the silica formation allows for the precise control of the interparticle condensation, likely due to the change in the interaction between the tetramine surfactant and the silica precursors. Finally, a highly porous carbon replica with bimodal porosity was prepared by using the bimodal silica as a hard sacrificial template. The microstructure of the silica template was accurately transferred to the carbon material obtaining high surface areas (up to 1300 m² g⁻¹) and total pore volumes ≥2 cm³ g⁻¹.     

Development of mesophase pitch derived mesoporous carbons through a commercially nanosized template

Mesoporous carbons (MCs) with a high surface area (up to 900 m2/g), large pore volume (up to 2.1 cm3/g), high mesopore ratio (94%), and high yield (70%) were successfully prepared from an AR mesophase pitch, using a commercially nanosized silica template. The removal of the template provided some larger mesopores of 25-50 nm (pore I) with a surface area of ca. 300 m2/g, while the successive carbonization opened the closed pores within the carbon body to give smaller mesopores of 2-10 nm (pore II) with a similar surface area. During the carbonization of pitch precursor, the evaporation of volatile components swells the carbon to introduce the second mesopores among the domains and even microdomain units because of their rearrangements and overlappings in the process. The addition of iron salt with the silica template resulted in a remarkable increase of the surface area (ca. 300 m2/g) by introducing mesopores of 3-5 nm. The resultant MCs maintained some graphitizable natures derived from the anisotropic precursor. Their graphitization at 2400 degrees C provided the graphitic structure with large surface areas (270-460 m2/g) and mesoporosity.     

Elongated silica nanoparticles with a mesh phase mesopore structure by fluorosurfactant templating

Mesoporous silica materials with pore structures such as 2D hexagonal close packed, bicontinuous cubic, lamellar, sponge, wormhole-like, and rectangular have been made by using surfactant templating sol-gel processes. However, there are still some "intermediate" phases, in particular mesh phases, that are formed by surfactants but which have not been made into analogous silica pore structures. Here, we describe the one-step synthesis of mesoporous silica with a mesh phase pore structure. The cationic fluorinated surfactant 1,1,2,2-tetrahydroperfluorodecylpyridinium chloride (HFDePC) is used as the template. Like many fluorinated surfactants, HFDePC forms intermediate phases in water (including a mesh phase) over a wider range of compositions than do hydrocarbon surfactants. The materials produced by this technique are novel elongated particles in which the layers of the mesh phase are oriented orthogonal to the main axis of the particles.     

线型脲醛树脂的半结晶模板化作用

酸性条件下硅溶胶体系中尿素和甲醛聚合反应会产生脲醛树脂-氧化硅杂化沉淀. 沉淀的质量随有机组分比例的增加而增加, 当尿素和甲醛物质的量比≥1.0时生成沉淀的量为恒定最大值. 红外分析表明杂化材料在3348, 1635, 1572和784 cm^－1处产生了可被归结为线型结构(—[NHCONHCH₂]_n—)的特征吸收. XRD分析表明这种线型分子可形成氢键(C＝O…H—N)导向型的半结晶. 微分热重和XRD结果证明结晶物种在290 ℃完全分解. SEM表征显示半结晶杂化沉淀以三维网络结构为特征, 具有层状结晶的各向异性, 其初级粒子即使在室温下干燥也容易开裂. 随着反应时间的延长、酸性的增加或无机组分量的相对增加杂化粒子变得更加致密. 液氮吸附结果证明沉淀焙烧后所得氧化硅材料的结构具有层状孔结构性质, 其比表面积、孔尺寸和孔体积可以达到510 m²/g, 14.3 nm和1.68 cm³/g. 改变反应体系的酸性和反应组分配比等条件可以方便地控制杂化材料的结构.     

直接模板法合成三维立方介孔氧化硅HOM-5

0引言自1992年Mobil公司制备出M41S系列[1,2](包括MCM-41、MCM-48和MCM-50)介孔氧化硅以来,介孔材料以其有序度高、比表面积大、孔径可调等优异特性,引起了材料科学界的关注。不同类型的系列介孔材料,如SBA[3]、HMS[4]、MSU[5]等相继见诸报道。其中,空间群为Ia3d的MCM-48型三维立方介孔氧化硅具有完全相同,但互不相连的两套孔道[6],贯通性好,对称性高,对物料的传输优于二维孔道结构,在吸附、分离及催化等领域应用前景广泛。但这种结构对应的是溶致液晶相图的V1区域,对于多数表面活性剂来说,此相区较小,因此这种结构较难合成[7]。…     

介孔二氧化锆的水热合成和表征

以表面活性剂十二烷基磺酸钠为辅助模板剂,合成了具有较高稳定性的介孔二氧化锆。 采用TG、XRD、FT-IR以及N₂吸附-脱附等测试技术对产物进行了表征。 研究结果表明,以阴离子型表面活性剂为模板合成的二氧化锆前驱体具有层状介孔结构,经过NaOH溶液处理后再经500 ℃煅烧仍能保持其介孔结构,显示了良好的热稳定性。 在表面活性剂脱除后得到双孔分布的孔结构,其孔壁为四方晶相结构。 NaOH对其结构的形成起到了关键作用。     

Sol–gel synthesis,characterization and catalytic activity of mesoporous γ-alumina prepared from boehmite sol by different methods

In this study, boehmite sols were used as alumina precursors for preparing mesoporous γ-aluminas by two different methods. In one case polyethylenimine was used as a structure-directing agent, and in another case ultrasound treatment was applied. Nitrogen physisorption showed that aluminas that had been prepared by these methods demonstrated different porous structures. The sample obtained without additional treatment had closely packed spherical particles and pores had ink-bottle neck morphology. Ultrasound treatment led to the transformation of ink-bottle pores into cylindrical form and to the increase in surface area and pore volume. Aluminas prepared using polyethylenimine as a template showed larger cylindrical wormhole-like mesopores with a broader pore size distribution, high surface area and pore volume. Catalytic tests showed that textural properties as well as crystallite size were very important parameters of synthesized samples which affected the catalytic activity in the methanol dehydration reaction. It was found that γ-Al₂O₃ prepared by ultrasound treatment had large crystallite size and demonstrated high catalytic activity.     

Engineering the Mesopores of Fe3O4@Mesosilica Core–Shell Nanospheres through a Solvothermal Post‐Treatment Method

A solvothermal post‐treatment method was developed to synthesize Fe₃O₄@mesosilica core–shell nanospheres (CSNs) with a well‐preserved morphology, mesoporous structure, and tunable large pore diameters (2.5–17.6 nm) for the first time. N,N‐Dimethylhexadecylamine (DMHA), which was generated in situ during the heat‐treatment process, was mainly responsible for this pore‐size enlargement, as characterized by NMR spectroscopy. This pore‐size expansion can be strengthened with the aid of hexamethyldisilazane (HMDS), whilst the nature of the surface of the Fe₃O₄@mesosilica CSNs can be easily modified with trimethylsilyl groups during the pore‐size‐expansion process. The hydrophobicity of the Fe₃O₄@mesosilica CSNs increased for the enlarged mesopores and the adsorption capacity of these CSNs for benzene (up to 1.5 g g^?1) is the highest ever reported for Fe₃O₄@mesosilica CSNs. The resultant Fe₃O₄@mesosilica CSNs (pore size: 10 nm) showed a 3.6‐times higher adsorption capacity of lysozyme than those without the pore expansion (pore size: 2.5 nm), thus making them a good candidate for loading large molecules.     

High-temperature hydrothermal synthesis of magnetically active, ordered mesoporous resin and carbon monoliths with reusable adsorption for organic dye

Magnetically active, thermally stable, and ordered mesoporous resin (MOMR-200) and carbon (MOMC-200) monoliths were prepared by one-pot hydrothermal synthesis from resol, copolymer surfactant, and iron cations at high-temperature (200 ^°C), followed by calcination at 360 ^°C and carbonization at 600 ^°C. X-ray diffraction results show that both MOMR-200 and MOMC-200 have ordered hexagonal mesoporous symmetry, and N₂ isotherms indicate that these samples have uniform mesopores (3.71, 3.45 nm), high surface area (328, 621 m²/g) and large pore volume (0.31, 0.43 cm³/g). Transmission electron microscopy shows that iron nanoparticles, which are superparamagnetic in nature, are dispersed in the network. More importantly, the high temperature (200 ^°C) products exhibit much better stability than the samples synthesized at low temperature (100 ^°C). Interestingly, MOMC-200 has higher adsorption capacity for organic dyes when compared with commercial adsorbents (activated carbon and macroporous resin: XAD-4). Combining the advantages such as magnetically active, thermally stable networks, ordered and open mesopores, high surface area, large pore volume, adsorption of pollutants in water and desorption in ethanol solvent, MOMC-200 is potentially important for water treatments.     

Mesoporous Zirconium Phenylenesiliconate‐phosphonate Hybrids with Ordered Lamellar Nanostructures

Novel ordered lamellar mesostructure pZrPS‐2 was hydrothermally prepared by using zirconium propoxide and 4‐(EtO)₂OPC₆H₄Si(OEt)₃ (pPPS‐E), which was hydrolyzed to organic building units substituted with both siliconate and phosphonate groups, in the presence of C_nTAB and TMAOH. The pZrPS‐2 materials were obtained at a Zr/PPS ratio of 2 or higher and the basal spacing was increased by using a longer‐chain surfactant (n=12–18). Removal of the occluded surfactants at 300 °C resulted in retention of the lamellar structure with negligible shrinkage of the interlayer distance. Nitrogen adsorption studies revealed the ordered mesoporous nature of pZrPS‐2 with a pore diameter of approximately 2 to 3 nm. The lamellar structure is assumed to be composed of layers that include zirconia‐based crystalline nanodomains and interlayer pillars mainly based on PPS units. Although lamellar structures with the same crystalline phase also formed when no surfactant was added or when the meta isomer of PPS was used, no mesoporous materials were obtained except pZrPS‐2. A possible schematic model to elucidate these results is also proposed.     

Amphiphilic templating of magnesium hydroxide

The synthesis of lamellar mesostructured Mg(OH)2 was achieved through a surfactant templating route. Amphiphilic compounds with different anionic headgroups (phosphate, sulfate, sulfonate, and carboxylate) were used as surfactants. Control of d spacing was achieved through the use of different alkyl carboxylate amphiphiles. It is proposed that the interaction between the highly reactive oxygen atoms of the anionic surfactants and the highly electrophilic Mg atom leads to the formation of high charge density at the interface between the surfactant molecules and the inorganic precursor. This interaction is very strong and the existence of strong bonds between the headgroup molecules of the surfactant and the Mg atom locks the structure in a preferred orientation, i.e., lamellar mesostructure. The strong interaction thus precludes any phase transformation, and only the lamellar phase of Mg(OH)2 is obtained. Calcination of the surfactant by heating in oxygen flow leads to the collapse of the lamellar mesophase and results in the formation of nonporous MgO.     

Synthesis of double mesoporous core-shell silica spheres with tunable core porosity and their drug release and cancer cell apoptosis properties

In this work, we demonstrate a simple two-pot approach to double mesoporous core–shell silica spheres (DMCSSs) with uniform size of 245–790 nm, shell thickness of 41–80 nm and surface area and total pore volume of 141–618 m² g^?1 and 0.14–0.585 cc g^?1, respectively. First, solid silica spherical particles were synthesized by the Stöber method and used as a core. Second, a mesoporous shell could be formed around the silica cores by using an anionic surfactant and a co-structure directing agent. It was found that mesopores can be anchored within dense silica cores during mesoporous silica shell formation, synchronously the base group with surfactant assistant can etch the dense silica cores to re-organize new mesostructure, so that double mesoporous core–shell silica sphere (DMCSS) structure can be obtained by a single surfactant-templating step. The spherical size and porosity of the silica cores of DMCSS together with shell thickness can be tuned by controlling Stöber parameters, including the concentrations of ammonia, solvent and tetraethoxysilane and the reaction time. DMCSS were loaded with ketoprofen and thymoquinone, which are an anti-inflammatory and a potential novel anti-cancer drug, respectively. Both drugs showed controlled release behavior from the pores of DMCSS. Drug uptakes within DMCSS were ～27 and 81 wt.% for ketoprofen and thymoquinone, respectively. Furthermore, DMCSS loaded with thymoquinone was more effective in inducing cancer cell apoptosis than uncontained thymoquinone, because of the slow release of the drug from the mesoporous structure.     

Synthesis and adsorption properties of colloid-imprinted mesoporous carbons using poly(vinylidene chloride-co-vinyl chloride) as a carbon precursor

A facile synthesis of micro- and mesoporous carbons has been proposed using colloidal silica nanoparticles with diameter of ∼24 nm and poly(vinylidene chloride-co-vinyl chloride) (Saran) as a carbon precursor. The resulting carbons possessed large specific surface area, ∼800 m²/g, and approximately the same volume of micro- and mesopores, each about 50% of the total pore volume. While the size of micropores was around 1 nm, the large and uniform spherical mesopores (about 24 nm) resemble the diameters of silica colloids used. Nitrogen adsorption measurements proved that these mesopores were interconnected and accessible. The well-developed microporosity was created mainly by decomposition of Saran copolymer during carbonization.