Direct synthesis of hierarchical monolithic silica for high performance liquid chromatography

The silica-based monolith exhibiting a hierarchical bimodal porous structure has been directly synthesized via lytropic mesophase. The hydrolysis and condensation of tetramethoxysilane (TMOS) in the presence of poly(ethylene oxide)-block-poly(propylene oxide)-block-poly(ethylene oxide) (P123) and acetic acid results in silica monolith with MSU-type mesoporous structure embedded in the skeleton of the interconnected macropore. The silica monolith with bimodal porous structure can separate benzene and phenol with high flow rate and low back-pressure. Moreover, the chromatographic property of C18-grafted silica monolith is investigated in the separation of aromatic molecules. Our primary result shows that the silica monolith with interconnected macropore and MSU-type mesopore is a promising packing material as stationary phase for high performance liquid chromatography.     

Self-formation phenomenon to hierarchically structured porous materials: design, synthesis, formation mechanism and applications

In this paper, we will thoroughly review a novel and versatile self-formation phenomenon that can be exploited to target porous hierarchies of materials without need of any external templates only on the basis of the chemistry of metal alkoxides and alkylmetals. These hierarchically porous materials have unique structures, which are made of either parallel funnel-like/straight macrochannels or 3D continuous interconnected macroporous foams with micro/mesoporous walls. The self-generated porogen mechanism has been proposed, leading to a series of techniques to tailor porous hierarchy, i.e. the use of different chemical precursors (single metal alkoxides, mixed metal alkoxides, single molecular precursors with two different alkoxide functionalities, alkylmetals, etc., …), the control of their hydrolysis and condensation rates (pH, chelating agents,…) and the addition of alkoxysilanes as co-reactant. Various chemical compositions from single or binary metal oxides, to aluminosilicates, aluminophosphates, silicoaluminophosphates, metallophosphates,… can be prepared, offering a panel of potential applications. Some perspectives have been proposed to transform the synthesized materials with a hierarchy of pore sizes to micro-meso-macroporous crystalline materials with zeolite architectures. The advantages of this self-formation preparation method have been discussed compared to traditional templating methods. The possibility to combine with other strategies, for example soft or hard templating, to target even more sophisticated hierarchically meso-macroporous materials with specific structure and function for various applications has been presented. The "hierarchical catalysis" concept has been re-visited.     

Self-generated hierarchically porous titania with high surface area: photocatalytic activity enhancement by macrochannel structure

Various hierarchical porous titania with high surface area over 600 m(2)/g have been synthesized via a spontaneous self-formation process from titanium alkoxides by a water adjusting approach using acetonitrile as reaction medium. The reactivity of metal alkoxides and the water content in acetonitrile medium on the resultant structure have been investigated. The porosities of the products were characterized by SEM, TEM and N(2) adsorption-desorption measurements. The observation on the evolution of porous structure with increasing water content in reaction system is essential for a better understanding of hierarchical porous structure formation over different length scales by this self-formation process. The creation of macro/micropores in photocatalytic titania materials has been found to enhance the photocatalytic activity due to both the action of macrochannels as light harvester and the easy diffusion effect of organic molecules. The present work shows clearly that hierarchically porous titania with the presence of macroporous structure and high surface area can be very efficient photocatalysts, suggesting their potential applications in water treatment as decontamination materials.     

Syntheses of ordered mesoporous silica by new hybrid template

Ordered mesoporous silica with macroscopic shape has been prepared with a hybrid template of gel and poly(ethylene oxide)₁₀₆–poly(propylene oxide)₇₀–poly(ethylene oxide)₁₀₆ (pluronic F127) surfactant, where both water-soluble agar gel and pluronic F127 significantly affect the mesoporous structure and morphology of silica. The thermal analysis revealed the noticeable interaction between agar and F127, which contributes to the formation of homogenous hybrid template. In the hybrid template, agar gel contributed to the maintenance of morphology structure, while F127 was responsible for the formation of ordered porous structure in silica solids.     

Formation of interpenetrating hierarchical titania structures by confined synthesis in inverse opal

Hierarchical periodic titania nanostructures composed of a macroporous crystalline scaffold and mesoporous titania were prepared by confined synthesis. The strategy for the generation of these hierarchical structures involves preparation of inverse opal titania layers and subsequent filling of the interstitial macroporous voids with surfactant-containing titania precursors to obtain a mesostructured titania phase using the surfactant Pluronic P123. The formation of mesostructure in the confined space of the macroporous scaffold upon thermal treatment was investigated with in situ grazing incidence small-angle X-ray scattering (GISAXS). The macroporous scaffold strongly influences the mesostructure assembly and leads to much larger structural parameters of the formed mesostructure, this effect becoming more pronounced with decreasing pore size of the macroporous host. Furthermore, the inverse opal scaffold acts as a stabilizing matrix, limiting the shrinkage of the mesopores upon heating. This effect is coupled with an enhanced crystallization of the mesophase, which is attributed to the crystalline walls of the macroporous host. Sorption measurements of the final hierarchical titania structure of 5 μm thickness show that the porous system is fully accessible, has a high total surface area of 154 m(2)/g, and has an average mesopore size of 6.1 nm, which is about 20% larger than the pore size of 5.1 nm for the reference mesoporous film obtained on a flat substrate. These hierarchical structures were implemented as anodes in dye-sensitized solar cells (DSCs), showing a conversion efficiency of 4% under one sun illumination, whereas the calcined macroporous scaffold alone shows an efficiency of only 0.4%.     

双模板法制备介孔／大孔复合孔结构硅胶独石

采用双模板法,向正硅酸甲酯的水解体系中同时引入聚乙二醇和三嵌段共聚物,成功制备出具有双连续大孔、同时孔壁中分布着有序介孔的复合孔结构硅胶独石材料. 产物的比表面积高达880 m2/g, 大孔孔径为0.2～5 μm, 介孔高度集中地分布在 5 nm. 结合物理吸附、扫描电镜、粉末X射线衍射和透射电镜等表征手段,发现合成条件如原料组成、反应温度和pH值等对反应体系中凝胶化转变和相分离发生的相对速度有重要影响,进而影响产物复合孔结构的生成. 此外,通过对合成条件的优化,一方面增强了无机骨架的强度,另一方面降低了湿凝胶干燥过程中的毛细管压力降,有效缓和了凝胶结构在干燥过程中的开裂和变形,使复合孔结构硅胶独石在厘米尺度内具有良好的整体性能.     

Hierarchically porous titania thin film prepared by controlled phase separation and surfactant templating

Poly(propylene glycol) (PPG) of moderately high molecular weight (M(n) = 3500 Da) exhibits amphibious behavior in aqueous solution in that it is hydrophilic at low temperature but hydrophobic at high temperature. This property is utilized to generate porous titania thin films with a hierarchical structure consisting of macroporous voids/cracks in films with mesoporous walls. The smaller mesopores result from the self-assembly of the Pluronic block copolymer P123 to form micellar templates in well-ordered arrays with hexagonal symmetry. The larger pores are generated from the phase separation of PPG during aging of the films. The PPG acts to a limited degree as a swelling agent for the P123 micelles, but because the films are aged at a low temperature where PPG is hydrophilic, much of the PPG remains in the polar titania phase. Upon heating, the PPG phase separates to form randomly dispersed, large pores throughout the film while retaining the ordered mesoporous P123-templated structure in the matrix of the material. TEM and SEM imaging confirm that calcined titania thin films have interconnected hierarchical porous structures consisting of ordered mesopores 4-12 nm in diameter and macroporous voids >100 nm in size. The density and size of the voids increase as more PPG is added to the films.     

Uniform hierarchical silica film with perpendicular macroporous channels and accessible ordered mesopores for biomolecule separation

Herein, we demonstrate that silica films with perpendicular macroporous channels and accessible ordered mesopores can be conveniently prepared. The hierarchical macroporous–mesoporous silica films are synthesized by using zinc oxide nanorod array as macroporous template and CTAB surfactant as mesoporous template. In basic surfactant-containing solution, ordered mesoporous silica shells homogeneously grow on the zinc oxide nanorod array. The growth of the mesostructures do not require any chemical modification for the zinc oxide nanorod, which opens a new way for preparing hierarchical silica films with perpendicular mesochannels. The prepared hierarchical macroporous–mesoporous silica films possess a uniform thickness of 2 mm, large perpendicular macropores with a length of 1.8 mm and a width of 80 nm, and accessible ordered mesopores. Separation experiment demonstrates that this macroporous–mesoporous film can effectively separate biomolecules with different sizes.     

Synthesis of Mesoporous TiO2/SiO2 Hybrid Films as an Efficient Photocatalyst by Polymeric Micelle Assembly

Thermally stable mesoporous TiO₂/SiO₂ hybrid films with pore size of 50 nm have been synthesized by adopting the polymeric micelle‐assembly method. A triblock copolymer, poly(styrene‐b‐2‐vinyl pyridine‐b‐ethylene oxide), which serves as a template for the mesopores, was utilized to form polymeric micelles. The effective interaction of titanium tetraisopropoxide (TTIP) and tetraethyl orthosilicate (TEOS) with the polymeric micelles enabled us to fabricate stable mesoporous films. By changing the molar ratio of TEOS and TTIP, several mesoporous TiO₂/SiO₂ hybrid films with different compositions can be synthesized. The presence of amorphous SiO₂ phase effectively retards the growth of anatase TiO₂ crystal in the pore walls and retains the original mesoporous structure, even at higher temperature (650 °C). These TiO₂/SiO₂ hybrid films are of very high quality, without any cracks or voids. The addition of SiO₂ phase to mesoporous TiO₂ films not only adsorbs more organic dyes, but also significantly enhances the photocatalytic activity compared to mesoporous pure TiO₂ film without SiO₂ phase.     

Synthesis and Characterisation of Hierarchically Structured Titanium Silicalite-1 Zeolites with Large Intracrystalline Macropores

The successful synthesis of hierarchically structured titanium silicalite-1 (TS-1) with large intracrystalline macropores by steam-assisted crystallisation of mesoporous silica particles is reported. The macropore topology was imaged in 3D by using electron tomography and synchrotron radiation-based ptychographic X-ray computed tomography, revealing interconnected macropores within the crystals accounting for about 30 % of the particle volume. The study of the macropore formation mechanism revealed that the mesoporous silica particles act as a sacrificial macropore template during the synthesis. Silicon-to-titanium ratio of the macroporous TS-1 samples was successfully tuned from 100 to 44. The hierarchically structured TS-1 exhibited high activity in the liquid phase epoxidation of 2-octene with hydrogen peroxide. The hierarchically structured TS-1 surpassed a conventional nano-sized TS-1 sample in terms of alkene conversion and showed comparable selectivity to the epoxide. The flexible synthesis route described here can be used to prepare hierarchical zeolites with improved mass transport properties for other selective oxidation reactions.     

SiO2阶层多孔结构搭建及块体材料制备机理

借助溶胶-凝胶结合相分离和模板法进行了阶层多孔结构的搭建及二氧化硅多孔块体材料的制备,表征了阶层多孔块体的显微结构及孔结构特性,分析了阶层多孔结构的搭建机理。研究结果表明,三嵌段共聚物聚环氧乙烷-聚环氧丙烷-聚环氧乙烷（P123）的加入不仅诱导共混体系发生相分离,调控大孔结构的形成,同时形成球形胶束并作为模板剂进入骨架,而1,3,5-三甲基苯（TMB）的加入使P123形成的胶束膨胀且更加稳定,在骨架上成功引入了球形介孔,骨架中凝胶粒子相互聚集形成微孔,从而搭建贯通大孔-球形介孔-微孔同时分布的阶层多孔结构,并获得相应的多孔块体材料;当正硅酸甲酯（TMOS）：P123：TMB摩尔比为1：0.015：0.353时,多孔块体材料的阶层多孔结构最优,大孔孔径为0.5-1.5 μm,介孔孔径为3-4 nm,显气孔率66.1%,比表面积为616 m²·g^-1。     

A co-templated approach to hierarchically mesoporous–macroporous bioactive glasses (MMBG) scaffolds for bone tissue regeneration

In this paper, one kind of well-ordered hierarchical mesoporous–macroporous bioactive glasses (MMBG) scaffolds with large pore size of 60–120 μm and mesoporous phase in inner-wall has synthesized successfully. This method used stem core of corn as macroporous template and P123 as mesoporous template. The final samples have replicated the structure of the macroporous plant templates precisely. Since the aperture and pore structure of different plants are variable, it provides a possible way for the synthesis of materials with various aperture holes and pore structure. The organizational structure of final sample is benefit to transport and storage guest molecule, making these hierarchical porous materials have more superior performance and application in the field of macromolecules separation, bone tissue regeneration, and drug delivery, etc. The in vitro tests indicated hierarchical MMBG scaffolds have well capacity for inducing the HA growth. They have the potential to satisfy the demands of bone tissue engineering regeneration.     

Synthesis and characterization of SiC materials with hierarchical porosity obtained by replication techniques

Porous silicon carbide monoliths were obtained using the infiltration of preformed SiO(2) frameworks with appropriate carbon precursors such as mesophase pitch. The initial SiO(2) monoliths possessed a hierarchical pore system, composed of an interpenetrating bicontinuous macropore structure and 13 nm mesopores confined in the macropore walls. After carbonization, further heat treatment at ca. 1,400 degrees C resulted in the formation of a SiC-SiO(2) composite, which was converted into a porous SiC monolith by post-treatment with ammonium fluoride solution. The resulting porous SiC featured high crystallinity, high chemical purity and showed a surface area of 280 m(2) g(-1) and a pore volume of 0.8 ml g(-1).     

P123-PMMA dual-templating generation and unique physicochemical properties of three-dimensionally ordered macroporous iron oxides with nanovoids in the crystalline walls

Three-dimensionally (3D) ordered macroporous (3DOM) iron oxides with nanovoids in the rhombohedrally crystallized macroporous walls were fabricated by adopting the dual-templating [Pluronic P123 and poly(methyl methacrylate) (PMMA) colloidal microspheres] strategy with ferric nitrate as the metal precursor in an ethanol or ethylene glycol and methanol mixed solution and after calcination at 550 °C. The possible formation mechanisms of such architectured materials were discussed. The physicochemical properties of the materials were characterized by means of techniques such as XRD, TGA/DSC, FT-IR, BET, HRSEM, HRTEM/SAED, UV-vis, XPS, and H(2)-TPR. The catalytic properties of the materials were also examined using toluene oxidation as a probe reaction. It is shown that 3DOM-structured α-Fe(2)O(3) without nanovoids in the macroporous walls was formed in the absence of P123 during the fabrication process, whereas the dual-templating strategy gave rise to α-Fe(2)O(3) materials that possessed high-quality 3DOM structures with the presence of nanovoids in the polycrystalline macropore walls and higher surface areas (32-46 m(2)/g). The surfactant P123 played a key role in the generation of nanovoids within the walls of the 3DOM-architectured iron oxides. There was the presence of multivalent iron ions and adsorbed oxygen species on the surface of each sample, with the trivalent iron ion and oxygen adspecies concentrations being different from sample to sample. The dual-templating fabricated iron oxide samples exhibited much better low-temperature reducibility than the bulk counterpart. The copresence of a 3DOM-structured skeleton and nanovoids in the macropore walls gave rise to a drop in the band-gap energy of iron oxide. The higher oxygen adspecies amounts, larger surface areas, better low-temperature reducibility, and unique nanovoid-containing 3DOM structures of the iron oxide materials accounted for their excellent catalytic performance in the oxidation of toluene.     

Templating mesoporous silica with chiral block copolymers and its application for enantioselective separation

In this paper we describe the synthesis of chiral mesoporous silica based on chiral block copolymers of poly(ethylene oxide) and of d-phenylalanine (PEO-b-D-Phe) as a surfactant template. The resulting porous structures are characterized by nitrogen sorption experiments, transmission electron microscopy, and small-angle XRD. It is shown that chiral block copolymers of PEO-b-D-Phe are effective as a surfactant template for the preparation of silica materials with highly ordered periodic mesoporous structures of hexagonal symmetry with a pore size of ca. 5 nm and high surface areas of ca. 700 m2/g. The enantioselectivity feature of this porous silica, after the extraction of the chiral copolymers, was examined by selective adsorption of enantiomers and racemic solutions of valine. The selective adsorption was measured by circular dichroism (CD) spectroscopy. A chiral selectivity factor of 2.34 was found with the D enantiomer of valine adsorbed preferably.     

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).     

有序多级孔N/Nd/TiO_2的制备及其在可见光下催化降解甲基橙的性能

以聚苯乙烯为胶晶模板,采用溶胶-凝胶法制备了有序多级孔N/Nd/TiO_2(1),其结构和形貌经SEM,XRD,XPS和N2吸附-脱附表征。研究了1在可见光下催化降解甲基橙的性能。结果表明:1为有序大孔/介孔多级结构,大孔孔道/介孔孔窗呈相互通透三维有序结构,大孔孔道内径约230 nm,介孔孔窗约30 nm,比表面积为125.50 m~2·g~(-1),比孔容为1.124 5 cm~3·g~(-1)。1催化甲基橙的脱色率为42.76%。     

Mesoporous nanotubes of iron phosphate: synthesis, characterization, and catalytic property

Iron phosphate nanotubes with mesoporous walls are solvothermally synthesized using sodium dodecyl sulfate (SDS) as a template. With different template concentrations, various shapes of nanosized iron phosphates can be obtained. When the concentration of SDS is set at the transition regions between the lamellar and the hexagonal mesophases, according to its phase diagram, the coassembly of iron phosphate precursor and SDS forms a flake-type mesoporous iron phosphate. Otherwise, nanoparticles or bulky sheets of iron phosphates are obtained. The followed solvothermal treatments on the mesoporous iron phosphate flakes produce iron phosphate nanotubes with mesoporous walls. The removal of the surfactant by acetate exchange and heat treatment results in the clean mesoporous nanotubes of iron phosphate with diameters of 50-400 nm and lengths of several microns. The nanotubular and mesoporous iron phosphate possesses a specific surface area of 232 m2/g and a bimodal distribution of pore sizes, corresponding to the size of mesopores in the walls and the diameter of the nanotubes, respectively. The novel nanotubular iron phosphate with composite meso-macroporous structure, in favor of the diffusion of reactive molecules, has been tested for direct hydroxylation of benzene with hydrogen peroxide and has shown better catalytic performance compared with the conventional particulate mesoporous iron phosphate.     

Nano-architectural silica thin films with two-dimensionally connected cagelike pores synthesized from vapor phase

Novel mesostructured silica thin films were prepared on a Si substrate by a vapor-phase synthesis. Vapor of tetraethoxysilane (TEOS) was infiltrated into a surfactant film consisting of a poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymer. Nanophase transition from a lamellar structure to a two-dimensional cage structure of a silica-surfactant nanocomposite was found under vapor infiltration. The rearrangement into the cage structure implies high mobility of the silica-surfactant composites in solid phase. The silica thin films have two-dimensionally connected cagelike mesopores and are isotropic parallel to the film surface. The structure of pores of the films is advantageous for next-generation low-k films. The mesoporous structure has a large lattice parameter d of approximately 102 A, silica layer thickness of approximately 58 A, pillar diameter in the middle of approximately 60 A, pore size of approximately 72 A, BET surface area of approximately 729 m(2)/g, and pore volume of approximately 1.19 cm(3)/g. The films synthesized by the vapor infiltration show a lower concentration of residual Si-OH groups compared to the films prepared by a conventional sol-gel method. The films show high thermal stability up to 900 degrees C and high hydrothermal stability. This method is a simpler process than conventional sol-gel techniques and attractive for mass production of a variety of organic-inorganic composite materials and inorganic porous films.     

Principles of hierarchical meso- and macropore architectures by liquid crystalline and polymer colloid templating

The generation of porous silica with hierarchically organized bimodal mesoporosity of adjustable size and well-defined shape was investigated by using surfactant mixtures and the nanocasting procedure (liquid crystalline templating). A systematic study of combinations of various block copolymers (Pluronics F127, KLE (poly(omega-hydroxypoly(ethylene-co-butylene)-co-poly(ethylene oxide))) and SE (PS-co-PEO)) with smaller surfactants (Pluronics P123, C16mimCl, and CTAB) revealed that hierarchical bimodal mesopore architectures could only be obtained by the usage of block copolymers with a strong hydrophilic-hydrophobic contrast, such as KLE and SE, giving rise to pores between 6 and 22 nm. Furthermore, the ionic liquid (IL) C16mimCl appeared to have advantageous templating properties, resulting in 2-3-nm pores being located between the block copolymer mesopores, whereas phase separation was observed for Pluronics and CTAB as small templates. Thereby, the study provided also general insights into the mixing and co-self-assembly behavior of block copolymers and ionic surfactants in water and confirmed the special templating properties of ILs, as recently proposed. In addition to the bimodal mesoporosity, additional tunable macroporosity was created by the presence of poly(styrene) or poly(methyl methacrylate) spheres, leading to well-defined trimodal hierarchical pore architectures with the small pores being located in the walls of the respective larger pores. As a major improvement, due to the pore hierarchy, these large-pore materials showed relatively large surface areas and pore volumes, and the size of densely packed macropores could even be decreased down to 90 nm. The materials were characterized by electron microscopy, small-angle X-ray scattering, and nitrogen sorption using a proper NLDFT (nonlocal density functional theory) approach for calculations of the pore size distribution in the entire range of micro- and mesopores.