Stability Of Mesostructure Research Articles

Shedding light on the formation and stability of mesostructures in ternary “Ouzo” mixtures

Hypothesis: Ternary systems made of water, a water-miscible solvent, and hydrophobic solutes spontaneously produce metastable particles by the “Ouzo effect” and thermodynamically stable “Surfactant-Free Micro Emulsions” (SFME). However, the use of different analyses has led to a variability in the criteria to determine the boundaries of the Ouzo domain. We hypothesized that this could be clarified by investigating the stability and the physical state of the particles.Experiments: We investigate four systems using both solid and liquid solutes and two different solvents, and achieved a careful investigation of their phase diagrams, using DLS, Nanoparticle Tracking Analysis, NMR, Multiple Light Scattering, electrophoretic mobility, and fluorescence analysis.Findings: Our results evidence that the transition from the monophasic to the Ouzo domains does not coincide with the cloudiness curve, and that compositions in the Ouzo domain can look fully transparent, in contrast to what is often considered. This transition is best determined by stability analysis. The cloudiness curve corresponds to the formation of particles with a large size dispersity. In the Ouzo domain, we observed an exchange of solute between the continuous phase and solute particles swollen with solvent. In addition, the particles are stabilized against coalescence by their high negative charge.

Near‐Linear Controllable Synthesis of Mesoporosity in Hierarchical UiO‐66 by Template‐Free Nucleation‐Competition

AbstractHierarchies design of porosity in metal‐organic frameworks (MOFs) has gained significant interest in recent years, and customization of mesoporous sizes in MOFs is still quite challenging. Herein, a template‐free method by nucleation‐competition has been developed to realize a near‐linear control of the mesopore sizes (3–13 nm) in the hierarchical MOF UiO‐66(Hf). High selectivity of enzyme adsorption, high activity of bulky‐molecular catalysis, high stability of mesostructure, and extension to other MOFs further prove the success in the potential customization synthesis and applications.

Surface-functionalization of mesoporous silica films for effective osteoblast-like cell culture

Abstract The transparent mesoporous silica (MPS) films prepared by a supramolecular templating method was immersed in simulated body fluid (SBF), and subsequently was sterilized to evaluate the film structural stability. With immersing in SBF, the calcium and phosphate ion adsorption on the film surfaces was promoted and the mesopore structures underwent the expansion, collapse and reconstruction processes for the SBF immersion time of 6 h. The MPS films immersed in SBF for 3 h exhibited the mesostructural stability with the sterilization processes. We also investigated the Fgn adsorption states on the sterilized MPS films, which were clearly changed with the immersion time in SBF because of the different adsorption states of calcium and phosphate ions at the mesopores. Furthermore, the proliferation and differentiation behaviors of the osteoblast-like cells on the sterilized MPS films were investigated to evaluate the cell culture ability. The osteoblast–like cells cultured on the sterilized MPS films had the fibrous morphologies while maintaining the high adhesion density and were promoted to be the bone tissue formation for 14 days, indicating the preferential film environment for the cells. Therefore, it was suggested that the MPS films of this study were useful for the cell culture substrate based on their high transparency, stability against sterilization treatment, and preferential cytocompatibility.

In-Situ GISAXS Investigation of Pore Orientation Effects on the Thermal Transformation Mechanism in Mesoporous Titania Thin Films

This study addresses the effects of mesopore orientation on mesostructural stability and crystallization of titania thin films during calcination based on measurements with in-situ grazing incidence small angle X-ray scattering (GISAXS). Complementary supporting information is provided by ex-situ electron microscopy. Pluronic surfactant P123 (with average structure (EO)20(PO)70(EO)20 where EO is an ethylene oxide unit and PO is a propylene oxide unit) serves as the template to synthesize titania thin films on P123-modified glass slides with 2D hexagonally close-packed cylindrical mesopores. The orientation of the pores at the top surface is controlled by sandwiching another P123-modified glass slide on top of the titania thin film to completely orient the pores orthogonal to the films in some samples. This provides the opportunity to directly observe how pore orientation affects the evolution of pore order and crystallinity during calcination. The results show that when the pores are oriented parallel to ...

Aquatic plant inspired hierarchical artificial leaves for highly efficient photocatalysis

The natural leaf provides a superior template for engineering the artificial leaf in order to perform light energy conversion. To adapt to the aquatic environments, the aquatic plant leaves usually are thin and soft with excellent mass transportation and light-harvesting capability. In this report, the aquatic leaf is directly employed as a template to construct bioinspired hierarchical photocatalyst while mesoporous directing agent act as a second template. The dual templates consequently ensure the obtained TiO2 with optimal light harvesting structure, high surface area and excellent mass transportation, which contribute to improve photocatalytic capability. Specially, SiO2 is also introduced to form TiO2–SiO2 composite in the final hierarchical replica in order to improve the stability of mesostructures, perfect replication of leaves' fine structures and the dye adsorption capability for facilitating photodegradation. Consequently, the photocatalytic activity of the as-synthesized leaf replicas in the photodegradation of methylene blue is ca. 3 times higher than that of P25, and one order of magnitude higher than that of common nanocrystalline TiO2, under commercial black lamp irradiation.

Efficient synthesis and sulfonation of ordered mesoporous carbon materials

Ordered mesoporous carbons (OMCs) with hexagonal structure were efficiently synthesized via cooperative self-assembly of phenol/formaldehyde resol and surfactant F127 under acidic aqueous conditions. Induced by HCl, a gel phase mainly containing phenol/formaldehyde resol and F127 was obtained within several hours. X-ray diffraction (XRD), transmission electron microscope (TEM) and nitrogen adsorption isotherms indicated that the synthesized samples possess 2-D hexagonal mesostructure. The influence of the synthesis conditions, including acid concentration and mass ratio of resol to F127, was investigated. When the acid concentration was fixed in the range of 0.6–2.0M and the mass ratio of resol to F127 in the range of 3.5–4.0, highly ordered mesoporous carbon could be synthesized. The synthesized OMCs could be easily sulfonated in concentrated sulfuric acid at elevated temperature. The results indicate that the mesostructural stability and the content of the surface sulfonic acid (SO3H) groups depend mainly on the pyrolysis temperature of the OMCs and the sulfonation temperature, suggesting that the combination of pyrolysis and sulfonation temperature is essential for developing OMCs with high densities of SO3H groups.

Influence of Preparation Conditions on Structural Stability of Ordered Mesoporous Carbons Synthesized by Evaporation-induced Triconstituent Co-assembly Method

Various ordered mesoporous carbons (OMCs) have been prepared by evaporation-induced triconstituent co-assembly method. Their mesostructural stability under different carbon content, aging time and acidity were conveniently monitored by X-ray diffraction, transmission electron microscopy, and N2 sorption isotherms techniques. The results show mesostructural stability of OMCs is enhanced as the carbon content increases from 36% to 46%, further increasing carbon content deteriorates the mesostructural stability. Increasing aging time from 0.5 h to 5.0 h make the mesostructural stability go through an optimum (2.0 h) and gradually reduce framework shrinkage of the OMCs. Highly OMCs can only be obtained in the acidity range of 0.2–1.2 mol/L HCl, when the acidity is near the isoelectric point of silica, the resulting OMCs have the best mesostructure stability. Under the optimum condition, the carbon content of 46%, aging time of 2.0 h, and 0.2 mol/L HCl, the resulting OMCs have the best mesostructure stability and the highest BET surface areas of 2281 m2/g.

Stabilizing Surfactant Templated Cylindrical Mesopores in Polymer and Carbon Films through Composite Formation with Silica Reinforcement

A facile approach to maintain the periodic mesostructure of cylindrical pores in polymer-resin and carbon films after thermal template removal is explored through the reactive coassembly of resol (carbon precursor) and tetraethylorthosilicate (silica precursor) with triblock copolymer Pluronic F127. Without silica, a low porosity, disordered film is formed after pyrolysis despite the presence of an ordered mesostructure prior to template removal. However for silica concentration greater than 25 wt %, pyrolysis at 350 °C yields a mesoporous silica−polymer film with well-defined pore mesostructure. These films remain well ordered upon carbonization at 800 °C. In addition to the mesostructural stability, the addition of silica to the matrix impacts other morphological characteristics. For example, the average pore size and porosity of the films increase from 3.2 to 7.5 nm and 12 to 45%, respectively, as the concentration of silica in the wall matrix increases from 0 to 32 wt %. The improved thermal stability...

Comprehensive Study of Pore Evolution, Mesostructural Stability, and Simultaneous Surface Functionalization of Ordered Mesoporous Carbon (FDU-15) by Wet Oxidation as a Promising Adsorbent

Fuctionalization of porous carbon materials through chemical methods orientates the development of new hybrid materials with specific functions. In this paper, a comprehensive study of pore evolution, mesostructural oxidation resistance, and simultaneous surface functionalization of ordered mesoporous carbon FDU-15 under various oxidation conditions is presented for the first time. The mesostructure and pore evolution with increasing oxidative strength are retrieved from XRD, TEM, and N(2) sorption techniques. The textural properties can be conveniently manipulated by changing the oxidation parameters, including different oxidative solution, temperature, and duration. It is revealed that the mesoporous carbon FDU-15 shows excellent structural stability under severe oxidation treatments by acidic (NH(4))(2)S(2)O(8), HNO(3), and H(2)O(2) solutions, much more stable than the mesostructural analogue CMK-3 carbon prepared by the nanocasting method. The surface area and porosity deteriorate to a large extent compared to the pristine carbon, with the micropores/small mesopores as the major contribution to the deterioration. The micropore/small mesopore can be blocked by the attached surface oxides under mild oxidation, while reopened with more carbon layer dissolution under more severe conditions. Simultaneously, high densities of surface oxygen complexes, especially carboxylic groups, can be generated. The contents and properties of the surface oxygen-containing groups are extensively studied by FTIR, TG, elemental analyses, and water and ammonia adsorption techniques. Such surface-functionalized mesoporous carbons can be used as a highly efficient adsorbent for immobilization of heavy metal ions as well as functional organic and biomolecules, with high capacities and excellent binding capabilities. Thus, we believe that the functionalized mesoporous carbon materials can be utilized as a promising solid and stable support for water treatment and organic/biomolecules immobilization and may be applicable in drug delivery, separation, adsorption technology, and columns for GC and HPLC systems in the near future.

Synthesis of thermally stable mesoporous TiO 2 and investigation of its photocatalytic activity

The effects of heat treatment, dopant type and thickness of sol layer, on the formation and stability of ordered TiO 2 mesostructure were investigated. Higher ageing temperature facilitates the separation of organic phase and inorganic phase, while thinner sol layer facilitates the formation of homogeneous system and improves the mesostructural order of TiO 2. Lanthanum dopant, which is more electropositive than Ti, can improve the thermal stability of mesostructure by enhancing the strength of Ti–O bond. On the contrary, Fe and Pd dopants, which are more electronegative than Ti, decrease the thermal stability of mesostructure. Furthermore, La doped mesoporous TiO 2 shows high activity in the photocatalytic degradation of Rhodamine B under the irradiation of visible light.

Synthesis of SBA-15 mesoporous silica via dry-gel conversion route

Dry-gel conversion method has been successfully applied for the synthesis of mesostructured silica SBA-15 materials with the particle size in submicron range. The effects of duration of self-assembly and dry-gel conversion on the structure of SBA-15 are investigated. Submicron particles with uniform mesoporous structure were formed during the first 2 h of static hydrolysis and self-assembly. The particle morphology and pore properties were not obviously influenced by the duration of self-assembly. Without dry-gel conversion, the mesoporous structure significantly shrank after calcination due to its weak stability of mesostructure. After steam-assisted dry-gel conversion at 100 °C, the pore wall is consolidated without damaging the mesostructure because of the support of surfactant micelles inside the pore channels. The larger surface area and pore volume of mesostructured silica were well preserved after calcination. In addition, the surface morphology and particle size were not affected by dry-gel conversion, and submicron particles of mesostructured silica SBA-15 materials were obtained after calcination at 550 °C.

Role of framework sodium versus local framework structure in determining the hydrothermal stability of MCM-41 mesostructures.

Two mesostructured MCM-41 silicas that differ dramatically in hydrothermal stability have been examined by (29)Si MAS NMR spectroscopy and pair distribution function (PDF) analysis of synchrotron X-ray scattering data. The less stable mesostructure assembled from sodium silicate and the substantially more stable derivative made from fumed silica possess equivalent local framework wall structures, as judged by NMR and PDF methods. Approximately 80% of the SiO(4) tetrahedra are fully cross-linked as Q(4) (Si(OSi)(4)) units in both calcined samples. Additionally, the structural correlation distances for the two materials are nearly identical, having values of 1.62(1), approximately 2.60, and 3.09(1) A for the Si-O, O-O, and nearest neighbor Si-Si distances in the framework. Sodium ions in the framework play a crucial role in limiting the hydrothermal stability of the mesostructure. Residual sodium ( approximately 0.05-0.10% Na(2)O) is retained in the MCM-41 made from sodium silicate, even after two ion exchange reactions with ammonium ions in more than 300 - fold excess. The entrapped framework sodium ions catalyze the collapse of the mesopores upon exposure to 20% steam at 800 degrees C for 5 h. The sodium - free mesostructure assembled from fumed silica retains an open framework under the same hydrothermal conditions. The stability of the fumed silica derivative, however, is greatly compromised when doped with as little as 0.10% Na(2)O, thus confirming the deleterious effect of sodium on hydrothermal stability.