Synthesis of lamellar mesoporous silica materials using LCs as templates

The study focuses on the synthesis of mesoporous silica materials using liquid crystals (LCs) formed in an aqueous mixture of cationic cetyltrimethylammonium bromide (CTAB) and anionic sodium dodecyl sulfate (SDS) as templates and tetrathoxysilane (TEOS) as precursor. For this purpose, the phase behavior and range of LC areas were determined at different temperatures, concentrations, and ratios of CTAB/SDS. It was found that LCs became denser with the increased of concentration of surfactants. The mesoporous materials were synthesized using LCs as templates at various temperatures, surfactant concentrations, and pH values. The mesoporous samples were characterized using SEM and nitrogen sorption analysis. The research results showed that the structure of synthesized samples were lamellar and their surface areas increased significantly with the increase of temperature in the temperature range of LCs, reaching about 900?m²/g at 60°C. The surfactant concentrations affect the thickness of pore wall and thereby the specific surface area of products. The specific surface area and the order of mesoporous sample increased gradually with the decrease of pH.     

Silica-based mesoporous organic-inorganic hybrid materials

Mesoporous organic-inorganic hybrid materials, a new class of materials characterized by large specific surface areas and pore sizes between 2 and 15 nm, have been obtained through the coupling of inorganic and organic components by template synthesis. The incorporation of functionalities can be achieved in three ways: by subsequent attachment of organic components onto a pure silica matrix (grafting), by simultaneous reaction of condensable inorganic silica species and silylated organic compounds (co-condensation, one-pot synthesis), and by the use of bissilylated organic precursors that lead to periodic mesoporous organosilicas (PMOs). This Review gives an overview of the preparation, properties, and potential applications of these materials in the areas of catalysis, sorption, chromatography, and the construction of systems for controlled release of active compounds, as well as molecular switches, with the main focus being on PMOs.     

Inorganic-Macroion-Induced Formation of Bicontinuous Block Copolymer Nanocomposites with Enhanced Conductivity and Modulus

A facile and electrostatically driven approach has been developed to prepare bicontinuous polymer nanocomposites that is based on the polyoxometalate (POM) macroion induced phase transition of PS-b-P2VP from an initial lamellar phase to a stable bicontinuous phase. The multi-charged POMs can electrostatically cross-link P2VP blocks and give rise to bicontinuous phases in which the POM hybrid conductive domains occupy a large volume fraction of more than 50 %. Furthermore, the POMs can give rise to high proton conductivity and serve as nanoenhancers, endowing the bicontinuous nanocomposites with a conductivity of 0.1 mS cm⁻¹ and a Young's modulus of 7.4 GPa at room temperature; these values are greater than those of pristine PS-b-P2VP by two orders of magnitude and a factor of 1.8, respectively. This approach can provide a new concept based on electrostatic control to design functional bicontinuous polymer materials.     

Bicontinuous Nanoporous Frameworks: Caged Longevity for Enzymes

The preparation of bicontinuous nanoporous covalent frameworks, which are promising for caging active enzymes, is demonstrated. The frameworks have three‐ dimensionally continuous, hydrophilic pores with widths varying between 5 and 30 nm. Enzymes were infiltrated into the bicontinuous pore by applying a pressured enzyme solution. The new materials and methods allowed the amount of caged proteins to be controlled precisely. The resulting enzyme‐loaded framework films could be recycled many times with nearly no loss of catalytic activity. Entropic trapping of proteins by a bicontinuous pore with the right size distribution is an unprecedented strategy toward facile in vitro utilization of biocatalysts.     

Double-Gyroid Nanostructure Formation by Aggregation-Induced Atropisomerization and Co-Assembly of Ionic Liquid-Crystalline Amphiphiles

We report a new molecular-design principle for creating double-gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol⁻¹ in DMSO-d₆ solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol⁻¹). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co-organize into -type bicontinuous cubic liquid-crystalline mesophases through nanosegregation of the ionic and non-ionic parts. Considering the intrinsic characteristic of -type bicontinuous cubic structures that they are composed of intertwined right- and left-handed single gyroids, we propose that the simultaneous presence of both R- and S-atropisomers is an important contributor to the formation of double-gyroid structures.     

Double‐Gyroid Nanostructure Formation by Aggregation‐Induced Atropisomerization and Co‐Assembly of Ionic Liquid‐Crystalline Amphiphiles

We report a new molecular‐design principle for creating double‐gyroid nanostructured molecular assemblies based on atropisomerization. Ionic amphiphiles containing two imidazolium rings close to each other were designed and synthesized. NMR data revealed that the rotation of the imidazolium rings is restricted, with an activation energy as high as 63 kJ mol^?1 in DMSO‐d₆ solution (DFT prediction for a model compound in the vacuum: 90–100 kJ mol^?1). Due to the restricted rotation, the amphiphiles feature “double” atropisomeric axes in their ionic segments and form three stable atropisomers: meso, R, and S. These isomers co‐organize into ‐type bicontinuous cubic liquid‐crystalline mesophases through nanosegregation of the ionic and non‐ionic parts. Considering the intrinsic characteristic of ‐type bicontinuous cubic structures that they are composed of intertwined right‐ and left‐handed single gyroids, we propose that the simultaneous presence of both R‐ and S‐atropisomers is an important contributor to the formation of double‐gyroid structures.     

Study of adsorption properties of synthesized mesoporous silica doped with dysprosium and modified with nickel

Mesoporous silica (MPS) modified with nickel and MPS doped with dysprosium and modified with nickel have been synthesized by the template method. The adsorbents are characterized by various techniques such as transmission electron microscopy, scanning electron microscopy, X-ray diffraction, inductively coupled plasma spectroscopy, and X-ray fluorescence analyses. The adsorption properties of the synthesized samples have been investigated by inverse gas chromatography. Furthermore, thermodynamic characteristics of the adsorption of test compound belonging to different classes of organic compounds were obtained. In addition, the contributions of the energy of specific interactions to the total adsorption energy were calculated. It is also shown that entropy plays the determining role in the adsorption of test compounds on synthesized mesoporous materials.     

Biomolecule-assisted route to prepare titania mesoporous hollow structures

Amino acids, as a particularly important type of biomolecules, have been used as multifunctional templates to intelligently construct mesoporous TiO(2) hollow structures through a simple solvothermal reaction. The structure-directing behaviors of various amino acids were systematically investigated, and it was found that these biomolecules possess the general capability to assist mesoporous TiO(2) hollow-sphere formation. At the same time, the nanostructures of the obtained TiO(2) are highly dependent on the isoelectric points (pI) of amino acids. Their molecular-structure variations can lead to pI differences and significantly influence the final TiO(2) morphologies. Higher-pI amino acids (e.g., L-lysine and L-arginine) have better structure-directing abilities to generate nanosheet-assembled hollow spheres and yolk/shell structures. The specific morphologies and mesopore size of these novel hollow structures can also be tuned by adjusting the titanium precursor concentration. Heat treatment in air and vacuum was further conducted to transform the as-prepared structures to porous nanoparticle-assembled hollow TiO(2) and TiO(2)/carbon nanocomposites, which may be potentially applied in the fields of photocatalysts, dye-sensitized solar cells, and Li batteries. This study provides some enlightenment on the design of novel templates by taking advantage of biomolecules.