Chirality is widely expressed in organic materials, perhaps most notably in biological molecules such as DNA, and in proteins, owing to the homochirality of their components (d-sugars and l-amino acids). But the occurrence of large-scale chiral pores in inorganic materials is rare. Although some progress has been made in strategies to synthesize helical and chiral zeolite-like materials, the synthesis of enantiomerically pure mesoporous materials is a challenge that remains unsolved. Here we report the surfactant-templated synthesis of ordered chiral mesoporous silica, together with a general approach for the structural analysis of chiral mesoporous crystals by electron microscopy. The material that we have synthesized has a twisted hexagonal rod-like morphology, with diameter 130-180 nm and length 1-6 micro m. Transmission electron microscopy combined with computer simulations confirm the presence of hexagonally ordered chiral channels of 2.2 nm diameter winding around the central axis of the rods. Our findings could lead to new uses for mesoporous silica and other chiral pore materials in, for example, catalysis and separation media, where both shape selectivity and enantioselectivity can be applied to the manufacturing of enantiomerically pure chemicals and pharmaceuticals.
Anionic surfactants are used in greater volume than any other surfactants because of their highly potent detergency and low cost of manufacture. However, they have not been used as templates for synthesizing mesoporous silica. Here we show a templating route for preparing mesoporous silicas based on self-assembly of anionic surfactants and inorganic precursors. We use aminosilane or quaternized aminosilane as co-structure-directing agent (CSDA), which is different from previous pathways. The alkoxysilane site of CSDA is co-condensed with inorganic precursors; the ammonium site of CSDA, attached to silicon atoms incorporated into the wall, electrostatically interacts with the anionic surfactants to produce well-ordered anionic-surfactant-templated mesoporous silicas (AMS). These have new structures with periodic modulations as well as two-dimensional hexagonal and lamellar phases. The periodic modulations may be caused by the coexistence of micelles that differ in size or curvature, possibly owing to local chirality. These mesoporous silicas provide a new family of mesoporous materials as well as shedding light on the structural behaviour of anionic surfactants.
Hierarchical porous TiO(2)-B with thin nanosheets is successfully synthesized. TiO(2)-B polymorph ensures fast insertion of Li-ion due to its pseudocapacitive mechanism. The thin nanosheet walls with porous structure allow exposure to electrolytes for facile ionic transport and interfacial reaction. The joint advantages endow this material with high reversible capacity, excellent cycling performance, and superior rate capability.
One of the challenges in material science has been to prepare macro-or mesoporous zeolite. Although examples of their synthesis exist, there is a need for a facile yet versatile approach to such hierarchical structures. Here we report a concept for designing a single quaternary ammonium head amphiphilic template with strong ordered self-assembling ability through p-p stacking in hydrophobic side, which stabilizes the mesostructure to form singlecrystalline mesostructured zeolite nanosheets. The concept is demonstrated for the formation of a new type of MFI (zeolite framework code by International Zeolite Association) nanosheets joined with a 90°rotational boundary, which results in a mesoporous zeolite with highly specific surface area even after calcination. Low binding energies for this selfassembling system are supported by a theoretical analysis. A geometrical matching between the arrangement of aromatic groups and the zeolitic framework is speculated for the formation of single-crystalline MFI nanosheets.
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