Two-dimensional (2D) nanomaterials have been the focus of substantial research interest recently owing to their fascinating and excellent properties. However, 2D porous materials have remained quite rare due to the difficulty of creating pores in 2D nanostructures. Here, we have synthesized a novel type of single-layered 2D mesoporous TiO nanosheets with very uniform size and thickness as well as ordered mesostructure from an unprecedented hydrothermal-induced solvent-confined assembly approach. The F127/TiO spherical monomicelles are first formed and redispersed in ethanol and glycerol, followed by a hydrothermal treatment to assemble these subunits into single-layered 2D mesostructure owing to the confinement effect of highly adhered glycerol solvent. The obtained 2D mesoporous TiO nanosheets have a relative mean size at around 500 × 500 nm and can be randomly stacked into a bulk. The TiO nanosheets possess only one layer of ordered mesopores with a pore size of 4.0 nm, a very high surface area of 210 m g and a uniform thickness of 5.5 nm. The thickness can be further manipulated from 5.5 to 27.6 nm via simply tuning precursor concentration or solvent ratio. Due to the well-defined 2D morphology and large mesoporosity as well as crystalline anatase mesopore walls, these uniform TiO nanosheets are capable of providing large accessible voids for sodium ion adsorption and intercalation as well as preventing volume expansion. As expected, these mesoporous TiO nanosheets have exhibited an excellent reversible capacity of 220 mAh g at 100 mA g as sodium-ion battery anodes, and they can retain at 199 mAh g after numerous cycles at different current densities. The capacity is retained at 44 mAh g even at a large current density of 10 A g after 10 000 cycles, demonstrating a remarkable performance for energy storage.
We have demonstrated a facile hydrothermal approach to synthesize a novel type of mesoporous TiO 2 material with highly controllable structure. By regulating the synthetic conditions, the mesoporous TiO 2 can be well controlled with desired crystallites and architectures. The resulting mesoporous TiO 2 exhibits excellent penetration properties and photocatalytic performance. These unique mesoporous TiO 2 microspheres produced at moderate conditions could afford great opportunities in achieving high performance in various practical applications.
Oriented
self-assembly between inorganic nanocrystals and surfactants is emerging
as a route for obtaining new mesocrystalline semiconductors. However,
the actual synthesis of mesoporous semiconductor mesocrystals with
abundant surface sites is extremely difficult, and the corresponding
new physical and chemical properties arising from such an intrinsic
porous mesocrystalline nature, which is of fundamental importance
for designing high-efficiency nanostructured devices, have been rarely
explored and poorly understood. Herein, we report a simple evaporation-driven
oriented assembly method to grow unprecedented olive-shaped mesoporous
TiO2 mesocrystals (FDU-19) self-organized by ultrathin
flake-like anatase nanocrystals (∼8 nm in thickness). The mesoporous
mesocrystals FDU-19 exhibit an ultrahigh surface area (∼189
m2/g), large internal pore volume (0.56 cm3/g),
and abundant defects (oxygen vacancies or unsaturated Ti3+ sites), inducing remarkable crystallite-interface reactivity. It
is found that the mesocrystals FDU-19 can be easily fused in situ
into mesoporous anatase single crystals (SC-FDU-19) by annealing in
air. More significantly, by annealing in a vacuum (∼4.0 ×
10–5 Pa), the mesocrystals experience an abrupt
three-dimensional to two-dimensional structural transformation to
form ultrathin anatase single-crystal nanosheets (NS-FDU-19, ∼8
nm in thickness) dominated by nearly 90% exposed reactive (001) facets.
The balance between attraction and electrostatic repulsion is proposed
to determine the resulting geometry and dimensionality. Dye-sensitized
solar cells based on FDU-19 and SC-FDU-19 samples show ultrahigh photoconversion
efficiencies of up to 11.6% and 11.3%, respectively, which are largely
attributed to their intrinsic single-crystal nature as well as high
porosity. This work gives new understanding of physical and chemical
properties of mesoporous semiconductor mesocrystals and opens up a
new pathway for designing various single-crystal semiconductors with
desired mesostructures for applications in catalysis, sensors, drug
delivery, optical devices, etc.
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