High thermoelectric performance of flexible nanocomposite films based on Bi2Te3 nanoplates and carbon nanotubes selected using ultracentrifugation.

Thermoelectric generators with flexibility and high performance near 300 K have the potential to be employed in self-supporting power supplies for Internet of Things (IoT) devices. Bismuth telluride (Bi2Te3) exhibits high thermoelectric performance, and single-walled carbon nanotubes (SWCNTs) show excellent flexibility. Therefore, composites of Bi2Te3 and SWCNTs should exhibit an optimal structure and high performance. In this study, flexible nanocomposite films based on Bi2Te3 nanoplates and SWCNTs were prepared by drop casting on a flexible sheet, followed by thermal annealing. Bi2Te3 nanoplates were synthesized using the solvothermal method, and SWCNTs were synthesized using the super-growth method. To improve the thermoelectric properties of the SWCNTs, ultracentrifugation with a surfactant was performed to selectively obtain suitable SWCNTs. This process selects thin and long SWCNTs but does not consider the crystallinity, chirality distribution, and diameters. A film consisting of Bi2Te3 nanoplates and the thin and long SWCNTs exhibited high electrical conductivity, which was six times higher than that of a film with SWCNTs obtained without ultracentrifugation; this is because the SWCNTs uniformly connected the surrounding nanoplates. The power factor was 6.3 µW/(cm K2), revealing that this is one of the best-performing flexible nanocomposite films. The findings of this study can support the application of flexible nanocomposite films in thermoelectric generators to provide self-supporting power supplies for IoT devices.

Flexible thermoelectric films formed using integrated nanocomposites with single-wall carbon nanotubes and Bi2Te3 nanoplates via solvothermal synthesis.

Single-wall carbon nanotubes (SWCNTs) and Bi2Te3 nanoplates are very promising thermoelectric materials for energy harvesting. When these two materials are combined, the resulting nanocomposites exhibit high thermoelectric performance and excellent flexibility. However, simple mixing of these materials is not effective in realizing high performance. Therefore, we fabricated integrated nanocomposites by adding SWCNTs during solvothermal synthesis for the crystallization of Bi2Te3 nanoplates and prepared flexible integrated nanocomposite films by drop-casting. The integrated nanocomposite films exhibited high electrical conductivity and an n-type Seebeck coefficient owing to the low contact resistance between the nanoplates and SWCNTs. The maximum power factor was 1.38 µW/(cm K2), which was 23 times higher than that of a simple nanocomposite film formed by mixing SWCNTs during drop-casting, but excluding solvothermal synthesis. Moreover, the integrated nanocomposite films maintained their thermoelectric properties through 500 bending cycles.

Solvothermal synthesis of n-type Bi2(SexTe1-x)3 nanoplates for high-performance thermoelectric thin films on flexible substrates.

To improve thermoelectric performance of materials, the utilization of low-dimensional materials with a multi-alloy system is a promising approach. We report on the enhanced thermoelectric properties of n-type Bi2(SexTe1-x)3 nanoplates using solvothermal synthesis by tuning the composition of selenium (Se). Variation of the Se composition within nanoplates is demonstrated using X-ray diffraction and electron probe microanalysis. The calculated lattice parameters closely followed Vegard's law. However, when the Se composition was extremely high, an impurity phase was observed. At a reduced Se composition, regular-hexagonal-shaped nanoplates with a size of approximately 500 nm were produced. When the Se composition was increased, the shape distribution became random with sizes more than 5 µm. To measure the thermoelectric properties, nanoplate thin films (NPTs) were formed on a flexible substrate using drop-casting, followed by thermal annealing. The resulting NPTs sufficiently adhered to the substrate during the bending condition. The electrical conductivity of the NPTs increased with an increase in the Se composition, but it rapidly decreased at an extremely high Se composition because of the presence of the impurity phase. As a result, the Bi2(SexTe1-x)3 NPTs exhibited the highest power factor of 4.1 µW/(cm∙K2) at a Se composition of x = 0.75. Therefore, it was demonstrated that the thermoelectric performance of Bi2(SexTe1-x)3 nanoplates can be improved by tuning the Se composition.

Nickel(0)-Catalyzed Enantio- and Diastereoselective Synthesis of Benzoxasiloles: Ligand-Controlled Switching from Inter- to Intramolecular Aryl-Transfer Process.

A highly enantioselective synthesis of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles (up to 99.9% ee and 99% yield) was achieved via the sequential activation of an aldehyde and a silane by nickel(0). This strategy was applied to a simultaneous generation of carbon- and silicon-stereogenic centers with excellent selectivity (dr = 99:1) via diastereotopic aryl transfer. Initial mechanistic studies revealed the complete switching of an aryl-transfer process from an intermolecular (racemic synthesis in the presence of IPr) to an intramolecular (enantioselective synthesis using chiral NHC, L5) fashion. A plausible rationale for the switching of the aryl-transfer process is given by a preliminary DFT calculation, which suggests that the coordination of 1 to the nickel(0)/L5 fragment in an η(2)-arene:η(2)-aldehyde fashion would be a key to the intramolecular process, while the formation of the corresponding intermediate is not possible in the presence of IPr. Owing to the chemically labile nature of its C-Si and O-Si bonds, enantioenriched benzoxasiloles are utilized for the synthesis of chiral building blocks and antihistaminic and anticholinergic drug molecules such as (R)-orphenadrine and (S)-neobenodine with no erosion of the enantiomeric excess.

Highly efficient activation of organosilanes with η2-aldehyde nickel complexes: key for catalytic syntheses of aryl-, vinyl-, and alkynyl-benzoxasiloles.

An η(2)-aldehyde nickel complex was utilized as an effective activator for an organosilane in order to generate a hypervalent silicate reactant for the first time. This method was successfully applied to the highly efficient syntheses of 3-aryl-, vinyl-, and alkynyl-2,1-benzoxasiloles from benzaldehydes with aryl-, vinyl-, and alkynylsilyl groups at the ortho position. Initial mechanistic studies revealed that an intermolecular aryl transfer process was involved in the reaction mechanism. The formation of an η(2)-aldehyde complex was directly confirmed by NMR.