Inorganic zeolites are used for many practical applications that exploit the microporosity intrinsic to their crystal structures. Organic analogues, which are assembled from modular organic building blocks linked through non-covalent interactions, are of interest for similar applications. These range from catalysis, separation and sensor technology to optoelectronics, with enantioselective separation and catalysis being especially important for the chemical and pharmaceutical industries. The modular construction of these analogues allows flexible and rational design, as both the architecture and chemical functionality of the micropores can, in principle, be precisely controlled. Porous organic solids with large voids and high framework stability have been produced, and investigations into the range of accessible pore functionalities have been initiated. For example, catalytically active organic zeolite analogues are known, as are chiral metal-organic open-framework materials. However, the latter are only available as racemic mixtures, or lack the degree of framework stability or void space that is required for practical applications. Here we report the synthesis of a homochiral metal-organic porous material that allows the enantioselective inclusion of metal complexes in its pores and catalyses a transesterification reaction in an enantioselective manner. Our synthesis strategy, which uses enantiopure metal-organic clusters as secondary building blocks, should be readily applicable to chemically modified cluster components and thus provide access to a wide range of porous organic materials suitable for enantioselective separation and catalysis.
The assembly of nanowires and nanotubes into arrays patterned on multiple length scales is critical to the realization of integrated electronic and photonic nanotechnologies. A general and efficient solution-based method for controlling organization and hierarchy of nanowire structures over large areas has been developed. Nanowires were aligned with controlled nanometer to micrometer scale pitch using the Langmuir− Blodgett technique and transferred to planar substrates in a layer-by-layer process to form parallel and crossed nanowire structures. The parallel and crossed nanowire structures were efficiently patterned into repeating arrays of controlled dimensions and pitch using photolithography to yield hierarchical structures with order defined from the nanometer through centimeter length scales. In addition, electrical transport studies show that reliable electrical contacts can be made to the hierarchical nanowire arrays prepared by this method. This solution-based process offers a flexible pathway for bottom-up assembly of virtually any nanowire material into highly integrated and hierarchically organized nanodevices needed for a broad range of functional nanosystems.
12) Formation constants of the inclusion complexes for benzene, cyclopentanone, and furan are estimated to be 2.7 × 10 1 , 2.2 × 10 3 , and 7.1 × 10 3 M -1 , respectively, at room temperature.
A general strategy for the parallel and scalable integration of nanowire devices over large areas without the need to register individual
nanowire−electrode interconnects has been developed. The approach was implemented using a Langmuir−Blodgett method to organize nanowires
with controlled alignment and spacing over large areas and photolithography to define interconnects. Centimeter-scale arrays containing
thousands of single silicon nanowire field-effect transistors were fabricated in this way and were shown to exhibit both high performance with
unprecedented reproducibility and scalability to at least the 100-nm level. Moreover, scalable device characteristics were demonstrated by
interconnecting a controlled number of nanowires per transistor in “pixel-like” device arrays. The general applicability of this approach to
other nanowire and nanotube building blocks could enable the assembly, interconnection, and integration of a broad range of functional
nanosystems.
The strongly correlated thermoelectric properties have been a major hurdle for high-performance thermoelectric energy conversion. One possible approach to avoid such correlation is to suppress phonon transport by scattering at the surface of confined nanowire structures. However, phonon characteristic lengths are broad in crystalline solids, which makes nanowires insufficient to fully suppress heat transport. Here, we employed Si-Ge alloy as well as nanowire structures to maximize the depletion of heat-carrying phonons. This results in a thermal conductivity as low as ∼1.2 W/m-K at 450 K, showing a large thermoelectric figure-of-merit (ZT) of ∼0.46 compared with those of SiGe bulks and even ZT over 2 at 800 K theoretically. All thermoelectric properties were "simultaneously" measured from the same nanowires to facilitate accurate ZT measurements. The surface-boundary scattering is prominent when the nanowire diameter is over ∼100 nm, whereas alloying plays a more important role in suppressing phonon transport for smaller ones.
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