九州大学 · 材料科学
ベンジャミン・ル・オワ教授の研究室は、金属有機フレームワーク(MOFs)や金属有機ポリヘドロン(MOPs)を基盤とした機能性ハイブリッド材料の設計・創出を主眼としています。特に、ポリマーをホストフレームワーク内に組み込むことで、導電性と多孔性を両立するナノテクスチャード材料の開発を進めています。また、分子サイズのわずかな違いを示すポリマーの分離や、タンパク質とハイブリッドを形成するイオン性MOPの開発など、生体分子との相互作用や分離応用にも注力しています。
Figures are computed from collected data and may differ slightly.
A series of conductive porous composites were obtained by the polymerization of 3,4-ethylenedioxythiophene (EDOT) in the cavities of MIL-101(Cr). By controlling the amount of EDOT loaded into the host framework, it was possible to modulate the conductivity as well as the porosity of the composite. This approach yields materials with a reasonable electronic conductivity (1.1 × 10(-3) S·cm(-1)) while maintaining high porosity (SBET = 803 m(2)/g). This serves as a promising strategy for obtaining h
The development of highly porous metal-organic frameworks (MOFs) is greatly sought after, due to their wide range of applications. As an alternative to the development of new structures, we propose to obtain new stable configurations for flexible MOFs by insertion of polymeric guests. The guests prevent the otherwise spontaneous closing of the host frameworks and result in stable opened forms. Introduced at a fraction of the maximal capacity, polymer chains cause an opening of the occupied nanoc
Separation of high-molecular-weight polymers differing just by one monomeric unit remains a challenging task. Here, we describe a protocol using metal-organic frameworks (MOFs) for the efficient separation and purification of mixtures of polymers that differ only by their terminal groups. In this process, polymer chains are inserted by threading one of their extremities through a series of MOF nanowindows. Selected termini can be adjusted by tuning the MOF structure, and the insertion methodolog
Charge-driven self-assembly of cationic zirconium-based metal-organic polyhedra (MOPs) with polyoxometalates (POMs) leads to a series of porous crystalline salts, prepared by simple mixing of soluble precursors. The reactivity of immobilized POMs was greatly increased, as demonstrated by their fast reduction by hydrazine vapors, without loss of structural integrity.
Metal-organic polyhedra (MOPs) can act as elementary structural units for the design of modular porous materials; however, their association with biological systems remains greatly restricted by their typically low stabilities and solubilities in water. Herein, we describe the preparation of novel MOPs bearing either anionic or cationic groups and exhibiting a high affinity for proteins. Simple mixing of the protein bovine serum albumin (<b>BSA</b>) and ionic MOP aqueous solutions resulted in th
The preparation of metal-organic structures with a controlled degree of disorder is currently one of the most promising fields of materials science. Here, we describe the effect of guest polymer chains on the transformation of a metal-organic framework (MOF). Heating a pillared MOF at a controlled temperature resulted in the exclusive removal of the pillar ligands, while the connectivity of the metal-organic square-grid layers was maintained. In the absence of a polymer, 2D-layers rearranged to
Abstract Preparation of composites by inclusion of polymers inside metal‐organic frameworks (MOFs) is a very powerful strategy to prepare innovative functional materials. MOF's nanosized pores disrupt polymer chains natural coiling and constrain them in an extended conformation, bringing new properties. At the single nanochannel scale, polymerization reactions are significantly modified due to confinement, and control over the primary structure (sequence, tacticity or branching) can be achieved.
An easy, <i>in situ</i> growth approach led to the formation of several composites of metal-organic framewoks and Nb<sub>4</sub>C<sub>3</sub>T<sub><i>x</i></sub> MXenes mixed intimately at the submicron scale. The high affinity of MXene surface for dopamine, enhanced by a nanostructuration induced by MOFs, resulted in superior sensing performances. The system exhibited good linearity over the 1-100 nM range, with an excellent limit of detection of 0.2 nM.
A synthetic route is presented for the realization of ultrathin freestanding nanoparticle membranes that are built of gold nanoparticles protected with trimethoxysilane‐bearing ligands. The mechanism relies on interfacial assembly in an oil–water mixture. Upon shaking, nanoparticles are transported to the liquid–liquid interface of the oil droplets and form a network through the formation of Si–O–Si bridges. Reticulation of the nanoparticles during the dynamic process of droplet coalescence allo
Bioelectrodes were prepared by encapsulating bacteria in a silica hydrogel, in the pores of graphite felt, which acts as a conductive network in the material. We observed the conversion of glucose into metabolites that could diffuse into the mesopores of the silica network and be oxidised at the graphite surface.
Silica gels doped with double-walled carbon nanotubes (DWCNTs) were prepared using an aqueous sol–gel route in mild conditions (neutral pH, room temperature). The wet gels exhibited both ionic and electronic conduction. Electrochemical impedance spectroscopy was used to study these two different conduction pathways that prevail at different characteristic time scales. The ionic conduction in the silica network was found to be independent of the DWCNT-doping rate. The electronic conduction throug
Mass transport properties of electrodes prepared from graphite felt, as such and after silicification, have been studied using cyclic voltammetry. Within the graphite felt, the mass transport of a probe changes with decreasing scan rate, from a radial diffusion around fibers to a regime that is analogous to “thin-layer” systems. Furthermore, unlike classical “thin-layer” systems, the volume comprised in the felt is macroscopic (resulting in high current densities), while the time required to con
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