論文

A repeatable enhancement of the photoluminescence (PL) from CsPbBr3 nanocubes (NCs) is promoted by the assembling of NCs. The PL quantum yield (QY) of ordered NC arrays increases with photoirradiation and decreases in the dark. The repeatable enhancement of the PLQY cannot be observed from isolated NCs. The nanospaces between NCs in the ordered arrays allow a reversible change in thermally stimulated desorption and photo-induced adsorption of surface ligands that affect the PLQY.

Biosilicas that are produced in vascular plants (plant opal), such as Poaceae, have a variety of shapes and functions and are regarded as an excellent model for the architectural design of artificial amorphous materials. In this work, we studied the micro- and nanostructures and mechanical and optical functions of plant opals on the bamboo culm, which is available as an important natural material. The surface of the culm wall is totally covered with silicified epidermal cells containing silica wedges. The biogenic silicious architectures, such as silicified cell walls and wedges, are composed of nanoscale particles ~ 20–80 nm in diameter with cellulose nanofibrils. Silica wedges, which have a relatively low organic content and relatively high hardness and Young’s modulus, are initially formed on cellulose nanofibrils in an organic frame as a scaffold within a few weeks after the emergence of a bamboo shoot. Several months after the formation of the wedges, the epidermal cell walls, which protect the culm surface, are lightly silicified with cellulose nanofibrils. According to a numerical simulation, the silica wedges would have an optical function delivering sunlight to chloroplasts located under the epidermal cells.

Unique architectures of microbial skeletons are viewed as a model for the architectural design of artificial structural materials. In particular, the specific geometric arrangement of a spherical skeleton 0.5–1.5 mm in diameter of shell-bearing protists, Phaeodaria (Aulosphaera sp.), is remarkably interesting because of its similarity to a geodesic polyhedron, which is a hollow framework with 6-branched nodes that requires minimal building material for maximal strength. A phaeodarian skeleton composed of silica rods 5–10 µm in diameter was characterized as a distorted dome that is based on an icosahedron sectioned with a 7-frequency subdivision. The major difference of the biogenic architecture from the ideal geodesic dome is the coexistence of 7- and 5-branched nodes with the distortion of the frames and the presence of radial spines. From a microscopic perspective, the frames and radial spines were revealed to be hollow tubes having inner fibers and lamellar walls consisting of silica nanoparticles 4–8 nm in diameter with interlayer organic matter. The high degradability of the silica skeleton in seawater after cell mortality is ascribed to the specific nanometric composite structure. The biological architectonics sheds light on the production of environmentally friendly, lightweight structural materials and microdevices.

Measurement of mechanical stresses, such as compression, shear, and tensile stresses, contributes toward achieving a safer and healthier life. In particular, the detection of weak compression stresses is required for healthcare monitoring and biomedical applications. Compression stresses in the order of 106–1010 Pa have been visualized and/or quantified using mechano-responsive materials in previous works. However, in general, it is not easy to detect compression stresses weaker than 103 Pa using conventional mechano-responsive materials because the dynamic motion of the rigid mechano-responsive molecules is not induced by such a weak stress. In the present work, weak compression stresses in the order of 100–103 Pa are visualized and measured via the integration of stimuli-responsive materials, such as layered polydiacetylene (PDA) and dry liquid (DL), through response cascades. DLs consisting of liquid droplets covered by solid particles release the interior liquid and collapse with application of a weak compression stress. The color of the layered PDA is changed by the spilled liquid as a chemical stress. A variety of weak compression stresses, such as expiratory pressure, are visualized and colorimetrically measured using the paper-based device of the integrated stimuli-responsive materials. Diverse mechano-sensing devices can be designed via the integration of stimuli-responsive materials.

Water-splitting dye-sensitized photoelectrochemical cells are promising devices for resolving energy and environmental problems by producing H2, a clean energy source, from water and sunlight. However, their performance is still limited because of dye desorption from the electrode and their weak light-absorption efficiency. In this study, we fabricated two water-reducing photocathodes, NiO|RuCP/BQPy and NiO|RuCP-Zr-RuP/BQPy, by combining the layer-by-layer formation of mono- (RuCP) and bi- (RuCP and RuP with Zr4+cations) layer molecular films of Ru(II) dyes, respectively, on a p-type NiO substrate with the chemical vapor deposition of the nanosheet catalyst based on the BQPy organic polymer comprising benzoquinone and pyrrole moieties. These photocathodes produced H2under visible light irradiation and a small electrical bias in a 0.1 M Na2SO4aqueous solution (λ > 420 nm, 65 mW cm-2, E = -0.254 V versus normal hydrogen electrode, and pH 3). Both the photocurrent value and amount of H2produced by double-dye-layered NiO|RuCP-Zr-RuP/BQPy were smaller than those of NiO|RuCP/BQPy, probably because of the energy transfer inactivation between the Ru(II) dyes, which competes with the reductive quenching (i.e., electron injection) by NiO. Ru(II) dye desorption from the NiO|RuCP/BQPy photocathode was significantly reduced to approximately a third of that of NiO|RuCP, indicating that the deposited BQPy polymer improved the durability of the photocathode. The deposition of the BQPy polymer can be easily performed under mild conditions (60 °C in air); therefore, this technique shows great potential application for the construction of various types of dye-sensitized water-reducing photocathodes.

Graphene and graphene oxide (GO) are promising two-dimensional nanomaterials. An ultimate goal is to achieve large-scale bottom-up syntheses of perfect graphene and GO. However, controlled syntheses of perfect graphitic structures still remain challenges in chemistry and materials science. Moreover, amorphous types have not received much attention. The present work shows syntheses, structures, and applications of amorphous graphene and GO analogues alternative to the ideal ones. The simultaneous multiple reactions of two conjugated monomers provide amorphous conjugated polymer networks containing low-crystalline graphitic domains and their stacking. The stacked amorphous graphene and GO are exfoliated into thin nanosheets including few-layers and monolayers. Moreover, in situ syntheses of the amorphous GO analogues are applied to obtain a reinforced plastic with high mechanical strength. The present work implies that various functional nanocarbons can be designed and synthesized by tailored combinations of conjugated monomers.

Detection of mechanical stresses requires microscopic molecular motion triggered by macroscopically applied force. Polydiacetylene (PDA), a stimuli-responsive color-changing material, generally has no responsiveness to compression stresses. We found that a layered PDA with weakened interlayer interactions exhibits direct visible color changes in response to compression stresses. An amphiphilic diacetylene (DA) monomer, 1-(10,12-pentacosadiynyl) pyridinium bromide (PCPy+Br−), formed a lamellar structure with weakened interlayer and intermolecular interactions originating from the bulky cations and anions in the interlayer space. The resultant PDA exhibited blue-to-red color changes in response to compression stresses (P) in the range of 2.5-125 MPa. In previous works, visible detection of P < 50 MPa without excitation light has not been achieved using only mechanoresponsive materials. Moreover, the compression-stress distribution was visualized using the PDA-coated paper substrate.