Search

Polymer nanofibers prepared via continuous spinning using anodic porous alumina are reported.

Herein, we give an overview of several less explored structural and optical characterization techniques useful for biomaterials. New insights into the structure of natural fibers such as spider silk can be gained with minimal sample preparation. Electromagnetic radiation (EMR) over a broad range of wavelengths (from X-ray to THz) provides information of the structure of the material at correspondingly different length scales (nm-to-mm). When the sample features, such as the alignment of certain fibers, cannot be characterized optically, polarization analysis of the optical images can provide further information on feature alignment. The 3D complexity of biological samples necessitates that there be feature measurements and characterization over a large range of length scales. We discuss the issue of characterizing complex shapes by analysis of the link between the color and structure of spider scales and silk. For example, it is shown that the green-blue color of a spider scale is dominated by the chitin slab’s Fabry–Pérot-type reflectivity rather than the surface nanostructure. The use of a chromaticity plot simplifies complex spectra and enables quantification of the apparent colors. All the experimental data presented herein are used to support the discussion on the structure–color link in the characterization of materials.

The modification of the phosphonium-type ionic liquid onto the TiO2 electrode reduced the amount of dye adsorbed on the electrode and showed significant aggregation effect, thereby improving the photovoltaic performance of DSSCs.

Anodic porous oxides with ordered nanohole array structures were prepared by the formation of concave arrays on the surface of Cu, Zn, and Ni substrates and the subsequent anodization of the prepatterned substrates. The concave arrays on the surface of the substrate were formed by Ar ion milling using an alumina mask. Although the anodization of Cu, Zn, and Ni substrates without prepatterning generates spongelike porous structures, ordered arrays of cylindrical nanoholes were obtained by the anodization of prepatterned substrates. The interpore distance of the obtained nanohole arrays was controlled by changing the period of the concave arrays. Crystallized ordered nanohole arrays of Cu

Ordered alumina through-hole membrane with an interhole distance of 1 μm.

Renewable superhydrophobic surfaces based on laminated polymer films with nanopillar array structures were prepared. Polymer nanopillar arrays exhibiting superhydrophobic properties were prepared by nanoimprinting using anodic porous alumina as a mold. The hydrophobic properties of the obtained polymer nanopillar arrays could be controlled and optimized by changing the geometrical structures of anodic porous alumina molds used for nanoimprinting. The polymer films were laminated using a photocurable monomer. The ordered polymer nanopillar array structures could be maintained even after delamination of the films. Renewed polymer nanopillar arrays exposed by peeling off the upper films exhibited a water contact angle higher than 150°. Using this process, superhydrophobic surfaces could be obtained repeatedly by delamination of a film even when superhydrophobicity deteriorated with the collapse of surface patterns. The obtained renewable superhydrophobic surfaces can be used for various applications requiring high durability.

Ordered anodic porous alumina with controlled-size holes on the order of a single-nanometer scale was obtained by the atomic layer deposition (ALD) of Al2O3 or TiO2. The thin metal oxide layers of uniform thickness were formed successfully on the inner wall of the hole of the ordered anodic porous alumina with high aspect ratios by ALD. The hole diameter of the ordered anodic porous alumina could be controlled precisely by adjusting the number of cycles of ALD. The obtained anodic porous alumina with an ordered hole arrangement of reduced holes will be applied to various application fields requiring uniform-sized holes on the order of a single-nanometer scale, such as the starting material for preparing various types of quantum effect devices.

We previously reported the preparation and characterization of a Ni(II) complex capable of electrocatalytic hydrogen generation. The complex [Ni(LNH2)2Cl]Cl (1) includes a 6-((diphenylphosphino)methyl)pyridin-2-amine ligand (LNH2), which has an amino group as a base that acts as a proton transfer site by virtue of its location near the metal center. In order to study the effect of counteranions in hydrogen generation, two additional NiII(LNH2) complexes with weakly coordinating/noncoordinating counteranions, [Ni(LNH2)2](OTs)2 (OTs- = p-toluenesulfonate) (2) and [Ni(LNH2)2](BF4)2 (3), were synthesized. Their X-ray crystal structures reveal that the Ni(II) ion is coordinated with two bidentate LNH2 ligands in both complexes. Complex 2 contains both trans and cis isomers in the unit cell. The former is in an axially elongated square-pyramidal geometry (τ5 = 0.17), and the latter is in a nearly square planar geometry (τ4 = 0.11) with two weakly interacting OTs- anions at the axial sites. Complex 3 has only the cis isomer in the solid state, which is in a nearly square planar geometry (τ4 = 0.10). These complexes are slightly different from 1, which has a distorted-square-pyramidal geometry (τ5 = 0.25) with a coordinated chloride anion. UV-vis spectra of 2 and 3 in MeCN show a spectral pattern characteristic of a square-planar Ni(II) complex. These spectra are slightly different from the unique spectrum of 1, which is typical of an axially coordinating Ni(II) species as a result of having a Cl- anion at the apical position. Electrocatalytic hydrogen generation promoted by these three Ni(II) complexes (1.0 mmol) demonstrates an increase in the catalytic current induced by stepwise addition of HOAc (pKa = 22.3 in MeCN) as a proton source. The complexes demonstrate turnover frequencies (TOF) of 3800 s-1 for 1, 5400 s-1 for 2, and 8800 s-1 for 3 in MeCN (3 mL) containing 0.1 M [n-Bu4N](ClO4) in the presence of HOAc (145 equiv) at overpotentials of ca. 530, 490, and 430 mV, respectively.

Germyl cations are one of the heavier group 14 element analogues of carbocations and have been extensively studied for their structures, spectroscopic features, and reactivities to various molecule...

Electrochemical CO2 reduction is a key technology to recycle CO2 as a renewable resource, but adsorbing CO2 on the catalyst surface is challenging. We explored the effects of reduced graphene oxide...

Self-ordered anodic porous alumina with a long-range ordered hole arrangement having an inter-hole spacing of over 1.5 μm was prepared by anodization in a citric acid electrolyte containing a small amount of phosphoric acid. The inter-hole spacing of the ordered anodic porous alumina could be controlled within a range of 700 nm to 1.8 μm by adjusting the anodization conditions. The use of an electrolyte with a mixture of water and ethylene glycols, especially tetraethylene glycol, was effective for preparing ordered anodic porous alumina with large inter-hole spacings. The obtained anodic porous alumina is suitable for various applications that require highly ordered hole array structures with large inter-hole spacings.

Cu electrode-based electrochemical CO2 reduction using renewable energy is a promising method for conversion of CO2 to useful compounds such as methane, ethylene, and ethanol. Heteroatom-doped and/...

Modern integrated devices and electrical circuits have often been designed with carbon nanostructures, such as carbon nanotubes (CNTs) and graphene due to their high thermal and electrical transport properties. These transport properties are strongly correlated to their acoustic phonon and carrier dynamics. Thus, understanding the phonon and carrier dynamics of carbon nanostructures in extremely small regions will lead to their further practical applications. Here, we demonstrate ultrafast time-resolved electron diffraction and ultrafast transient spectroscopy to characterize the phonon and carrier dynamics at the boundary of quasi-one-dimensional CNTs before and after Joule annealing. The results from ultrafast time-resolved electron diffraction show that the CNTs after Joule annealing reach the phonon equilibrium state extremely fast with a timescale of 10 ps, which indicates that thermal transport in CNTs improves following Joule annealing. The methodology described in this study connects conventional macroscopic thermo- and electrodynamics to those at the nanometer scale. Realistic timescale kinetic simulations were performed to further elaborate on the phenomena that occur in CNTs during Joule annealing. The insights obtained in this study are expected to pave the way to parameterize the unexplored thermal and electrical properties of carbon materials at the nanometer scale.

Ideally ordered TiO2 through-hole membranes were obtained by a combination of Ti substrate pre-patterning and two-layer anodization. The Ti substrate was pre-patterned by Ar ion milling using ideally ordered porous alumina as an etching mask. Each concave pit formed by dry etching acted as an initiation site for hole development during anodization, and ideally ordered anodic porous TiO2 was produced by anodization using an electrolyte containing fluoride ions. Two-layered anodic porous TiO2 samples with different solubilities were formed by heat treatment for the crystallization of the first anodized oxide layer and a subsequent second anodization. The selective dissolution of the lower part of the two-layered porous TiO2 produced an ideally ordered TiO2 through-hole membrane. Using the present process, the repeated preparation of ideally ordered TiO2 membranes can be conducted because the ideally ordered concave array, which corresponds to the hole arrangement at the bottom of the detached TiO2 membrane, is maintained even after detaching the membrane. The obtained samples can be applied to various functional devices, such as photonic crystals and filtration membranes with photocatalytic properties.

Ordered alumina through-hole membranes were obtained by a combination of the anodization of Al, formation of a TiO

A strong Lewis acid silylium ion was utilized for dehydrogenative annulation between dialkyl(1-naphthyl)silanes

To develop low-cost and efficient dye-sensitized solar cells (DSSCs), we designed and prepared three homoleptic Cu(I) complexes with asymmetric ligands, M1, M2, and Y3, which have the advantages of heteroleptic-type complexes and compensate for their synthetic challenges. The three copper(I) complexes were characterized by elemental analysis, UV-vis absorption spectroscopy, and electrochemical measurements. Their absorption spectra and orbital energies were evaluated and are discussed in the context of TD-DFT calculations. The complexes have high VOC values (0.48, 0.60, and 0.66 V for M1, M2, and Y3, respectively) which are similar to previously reported copper(I) dyes with symmetric ligands, although their energy conversion efficiencies are relatively low (0.17, 0.64, and 2.66%, respectively).

A surface with a simple nanopillar array and hierarchical micro-/nano structures consisting of microconvexes and a surface with a nanopillar array were fabricated by nanoimprinting using two types of anodic porous alumina mold. On both surfaces, the height of polymer nanopillars could be controlled by adjusting the anodization time for the preparation of the anodic porous alumina mold. Regarding water-repellent properties, a higher contact angle was observed on the surface with a hierarchical structure than on the surface with a simple nanopillar array. In the measurement of the water droplet sliding angle, the surface with a hierarchical structure showed higher performance characteristics than the surface with a simple nanopillar array. This is because the surface with a hierarchical structure can more easily trap air between the substrate surface and the water droplet than the surface with a simple nanopillar array. The hierarchical micro-/nano structures could be prepared repeatedly by nanoimprinting using a single mold. The method developed here for preparing a superhydrophobic surface is used for various applications, such as those requiring superhydrophobic surfaces with sliding angles.

Electrochemical water splitting is an ecofriendly technology for generating oxygen and hydrogen from water. The electrode is a key component that controls the efficiency of water splitting. Althoug...

Energy storage devices using electrochemical reactions have become an integral part of our daily lives, and further improvement of their performance is highly demanded. An important task for this purpose is to thoroughly understand the electrochemical processes governing their chemistry. Here we develop a method based on Kelvin probe force microscopy that enables dynamic visualization of changes in the internal potential distribution in an operating electrochemical device and use it to characterize an all-solid-state lithium ion battery. Observation of the cathode composite regions during a cyclic voltammetry operation reveals differences between the behavior of local electrochemical reactions in the charge and discharge processes. Based on careful inspection of the results, we show that the difference arises from a change in the state of an electronic conductive path network in the composite electrode. Our method provides new insights into the local electrochemical reactions during electrochemical operation of devices. Understanding the working mechanisms of electrochemical energy storage devices is crucial for the design of those with improved performances. Here the authors use Kelvin probe force microscopy to dynamically image the internal potential distribution in an operating all-solid-state Li ion battery.

Polymer nanofibers with controlled diameters were formed by continuous spinning using ordered anodic porous alumina as a spinneret. The diameter of the polymer nanofibers could be controlled by cha...

Electrodeposition and electrodissolution of Li metal in an anodic porous alumina that has an ideal hole array structure were demonstrated. Electrodeposition and electrodissolution of Li metal in the hole array structures could be repeatedly carried out without any formation of dendritic Li. Although the hole diameter of the anodic porous alumina was reduced from the micrometer to nanometer scale, deposition and dissolution of Li metal could be stably conducted. The present process is expected to be applicable to the fabrication of a safe rechargeable Li-metal battery.

Ordered anodic porous WO3 was prepared by the anodization of a W substrate with a depression pattern under a constant voltage of 18 V in concentrated phosphoric acid at 120 °C. However, the behavior of hole formation induced in depressions was found to be strongly affected by the depth and diameter of the depressions. Multiple holes were formed in a shallow depression during the initial stage of anodization, whereas only one hole was formed in a deep depression. In addition, when the depression diameter was small, the growth of fine holes around the induced holes was observed. Since the fine holes formed on the surface of anodic porous WO3 prevented the induced holes from growing in the depth direction, the formation of large-diameter depressions allowed the induced holes to grow deeper. The obtained ordered anodic porous WO3 can be used for various applications such as in photocatalysis and electrochromic devices.

We have investigated the uptake mechanism of palladium (Pd: one of the most important elements in industry used as a catalyst) ions into Prussian-blue nanoparticles (PBNPs) in a nitric acid solution via high-resolution electron transmission microscopy, inductively coupled plasma atomic emission spectroscopy, powder X-ray diffraction, and ultraviolet-visible-near infrared spectroscopy in combination with first principles calculations. Comparison of the structural and electronic properties of PBNPs between before and after a 24 h sorption test reveals that the Pd2+ ions incorporated into PBNPs by the substitution of Fe2+ ions of the PB framework while maintaining the crystal structure, and the substitution efficiency is estimated to be 87% per PB unit cell. This implies that 0.30 g of Pd can be recovered by using 1 g of PB having the chemical formula KFe(III)[Fe(II)(CN)6]. The present finding suggests that PB (or its analogues) can be applied to recycle noble and rare metals from electronic and nuclear wastes.

In this study, highly ordered anodic porous metal oxides of transition metals (W, Fe, Co, and Nb) were prepared by anodization combined with a pretexturing process. The formation of an array of dimples on the metal surface was achieved by dry etching using ordered anodic porous alumina as a mask. Subsequent anodization of the pretextured metals generated metal oxides (WO3, Fe2O3, Co3O4, and Nb2O4) with an ordered hole array structure because each dimple acted as a starting point for hole development. The hole periodicity of the resulting ordered anodic porous metal oxide could be controlled by changing the periodicity of the dimples formed on the substrate. Ordered anodic porous films obtained by this process could be used in various functional devices that require ordered hole array structures.