Production of Noble-Metal Nanohelices Based on Nonlinear Dynamics in Electrodeposition of Binary Copper Alloys.

Spatiotemporal pattern formation is dynamic self-organization widely observed in nature and drives various functions. Among these functions, chirality plays a central role. The relationship between dynamic self-organization and chirality has been an open question; therefore, the production of chiral nanomaterials by dynamic self-organization has not been achieved. Here, we show that the confinement of a two-dimensional spatiotemporal micropattern via the electrodeposition of a binary Cu alloy into a nanopore induces mirror symmetry breaking to produce a helical nanostructure of the noble-metal component although it is still not yet possible to control the handedness at this stage. This result suggests that spatiotemporal symmetry breaking functions as a mirror symmetry breaking if cylindrical pores are given as the boundary condition. This study can be a model system of how spatiotemporal symmetry breaking plays a role in mirror symmetry breaking, and it proposes a new approach to producing helical nanomaterials through dynamic self-organization.

Proton conduction in hydronium solvate ionic liquids affected by ligand shape.

We investigated the ligand dependence of the proton conduction of hydronium solvate ionic liquids (ILs), consisting of a hydronium ion (H3O+), polyether ligands, and a bis[(trifluoromethyl)sulfonyl]amide anion (Tf2N-; Tf = CF3SO2). The ligands were changed from previously reported 18-crown-6 (18C6) to other cyclic or acyclic polyethers, namely, dicyclohexano-18-crown-6 (Dh18C6), benzo-18-crown-6 (B18C6) and pentaethylene glycol dimethyl ether (G5). Pulsed-field gradient spin echo nuclear magnetic resonance results revealed that the protons of H3O+ move faster than those of cyclic 18C6-based ligands but as fast as those of acyclic G5 ligands. Based on these results and density functional theory calculations, we propose that the coordination of a cyclic ether ligand to the H3O+ ion is essential for fast proton conduction in hydronium solvate ILs. Our results attract special interest for many electro- and bio-chemical applications such as electrolyte systems for fuel cells and artificial ion channels for biological cells.

In situ semi-quantitative analysis of zinc dissolution within nanoporous silicon by X-ray absorption fine-structure spectroscopy employing an X-ray compatible cell.

The in situ study of the discharge process in a zinc-based half-cell employing a porous electrode as a structural scaffold is reported. The in situ characterization has been performed by synchrotron X-ray absorption fine-structure spectroscopy and, for this purpose, an inexpensive, simple and versatile electrochemical cell compatible with X-ray experiments has been designed and described. The experimental results reported here have been employed to semi-quantify the dissolved and undissolved zinc species during the discharge, allowing the cell feasibility to be tested and to better understand the functioning of the zinc half-cell based on porous electrodes.

Dynamic manipulation of the local pH within a nanopore triggered by surface-induced phase transition.

Manipulating the local pH within nanoconfinement is essential in nanofluidics technology and its applications. Since the conventional strategy utilizes the overlapping of an electric double layer formed for charge compensation by protons near a negatively charged pore-wall surface, pH variation within a pore is limited to the acidic side. To achieve the variation at the alkaline side, we developed a system comprising a hydrophobic pore-wall surface and aqueous solution containing hydrophobic cations. Beyond a threshold cation concentration, a nanopore is filled with the second phase where the cations are remarkably enriched due to surface-induced phase transition (SIFT) originating from the hydrophobic effect. It is accompanied by the enrichment of coexisting anions. We experimentally show that pH in the second phase is much higher than in the bulk solution. Electrochemical measurements strongly suggest that the pH value can be increased from 4.8 to 10.7 within a 10 nm nanopore in the most significant case. This is ascribed to the enrichment of hydroxide anions. We argue that the extent and rate of pH variation are controlled as desired.

Number Density Distribution of Small Particles around a Large Particle: Structural Analysis of a Colloidal Suspension.

Some colloidal suspensions contain two types of particles-small and large particles-to improve the lubricating ability, light absorptivity, and so forth. Structural and chemical analyses of such colloidal suspensions are often performed to understand their properties. In a structural analysis study, the observation of the number density distribution of small particles around a large particle (gLS) is difficult because these particles are randomly moving within the colloidal suspension by Brownian motion. We obtain gLS using the data from a line optical tweezer (LOT) that can measure the potential of mean force between two large colloidal particles (ΦLL). We propose a theory that transforms ΦLL into gLS. The transform theory is explained in detail and tested. We demonstrate for the first time that LOT can be used for the structural analysis of a colloidal suspension. LOT combined with the transform theory will facilitate structural analyses of the colloidal suspensions, which is important for both understanding colloidal properties and developing colloidal products.

Correction: Number density distribution of solvent molecules on a substrate: a transform theory for atomic force microscopy.

Correction for 'Number density distribution of solvent molecules on a substrate: a transform theory for atomic force microscopy' by Ken-ichi Amano et al., Phys. Chem. Chem. Phys., 2016, 18, 15534-15544.

Number density distribution of solvent molecules on a substrate: a transform theory for atomic force microscopy.

Atomic force microscopy (AFM) in liquids can measure a force curve between a probe and a buried substrate. The shape of the measured force curve is related to hydration structure on the substrate. However, until now, there has been no practical theory that can transform the force curve into the hydration structure, because treatment of the liquid confined between the probe and the substrate is a difficult problem. Here, we propose a robust and practical transform theory, which can generate the number density distribution of solvent molecules on a substrate from the force curve. As an example, we analyzed a force curve measured by using our high-resolution AFM with a newly fabricated ultrashort cantilever. It is demonstrated that the hydration structure on muscovite mica (001) surface can be reproduced from the force curve by using the transform theory. The transform theory will enhance AFM's ability and support structural analyses of solid/liquid interfaces. By using the transform theory, the effective diameter of a real probe apex is also obtained. This result will be important for designing a model probe of molecular scale simulations.

On-site quantitative elemental analysis of metal ions in aqueous solutions by underwater laser-induced breakdown spectroscopy combined with electrodeposition under controlled potential.

We propose a technique of on-site quantitative analysis of Zn(2+) in aqueous solution based on the combination of electrodeposition for preconcentration of Zn onto a Cu electrode and successive underwater laser-induced breakdown spectroscopy (underwater LIBS) of the electrode surface under electrochemically controlled potential. Zinc emission lines are observed with the present technique for a Zn(2+) concentration of 5 ppm. It is roughly estimated that the overall sensitivity over 10 000 times higher is achieved by the preconcentration. Although underwater LIBS suffers from the spectral deformation due to the dense plasma confined in water and also from serious shot-to-shot fluctuations, a linear calibration curve with a coefficient of determination R(2) of 0.974 is obtained in the range of 5-50 ppm.

Spontaneous Formation of Microgroove Arrays on the Surface of p-Type Porous Silicon Induced by a Turing Instability in Electrochemical Dissolution.

Self-organization plays an imperative role in recent materials science. Highly tunable, periodic structures based on dynamic self-organization at micrometer scales have proven difficult to design, but are desired for the further development of micropatterning. In the present study, we report a microgroove array that spontaneously forms on a p-type silicon surface during its electrodissolution. Our detailed experimental results suggest that the instability can be classified as Turing instability. The characteristic scale of the Turing-type pattern is small compared to self-organized patterns caused by the Turing instabilities reported so far. The mechanism for the miniaturization of self-organized patterns is strongly related to the semiconducting property of silicon electrodes as well as the dynamics of their surface chemistry.

Two-dimensional array of particles originating from dipole-dipole interaction as evidenced by potential curve measurements at vertical oil/water interfaces.

We propose a new method to evaluate the interaction potential energy between the particles adsorbed at an oil/water interface as a function of interparticle distance. The method is based on the measurement of the interparticle distance at a vertical oil/water interface, at which the gravitational force is naturally applied to compress the particle monolayer in the in-plane direction. We verified the method by examining whether we obtained the same potential curve upon varying the gravitational acceleration by tilting the interface. The present method is applicable in the force range from ∼0.1 to ∼100 pN, determined by the effective weight of the particles at the interface. The method gives a rather simple procedure to estimate a long range interaction among the particles adsorbed at oil/water interfaces. We applied this method to polystyrene particles at the decane/aqueous surfactant solution interface, and obtained the interparticle potential curves. All the potential curves obtained by the present method indicated that the interparticle repulsion is due to the electrical dipole-dipole interaction based on the negative charge of the particles. The mechanism of the dipole-dipole interaction is further discussed on the basis of the effects of surfactants.

Effect of cation species on surface-induced phase transition observed for platinum complex anions in platinum electrodeposition using nanoporous silicon.

In an earlier work [K. Fukami et al., J. Chem. Phys. 138, 094702 (2013)], we reported a transition phenomenon observed for platinum complex anions in our platinum electrodeposition experiment using nanoporous silicon. The pore wall surface of the silicon electrode was made hydrophobic by covering it with organic molecules. The anions are only weakly hydrated due to their large size and excluded from the bulk aqueous solution to the hydrophobic surface. When the anion concentration in the bulk was gradually increased, at a threshold the deposition behavior exhibited a sudden change, leading to drastic acceleration of the electrochemical deposition. It was shown that this change originates from a surface-induced phase transition: The space within a nanopore is abruptly filled with the second phase in which the anion concentration is orders of magnitude higher than that in the bulk. Here we examine how the platinum electrodeposition behavior is affected by the cation species coexisting with the anions. We compare the experimental results obtained using three different cation species: K(+), (CH3)4N(+), and (C2H5)4N(+). One of the cation species coexists with platinum complex anions [PtCl4](2-). It is shown that the threshold concentration, beyond which the electrochemical deposition within nanopores is drastically accelerated, is considerably dependent on the cation species. The threshold concentration becomes lower as the cation size increases. Our theoretical analysis suggests that not only the anions but also the cations are remarkably enriched in the second phase. The remarkable enrichment of the anions alone would give rise to the energetic instability due to electrostatic repulsive interactions among the anions. We argue that the result obtained cannot be elucidated by the prevailing view based on classical electrochemistry. It is necessitated to consult a statistical-mechanical theory of confined aqueous solutions using a molecular model for water.

Structure and complexation mechanism of aqueous Zn(II)-acetate complex studied by XAFS and Raman spectroscopies.

In this work, the structure of Zn acetate has been determined by a combination of X-ray absorption fine structure and Raman spectroscopy. We have analyzed the local atomic environment and the main vibrational bands of the acetate and Zn acetate at different pH. The results suggest that Zn acetate complex acquires a bidentate structure that modifies its first coordination shell. Meanwhile, the coordination shell of the hydrated Zn cation is formed by 6 hydroxides at a mean distance of 2.06 Å, the coordination shell of the Zn cation in the complex is formed by 2 hydroxides and 2 oxygens from the carboxyl group of the acetate, at a mean Zn-O distance of 1.96 Å. The structure of the Zn acetate complex is compared to those of Zn malonate and Zn citrate, none of which present a reduction in the coordination shell neither a shrinkage of the Zn-O shell distance.

Surface-Modified Ruthenium Nanorods for an Ampere-Level Bifunctional Hydrogen Evolution Reaction/Oxygen Evolution Reaction Electrocatalyst.

The practical applications of bifunctional ruthenium-based electrocatalysts with two active sites of Ru nanoparticles covered with RuO2 skins are limited. One reason is the presence of multiple equally distributed facets, some of which are inactive. In contrast, ruthenium nanorods with a high aspect ratio have multiple unequally distributed facets containing the dominance of active faces for efficient electrocatalysis. However, the synthesis of ruthenium nanorods has not been achieved due to difficulties in controlling the growth. Additionally, it is known that the adsorption capacity of intermediates can be impacted by the surface of the catalyst. Inspired by these backgrounds, the surface-modified (SM) ruthenium nanorods having a dominant active facet of hcp (100) through chemisorbed oxygen and OH groups (SMRu-NRs@NF) are rationally synthesized through the surfactant coordination method. SMRu-NRs@NF exhibits excellent hydrogen evolution in acid and alkaline solutions with an ultralow overpotential of 215 and 185 mV reaching 1000 mA cm-2, respectively. Moreover, it has also shown brilliant oxygen evolution electrocatalysis in alkaline solution with a low potential of 1.58 V to reach 1000 mA cm-2. It also exhibits high durability over 143 h for the evolution of oxygen and hydrogen at 1000 mA cm-2. Density functional theory studies confirmed that surface modification of a ruthenium nanorod with chemisorbed oxygen and OH groups can optimize the reaction energy barriers of hydrogen and oxygen intermediates. The surface-modified ruthenium nanorod strategy paves a path to develop the practical water splitting electrocatalyst.

Electrochemical on-surface synthesis of a strong electron-donating graphene nanoribbon catalyst.

On-surface synthesis of edge-functionalized graphene nanoribbons (GNRs) has attracted much attention. However, producing such GNRs on a large scale through on-surface synthesis under ultra-high vacuum on thermally activated metal surfaces has been challenging. This is mainly due to the decomposition of functional groups at temperatures of 300 to 500 °C and limited monolayer GNR growth based on the metal catalysis. To overcome these obstacles, we developed an on-surface electrochemical technique that utilizes redox reactions of asymmetric precursors at an electric double layer where a strong electric field is confined to the liquid-solid interface. We successfully demonstrate layer-by-layer growth of strong electron-donating GNRs on electrodes at temperatures <80 °C without decomposing functional groups. We show that high-voltage facilitates previously unknown heterochiral di-cationic polymerization. Electrochemically produced GNRs exhibiting one of the strongest electron-donating properties known, enable extraordinary silicon-etching catalytic activity, exceeding those of noble metals, with superior photoconductive properties. Our technique advances the possibility of producing various edge-functional GNRs.

Platinum Nanoparticles Bonded with Carbon Nanotubes for High-Performance Ampere-Level All-Water Splitting.

Platinum nanoparticles loaded on a nitrogen-doped carbon nanotubes exhibit a brilliant hydrogen evolution reaction (HER) in an alkaline solution, but their bifunctional hydrogen and oxygen evolution reaction (OER) has not been reported due to the lack of a strong Pt-C bond. In this work, platinum nanoparticles bonded in carbon nanotubes (Pt-NPs-bonded@CNT) with strong Pt-C bonds are designed toward ultralow overpotential water splitting ability in alkaline solution. Benefit from the strong interaction between platinum and high conductivity carbon nanotube substrates through the Pt-C bond also the platinum nanoparticles bonded in carbon nanotube can provide more stable active sites, as a result, the Pt-NPs-bonded@CNT exhibits excellent hydrogen evolution in acid and alkaline solution with ultralow overpotential of 0.19 and 0.23 V to reach 1000 mA cm-2, respectively. Besides, it shows superior oxygen evolution electrocatalysis in alkaline solution with a low overpotential of 1.69 V at 1000 mA cm-2. Furthermore, it also exhibits high stability over 110 h against the evolution of oxygen and hydrogen at 1000 mA cm-2. This strategy paves the way to the high performance of bifunctional electrocatalytic reaction with extraordinary stability originating from optimized electron density of metal active sites due to strong metal-substrate interaction.

Single-pulse underwater laser-induced breakdown spectroscopy with nongated detection scheme.

We investigated spatially resolved emission spectra of Al atoms in a very small (∼0.1 mm) laser ablation plasma produced by a single long-pulse (∼100 ns) irradiation of an Al target in water. The spectral feature varied considerably, depending on the position to be measured. The density of the plasma periphery was low enough to neglect the self-absorption effect, even when resonance lines were observed. By properly selecting the position, we successfully obtained well-resolved spectral lines even without time-gated detection. This suggests that time-gating is not necessary anymore in the practical applications of underwater laser-induced breakdown spectroscopy when employing spatially resolved detection system.

Electrochemical deposition of platinum within nanopores on silicon: drastic acceleration originating from surface-induced phase transition.

An electrochemical reaction within nanopores is remarkably decelerated once a diffusion-limited condition is reached due to the difficulty in supply of reactants from the bulk. Here, we report a powerful method of overcoming this problem for electrochemical deposition of platinum within nanopores formed on silicon. We made the pore wall surface of the silicon electrode hydrophobic by covering it with organic molecules and adopted platinum complex ions with sufficiently large sizes. Such ions, which are only weakly hydrated, are excluded from the bulk aqueous electrolyte solution to the surface and rather hydrophobic in this sense. When the ion concentration in the bulk was gradually increased, at a threshold the deposition behavior exhibited a sudden change, leading to drastic acceleration of the electrochemical deposition. Using our statistical-mechanical theory for confined molecular liquids, we show that this change originates from a surface-induced phase transition: The space within nanopores is abruptly filled with the second phase within which the ion concentration is orders of magnitude higher. When the affinity of the surface with water was gradually reduced with fixing the ion concentration, qualitatively the same transition phenomenon was observed, which can also be elucidated by our theory. The utilization of the surface-induced phase transition sheds new light on the design and control of a chemical reaction in nanospace.

Synergetic effects of double laser pulses for the formation of mild plasma in water: toward non-gated underwater laser-induced breakdown spectroscopy.

We experimentally study the dynamics of the plasma induced by the double-laser-pulse irradiation of solid target in water, and find that an appropriate choice of the pulse energies and pulse interval results in the production of an unprecedentedly mild (low-density) plasma, the emission spectra of which are very narrow even without the time-gated detection. The optimum pulse interval and pulse energies are 15-30 µs and about ~1 mJ, respectively, where the latter values are much smaller than those typically employed for this kind of study. In order to clarify the mechanism for the formation of mild plasma we examine the role of the first and second laser pulses, and find that the first pulse produces the cavitation bubble without emission (and hence plasma), and the second pulse induces the mild plasma in the cavitation bubble. These findings may present a new phase of underwater laser-induced breakdown spectroscopy.

Enhancement of Oxidation of Silicon Carbide Originating from Stacking Faults Formed by Mode-Selective Phonon Excitation Using a Mid-Infrared Free Electron Laser.

Silicon carbide (SiC) is a promising material for wide applications due to its excellent material properties including high physical and chemical stability as well as great electronic properties of a wide bandgap. The high stability, however, makes its surface processing difficult. Especially, electrochemical processing is not well-established because of low electrochemical reactivity. Here, we show that selective phonon excitation by a mid-infrared free electron laser (MIR-FEL) enhances the anodic reactions. The selective excitation of two different vibration modes of the Si-C bond induces two different stacking faults, which act as a current path. As an application, we discovered that MIR-FEL irradiation enables Pt electroless deposition. This work reveals the interactions among phonons, lattice defects, and electrochemical reactions, encouraging further development of not only electrochemical surface processing but also a new application of MIR-FEL.

Structural considerations on multistopband mesoporous silicon rugate filters prepared for gas sensing purposes.

Different designs for producing multiple stopband mesoporous silicon rugate filters via electrochemical anodization are compared. The effects of light absorption and dispersion to visible range filter design are investigated. Thermal oxidation is applied for passivating the chemically reactive porous silicon surface, and the response of the passivated structures to ethanol vapor is examined. Differences in gas sensing properties for the various designs are evaluated and possible reasons for the observed differences are discussed. Methods for sidelobe suppression in multipeak filters are discussed and demonstrated, and their effects in gas sensing applications are estimated.