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.

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.

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.

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.

Liquid Madelung energy accounts for the huge potential shift in electrochemical systems.

Achievement of carbon neutrality requires the development of electrochemical technologies suitable for practical energy storage and conversion. In any electrochemical system, electrode potential is the central variable that regulates the driving force of redox reactions. However, quantitative understanding of the electrolyte dependence has been limited to the classic Debye-Hückel theory that approximates the Coulombic interactions in the electrolyte under the dilute limit conditions. Therefore, accurate expression of electrode potential for practical electrochemical systems has been a holy grail of electrochemistry research for over a century. Here we show that the 'liquid Madelung potential' based on the conventional explicit treatment of solid-state Coulombic interactions enables quantitatively accurate expression of the electrode potential, with the Madelung shift obtained from molecular dynamics reproducing a hitherto-unexplained huge experimental shift for the lithium metal electrode. Thus, a long-awaited method for the description of the electrode potential in any electrochemical system is now available.

An oxyhydride of BaTiO3 exhibiting hydride exchange and electronic conductivity.

In oxides, the substitution of non-oxide anions (F(-),S(2-),N(3-) and so on) for oxide introduces many properties, but the least commonly encountered substitution is where the hydride anion (H(-)) replaces oxygen to form an oxyhydride. Only a handful of oxyhydrides have been reported, mainly with electropositive main group elements or as layered cobalt oxides with unusually low oxidation states. Here, we present an oxyhydride of the perhaps most well-known perovskite, BaTiO(3), as an O(2-)/H(-) solid solution with hydride concentrations up to 20% of the anion sites. BaTiO(3-x)H(x) is electronically conducting, and stable in air and water at ambient conditions. Furthermore, the hydride species is exchangeable with hydrogen gas at 400 °C. Such an exchange implies diffusion of hydride, and interesting diffusion mechanisms specific to hydrogen may be at play. Moreover, such a labile anion in an oxide framework should be useful in further expanding the mixed-anion chemistry of the solid state.

Selective preparation of macroporous monoliths of conductive titanium oxides Ti(n)O(2n-1) (n = 2, 3, 4, 6).

Monolithic conductive titanium oxides Ti(n)O(2n-1) (n = 2, 3, 4, 6) with well-defined macropores have been successfully prepared as a single phase, via reduction of a macroporous TiO(2) precursor monolith using zirconium getter. Despite substantial removal of oxide ions, all the reduced monoliths retain the macropore properties of the precursor, i.e., uniform pore size distribution and pore volume. Furthermore, compared to commercial porous Ebonex (shaped conductive Ti(n)O(2n-1)), the bulk densities (1.8 g cm(-3)) are half, and the porosities (60%) are about 3 times higher. The obtained Ti(n)O(2n-1) (n = 2, 3, 4, 6) macroporous monoliths could find applications as electrodes for many electrochemical reactions.

Epitaxial thin films of ATiO(3-x)H(x) (A = Ba, Sr, Ca) with metallic conductivity.

Epitaxial thin films of titanium perovskite oxyhydride ATiO(3-x)H(x) (A = Ba, Sr, Ca) were prepared by CaH(2) reduction of epitaxial ATiO(3) thin films deposited on a (LaAlO(3))(0.3)(SrAl(0.5)Ta(0.5)O(3))(0.7) substrate. Secondary ion mass spectroscopy detected a substantial amount and uniform distribution of hydride within the film. SrTiO(3)/LSAT thin film hydridized at 530 °C for 1 day had hydride concentration of 4.0 × 10(21) atoms/cm(3) (i.e., SrTiO(2.75)H(0.25)). The electric resistivity of all the ATiO(3-x)H(x) films exhibited metallic (positive) temperature dependence, as opposed to negative as in BaTiO(3-x)H(x) powder, revealing that ATiO(3-x)H(x) are intrinsically metallic, with high conductivity of 10(2)-10(4) S/cm. Treatment with D(2) gas results in hydride/deuteride exchange of the films; these films should be valuable in further studies on hydride diffusion kinetics. Combined with the materials' inherent high electronic conductivity, new mixed electron/hydride ion conductors may also be possible.

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.

Fe-site substitution effect on the structural and magnetic properties in SrFeO2.

We investigated the Fe-site substitution effect on the structural and magnetic properties of the infinite layer iron oxide Sr(Fe(1-x)M(x))O(2) (M = Co, Mn) using synchrotron X-ray diffraction, neutron diffraction, and (57)Fe Mössbauer spectroscopy. Both systems have a similar solubility limit of x ≈ 0.3, retaining the ideal infinite layer structure with a space group of P4/mmm. For the Fe-Co system, both in-plane and out-of-plane axes decrease linearly and only slightly with x, reflecting the ionic radius difference between Fe(2+) and Co(2+). For the Fe-Mn system the lattice evolution also follows Vegard's law but is anisotropic: the in-plane axis increases, while the out-of-plane decreases prominently. The magnetic properties are little influenced by Co substitution. On the contrary, Mn substitution drastically destabilizes the G-type magnetic order, featured by a significant reduction and a large distribution of the hyperfine field in the Mössbauer spectra, which suggests the presence of magnetic frustration induced presumably by a ferromagnetic out-of-plane Mn-Fe interaction.

Hydro-nium bis-(tri-fluoro-methane-sulfon-yl)amide-18-crown-6 (1/1).

The structure of the title compound, H3O+·C2F6NO4S2 -·C12H24O6 or [H3O+·C12H24O6][N(SO2CF3)2 -], which is an ionic liquid with a melting point of 341-343 K, has been determined at 113 K. The asymmetric unit consists of two crystallographically independent 18-crown-6 mol-ecules, two hydro-nium ions and two bis-(tri-fluoro-methane-sulfon-yl)amide anions; each 18-crown-6 mol-ecule complexes with a hydro-nium ion. In one 18-crown-6 mol-ecule, a part of the ring exhibits conformational disorder over two sets of sites with an occupancy ratio of 0.533 (13):0.467 (13). One hydro-nium ion is complexed with the ordered 18-crown-6 mol-ecule via O-H⋯O hydrogen bonds with H2OH⋯OC distances of 1.90 (6)-2.19 (7) Å, and the other hydro-nium ion with the disordered crown mol-ecule with distances of 1.85 (6)-2.36 (6) Å. The hydro-nium ions are also linked to the anions via O-H⋯F hydrogen bonds. The crystal studied was found to be a racemic twin with a component ratio of 0.55 (13):0.45 (13).

A Concentrated AlCl3-Diglyme Electrolyte for Hard and Corrosion-Resistant Aluminum Electrodeposits.

A concentrated aluminum chloride (AlCl3)-diglyme (G2) electrolyte is used to prepare hard and corrosion-resistant aluminum (Al) electrodeposited films. The Al electrodeposits obtained from the electrolyte with an AlCl3/G2 molar ratio x = 0.4 showed a void-free microstructure composed of spherical particles, in stark contrast to flake-like morphologies with micro-voids for lower x. Neutral complexes rarely exist in the x = 0.4 electrolyte, resulting in a relatively high conductivity despite the high concentration and high viscosity. Nanoindentation measurements for the Al deposits with >99% purity revealed that the nanohardness was 2.86 GPa, three times higher than that for Al materials produced through electrodeposition from a well-known ionic liquid bath or through severe plastic deformation. Additionally, the void-free Al deposits had a <100> preferential crystal orientation, which accounted for better resistance to free corrosion and pitting corrosion. Discussions about the compact microstructure and <100> crystal orientation of deposits obtained only from the x = 0.4 concentrated electrolyte are also presented.

Reactivity of Zinc Cations under Spontaneous Accumulation of Hydrophobic Coexisting Cations in Hydrophobic Nanoporous Silicon.

The ion enrichment behavior due to surface-induced phase separation and the concomitant phase transition of electrolyte solutions between a liquid and a solid confined within nanopores of porous silicon is examined using concentrated aqueous solutions. We performed open-circuit potential measurements and differential scanning calorimetry (DSC) while varying the concentration of aqueous tetraethylammonium chloride (TEACl) solution. Open-circuit potential measurements revealed that the local OH- concentration within the nanopores increases as the bulk TEACl concentration increases. DSC measurements indicated that TEA+ cations are enriched within the nanopores and an extremely high concentration of TEA+ remarkably increases the local OH- concentration. This increase in the local pH should realize the selective precipitation of metal hydroxides within the nanopores. However, such precipitation was not observed in our investigations using aqueous solutions containing zinc cations. The experimental results suggest that ionic species within the nanopores of porous silicon are more stable than those in a bulk solution due to the formation of ion pairs with enhanced stability as well as kinetic factors that increase the activation energy for precipitation.

CaFeO2: a new type of layered structure with iron in a distorted square planar coordination.

CaFeO(2), a material exhibiting an unprecedented layered structure containing 3d(6) iron in a high-spin distorted square-planar coordination, is reported. The new phase, obtained through a low-temperature reduction procedure using calcium hydride, has been characterized through powder neutron diffraction, synchrotron X-ray diffraction, Mossbauer spectroscopy, XAS experiments as well as first-principles DFT calculations. The XAS spectra near the Fe-K edge for the whole solid solution (Sr(1-x)Ca(x))FeO(2) supports that iron is in a square-planar coordination for 0

Spontaneous Symmetry Breaking of Nanoscale Spatiotemporal Pattern as the Origin of Helical Nanopore Etching in Silicon.

Nanometric chiral objects such as twisted or helical nanoribbons represent a new class of objects having important potential in a large panel of applications, taking advantage, for example, of electromechanical or optical chirality, local chiral environment for catalysis, and chiral recognition. Supramolecular chemistry has played a central role in the production of such structures through either chiral macromolecules/foldamers or the self-assembly of chiral molecules; the latter can also be used as templates for the sol-gel transcription to silica materials, offering them polymorphisms with further structural stability. Here, we report a totally different and dynamic approach to produce helical mesostructures. This study focuses on helical nanopores that are spontaneously formed in the platinum-assisted chemical etching of silicon by dynamic self-organization under a nonequilibrium state. The symmetry breaking of a helical nanopore formation is achieved by the spatial symmetry breaking of a spatiotemporal pattern at the nanoscale and without incorporation of chiral molecules. Rotational motion of the platinum nanocatalyst, which is regarded as a spatiotemporal pattern at the etching frontier (the platinum/silicon interface), induces precession movement of the nanocatalyst, and movement of the catalyst during etching forms helical nanopores in the silicon. We consider that this study is an important milestone to understand the close relation between spatiotemporal pattern formation and the dynamic emergence of symmetry breaking in chemical reactions.

Stability of the infinite layer structure with iron square planar coordination.

The recently discovered SrFeO2 prepared by a soft chemical route from a precursor SrFeO3 has the "infinite layer" (IL) structure with an unprecedented FeO4 square-planar coordination. We show that the IL structure has significant solubility to yield Sr1-xCaxFeO2 (0

First single-crystal synthesis and low-temperature structural determination of the quasi-2D quantum spin compound (CuCl)LaNb2O7.

We provide a full description of the first single-crystal synthesis of the low-dimensional quantum spin compound (CuCl)LaNb(2)O(7) through the low-temperature topotactic ion exchange route. Very fast diffusion of ion-exchanged CuCl and Cs ions is observed. In addition, thorough structure determination at very low temperature is outlined following use of single-crystal X-ray diffraction and powder neutron diffraction, taking advantage of the better sensitivity of the latter method for describing O and Cl atoms. State-of-the-art calculations (Maximum Entropy Method) are used for visualising the fine structural features of this unusual pseudo-tetragonal superstructure. Our study unambiguously throws light on the long-standing controversy concerning the crystal structure of this compound, and allows for a relevant description of its magnetic properties. Incidentally, it is demonstrated that the low-temperature structural model tentatively proposed very recently by Tsirlin et al. (Phys. Rev. B, 2010, 82, 054107), according to powder synchrotron X-ray diffraction, is correct.