Ternary CNTs@TiO₂/CoO Nanotube Composites: Improved Anode Materials for High Performance Lithium Ion Batteries.

TiO₂ nanotubes (NTs) synthesized by electrochemical anodization are discussed as very promising anodes for lithium ion batteries, owing to their high structural stability, high surface area, safety, and low production cost. However, their poor electronic conductivity and low Li⁺ ion diffusivity are the main drawbacks that prevent them from achieving high electrochemical performance. Herein, we report the fabrication of a novel ternary carbon nanotubes (CNTs)@TiO₂/CoO nanotubes composite by a two-step synthesis method.

Selective sensitivity in Kerr microscopy.

A new technique for contrast separation in wide-field magneto-optical Kerr microscopy is introduced. Utilizing the light from eight light emitting diodes, guided to the microscope by glass fibers and being switched synchronously with the camera exposure, domain images with orthogonal in-plane sensitivity can be displayed simultaneously at real-time, and images with pure in-plane or polar contrast can be obtained. The benefit of this new method of contrast separation is demonstrated for Permalloy films, a NdFeB sinter magnet, and a cobalt crystal.

Signatures of a magnetic field-induced unconventional nematic liquid in the frustrated and anisotropic spin-chain cuprate LiCuSbO.

Modern theories of quantum magnetism predict exotic multipolar states in weakly interacting strongly frustrated spin-1/2 Heisenberg chains with ferromagnetic nearest neighbor (NN) inchain exchange in high magnetic fields. Experimentally these states remained elusive so far. Here we report strong indications of a magnetic field-induced nematic liquid arising above a field of ~13 T in the edge-sharing chain cuprate LiSbCuO ≡ LiCuSbO.

Confining the spin between two metal atoms within the carbon cage: redox-active metal-metal bonds in dimetallofullerenes and their stable cation radicals.

Lanthanide-lanthanide bonds are exceptionally rare, and dimetallofullerenes provide a unique possibility to stabilize and study these unusual bonding patterns. The presence of metal-metal bonds and consequences thereof for the electronic properties of M@C (M = Sc, Er, Lu) are addressed by electrochemistry, electron paramagnetic resonance, SQUID magnetometry and other spectroscopic techniques. A simplified non-chromatographic separation procedure is developed for the isolation of Er@C (C(6) and C(8) cage isomers) and Sc@C (C(8) isomer) from fullerene mixtures.

Tuning the spin coherence time of Cu(II)-(bis)oxamato and Cu(II)-(bis)oxamidato complexes by advanced ESR pulse protocols.

We have investigated with the pulsed ESR technique at X- and Q-band frequencies the coherence and relaxation of Cu spins = 1/2 in single crystals of diamagnetically diluted mononuclear [-BuN][Cu(opba)] (1%) in the host lattice of [-BuN][Ni(opba)] (99%, opba = -phenylenebis(oxamato)) and of diamagnetically diluted mononuclear [-BuN][Cu(opbo-Pr)] (1%) in the host lattice of [-BuN][Ni(opbo-Pr)] (99%, opbo-Pr = -phenylenebis((propyl)oxamidato)). For that we have measured the electron spin dephasing time at different temperatures with the two-pulse primary echo and with the special Carr-Purcell-Meiboom-Gill (CPMG) multiple microwave pulse sequence. Application of the CPMG protocol has led to a substantial increase of the spin coherence lifetime in both complexes as compared to the primary echo results.

Probing the magnetic superexchange couplings between terminal Cu ions in heterotrinuclear bis(oxamidato) type complexes.

The reaction of one equivalent of [-BuN][Ni(opboR)] with two equivalents of [Cu(pmdta)(X)] afforded the heterotrinuclear CuNiCu containing bis(oxamidato) type complexes [CuNi(opboR)(pmdta)]X (R = Me, X = NO (); R = Et, X = ClO (); R = Pr, X = NO (); opboR = -phenylenebis(NR-substituted oxamidato); pmdta = ,,',","-pentamethyldiethylenetriamine). The identities of the heterotrinuclear complexes - were established by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction studies, which revealed the cationic complex fragments [CuNi(opboR)(pmdta)] as not involved in any further intermolecular interactions. As a consequence thereof, the complexes - possess terminal paramagnetic [Cu(pmdta)] fragments separated by [Ni(opboR)] bridging units representing diamagnetic = 0 states.

Anodically Grown Binder-Free Nickel Hexacyanoferrate Film: Toward Efficient Water Reduction and Hexacyanoferrate Film Based Full Device for Overall Water Splitting.

One of the challenges in obtaining hydrogen economically by electrochemical water splitting is to identify and substitute cost-effective earth-abundant materials for the traditionally used precious-metal-based water-splitting electrocatalysts. Herein, we report the electrochemical formation of a thin film of nickel-based Prussian blue analogue hexacyanoferrate (Ni-HCF) through the anodization of a nickel substrate in ferricyanide electrolyte. As compared to the traditionally used Nafion-binder-based bulk film, the anodically obtained binder-free Ni-HCF film demonstrates superior performance in the electrochemical hydrogen evolution reaction (HER), which is highly competitive with that shown by a Pt-plate electrode.

Novel Solid-State Solar Cell Based on Hole-Conducting MOF-Sensitizer Demonstrating Power Conversion Efficiency of 2.1.

This work reports on designing of first successful MOF-sensitizer based solid-state photovoltaic device, perticularly with a meaningful output power conversion efficiency. In this study, an intrinsically conductive cobalt-based MOFs (Co-DAPV) formed by the coordination between Co (II) ions and a redox active di(3-diaminopropyl)-viologen (i.e.

Theoretical and computational validation of the Kuhn barrier friction mechanism in unfolded proteins.

A long time ago, Kuhn predicted that long polymers should approach a limit where their global motion is controlled by solvent friction alone, with ruggedness of their energy landscapes having no consequences for their dynamics. In contrast, internal friction effects are important for polymers of modest length. Internal friction in proteins, in particular, affects how fast they fold or find their binding targets and, as such, has attracted much recent attention.

Ni formate complexes with bi- and tridentate nitrogen-donor ligands: synthesis, characterization, and magnetic and thermal properties.

The synthesis of four Ni formate complexes of the type [Ni(NN)][OCH] (2, adduct with 3/4 EtOH, NN = en, e[combining low line]thylen[combining low line]ediamine, n = 3; 4, NN = dien, N,N',N''-d[combining low line]i[combining low line]e[combining low line]thylen[combining low line]etriamine, n = 2), [Ni(OCH)(HO)(tmeda)] (3, tmeda = N,N,N',N'-t[combining low line]etram[combining low line]ethyle[combining low line]thylened[combining low line]ia[combining low line]mine) and [{Ni(OCH)(pmdta)}·HO] (5, pmdta = N,N',N',N'',N''-p[combining low line]entam[combining low line]ethyld[combining low line]iethylenet[combining low line]ria[combining low line]mine) by a reaction of [{Ni(OCH)}·2HO] (1) with the respective N-donor bases is reported. The structures of 2-5 in the solid state were determined by single X-ray structure analysis, revealing a discrete dinuclear structure of 3 and the formation of polymeric networks in the case of 2, 4 and 5 due to intermolecular hydrogen bonding. SQUID and ESR measurements of 3 evidenced a weak antiferromagnetic coupling between the Ni ions and an easy plane magnetic anisotropy.

Redox properties and electron transfer in a triarylamine-substituted HS-Co/LS-Co redox couple.

A new tridentate phenanthroline-pyridyl-based ligand 1 containing a redox active Tara (triaryl amine) unit has been developed (1 = 4-((6-(1,10-phenanthrolin-2-yl)pyridin-2-yl)oxy)-N,N-di-p-tolylaniline). The complex [Co(1)](ClO/BF) was prepared and the order of the oxidation steps was analysed by cyclic voltammetry and EPR/UV-vis-NIR spectroelectrochemistry. Oxidation of [Co(1)] to [Co(1)] proceeds in two steps.

Self-organized double-wall oxide nanotube layers on glass-forming Ti-Zr-Si(-Nb) alloys.

In this work, we report for the first time on the use of melt spun glass-forming alloys - TiZrSi (TZS) and TiZrSiNb (TZSN) - as substrates for the growth of anodic oxide nanotube layers. Upon their anodization in ethylene glycol based electrolytes, highly ordered nanotube layers were achieved. In comparison to TiO nanotube layers grown on Ti foils, under the same conditions for reference, smaller diameter nanotubes (~116nm for TZS and ~90nm for TZSN) and shorter nanotubes (~11.

Berry phase and band structure analysis of the Weyl semimetal NbP.

Weyl semimetals are often considered the 3D-analogon of graphene or topological insulators. The evaluation of quantum oscillations in these systems remains challenging because there are often multiple conduction bands. We observe de Haas-van Alphen oscillations with several frequencies in a single crystal of the Weyl semimetal niobium phosphide.

Signal enhancement in cantilever magnetometry based on a co-resonantly coupled sensor.

Cantilever magnetometry is a measurement technique used to study magnetic nanoparticles. With decreasing sample size, the signal strength is significantly reduced, requiring advances of the technique. Ultrathin and slender cantilevers can address this challenge but lead to increased complexity of detection.

Synthesis and Isolation of the Titanium-Scandium Endohedral Fullerenes-Sc2 TiC@Ih -C80 , Sc2 TiC@D5h -C80 and Sc2 TiC2 @Ih -C80 : Metal Size Tuning of the Ti(IV) /Ti(III) Redox Potentials.

The formation of endohedral metallofullerenes (EMFs) in an electric arc is reported for the mixed-metal Sc-Ti system utilizing methane as a reactive gas. Comparison of these results with those from the Sc/CH4 and Ti/CH4 systems as well as syntheses without methane revealed a strong mutual influence of all key components on the product distribution. Whereas a methane atmosphere alone suppresses the formation of empty cage fullerenes, the Ti/CH4 system forms mainly empty cage fullerenes.

High Area Capacity Lithium-Sulfur Full-cell Battery with Prelitiathed Silicon Nanowire-Carbon Anodes for Long Cycling Stability.

We show full Li/S cells with the use of balanced and high capacity electrodes to address high power electro-mobile applications. The anode is made of an assembly comprising of silicon nanowires as active material densely and conformally grown on a 3D carbon mesh as a light-weight current collector, offering extremely high areal capacity for reversible Li storage of up to 9 mAh/cm(2). The dense growth is guaranteed by a versatile Au precursor developed for homogenous Au layer deposition on 3D substrates.

Enhanced polysulphide redox reaction using a RuO2 nanoparticle-decorated mesoporous carbon as functional separator coating for advanced lithium-sulphur batteries.

A multi-functional RuO2 nanoparticle-embedded mesoporous carbon-coated separator is used as an electrocatalytic and adsorbing polysulphide-net to enhance the redox reaction of migrating polysulphides, to improve active material utilization and boost the electrochemical performance of lithium-sulphur batteries.

Synergistically Enhanced Polysulfide Chemisorption Using a Flexible Hybrid Separator with N and S Dual-Doped Mesoporous Carbon Coating for Advanced Lithium-Sulfur Batteries.

Because of the outstanding high theoretical specific energy density of 2600 Wh kg(-1), the lithium-sulfur (Li-S) battery is regarded as a promising candidate for post lithium-ion battery systems eligible to meet the forthcoming market requirements. However, its commercialization on large scale is thwarted by fast capacity fading caused by the Achilles' heel of Li-S systems: the polysulfide shuttle. Here, we merge the physical features of carbon-coated separators and the unique chemical properties of N and S codoped mesoporous carbon to create a functional hybrid separator with superior polysulfide affinity and electrochemical benefits.

Dispersibility of vapor phase oxygen and nitrogen functionalized multi-walled carbon nanotubes in various organic solvents.

The synthesis and characterization of gas phase oxygen- and nitrogen-functionalized multi-walled carbon nanotubes (OMWCNTs and NMWCNTs) and the dispersibility of these tubes in organic solvents were investigated. Recently, carbon nanotubes have shown supreme capacity to effectively enhance the efficiency of organic solar cells (OSCs). A critical challenge is to individualize tubes from their bundles in order to provide homogenous nano-domains in the active layer of OSCs.

STM Study of Au(111) Surface-Grafted Paramagnetic Macrocyclic Complexes [Ni2L(Hmba)](+) via Ambidentate Coligands.

Molecular anchoring and electronic properties of macrocyclic complexes fixed on gold surfaces have been investigated mainly by using scanning tunnelling microscopy (STM) and complemented with X-ray photoelectron spectroscopy (XPS). Exchange-coupled macrocyclic complexes [Ni2L(Hmba)](+) were deposited via 4-mercaptobenzoate ligands on the surface of a Au(111) single crystal from a mM solution of the perchlorate salt [Ni2L(Hmba)]ClO4 in dichloromethane. The combined results from STM and XPS show the formation of large monolayers anchored via Au-S bonds with a height of about 1.

Dynamic Polymeric Microtubes for the Remote-Controlled Capture, Guidance, and Release of Sperm Cells.

Remote-controlled release of single sperm cells is demonstrated by the use of polymeric microtubes that unfold upon temperature increase to 38 °C. Thermoresponsive, ferromagnetic multilayers are tailored to catch sperm cells and remotely control them by external magnetic fields. These polymeric spermbots are propelled by the sperm flagella.

Nematicity in stripe-ordered cuprates probed via resonant x-ray scattering.

In underdoped cuprate superconductors, a rich competition occurs between superconductivity and charge density wave (CDW) order. Whether rotational symmetry-breaking (nematicity) occurs intrinsically and generically or as a consequence of other orders is under debate. Here, we employ resonant x-ray scattering in stripe-ordered superconductors (La,M)2CuO4 to probe the relationship between electronic nematicity of the Cu 3d orbitals, structure of the (La,M)2O2 layers, and CDW order.

Orbital symmetry of charge-density-wave order in La1.875Ba0.125CuO4 and YBa2Cu3O6.67.

Recent theories of charge-density-wave (CDW) order in high-temperature superconductors have predicted a primarily d CDW orbital symmetry. Here, we report on the orbital symmetry of CDW order in the canonical cuprate superconductors La1.875Ba0.

Complex Field-Induced States in Linarite PbCuSO4(OH)2 with a Variety of High-Order Exotic Spin-Density Wave States.

Low-temperature neutron diffraction and NMR studies of field-induced phases in linarite are presented for magnetic fields H∥b axis. A two-step spin-flop transition is observed, as well as a transition transforming a helical magnetic ground state into an unusual magnetic phase with sine-wave-modulated moments ∥H. An effective J[over ˜]_{1}-J[over ˜]_{2} single-chain model with a magnetization-dependent frustration ratio α_{eff}=-J[over ˜]_{2}/J[over ˜]_{1} is proposed.

Self-assembly of endohedral metallofullerenes: a decisive role of cooling gas and metal-carbon bonding.

The endohedral metallofullerene (EMF) self-assembly process in Sc/carbon vapor in the presence and absence of an inert cooling gas (helium) is systematically investigated using quantum chemical molecular dynamics simulations. It is revealed that the presence of He atoms accelerates the formation of pentagons and hexagons and reduces the size of the self-assembled carbon cages in comparison with analogous He-free simulations. As a result, the Sc/C/He system simulations produce a larger number of successful trajectories (i.