Thermodynamic properties in the normal and superconducting states of Na(x)CoO(2)*yH(2)O powder measured by heat capacity experiments

The heat capacity of superconducting Na(x)CoO(2)*yH(2)O was measured and the data are discussed based on three different models: The thermodynamic Ginzburg-Landau model, the BCS theory, and a model including the effects of line nodes in the superconducting gap function. The electronic heat capacity is separated from the lattice contribution in a thermodynamically consistent way maintaining the entropy balance of superconducting and normal states at the critical temperature. It is shown that for a fully gapped superconductor the data can only be explained by a reduced (about 55 %) superconducting volume fraction. The data are compatible with 100 % superconductivity in the case where line nodes are present in the superconducting gap function.Comment: Revised, 19 pages, 3 figure

Order and disorder in the triangular-lattice t-J-V model at 2/3 electron density

Motivated by the recent discovery of superconductivity in Na$_x$CoO$_2\cdot y$H$_2$O, we use series expansion methods and cluster mean-field theory to study spontaneous charge order, Neel order, ferromagnetic order, dimer order and phase-separation in the triangular-lattice t-J-V model at 2/3 electron density. We find that for t<0, the charge ordered state, with electrons preferentially occupying a honeycomb lattice, is very robust. Quite surprisingly, hopping to the third sublattice can even enhance Neel order. At large negative t and small V, the Nagaoka ferromagnetic state is obtained. For large positive t, charge and Neel order vanish below a critical V, giving rise to an itinerant antiferromagnetically correlated state.Comment: 4 pages, 5 figure

Hole Doping Effects on Spin-gapped Na2Cu2TeO6 via Topochemical Na Deficiency

We report the magnetic susceptibility and NMR studies of a spin-gapped layered compound Na2Cu2TeO6 (the spin gap $\Delta\sim$ 250 K), the hole doping effect on the Cu2TeO6 plane via a topochemical Na deficiency by soft chemical treatment, and the static spin vacancy effect by nonmagnetic impurity Zn substitution for Cu. A finite Knight shift at the $^{125}$Te site was observed for pure Na2Cu2TeO6. The negative hyperfine coupling constant $^{125}A_{tr}$ is an evidence for the existence of a superexchange pathway of the Cu-O-Te-O-Cu bond. It turned out that both the Na deficiency and Zn impurities induce a Curie-type magnetism in the uniform spin susceptibility in an external magnetic field of 1 T, but only the Zn impurities enhance the low-temperature $^{23}$Na nuclear spin-lattice relaxation rate whereas the Na deficiency suppresses it. A spin glass behavior was observed for the Na-deficient samples but not for the Zn-substituted samples. The dynamics of the unpaired moments of the doped holes are different from that of the spin vacancy in the spin-gapped Cu2TeO6 planes.Comment: 4 pages, 7 figures, to be published in J. Phys. Soc. Jpn. Vol. 75, No. 8 (2006

Synthesis of H_xLi_1-xLaTiO₄ from quantitative solid-state reactions at room temperature

The layered perovskite HLaTiO4 reacts stoichiometrically with LiOH·H2O at room temperature to give targeted compositions in the series HxLi1-xLaTiO4. Remarkably, the Li+ and H+ ions are quantitatively exchanged in the solid state and this allows stoichiometric control of ion exchange for the first time in this important series of compounds

Structure and Dynamics of Superconducting NaxCoO(2) Hydrate and Its Unhydrated Analog

Neutron scattering has been used to investigate the crystal structure and lattice dynamics of superconducting Na0.3CoO2 1.4(H/D)2O, and the parent Na0.3CoO2 material. The structure of Na0.3CoO2 consists of alternate layers of CoO2 and Na and is the same as the structure at higher Na concentrations. For the superconductor, the water forms two additional layers between the Na and CoO2, increasing the c-axis lattice parameter of the hexagonal P63/mmc space group from 11.16 A to 19.5 A. The Na ions are found to occupy a different configuration from the parent compound, while the water forms a structure that replicates the structure of ice. Both types of sites are only partially occupied. The CoO2 layer in these structures is robust, on the other hand, and we find a strong inverse correlation between the CoO2 layer thickness and the superconducting transition temperature (TC increases with decreasing thickness). The phonon density-of-states for Na0.3CoO2 exhibits distinct acoustic and optic bands, with a high-energy cutoff of ~100 meV. The lattice dynamical scattering for the superconductor is dominated by the hydrogen modes, with librational and bending modes that are quite similar to ice, supporting the structural model that the water intercalates and forms ice-like layers in the superconductor.Comment: 14 pages, 7 figures, Phys. Rev. B (in press). Minor changes + two figures removed as requested by refere

59Co Nuclear Quadrupole Resonance Studies of Superconducting and Non-superconducting Bilayer Water Intercalated Sodium Cobalt Oxides NaxCoO2.yH2O

We report 59Co nuclear quadrupole resonance (NQR) studies of bilayer water intercalated sodium cobalt oxides NaxCoO2.yH2O (BLH) with the superconducting transition temperatures, 2 K < T_c <= 4.6 K, as well as a magnetic BLH sample without superconductivity. We obtained a magnetic phase diagram of T_c and the magnetic ordering temperature T_M against the peak frequency nu_3 59Co NQR transition I_z = +- 5/2 +-7/2 and found a dome shape superconducting phase. The 59Co NQR spectrum of the non-superconducting BLH shows a broadening below T_M without the critical divergence of 1/T_1 and 1/T_2, suggesting an unconventional magnetic ordering. The degree of the enhancement of 1/T_1T at low temperatures increases with the increase of nu_3 though the optimal nu_3~12.30 MHz. In the NaxCoO2.yH2O system, the optimal-T_c superconductivity emerges close to the magnetic instability. T_c is suppressed near the phase boundary at nu_3~12.50 MHz, which is not a conventional magnetic quantum critical point.Comment: 4 pages, 5 figure

A novel route to phase formation of cobalt oxyhydrates using KMnO4 as an oxidizing agent

We have first succeefully synthesized the sodium cobalt oxyhydrate superconductors using KMnO4 as a de-intercalating and oxidizing agent. It is a novel route to form the superconductive phase of NaxCoO2.yH2O without resorting to the commonly used Br2/CH3CN solution. The role of the KMnO4 is to de-intercalate the Na+ from the parent compound Na0.7CoO2 and oxidize the Co ion as a result. The higher molar ratio of KMnO4 relative to the sodium content tends to remove more Na+ from the parent compound and results in a slight expansion of the c-axis in the unit cell. The superconducting transition temperature is 4.6-3.8 K for samples treated by the aqueous KMnO4 solution with the molar ratio of KMnO4 relative to the sodium content in the range of 0.3 and 2.29.Comment: 10 pages, 3 figure

Novel phase diagram of superconductor NaxCoO2-yH2O in a 75 % relative humidity

We succeeded in synthesizing the powder samples of bilayer-hydrate sodium cobalt oxide superconductors NaxCoO2-yH2O with Tc = 0 ~ 4.6 K by systematically changing the keeping duration in a 75 % relative humidity atmosphere after intercalation of water molecules. From the magnetic measurements, we found that the one-day duration sample does not show any superconductivity down to 1.8 K, and that the samples kept for 2 ~ 7 days show superconductivity, in which Tc increases up to 4.6 K with increasing the duration. Tc and the superconducting volume fraction are almost invariant between 7 days and 1month duration. The 59Co NQR spectra indicate a systematic change in the local charge distribution on the CoO2 plane with change in duration.Comment: 4 pages, 5 figures, submitted to Journal of the Physical Society of Japa

Nanostructured Nickel Phosphide as an Electrocatalyst for the Hydrogen Evolution Reaction

Nanoparticles of nickel phosphide (Ni_2P) have been investigated for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic solutions, under which proton exchange membrane-based electrolysis is operational. The catalytically active Ni_2P nanoparticles were hollow and faceted to expose a high density of the Ni_2P(001) surface, which has previously been predicted based on theory to be an active HER catalyst. The Ni2P nanoparticles had among the highest HER activity of any non-noble metal electrocatalyst reported to date, producing H_2(g) with nearly quantitative faradaic yield, while also affording stability in aqueous acidic media

Electrocatalytic hydrogen evolution using amorphous tungsten phosphide nanoparticles

Amorphous tungsten phosphide (WP), which has been synthesized as colloidal nanoparticles with an average diameter of 3 nm, has been identified as a new electrocatalyst for the hydrogen-evolution reaction (HER) in acidic aqueous solutions. WP/Ti electrodes produced current densities of −10 mA cm^(−2) and −20 mA cm^(−2) at overpotentials of only −120 mV and −140 mV, respectively, in 0.50 M H_2SO_4(aq)