Development of catalytically enhanced sodium aluminum hydride as a hydrogen-storage material

The dehydriding of sodium aluminum hydride, NaAlH₄, is kinetically enhanced and rendered reversible in the solid state upon doping with selected titanium compounds. Following the initial reports of this catalytic effect, further kinetic improvement and stabilization of the cyclable hydrogen capacity have been achieved upon variation in the method of the introduction of titanium and particle-size reduction. Rapid evolution of 4.0-wt % hydrogen at 100 °C has been consistently achieved for several dehydriding/rehydriding cycles. An improved, 4.8-wt % cyclable capacity has been observed in the material doped with a combination of Ti and Zr alkoxide complexes. Doping the hydride with Ti(OBuⁿ)₄ and Fe(OEt)₂ also produces a synergistic effect, resulting in materials that can be rehydrided to 4 wt % at 104 °C and 87 atm of hydrogen within 17 h. The improved kinetics allowed us to carry out constant-temperature, equilibrium-pressure studies of NaAlH₄ that extended to temperatures well below the melting point of the hydride. The 37-kJ/mol value determined for enthalpy of the dehydriding of NaAlH₄(s) to Na₃AlH₆ and Al and the hydrogen plateau pressure of 7 atm at 80 °C are in line with the predictions of earlier studies. The nature of the active catalyst and the mechanism of catalytic action are unknown. The catalytically enhanced hydrides appear to be strong candidates for development as hydrogen carriers for onboard proton exchange membran (PEM) fuel cells. However, further research and development in the areas of rehydriding catalysts, large-scale, long-term cycling, safety and adjustment of the plateau hydrogen pressure associated with dehydriding of AlH₆ ^- are required before these materials can be utilized in commercial onboard hydrogen-storage systems. Received: 7 September 2000 / Accepted: 14 November 2000 / Published online: 9 February 2001     

Intermetallic compounds as negative electrodes of Ni/MH batteries

This review is devoted to the main families of thermodynamically stable intermetallic compounds (AB₅-, AB₂- and AB-type alloys) that have been researched in the last thirty years as materials for negative electrodes in nickel–metal hydride batteries. The crystal structure of these compounds and their hydrides is widely described. Their solid–gas hydrogenation properties and, particularly, the related desorption isotherm curves are examined as a useful criterion for the selection of suitable battery materials. The electrochemical performances obtained with these alloys are reported and the given solutions to common problems such as corrosion, passivation, decrepitation and short cycle life are discussed. Only AB₅-based compounds have achieved, up to now, enough development for being widely present on the market, and exhibit improved battery performances in comparison with the polluting Ni/Cd batteries. The high capacity of AB₂-based compounds and the remarkable electrochemical activity of some AB-based alloys make, however, further research on all the reviewed families still valuable. Received: 16 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Synthesis,spectroscopic, thermal and electrical conductivity studies of three charge transfer complexes formed between 1,3-di[(<Emphasis Type="Italic">E</Emphasis>)-1-(2-hydroxyphenyl)methylideneamino]-2-propanol Schiff base and different acceptors

Charge-transfer complexes (CTC) resulting from interactions of 1,3-di[(E)-1-(2-hydroxyphenyl) methylideneamino]-2-propanol Schiff base with some acceptors such as iodine (I₂), bromine (Br2), and picric acid (PiA) have been isolated in the solid state in a chloroform solvent at room temperature. Based on elemental analysis, UV-Vis, infrared, and ¹H NMR spectra, and thermogravimetric analysis (TG/DTG) of the solid CTC, [(Schiff)(I₂)] (1), [(Schiff)(Br₂)] complexes with a ratio of 1:1 and [(Schiff)(PiA)₃] complexes with 1:3 have been prepared. In the picric acid complex, infrared and ¹H NMR spectroscopic data indicate that the charge-transfer interaction is associated with a hydrogen bonding, whereas the iodine and bromine complexes were interpreted in terms of the formation of dative ion pairs [Schiff⁺, I₂^∙−] and [Schiff⁺, Br₂^∙−], respectively. Kinetic parameters were obtained for each stage of thermal degradation of the CT complexes using Coats–Redfern and Horowitz–Metzger methods. DC electrical properties as a function of temperature of these charge transfer complexes have been studied.     

Room-temperature photoluminescence in amorphous SrTiO3– the influence of acceptor-type dopants

Room-temperature photoluminescence (PL) was observed in undoped and 2 mol % Cr-, Al- and Y-doped amorphous SrTiO₃ thin films. Doping increased the PL, and in the case of Cr significantly reduced the associated PL wavelength. The optical bandgaps, calculated by means of UV–vis absorption spectra, increased with crystallinity and decreased with the doping level. It was considered that yttrium and aluminum substituted Sr²⁺, whereas chromium replaced Ti⁴⁺. It is believed that luminescence centers are oxygen-deficient BO₆ complexes, or the same centers with some other defects, such as oxygen or strontium vacancies, or BO₆ complexes with some other defects placed in their neighborhood. The character of excitation and the competition for negatively charged non-bridging oxygen (NBO) among numerous types of BO₆ defect complexes in doped SrTiO₃ results in various broadband luminescence peak positions. The results herein reported are an indicative that amorphous titanates are sensitive to doping, which is important for the control of the electro-optic properties of these materials. The probable incorporation of Cr into the Ti site suggests that the existence of a double network former can lead to materials displaying a more intense photoluminescence. Received: 20 November 2001 / Accepted: 22 November 2001 / Published online: 27 March 2002     

Electric-field-enhanced metal-induced crystallization of hydrogenated amorphous silicon at room temperature

A novel simple method of crystallization of hydrogenated amorphous silicon (a-Si:H) thin films is described. Namely, we studied a metal-induced crystallization enhanced by a dc electric field in sandwich p⁺–i–n⁺structures. The samples were fabricated from wide-bandgap a-Si:H with high hydrogen content (13–51 at. % H). Macroscopic islands of a-Si:H (up to ∼1 mm in diameter) in the region between upper (CrNi) and lower (ITO) contacts crystallize instantaneously when a sufficiently high dc electric field (≳10⁵ V cm^-1) is applied. The crystallization sets in at room temperature and ambient atmosphere and is spatially selective. A proposed microscopic mechanism of such an easy macroscopic crystallization consists in easy diffusion of Ni and/or Ni silicides (representing nucleation sites) through a dense network of voids in hydrogen-rich a-Si:H. Received: 30 November 2000 / Accepted: 3 May 2001 / Published online: 27 June 2001     

Measurement of wurtzite ZnO/rutile TiO2 heterojunction band offsets by x-ray photoelectron spectroscopy

Four novel dmit complexes: [(C₂H₅)₄N][Ni (dmit)₂], [(C₃H₇)₄N][Ni(dmit)₂], [(C₂H₅)₄N][Au(dmit)₂] and [(C₃H₇)₄N][Au(dmit)₂], abbreviated as EtNi, PrNi, EtAu, and PrAu, were synthesized. The third-order nonlinear optical properties of them in acetonitrile solutions were investigated by using the Z-scan technique with 20 ps pulses width at 1064 nm. When the on-axis irradiance at focus I ₀ was 5.025 GW/cm², the nonlinear refraction coefficient n ₂, the third-order nonlinear susceptibility χ ⁽³⁾, the molecular second-order hyperpolarizability γ of the four types of material were obtained with subject to Z-scan curves, and these indexes were with the magnitudes of 10⁻¹⁸ m²/W, 10⁻¹³ esu, and 10⁻³¹ esu, respectively. The nonlinear absorption coefficient β of Ni samples had the 10⁻¹² m/W scale. The impact of different metals and cations on the third-order nonlinear optical properties of materials was analyzed. Through the derivation, the result suggests that these dmit complexes are promising candidates for applications to nonlinear optical devices manufacture in the near-infrared waveband.     

Covalency Measurements via NMR in Lithium Metal Phosphates

³¹P nuclear magnetic resonance (NMR) shifts on the order of thousands of parts per million are observed for olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples, a promising class of Li ion rechargeable battery electrode materials. Variable-temperature ³¹P NMR measurements of shift are used to determine that the supertransferred hyperfine interaction is the dominant mechanism giving rise to these unusually large observed ³¹P shifts. Various models for predicting ³¹P and ⁷Li shifts in LiMPO₄ (M = Mn, Fe, Co, Ni) were investigated. Alloys of LiFe_1−x Mn _x PO₄, where x varies from 0 to 1, were also investigated by ⁷Li NMR. Covalency constants, calculated from variable-temperature NMR shifts and magnetic susceptibility data, are determined for the P–O–M bonds in LiMPO₄ (M = Mn, Fe, Co, Ni) and compared to the covalency constants of the Li–O–M bond. The sign and relative magnitude of the covalency constants are discussed in terms of positive and negative spin densities at the nuclei of interest. The covalency constants for the Li–O–M and P–O–M bonds were measured for Li_1.8Na_0.2FeMn₂(PO₄)₃ and compared to the covalency constants measured in the olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples. The Li_1.8Na_0.2FeMn₂(PO₄)₃ structure has a volume per transition metal atom and Li–O–M bond distances that are similar to those of the olivine LiMPO₄ (M = Mn, Fe, Co, Ni) samples. Authors' address: Jeffrey A. Reimer, Department of Chemical Engineering, University of California Berkeley, Berkeley, CA 94720, USA     

Relative line intensity measurement in absorption spectra using a tunable diode laser at 1.6 μm: application to the determination of 13CO2/12CO2 isotope ratio

The measurement of relative intensities in CO₂ combination bands spectrum is performed using wavelength modulation spectroscopy (WMS) and a DFB (distributed feedback) diode laser operating at 1.6 μm. The diode laser is stabilized with an external Fabry–Pérot interferometer and absorption spectroscopy is performed in a multipass gas cell. A spectrum containing spectral lines of both ¹³CO₂ and ¹²CO₂ isotopic species is recorded. The variation of laser power during frequency scanning and the line shape are taken into account to accurately extract line intensities from experimental data. The isotopic concentration ratio is deduced from the intensity ratio. Both ratios are measured with an accuracy of about 0.5% in pure CO₂. Received: 9 June 2000 / Published online: 8 November 2000     

Stability of aqueous silica nanoparticle dispersions

In this study, we present quantification methods for nanoparticle stability analysis using non-intrusive analytical techniques: attenuated total reflectance, Fourier transform infrared (ATR-FTIR) spectroscopy, ultraviolet–visible (UV–vis) spectrophotometer, zeta potential analyses, and dynamic light scattering (DLS). We use these techniques to study the stability of silica nanoparticle dispersions and the effects of pH, temperature, and electrolytes that would be encountered in oil field brines in a reservoir. Spectral analysis of the Si–O bond at wavenumber of 1110 cm⁻¹ with the ATR-FTIR indicates a structural change on the surface of silica particles as the dispersion pH changes, which agrees with zeta potential measurements. We define a critical salt concentration (CSC) for different salts, NaCl, CaCl₂, BaCl₂, and MgCl₂, above which the silica dispersion becomes unstable. Three distinct stages of aggregation occur in the presence of salt: clear dispersed, turbid, and separated phases. Divalent cations Mg²⁺, Ca²⁺, and Ba²⁺ are more effective in destabilizing silica nanoparticle dispersion than the monovalent cation Na⁺. The CSC for Na⁺ is about 100 times more than for Ca²⁺, Ba²⁺, and Mg²⁺. Among the divalent cations studied, Mg²⁺ is the most effective in destabilizing the silica particles. The CSC is independent of silica concentration, and lowers at high temperature.     

Ti-doped NaAlH4 as a hydrogen-storage material – preparation by Ti-catalyzed hydrogenation of aluminum powder in conjunction with sodium hydride

Ti-doped NaAlH₄ can be prepared in a simple way by hydrogenation of aluminum powder in conjunction with sodium hydride in the presence of Ti(OBuⁿ)₄ (Buⁿ= n-C₄Hg) as a dopant. After a few hydrogenation/dehydrogenation cycles the material reaches a storage capacity of ∼4 wt %H₂ and exhibits reaction rates comparable to or exceeding those previously found for NaAlH₄ doped with Ti(OBuⁿ)₄ in organic solvents [Bogdanović et al.: J. Alloys Compd. 302, 36 (2000)]. Received: 25 August 2000 / Accepted: 6 November 2000 / Published online: 9 February 2001     

Hydrogen storage characteristics of nanograined free-standing magnesium–nickel films

Free-standing magnesium–nickel (Mg–Ni) films with extensive nanoscale grain structures were fabricated using a combination of pulsed laser deposition and film delaminating processes. Hydrogen sorption and desorption properties of the films, free from the influence of substrates, were investigated. Oxidation of the material was reduced through the use of a sandwiched free-standing film structure in which the top and bottom layers consist of nanometer-thick Pd layers, which also acted as a catalyst to promote hydrogen uptake and release. Hydrogen storage characteristics were studied at three temperatures, 296, 232, and 180°C, where multiple sorption/desorption cycles were measured gravimetrically. An improvement in hydrogen storage capacity over the bulk Mg–Ni target material was found for the free-standing films. As shown from a Van’t Hoff plot, the thermodynamic stability of the nanograined films is similar to that of Mg₂Ni. These results suggest that free-standing films, of which better control of material compositions and microstructures can be realized than is possible for conventional ball-milled powders, represent a useful materials platform for solid-state hydrogen storage research.     

Fabrication and performance of LaGaO3-Based tubular SOFC’s

Yttria stabilized zirconia (YSZ) is the most commonly used electrolyte material in solid oxide fuel cells (SOFC’s). However, doped lanthanum gallate is an interesting alternative for use at intermediate temperatures (typically 600 – 750 °C). Commercially available La_0.8Sr_0.2Ga_0.8Mg_0.2O_2.8 (LSGM) powder was mixed with a polymer-based binder system and extruded into two different size tubes. After sintering, the electrolyte tubes were approximately (a) 6 mm outside diameter, 0.55 mm wall thickness and 100–200 mm long and (b) 4 mm outside diameter, 0.22 mm wall thickness and 50–100 mm long. The tubes were then fabricated into SOFC’s, using a range of anode and cathode morphologies. The electrical performance of the cells was then tested using hydrogen as a fuel. A repeatable and constant power of over 2.5 W per cell was obtained at 800 °C and 0.7 V. The maximum power density of the tubular fuel cell with La_0.6Sr_0.4CoO₃ cathode, Ce_0.8Sm_0.2O_1.9 interlayer and a Ni anode was 482 mW/cm². This paper will present the fabrication procedure and parameters, fuel cell performance test results, and the effect of electrode morphologies on the performance of the fuel cells. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Structural and ferroelectric properties of Bi4Ti3O12 thin films on IrO2 prepared by rf magnetron sputtering

Bismuth titanate, Bi₄Ti₃O₁₂, thin films were grown on IrO₂/SiO₂/Si substrates by radio-frequency magnetron sputtering. Crystallinity and microstructure of the films were characterized over a wide range of oxygen mixing ratio (OMR) during deposition. X-ray fluorescence spectra reveal that the cation content of the films is dependent upon the OMR, suggesting that control of Bi to Ti ratio is possible by the oxygen content in the sputtering atmosphere. Rutherford backscattering spectrometry measurements also show that oxygen content of the BTO film grown with an OMR = 0.5is close to a stoichiometric phase. In addition, Bi–O bonding chemistry is studied by X-ray photoelectron spectroscopy. Polarization vs. voltage loop shows that remnant polarization, P_r, is +12 μC/cm². Received: 26 November 1999 / Accepted: 26 November 1999 / Published online: 9 August 2000     

Hydrogenation of carbon monoxide over nanostructured systems: A mechanochemical approach

In this study we investigated the mechanochemical hydrogenation of carbon monoxide over nanostructured FeCo- and Mg₂Ni-based catalysts. To this aim powdered materials, prepared by mechanical alloying, were subjected to mechanical treatment under CO + H₂ atmosphere. A methodology to evaluate the activity of the solid catalysts on an absolute basis was developed. Conversion data were, indeed, expressed as turnover frequency, TOF, and related to the occurrence of ball to powder collision events through the mechanochemical turnover frequency parameter, MTOF. Differences in the catalytic activity and selectivity were observed for the two FeCo-based studied systems, the solid solution Fe₅₀Co₅₀ and its dispersion on TiO₂ support. As for the Mg₂Ni system, we explored the possibility to estimate the specific role of hydrogen pre-activation step. The catalytic properties of the mechanically alloyed Mg₂Ni system were compared with the conversion data shown by the same system pre-hydrogenated and subsequently milled under CO atmosphere.     

Synthesis, characterization, DNA binding and cleavage studies of mixed-ligand Cu(II) complexes of 2,6-bis(benzimidazol-2-yl)pyridine

Four novel copper(II) complexes of the composition [CuLX] where L = 2,6-bis(benzimidazole-2yl)pyridine, X = dipyridophenazine (L₁), 1,10-phenanthroline (L₂), hydroxyproline (L₃) and 2,6-pyridine dicarboxylic acid (L₄) were synthesized and characterized by using elemental analysis, FT-IR, UV–vis, ESI-MS, molar conductance and magnetic susceptibility measurements. The complexes [CuLL₁](NO₃)₂ [1], [CuLL₂](NO₃)₂ [2], [CuLL₃](NO₃) [3] and [CuLL₄] (NO₃) [4] are stable at room temperature. In DMSO the complexes [1] and [2] are 1:2 electrolytes, [3] and [4] are 1:1 electrolytes. Based on elemental and spectral studies five coordinated geometry is assigned to all the four complexes. The interaction of four copper ion complexes with calf thymus DNA were carried out by UV–vis titrations, fluorescence spectroscopy, thermal melting and viscosity measurements .The binding constant (K_b) of the above four metal complexes were determined as 5.43 × 10⁴ M_,⁻¹ 2.56 × 10⁴ M⁻¹, 1.21 × 10⁴ M⁻¹ and 1.57 × 10⁴ M⁻¹ respectively. Quenching studies of the four complexes indicates that these complexes strongly bind to DNA, out of all complex 1 is binding more strongly. Viscosity measurements indicate the binding mode of complexes with CT DNA by intercalation through groove. Thermal melting studies also support intercalative binding. The nuclease activity of the above metal complexes shows that 1, 2 and 3 complexes cleave DNA through redox chemistry.     

Complexation between variable-valency uranium and organic ligands in solutions,their photostability and spectral identification

We discuss possible directions for searching for prospective materials based on low-valency uranium (III–V) as detection media for hard electromagnetic radiation. We have studied the processes of formation of tetravalent and pentavalent uranium complexes from UO₂(NO₃)₃·6H₂O and UO₂Cl₂·H₂O in DMF and with addition of CCl₄, including when the systems are exposed to radiation in the visible range (400–450 nm). In the first case (UO₂(NO₃)₃·6H₂O solutions in DMF), upon irradiation we observe stable complexes of pentavalent uranium, and when CCl₄ is added to the solution we observe complexes of tetravalent uranium. In the system UO₂Cl₂·3H₂O in DMF, we do not observe the appearance of new forms of uranium; but when CCl₄ is added, then complexes of tetravalent uranium are formed. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 184–187, March–April, 2007.     

Enhancement of Europium Luminescence in Tetracycline–Europium Complexes in the Presence of Urea Hydrogen Peroxide

An increase in the europium emission band was observed, for the first time, with addition of urea hydrogen peroxide to the tetracycline–europium (Tc–Eu)solution. We have observed that the wavelength, the band width and the area of ⁵D₀→⁷F₂ europium transition change with the urea hydrogen peroxide concentration. We claim that the tetracycline–europium complexes can be used as probes of urea hydrogen peroxide concentration.     

Integrity of ultrathin gate oxides with different oxide thickness, substrate wafers and metallic contaminations

The integrity of ultrathin gate oxides was investigated as a function of polished and epitaxial wafer surfaces with various gettering sites. After intentional contamination of wafers with 1×10¹¹ atoms/cm² and 5×10¹² atoms/cm² Cu and Ni by a spin-on technique of high reproducibility, we performed 0.18-μm low-thermal-budget CMOS process runs. Thermal oxides were grown with various gate oxides in the range of 5–17 nm. After a MOS-capacitor fabrication we applied a ramped current-density test to study the gate-oxide integrity. Generally, thinner gate oxides exhibited a much more robust behavior than thicker oxides. The gate-oxide integrity was strongly influenced by different gettering sites. Although a higher Ni contamination led to a higher number of gate-oxide failures, Cu contamination exhibited a higher impact on the gate-oxide integrity than Ni. Received: 12 September 2000 / Accepted: 21 September 2000 / Published online: 22 November 2000     

Ultrafine layered LiCoO2 obtained from citrate precursors

A new method for the preparation of ultrafine LiCoO₂ with a layered crystal structure was developed, which consists in thermal pyrolysis of homogeneous lithium-cobalt-citrate precursors. Atomic scale mixing of Li and Co is achieved by citric acid acting as a chelating agent. Electron spectroscopy of concentrated Li-Co-citrate solutions with Li:Co:Cit=1:1:1 and Li:Co:Cit=1:1:2 reveals that the predominant species at pH=7 are [Co(C₆H₅O₇)]⁻ and [Co(C₆H₅O₇)₂]⁴⁻ complexes. Freeze-drying of the two types of solutions leads to the formation of LiCo(C₆H₅O₇).nH₂O and (NH₄)₃LiCo(C₆H₅O₇)₂.nH₂O precursors, where Co²⁺ ions are complexed by one and two triionized citrate ions, respectively, and Li⁺ ions serve as counter ions. Between 400–600 °C, the thermal decomposition of these metal-citrate precursors yields LiCoO₂ with layered and pseudo-spinel structure, the proportion between them being depending on: (i) the Co/citrate ratio; (ii) the concentration of the freeze-dried solution; (iii) the heating rate. At 400 °C, the most defectless layered LiCoO₂, consisting of hexagonal individual particles with dimensions of 120–170 nm, is a product of the bis-citrate decomposition with a slow heating rate. For this sample, heating up to 600 °C does not affect the crystal size dimensions. For ultrafine layered LiCoO₂ and LiCoO₂ obtained by solid state reaction at high-temperatures (850 °C), the deintercalation and intercalation reactions proceed in the 3.95 – 3.99 and 3.86 – 3.88 voltage intervals, respectively. For defect trigonal LiCoO₂, additional oxidation and reduction peaks at 3.7 – 3.8 and 3.4 – 3.5 V were observed. We did not succeed in preparing monophase LiCoO₂ with pseudo-spinel structure. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Sept. 14–21, 1996     

Unique magnetism observed in single-wall carbon nanohorns

The magnetic properties of single-wall carbon nanohorns (SWNH) were studied by electron spin resonance (ESR) and static magnetic susceptibility measurements. The SWNHs were ESR active with linewidth (ΔH) of ∼6 G in vacuo at room temperature. ΔH was susceptible to the partial pressure of O₂ and became 53 G at 1 atmospheric pressure of O₂, while the integrated ESR intensity was independent on O₂ pressure and behaved as Curie-like, suggesting an intrinsic ESR origin with localized electron spin character. The diamagnetic susceptibility for SWNHs indicated a value smaller than that of randomly oriented graphite by an order of magnitude, but showing a magnitude comparable to those of C₆₀ and C₇₀. It is suggested that the large diamagnetism expecting for sp² networked carbon materials will be canceled by the Van Vleck constant paramagnetism. Received: 20 November 2000 / Accepted: 21 November 2000 / Published online: 25 July 2001