Structure transformations and hydrogen storage properties of co-sputtered MgNi films

The quantity of accommodated and distribution profiles of hydrogen in 1.5-μm thick co-sputtered MgNi films after uptake of hydrogen at 800 kPa pressure within the temperature range 200-250 °C during 1 h, 3 h, 6 h and 72 h are measured. The occurring phase changes are followed by X-ray diffraction measurements at room temperature. We conclude that the hydrogenation process involves two stages: (i) the fast nucleation of the initial Mg₂NiH₄ layer near the substrate interface and (ii) the slow random nucleation of the same phase within the remaining part of the film. The growth of the initial hydride layer may be blocked by the surface oxide barrier layer formed during hydrogenation. We find that hydrogen-induced structural transformations are correlated with oxygen contamination and modify hydrogen storage properties.     

Investigation of hydrogen storage in MWCNT–TiO2 composite

The hydrogen storage capacity of MWCNT–TiO₂ composite has been evaluated in the present work. The composite has been prepared by means of ultrasonication followed by drop casting on substrates. Morphology, structural and functional group studies of the prepared samples are carried out by transmission electron microscopy (TEM), scanning electron microscopy (SEM), powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. Then, the samples are hydrogenated in the hydrogenation chamber as a function of time. Hydrogen storage capacity of the composite sample is found to be 0.9 wt% at 100 °C. Hydrogen uptake of the composite is accounted for the spillover mechanism in CNTs–metal oxide composite. Desorption temperature range, activation energy of desorption, binding energy of hydrogen are determined from thermogravimetric (TG) analysis.     

Electrochemical performance of Mo-doped LiFePO4/C composites prepared by two-step solid-state reaction

To improve the performance of LiFePO₄, LiFe_1?x Mo _x PO₄/C (x?=?0, 0.005, 0.010, 0.015, 0.020, 0.025) cathode materials were synthesized via two-step ball milling solid-state reaction. The prepared samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy, cyclic voltammetry, electrochemical impedance spectra, and galvanostatic charge–discharge test. It is apparent from XRD analysis that Mo doping enlarges the interplanar distance of crystal plane parallel to [010] direction in LiFePO₄. In other words, it widens one-dimensional diffusion channels of Li⁺ along the [010] direction. The results of electrochemical test indicate that the LiFe_0.99Mo_0.01PO₄/C composite exhibits a discharge capacity of 144.8 mAh g^?1 at 1 C rate, a decreased charge transfer resistance of 162.4 Ω and better reversibility of electrode reactions. The present synthesis route is promising and practical for the preparation of LiFePO₄ materials.     

Evolution of the negative electrode (tin/silicate) for Li-ion batteries studied by 119 Sn Mössbauer spectroscopy

A novel tin composite Sn/CaSiO₃ for the anode of Li-ion batteries was prepared by solid-state reaction. The CaSiO₃ matrix was synthesized by a sol-gel route. The crystalline structures and morphology were determined by X-ray diffraction (XRD) and ¹¹⁹Sn Mössbauer spectroscopy; the electrochemical properties were evaluated by galvanostatic charge and discharge. The results obtained show that the Sn/CaSiO₃ composite presents very interesting electrochemical performances in terms of specific capacity in the first discharge (591 mAh/g) and a good reversibility due to both the formation of an interface between active and inactive materials and the reversible formation of Li _x Sn alloys. We have also highlighted, by ¹¹⁹Sn Mössbauer spectroscopy, the various tin species constituting the material of the starting electrode, as well as the chemical evolutions occurring during the discharge and the charge of the electrode.     

Hydrogen-induced Ostwald ripening at room temperature in a Pd nanocluster film

The structural and morphological changes occurring in an ensemble of vapor deposited palladium nanoclusters have been studied after several hydrogenation cycles with x-ray diffraction, extended x-ray-absorption fine structure spectroscopy, Rutherford backscattering spectrometry, and STM. Initial hydrogenation increased the cluster size, a result that is attributed to hydrogen-induced Ostwald ripening. This phenomenon originates from the higher mobility of palladium atoms resulting from the low sublimation energy of the palladium hydride as compared to that of the palladium metal. The universality of this phenomenon makes it important for the application of future nanostructured hydrogen storage materials.     

Effects of processing on the electrical and structural properties of spray deposited CdS:In thin films

Polycrystalline CdS:In thin films were prepared by the Spray pyrolysis technique (SP) at a substrate temperature T_s=490 °C. The effects of annealing in nitrogen atmosphere at 400 °C and HCl-etching on the electrical and structural properties of the films were investigated. The electrical properties were studied through the analysis of the I-V curves, while the structural properties were studied through the analysis of the X-ray diffraction (XRD) patterns and the scanning electron microscope (SEM) images. An increase in the films’ resistivity was occurred after annealing and/or HCl-etching, which was accompanied by changes in the XRD patterns and SEM images. These changes were related to a phase change from the mixed (cubic and hexagonal) phase to the hexagonal phase which was expected to occur during the aforementioned processes. The X-ray diffraction (XRD) patterns and the scanning electron microscope images confirm this expectation.     

The hydrogen‐bond effect on the high pressure behavior of hydrazinium monochloride

The first high pressure study of solid hydrazinium monochloride has been performed by in situ Raman spectroscopy and synchrotron X‐ray diffraction (XRD) experiments in diamond anvil cell (DAC) up to 39.5 and 24.6 GPa, respectively. The structure of phase I at room temperature is confirmed to be space group C2/c by the Raman spectral analysis and Rietveld refinement of the XRD pattern. A structural transition from phase I to II is observed at 7.3 GPa. Pressure‐induced position variation of hydrogen atoms in NH₃⁺ unit during the phase transition is attributed to the formation of N―H…Cl hydrogen‐bonds, which play a vital role in the stability and subsequent structural changes of this high energetic material under pressure. This inference is proved from the abnormal pressure shifts and obvious Fermi resonance in NH stretching mode of N₂H₅⁺ ion in the Raman experiment. Finally, a further transition from phase II to III accompanied with a slight internal distortion in the N₂H₅⁺ ions occurs above 19.8 GPa, and phase III persists up to 39.5 GPa. Copyright © 2015 John Wiley & Sons, Ltd.     

Role of MW-ECR hydrogen plasma on dopant deactivation and open-circuit voltage in crystalline silicon solar cells

Plasma hydrogenation is an efficient method to passivate intergrain and intragrain defects of polycrystalline silicon (pc-Si) solar cells. The hydrogenation experiments were carried out in hydrogen plasma generated in an electron cyclotron resonance system controlling different operating parameters such as microwave power (P _MW), process time (t _H) and hydrogenation temperature (T _H) for a fixed hydrogen flux of 30 sccm. The hydrogenation of n⁺pp⁺ pc-Si solar cells resulted in an improvement in the open-circuit voltage. The improvement was correlated with the dopant deactivation due to the formation of boron–hydrogen bonding. This was demonstrated from the changes in the doping level after hydrogenation of n⁺p diode structures made using single crystalline silicon as a reference material. It was found that deactivation of boron was more pronounced at high microwave plasma power, in good agreement with the high open-circuit voltage values obtained on pc-Si mesa cells. On the other hand, the effect of longer hydrogenation time and higher temperature resulted in a decrease of boron deactivation, while an increase in V _oc with a tendency of saturation at high T _H was observed. Reasons for such behavior were thoroughly explained.     

Pd8Ni92(1 1 0) surface structure from surface X-ray diffraction. Surface evolution under hydrogen and butadiene reactants at elevated pressure

The (N × 1) reconstruction (N = 5-6) of the clean Pd₈Ni₉₂(1 1 0) surface has been investigated by surface X-ray diffraction. A good fit with experimental data collected under UHV conditions is obtained when introducing undulations in the outer dense rows, constituted mainly of Pd atoms which strongly segregate to the surface. This reconstruction can be regarded as a way to relax the strains induced on the bigger Pd surface atoms, at least partially. The modifications of the surface were studied under butadiene then hydrogen as well as during butadiene hydrogenation at elevated pressure at 300 K and the (N × 1) reconstruction was found to be still present. The main changes are observed under pure hydrogen and during butadiene hydrogenation.     

Field emission properties of electrophoretic deposition carbon nanotubes film

The field emission properties of electrophoretic deposition(EPD) carbon nanotubes (CNTs) film have been improved by depositing CNTs onto the titanium (Ti)-coated Si substrate, followed by vacuum annealing at 900 °C for 2 h, and the enhanced emission mechanism has been studied using X-ray diffraction (XRD), scanning electron microscope (SEM) and Raman spectroscopy. Field emission measurements showed that the threshold electric field was decreased and the emission current stability was improved compared to that of EPD CNTs film on bare Si substrate. XRD and Raman spectroscopy investigations revealed that vacuum annealing treatment not only decreased the structural defects of CNTs but made a titanium carbide interfacial layer formed between CNTs and substrate. The field emission enhancement could be attributed to the improved graphitization of CNTs and the improved contact properties between CNTs and substrate including electrical conductivity and adhesive strength due to the formed conductive titanium carbide.     

Effect of Nitrogenation and Hydrogenation on the Magnetic Properties and Structure of the Sm<Subscript>2</Subscript>Fe<Subscript>17</Subscript> Alloy: Analysis of XMCD Data

Changes in the local magnetic and structural properties of Sm₂Fe₁₇ alloys at nitrogenation and hydrogenation of samples have been studied by the X-ray magnetic circular dichroism (XMCD) technique at the Fe K absorption edge and Sm L₃ absorption edge using synchrotron radiation. The results have been discussed in comparison with X-ray diffraction data and macroscopic vibration magnetometry measurements. The observed changes in XMCD spectra indicate a noticeable effect of nitrogenation on the local magnetic properties of sublattices of both iron and samarium, whereas hydrogenation of samples makes a small effect. The mentioned effects have been analyzed and discussed in terms of the effect of nitrogen (N) and hydrogen (H) interstitial atoms on Sm 5d and Fe 4p electronic states. The effect of nitrogenation is larger than the effect of hydrogenation because the volume expansion of the crystal lattice of initial Sm₂Fe₁₇ in the case of nitrogenation is larger than that in the case of hydrogenation. The studied local magnetization curves for samarium and iron sublattices in magnetic fields up to 17 T also indicate a strong increase in the magnetocrystalline anisotropy at nitrogenation.     

Hydrogen-induced magnetic and structural transformations of GdCu

The magnetization of GdCu induced by hydrogen uptake was measured within the temperature range of 4.2 to 300 K, occurring phase changes were followed by X-ray diffraction measurements at ambient temperature. The prepared GdCu powder of CsCl-type structure readily absorbed hydrogen at ambient temperature, where hydrogen pressure was below 100 kPa. Hydrogenation changed the magnetism of GdCu in a complex manner from an antiferromagnetic-like type to a paramagnetic-like one. The changes in magnetic properties of GdCu by hydrogenation are governed by hydrogen-induced disproportionation. Within the composition range 0<[H]/[GdCu]<1, GdCu disproportionated according to 2GdCu+H₂→GdH₂+GdCu₂ . The magnetization was evaluated by the expression χ_total=(1-x)χ_GdCu+(x/2)(χ_GdH2+χ_GdCu2). GdCu hydride was not observed. Hydrogenation beyond [H]/[GdCu]>1 gave rise to the disproportionation of GdCu₂ causing the change in magnetization.     

真空热处理碳纳米管的储氢性能研究

研究了真空热处理对多壁碳纳米管(MWNTs)电化学储氢性能的影响.采用化学气相沉积法(CVD)制备碳纳米管，碳纳米管与LaNi₅储氢合金按质量比1∶10混合，制作成CNTs-LaNi₅电极.电解池采用三电极体系，6mol/L KOH为电解液，Ni(OH)₂为正极，Hg/HgO为参比电极.实验结果表明，在相同的充放电条件下，850℃时CNTs-LaNi₅电极的储氢性能最好，克容量最大为503.6mAh/g，相应的平台电压高达1.18V.从500—850℃随着温度升高，放电量有较大幅度的增加，但到950℃时放电量反而下降.由此可见，碳纳米管的热处理温度对碳纳米管的电化学储氢性能有着较大的影响. 关键词： 碳纳米管(CNTs) 储氢性能 5合金')" href="#">LaNi₅合金 化学气相沉积法(CVD法)     

Carbon nanotubes supported Pt-Ni catalysts and their properties for the liquid phase hydrogenation of cinnamaldehyde to hydrocinnamaldehyde

The Pt-Ni catalysts supported on CNTs have been prepared by wet impregnation and the selective hydrogenation of cinnamaldehyde (CMA) to the corresponding hydrocinnamaldehyde (HCMA) over the catalysts has been studied in ethanol at different reaction conditions. The results show that Pt-0.34 wt% Ni/CNTs catalyst exhibits the highest activity and selectivity at a reaction temperature of 70 °C under a pressure of around 2.0 MPa, and 98.6% for the conversion of CMA and 88.2% for the selectivity of CMA to HCMA, respectively. The selective hydrogenation for the CC bond in CMA would be improved as increasing the reaction temperature, and the hydrogenation for the CO bond in CMA is enhanced as increasing the H₂ pressure. In addition, these catalysts have also been characterized using TEM-EDS, XPS, H₂-TPR and H₂-TPD techniques. The results show that Pt particles are dispersed more homogeneously on the outer surface of the nanotubes, while the strong interaction between Pt and Ni would improve the increasing of activated hydrogen number because of the hydrogen spillover from reduced Pt⁰ onto CNTs and increase the catalytic activity and selectivity of CMA to HCMA.     

Characterization and sensing property studies of the Pt | Nafion electrode prepared by the chemical reduction method

A novel electrochemical hydrogen sensor which consists of a solid electrolyte polymer (SEP) and catalytic active electrode operating at room temperature was fabricated and investigated. Nafion is utilized as polymer proton conducting membrane onto which a catalytic electrode was deposited by anin-situ impregnation reduction (I-R) technique. In this work, Pt was selected as active catalyst for hydrogen oxidation and the deposition conditions were modified to optimise the parameters for application in hydrogen sensors and to improve the metal utilization so that the electrode loading could be reduced without loss of electrochemical performance. The hydrogen sensing characteristics with air as reference gas are reported. A maximum sensitivity of about 0.01 μA cm⁻² ppm⁻¹ was obtained. The response time was observed to be in the range of 10–50 seconds. The experimental results show that long term sensor stability exists at room temperature. The thin Pt films were characterized by XRD, infrared spectroscopy, optical microscopy, scanning electron microscopy and EDAX. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14–18, 2004.     

Intercalated hydrogen in yttrium barium cuprate: The state and mobility of a “Guest” and modification of the “Host” properties

The electric, magnetic, and physicochemical properties of yttrium barium hydrocuprate (H₂YBa₂Cu₃O₇) and its oxidized form (H₂YBa₂Cu₃O_7.8) are governed, to a large measure, by poorly studied behavior of hydrogen atoms in the lattice. The crystal chemical state and the mobility of a proton intercalated into yttrium barium cuprate have been investigated by the isotope exchange and inelastic neutron scattering techniques. By their behavior in the process of inelastic neutron scattering, a substantial fraction of protons can be considered mechanically free particles without chemical bonding with oxygen ions. The self-diffusion coefficient of a proton is estimated to be several orders of magnitude larger than that of oxygen ions, the latter coefficient being equal to 10^?13 cm² s^?1 at 490 K. Considerable changes in the lattice parameters and local charge distribution in the copper-oxygen subsystem are revealed by the x-ray powder diffraction analysis and nuclear quadrupole resonance (NQR). Discrete changes in the interplanar spacings along the c axis and in the Cu NQR frequencies with a gradual variation in the degrees of hydration and oxidation indicate the formation of hydrocuprate and (or) oxyhydrocuprate in the matrix of the initial material.     

Study of the structural modifications in activated clays by Mössbauer spectroscopy and X-ray diffractometry

In this work we study the changes induced on the structure of a smectite clay by chemical acid activation with HCl using X-ray diffractometry (XRD) and transmission Mössbauer spectroscopy (TMS) techniques. By XRD we were able to determine the mineralogical composition of the clay samples and measure the changes in the interplanar distance associated to the structural modifications in the clays. We measured a reduction in the interplanar distance and reflection intensity as the acid concentration in the activation process increased. TMS allowed us identify and characterize the structural sites occupied by ferric and ferrous iron cations. In addition, we were able to monitor the effects caused by the chemical acid activation on the valence state of the iron cations that occupy these structural sites in the clay. For the treatment at low acid concentration, keeping time and temperature of activation constant, our results showed a strong effect on the ferrous and ferric iron sites, reducing and increasing their adsorption relative areas respectively.     

Formation and structure of boron nitride conical nanotubes

Nanotubes exhibiting a novel structure - boron nitride (BN) conical nanotubes whose walls consist of conical layers with their cone axis parallel to the tube axis, as opposed to ordinary nanotubes, composed of concentric cylindrical layers with their normal perpendicular to the tube axis - were synthesized simultaneously with BN nanotubes by using carbon nanotubes (CNTs) as templates. The diameters of the BN conical nanotubes are typically about 15 nm, which is similar to those of the starting CNTs. Apex angles and inner diameters of most BN conical nanotubes are about 40° and 1 nm, respectively. The lengths of the BN conical nanotubes range from 50 nm to up to several micrometers.     

Electric field-induced unzipping of hydrogenated carbon nanotubes into graphene nanoribbons

We have investigated the electric field effect on horseshoe-shape carbon nanotubes (CNTs) resulting from hydrogen adsorption on the single-wall armchair (n,n)CNTs with 6 ≤ n ≤ 16 by using the density functional theory calculations. The horseshoe-shape CNT is completely unzipped into a graphene nanoribbon upon applying a critical electric field, which decreases with increasing CNT diameter, thus enabling one to select a nanoribbon width. A simple model based on the tensile force exerted on the tube walls by the applied electric field was introduced to understand the CNT-diameter dependence of the critical field.     

Changes in the thermoelectric response of vitreous carbon due to the irradiation by γ-rays

In order to study variations in the thermoelectric properties, some commercial glassy carbon samples were subjected to a sequence of steps consisting of a combination of irradiation with γ-rays produced by radioisotopes ⁶⁰Co, and hydrogen adsorption when the samples were put in an over pressured atmosphere of this gas. With this procedure it was possible to observe that the irradiation decreases the electrical conductivity of glassy carbon samples and the hydrogenation changes the sign of Seebeck coefficient. The material initially is an n-type semiconductor, but with hydrogenation changes to p-type semiconductor. X-ray diffraction analysis showed that the hydrogenated vitreous carbon is more amorphous than the pristine material and the γ-rays irradiation produces changes in the crystallite size and shape.