Function of Al on the cycling behavior of the La–Mg–Ni–Co-type alloy electrodes

The cycling behavior of the _{La0.7Mg0.3Ni2.65-xCo0.75Mn0.1Alx}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{2.65-x}{\mathrm{Co}}_{0.75}{\mathrm{Mn}}_{0.1}{\mathrm{Al}}_x$(x=0,0.3)$(x=0,0.3)$ alloy electrodes was systematically investigated by XRD, SEM, EIS, XPS and AES measurements, and the function of Al in the La–Mg–Ni-based alloys and the reasons for the improvement of the cycling stability of the alloy electrode with Al were discussed. Results show that the cycling behavior of the _{La0.7Mg0.3Ni2.35Co0.75Mn0.1Al0.3}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{2.35}{\mathrm{Co}}_{0.75}{\mathrm{Mn}}_{0.1}{\mathrm{Al}}_{0.3}$ alloy electrode can be divided into three stages, i.e., the pulverization and Mg oxidation stage, the Mg oxidation and La and/or Al oxidation stage, and the La and Al oxidation and Al oxide film protection stage. The improvement of the cycling stability of the alloy electrode with Al can be ascribed to two factors. One is the decrease in the pulverization of the alloy particles during charge/discharge cycling due to the alloy with Al undergoes a smaller cell volume expansion and contraction. The other is the increase in the anti-oxidation/corrosion due to the formation of a dense Al oxide film during cycling, which is believed to be the most important reason for the improvement of the cycling stability of the La–Mg–Ni–Co–Mn–Al-type alloy electrodes.     

Microstructures and electrochemical characteristics of the La0.75Mg0.25Ni2.5Mx (M=Ni, Co; x=0–1.0) hydrogen storage alloys

In order to investigate the influences of the stoichiometric ratios of B/A (A: gross A-site elements, B: gross B-site elements) and the substitution of Co for Ni on the structure and the electrochemical performances of the _AB2.5–3.5${\mathrm{AB}}_{2.5–3.5}$-type electrode alloys, the La–Mg–Ni–Co system _{La0.75Mg0.25Ni2.5Mx}${\mathrm{La}}_{0.75}{\mathrm{Mg}}_{0.25}{\mathrm{Ni}}_{2.5}{\mathrm{M}}_x$ (M=Ni$\mathrm{M}=\mathrm{Ni}$, Co; x=0$x=0$, 0.2, 0.4, 0.6, 0.8, 1.0) alloys were prepared by induction melting in a helium atmosphere. The structures and electrochemical performances of the alloys were systemically measured. The obtained results show that the structures and electrochemical performances of the alloys are closely relevant to the M content. All the alloys exhibit a multiphase structure, including _LaNi2${\mathrm{LaNi}}_2$, (La,Mg)_Ni3$(\mathrm{La},\mathrm{Mg}){\mathrm{Ni}}_3$ and _LaNi5${\mathrm{LaNi}}_5$ phases, and the major phase in the alloys changes from _LaNi2${\mathrm{LaNi}}_2$ to (La,Mg)_Ni3+_LaNi5$(\mathrm{La},\mathrm{Mg}){\mathrm{Ni}}_3+{\mathrm{LaNi}}_5$ with the variety of M content. The electrochemical performances of the alloys, involving the discharge capacity, the high rate discharge (HRD) ability, the activation capability and the discharge potential characteristics, significantly improve with increasing M content. When M content x$x$ increases from 0 to 1.0, the discharge capacity rises from 177.7 to 343.62  mAh/g for the alloy (M=Ni)$(\mathrm{M}=\mathrm{Ni})$, and from 177.7 to 388.7 mAh/g for the alloy (M=Co)$(\mathrm{M}=\mathrm{Co})$. The cycle stability of the alloy first mounts up then declines with growing M content. The substitution of Co for Ni significantly ameliorates the electrochemical performances. For a fixed M content (x=1.0)$(x=1.0)$, the substitution of Co for Ni enhances the discharge capacity from 343.62 to 388.7 mAh/g, and the capacity retention ratio (_S100)$(S_{100})$ after 100 charging–discharging cycles from 51.45% to 61.1%.     

CO2 reforming of CH4 by combination of thermal plasma and catalyst

Experiments on synthesis gas preparation from dry reforming of methane by carbon dioxide with thermal plasma only and cooperation of thermal plasma with commercial catalysts have been performed. In all experiments, nitrogen gas was used as the plasma gas to form a high-temperature jet injected into a tube reactor. A mixture of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ was fed vertically into the jet. Both kinds of experiments were conducted in the same conditions, such as total flux of feed gases, the molar ratio of _CH4/_CO2${\mathrm{CH}}_4/{\mathrm{CO}}_2$, and the plasma power except with or without catalysts in the tube reactor. Higher conversion of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$, higher selectivity of _H2${\mathrm{H}}_2$ and CO, and higher specific energy of the process were achieved by thermal plasma with catalysts. For example, the conversions of _CH4${\mathrm{CH}}_4$ and _CO2${\mathrm{CO}}_2$ were high to 96.33% and 84.63%, and the selectivies of CO and _H2${\mathrm{H}}_2$ were also high to 91.99% and 74.23%, respectively. Both were 10–20%$10–20\%$ higher than those by thermal plasma only.     

Kinetic characteristics of sodium borohydride formation when sodium meta-borate reacts with magnesium and hydrogen

Sodium borohydride is attracting considerable interests as a hydrogen storage medium. In this paper, we investigated the effects of hydrogen pressure, reaction temperature and transition metal addition on sodium borohydride synthesis by the reaction of sodium meta-borate with Mg and _H2${\mathrm{H}}_2$. It was found that higher _H2${\mathrm{H}}_2$ pressure was beneficial to _NaBH4${\mathrm{NaBH}}_4$ formation. The increase in reaction temperature first improved _NaBH4${\mathrm{NaBH}}_4$ formation kinetics but then impeded it when the temperature was raised to near the melting point of Mg. It was also found that some additions of transition metals such as Ni, Fe and Co in the _NaBO2+Mg+_H2${\mathrm{NaBO}}_2+\mathrm{Mg}+{\mathrm{H}}_2$ system promoted the _NaBH4${\mathrm{NaBH}}_4$ formation, but Cu addition showed little effect. The activation energy of the _NaBH4${\mathrm{NaBH}}_4$ formation from Mg, _NaBO2${\mathrm{NaBO}}_2$ and _H2${\mathrm{H}}_2$ was estimated to be 156.3 kJ/mol _NaBH4${\mathrm{NaBH}}_4$ according to Ozawa analysis method.     

Hydrogen production by autothermal reforming of LPG for PEM fuel cell applications

Indirect partial oxidation, or oxidative steam reforming, tests of a bimetallic Pt–Ni catalyst supported on δ$\delta$-alumina were conducted in propane–n  -butane mixtures (LPG) used as feed. _H2${\mathrm{H}}_2$ production activity and _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ selectivity were investigated in response to different S/C, C/_O2$\mathrm{C}/{\mathrm{O}}_2$ and W/F ratios. It was confirmed that higher steam content in the reactant stream increases both the activity and the _H2/CO${\mathrm{H}}_2/\mathrm{CO}$ selectivity of the process. Low residence times created a positive impact on catalyst activity not only for hydrogen but also for carbon monoxide production due to the increased amount of fresh hydrocarbon in the feed stream. Hence, the highest selectivity level was obtained at intermediate residence times. The response of the system to C/_O2$\mathrm{C}/{\mathrm{O}}_2$ ratio was found to depend on the available steam content due to the complex nature of IPOX. The Pt–Ni catalyst was very prone to catalyst deactivation at low S/C ratios accompanied by high C/_O2$\mathrm{C}/{\mathrm{O}}_2$ ratios, but this problem was not encountered at high S/C ratios. A comparison of catalyst performance for different propane-to-n-butane ratios in the LPG feed indicated that the Pt–Ni catalyst has slightly better activity and selectivity at higher n-butane contents at the expense of becoming more sensitive to coke deposition.     

H2 production with ultra-low CO selectivity via photocatalytic reforming of methanol on Au/TiO2 catalyst

_H2${\mathrm{H}}_2$ with ultra-low CO concentration was produced via photocatalytic reforming of methanol on Au/_TiO2$\mathrm{Au}/{\mathrm{TiO}}_2$ catalyst. The rate of _H2${\mathrm{H}}_2$ production is greatly increased when the gold particle size is reduced from 10 to smaller than 3 nm. The concentration of CO in _H2${\mathrm{H}}_2$ decreases with reducing the gold particle size of the catalyst. It is suggested that the by-product CO is mostly produced via decomposition of the intermediate formic acid species derived from methanol. The smaller gold particles possibly switch the HCOOH decomposition reaction mainly to _H2${\mathrm{H}}_2$ and _CO2${\mathrm{CO}}_2$ products while suppress the CO and _H2${\mathrm{H}}_2$O products. In addition, some CO may be oxidized to _CO2${\mathrm{CO}}_2$ by photogenerated oxidizing species at the perimeter interface between the small gold particles and _TiO2${\mathrm{TiO}}_2$ under photocatalytic condition.     

The effect of particle size on the electrode performance of Ti–V-based hydrogen storage alloys

The effect of particle size ranging from 100 mesh to below 500 mesh on the electrochemical properties of _{Ti0.8Zr0.2V2.7Mn0.5Cr0.8Nix}(x=0.75,1.75)${\mathrm{Ti}}_{0.8}{\mathrm{Zr}}_{0.2}{\mathrm{V}}_{2.7}{\mathrm{Mn}}_{0.5}{\mathrm{Cr}}_{0.8}{\mathrm{Ni}}_x(x=0.75,1.75)$ hydrogen storage alloy electrodes was investigated. SEM observation on the surface of the alloy electrodes after charge/discharge cycles revealed that the abilities of anti-pulverization and anti-corrosion of the x=0.75$x=0.75$ alloy were much lower than those of the x=1.75$x=1.75$ alloy. For both of the two alloys, the electrode performance is affected markedly by the particle size. With the increase of the initial particle size, the initial discharge capacity of the alloy electrode decreases and the pulverization of the alloy particles aggravates, especially for the particles of the x=0.75$x=0.75$ alloy with size larger than 400 mesh, the size of which was minimized obviously compared with their initial size. However, the maximum discharge capacity and the cycling stability almost do not correlate to the initial particle size but relate with their actual particle size. As the actual particle size decreases, the maximum discharge capacity increases and the cycling stability declines.     

Characterization of Fe–Zn–R (R = rare earth metal) crystalline alloys as electrocatalysts for hydrogen evolution

The electrocatalytic properties of some Fe–Zn–R crystalline alloys (R=rare$\mathrm{R}=\mathrm{rare}$ earth metals), _Fe80Zn10La10${\mathrm{Fe}}_{80}{\mathrm{Zn}}_{10}{\mathrm{La}}_{10}$, _Fe80Zn10Y10${\mathrm{Fe}}_{80}{\mathrm{Zn}}_{10}{\mathrm{Y}}_{10}$, _Fe80Zn10Gd10${\mathrm{Fe}}_{80}{\mathrm{Zn}}_{10}{\mathrm{Gd}}_{10}$ and _Fe80Zn10MM10${\mathrm{Fe}}_{80}{\mathrm{Zn}}_{10}{\mathrm{MM}}_{10}$ (MM=mischmetal$\mathrm{MM}=\mathrm{mischmetal}$: 50.2% Ce, 26.3% La, 17.5% Nd, 6.0% Pr, at%), were investigated for the hydrogen evolution reaction (HER) in 1 M NaOH solution at 298 K. The microstructure of the electrodes was examined by optical microscopy and scanning electron microscopy coupled with electron probe microanalysis; X-ray diffraction measurements were also performed. The performances towards the HER were investigated by dc polarization and ac   impedance techniques and the results were compared with those obtained on polycrystalline nickel. The microstructural features play an important role in determining the electrocatalytic activity of the investigated alloys. The overall experimental data indicate that interesting electrocatalytic performances are displayed by the _Fe80Zn10Gd10${\mathrm{Fe}}_{80}{\mathrm{Zn}}_{10}{\mathrm{Gd}}_{10}$ electrode, which exhibits the highest activity towards the HER.     

Investigation on the structure and electrochemical properties of the laser sintered La0.7Mg0.3Ni3.5 hydrogen storage alloys

The structure and electrochemical properties of the _{La0.7Mg0.3Ni3.5}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{3.5}$ alloys laser sintered at different powers were investigated. It is found that all alloys contain three phases _La3MgNi14${\mathrm{La}}_3{\mathrm{MgNi}}_{14}$ with the _Ce2Ni7${\mathrm{Ce}}_2{\mathrm{Ni}}_7$ structure, _LaNi5${\mathrm{LaNi}}_5$ and _LaMgNi4${\mathrm{LaMgNi}}_4$. The abundance of the main phase _La3MgNi14${\mathrm{La}}_3{\mathrm{MgNi}}_{14}$ is 43, 68 and 63 wt%, respectively, when sintering power varies from 1000 to 1200 and 1400 W. The laser sintered _{La0.7Mg0.3Ni3.5}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{3.5}$ alloys can be activated to their maximum discharge capacity within three cycles. The discharge capacities of those alloys prepared by laser sintering at 1000, 1200 and 1400 W are 324.6, 352.8 and 340.5 mAh/g, respectively. The _{La0.7Mg0.3Ni3.5}${\mathrm{La}}_{0.7}{\mathrm{Mg}}_{0.3}{\mathrm{Ni}}_{3.5}$ alloy laser sintered at 1200 W has a best cyclic stability (_S100=58.4%)$(S_{100}=58.4\%)$ and high-rate dischargeability (_HRD800=79.4%)$({\mathrm{HRD}}_{800}=79.4\%)$ due to the high amount of the main phase _La3MgNi14${\mathrm{La}}_3{\mathrm{MgNi}}_{14}$.     

Hydrogen generation from liquid phase catalytic reforming of sugar solutions using metal-supported catalysts

Most of the hydrogen production processes are designed for large-scale industrial uses and are not suitable for a compact hydrogen device to be used in systems like solid polymer fuel cells. Integrating the reaction step, the gas purification and the heat supply can lead to small-scale hydrogen production systems. The aim of this research is to study the influence of several reaction parameters on hydrogen production using liquid phase reforming of sugar solution over Pt, Pd, and Ni supported on nanostructured supports. It was found that the desired catalytic pathway for _H2${\mathrm{H}}_2$ production involves cleavage of C–C, C–H and O–H bonds that adsorb on the catalyst surface. Thus a good catalyst for production of _H2${\mathrm{H}}_2$ by liquid-phase reforming must facilitate C–C bond cleavage and promote removal of adsorbed CO species by the water–gas shift reaction, but the catalyst must not facilitate C–O bond cleavage and hydrogenation of CO or _CO2${\mathrm{CO}}_2$. Apart from studying various catalysts, a commercial Pt/γ$\gamma$-alumina catalyst was used to study the effect of temperature at three different temperatures of 458, 473 and 493 K. Some of the spent catalysts were characterised using TGA, SEM and XRD to study coke deposition. The amorphous and organised form of coke was found on the surface of the catalyst.     

Effect of Al and Ce substitutions of the electrochemical properties of amorphous MgNi-based alloy electrodes

Mg-based hydrogen storage alloys _{Mg0.9Al0.1-xCex}Ni${\mathrm{Mg}}_{0.9}{\mathrm{Al}}_{0.1-x}{\mathrm{Ce}}_x\mathrm{Ni}$(x=0.00,0.01,0.02,0.025,0.075)$(x=0.00,0.01,0.02,0.025,0.075)$ were successfully prepared by means of mechanical alloying (MA). The structure and the electrochemical characteristics of these Mg-based electrodes were also studied. The result of X-ray diffraction (XRD) shows that the main phases of the alloys exhibit amorphous structures. The charge–discharge cycle tests indicate these alloys have good electrochemical active characteristics. Among these alloys, the _{Mg0.9Al0.08Ce0.02}Ni${\mathrm{Mg}}_{0.9}{\mathrm{Al}}_{0.08}{\mathrm{Ce}}_{0.02}\mathrm{Ni}$ has the best cycle stability. After 50 cycles charge–discharge, the discharge capacity of _{Mg0.9Al0.08Ce0.02}Ni${\mathrm{Mg}}_{0.9}{\mathrm{Al}}_{0.08}{\mathrm{Ce}}_{0.02}\mathrm{Ni}$ alloy is 66.67% higher than MgNi alloy. The cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS) and anticorruption test (potentiodynamic polarization) were also studied, and the results show that the electrochemical cycle stability of these alloys was improved by Al and Ce substitutions.     

Synthesis and hydrogen storage properties of carbon nanotubes

Multi-walled carbon nanotubes (MWNT) have been synthesized by chemical vapor decomposition of acetylene over rare-earth (RE) based _AB2${\mathrm{AB}}_2$ alloy hydride catalysts. The _AB2${\mathrm{AB}}_2$ alloy hydride catalysts have been prepared by hydrogen decrepitation technique and characterized by scanning electron microscopy. The advantage of this novel method of obtaining catalysts has been discussed. The as-grown carbon nanotubes were purified by acid and heat treatments and characterized using powder X-ray diffraction, transmission electron microscopy, scanning electron microscopy, thermo gravimetric analysis and Raman spectroscopy. Hydrogen adsorption measurements were carried out on as-prepared and purified MWNT in the temperature range of 143–373 K and pressure range of 10–100 bar using a high pressure hydrogen adsorption setup and the results have been discussed. A maximum hydrogen storage capacity of 3.5 wt% is obtained for purified MWNT prepared with _DyNi2${\mathrm{DyNi}}_2$ alloy hydride catalyst at 143 K and 75 bar.     

Fuel-rich methane oxidation in a high-pressure flow reactor studied by optical-fiber laser-induced fluorescence,multi-species sampling profile measurements and detailed kinetic simulations

A versatile flow-reactor design is presented that permits multi-species profile measurements under industrially relevant temperatures and pressures. The reactor combines a capillary sampling technique with a novel fiber-optic Laser-Induced Fluorescence (LIF) method. The gas sampling provides quantitative analysis of stable species by means of gas chromatography (i.e. _CH4${\mathrm{CH}}_4$, _O2,CO,_CO2${\mathrm{O}}_2\text{,}\mathrm{CO}\text{,}{\mathrm{CO}}_2$, _H2O,_H2${\mathrm{H}}_2\mathrm{O}\text{,}{\mathrm{H}}_2$, _C2${\mathrm{C}}_2$_H6${\mathrm{H}}_6$, _C2${\mathrm{C}}_2$_H4${\mathrm{H}}_4$), and the fiber-optic probe enables in situ detection of transient LIF-active species, demonstrated here for C_H2${\mathrm{H}}_2$O. A thorough analysis of the LIF correction terms for the temperature-dependent Boltzmann fraction and collisional quenching are presented. The laminar flow reactor is modeled by solving the two-dimensional Navier–Stokes equations in conjunction with a detailed kinetic mechanism. Experimental and simulated profiles are compared. The experimental profiles provide much needed data for the continued validation of the kinetic mechanism with respect to _C1${\mathrm{C}}_1$ and _C2${\mathrm{C}}_2$ chemistry; additionally, the results provide mechanistic insight into the reaction network of fuel-rich gas-phase methane oxidation, thus allowing optimization of the industrial process.