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1.
The first member of a new class of phthalocyanine-based metal–organic frameworks, MOF-IP, has been synthesized in order to gauge the potential of this type of materials for hydrogen storage. Preliminary studies indicate that MOF-IP is a robust material with a hydrogen uptake capacity of 1.15 wt% at 77 K under atmospheric pressure.  相似文献   

2.
Metal–organic framework MOF-5 (Zn4O(BDC)3), a microporous material with a high surface area and large pore volume, was synthesized by three approaches: direct mixing of triethylamine (TEA), slow diffusion of TEA, and solvothermal synthesis. The obtained materials were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and nitrogen adsorption, and their hydrogen-storage capacities were measured. The different synthesis methods influenced the pore-structure parameters, morphologies and hydrogen-storage behavior of the obtained MOF-5. MOF-5 synthesized by the solvothermal approach showed a higher surface area and larger pore volume than the samples prepared by the other two approaches. Measurements of the hydrogen-storage behavior showed that the hydrogen-storage capacity was correlated with the specific surface area and pore volume of MOF-5.  相似文献   

3.
Hydrogen and methane are considered as the promising fuels in the future, however, one of the obstacles to their utilizations is the lack of efficient storage and safe transportation materials. In this theoretical work, a novel kind of metal–organic framework (MOF) is designed using heterofullerene as linker from density functional theory calculations and first-principles molecular dynamics simulations. Based on grand canonical Monte Carlo simulations, we explore the adsorption performances of H2 and CH4 in the proposed porous MOF materials, which exhibit spectacular capacities for hydrogen storage as well as for methane storage after Li doping, both achieving the targets set by U.S. Department of Energy at workable conditions.  相似文献   

4.
A heterometallic metal–organic framework, {[Ce(oda)3Zn1.5(H2O)3]·0.75H2O}n (1, H2oda = oxydiacetic acid), has been synthesized under hydrothermal condition. The single-crystal X-ray diffraction analysis reveals that compound 1 belongs to hexagonal crystal system with space group P6/mcc and exhibits 3D porous framework. The hydrogen adsorption experiments suggest that 1 possesses reversible hydrogen storage capacity, up to 1.34 wt.% at 77 K and 0.86 wt.% at 298 K, respectively.  相似文献   

5.
Pure CuO–CeO2 nanocomposites were synthesized by simple thermal decomposition method in presence of various Cu salts as a copper source and fructose as a green capping agent. In this study, the effect of various parameters such as the type of copper sources, temperature and time of reaction on the morphology and the particles size were studied. The products were characterized via X-ray diffraction (XRD) pattern, scanning electron microscopy (SEM), energy dispersive X-ray analysis (EDX), transmission electron microscopy (TEM), N2 adsorption (BET), vibrating sample magnetometer (VSM), and infrared spectrum (FT-IR). The optical property of the nanocomposite was examined via UV–vis (DRS) spectroscopy and the band gap was calculated to 3 eV. Also, the hydrogen storage capacity of CuO–CeO2 nanocomposites and CeO2 nanoparticles were investigated via chronopotentiometry method for the first time. The discharge capacity of CeO2 nanoparticles and CuO–CeO2 nanocomposites in 1 mA current and 20 cycles obtained 2150 and 2450 mAh/g, respectively.  相似文献   

6.
A nanoporous metal–organic framework material, exhibiting an IRMOF-1 type crystalline structure, was prepared by following a direct solvothermal synthesis approach, using zinc nitrate and terephthalic acid as precursors and dimethylformamide as solvent, combined with supercritical CO2 activation and vacuum outgassing procedures. A series of advanced characterization methods were employed, including scanning electron microscopy, Fourier-transform infrared radiation spectroscopy and X-ray diffraction, in order to study the morphology, surface chemistry and structure of the IRMOF-1 material directly upon its synthesis. Porosity properties, such as Brunauer–Emmet–Teller (BET) specific area (~520 m2/g) and micropore volume (~0.2 cm3/g), were calculated for the activated sample based on N2 gas sorption data collected at 77 K. The H2 storage performance was preliminary assessed by low-pressure (0–1 bar) H2 gas adsorption and desorption measurements at 77 K. The activated IRMOF-1 material of this study demonstrated a fully reversible H2 sorption behavior combined with an adequate gravimetric H2 uptake relative to its BET specific area, thus achieving a value of ~1 wt.% under close-to-atmospheric pressure conditions.  相似文献   

7.
Mixtures of XMg–Co containing different amounts of Mg (X = 2, 3 and 7) were reactive milled under hydrogen atmosphere. 2Mg–Co only formed the Mg2CoH5 complex hydride, while the mixtures 3Mg–Co and 7Mg–Co formed different contents of Mg2CoH5 and MgH2. Their structural features and hydrogen storage properties were analyzed by different techniques. In-situ synchrotron X-ray diffraction, combined with thermal analysis techniques, (differential scanning calorimetry, thermal gravimetric analysis and quadrupole mass spectrometer) was carried out to observe the behavior of the MgH2–Mg2CoH5 mixtures during the first H-desorption. It was found that the presence of the Mg2CoH5 complex hydride has a beneficial effect on the first H-desorption of the MgH2. Additionally, after first desorption, conventional hydrogenation under high pressure and high temperature of 3Mg–Co and 7Mg–Co samples led to the formation of the Mg6Co2H11 complex hydride. The presence of Mg6Co2H11 considerably impaired the desorption properties of the nanocomposites.  相似文献   

8.
Metal-organic frameworks (MOFs) have been the subject of intensive structural tuning via methods like pyrolysis for superior performance in electrocatalytic oxygen and hydrogen evolution processes (OER and HER) and supercapacitors. Here, a Co-MOF based on 2-methylimidazole was synthesized using a precipitation approach, and its electrochemical characteristics were tuned via pyrolysis at different temperatures, including 600, 700, and 800 °C. Characterization findings corroborated the formation of Co–N–C moieties from Co-MOF, and XPS analyses indicated that 700 °C was the optimal temperature for achieving a high density of Co–N–C moieties. The optimized Co-MOF-700 sample displayed remarkable HER and OER performance in terms of lower overpotentials of 75 mV and 370 mV as well as small Tafel slopes of 118 mV/dec and 79 mV/dec, respectively. Furthermore, at a current density of 1 A/g, the Co-MOF-700 sample had a specific capacitance of 210 F/g. The enhanced electrochemical properties of Co-MOF-700C as compared to other samples can be attributed to the availability of a high density of Co–N–C sites for catalytic reaction and its porous architecture. This study will expand the knowledge of how compositional and morphological changes in MOFs affect their utility in energy conversion and storage applications.  相似文献   

9.
Hydrogen is considered as one of the most important clean energy carriers for the future. Many experimental and theoretical investigations have focused on the adsorption and activation of H2 on the metal surfaces. Metal oxides and semiconductors are suitable materials for this purpose. Gelatin assisted Ni loaded SiO2 (g/Ni–SiO2) was prepared and its structural properties, morphology, composition and surface properties were analyzed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), Field emission scanning electron microscopy (FE-SEM), Elemental mapping and energy dispersive spectrum (EDS), High resolution transmission electron microscopy (HR-TEM) and Brunauer-Emmett-Teller (BET) surface area measurements. The prepared material was effectively utilized for H2 storage applications at room temperature. The H2 storage capacity of g/Ni–SiO2 was twice that of pristine SiO2. This may be due to large change in pore volume and pore diameter of g/Ni–SiO2, which may enhances the H2 storage capacity of the sample. The H2 storage capacity of other materials such as ZnO, anatase TiO2, g/TiO2, g/ZnO, g/TiO2–SO42-, Sb doped TiO2, Ag2S/TiO2, Sb2O3, CdS and SiO2/CdS also studied and compared with g-Ni/SiO2.  相似文献   

10.
In this work, macroporous Ni, Co and Ni–Co electrodes have been developed by co-deposition at high current density on stainless steel (AISI 304) substrates. The obtained materials were characterized both morphologically and chemically by confocal laser scanning microscopy, and SEM coupled with EDX analysis. The activity for hydrogen evolution reaction (HER) on the obtained layers was assessed by using pseudo-steady-state polarization curves and electrochemical impedance spectroscopy (EIS) in alkaline solution (30 wt.% KOH). The electrochemical results show that HER on these electrodes takes place by the Volmer–Heyrovsky mechanism. The synthesized coatings present higher catalytic activity for HER than commercial smooth Ni electrode. As the Co content increases in the electrodeposition bath the obtained structures show lower surface roughness factors. Ni–Co deposit with a Co content of 43 at.% manifests the highest intrinsic activity for HER as a consequence of the synergetic combination of Ni and Co.  相似文献   

11.
In this paper, the Mg95-X-Nix-Y5 (x = 5, 10, 15) alloy were prepared by vacuum induction melting. The X-ray diffraction was used to analytical phase composition in different states, and the Scanning Electron Microscope and Transmission Electron Microscope were used to characterize the microstructure and crystalline state. Meanwhile, the kinetic properties of isothermal hydrogen adsorption and desorption at different temperatures also were tested by the Sievert isometric volume method. The results indicate that the hydrogenated Mg–Ni–Y samples is a nanocrystalline structure consists of MgH2, Mg2NiH4, and YH3 phases. And, the in-situ formed YH3 phase not decompose in the process of dehydrogenation and evenly dispersed in the mother alloy, which plays a paly a positive the catalytic role for the reversible cyclic reaction of Mg and Mg2Ni phases. In addition, the Ni elements are effectively to improve the thermodynamic properties of the Mg-based hydrogen storage alloy, the desorption enthalpy of the Ni5, Ni10, and Ni15 samples successively decrease to 84.5, 69.1, and 63.5 kJ/mol H2. The hydrogen absorption and desorption kinetics of the Mg–Ni–Y alloy are improved obviously with the increase of Ni content, especially for Mg80Ni15Y5 alloy, which the optimal hydrogenated temperature is reduced to 200 °C, and the 90% of the maximum hydrogen storage capacity can be absorbed within 1 min, about 5.4 wt % H2. Besides, the dehydrogenated activation energy of the Mg80Ni15Y5 alloy also is reduced to 67.0 kJ/mol, and it can completely release hydrogen at 320 °C within 5 min, which is almost reached the hydrogen desorption capability of Ni5 alloy at 360 °C. This means that Ni element is a very positive element to reduce the hydrogen desorption temperature.  相似文献   

12.
We present in this paper an experimental study of a commercial diffusion-absorption refrigeration machine (DAR) operating on the Platen and Munters cycle. The temperatures at the inlet and outlet of every component of the machine, as well as the cabinet and ambient temperature are measured continuously. The tests are repeated for various electric power inputs to the refrigerator. The global heat transfer coefficient of the cabinet (UA)cab is determined using both theoretical and experimental methods. This coefficient is found equal to 0.2 W/°C. The global heat transfer coefficient of the evaporator (UA)evap is deduced using dynamic and steady state methods. This global heat transfer coefficient (UA)evap is found equal to 0.3 W/°C. Finally the cooling capacity of the unit and the coefficient of performance are evaluated. The heating power supply to the generator necessary to ensure the desired state of this machine is found to be in the range of 35 W–45 W.  相似文献   

13.
14.
In this work, three different states of Mg-9.1Y-1.8Zn alloys including as-cast, extruded and swaged were prepared by semi-continuous casting, extrusion and swaging processes, respectively. Their compositions, microstructures and hydrogen storage properties were investigated. The results show that Mg-9.1Y-1.8Zn alloys in three different states are all composed of Mg and long-period stacking ordered (LPSO) phases. The LPSO phases occurs to break and decompose after hydrogenation and in-situ forms the YHχ(χ = 2,3) nano-hydrides. The nano-hydrides can be used as in-situ catalysts to improve the hydrogen storage properties of alloys. Meanwhile, many nanocrystalline grains appear in the core of alloy after swaging, and the average grain size ranges from 80 to 200 nm. The presence of nanocrystals may increase the specific surface area of alloy, facilitating the diffusion and absorption of hydrogen. Comparatively, the swaged alloy exhibits the largest hydrogen storage capacity and excellent hydrogen sorption kinetics relative to other states of alloys.  相似文献   

15.
To analyse heat and mass transfer in a metal–hydrogen reactor, the hypothesis that disregards the radiative heat transfer in the reactor, is typically used. In this paper, we take into account the radiative heat transfer and we test the validity of this hypothesis in the case of the LaNi5 and in the case of the magnesium. A theoretical model is conducted for the two-dimensional system where conduction, convection radiation and chemical reaction take place simultaneously. This model is solved by the finite volume method. The numerical simulation is used to present the time–space evolutions of the temperature and the hydride density in the reactor and to determinate the sensitivity to some parameters (absorption coefficient, scattering coefficient, reactor wall emissivity).  相似文献   

16.
An attempt to prepare solid solutions in the system of LiNiO2, LiMnO2 and Li2MnO3 was performed by heating metal acetates. The solid solutions between end members LiNiO2 and Li2MnO3 can be successfully prepared in the overall compositional ranges. Both the structure and capacity were compared based on Rietveld analysis and electrochemical investigation on solid solutions between LiNiO2 and Li2MnO3. The result showed that the cationic disorder as well as capacity was closely related to the ratio of Li, Mn and Ni in formula. The investigation of chronopotentiogram and ex situ XRD on the solid solutions indicated that the complex phase transitions in LiNiO2 during delithiation were strongly suppressed with low Mn content (Mn/(Mn+Ni) ratio was 0.1 or 0.2) and completely suppressed with the ratio more than 0.5.  相似文献   

17.
Stacked nanorods of cobalt and nickel based hetero bimetallic organic frameworks (MOFs) of 2–amino benzene dicarboxylic acid are developed as photocatalyst for hydrogen evolution reaction. The ratio of metals in the catalyst is tuned to achieve a narrow band gap, and the MOF with optimized Ni to Co ratio of 1: 0.5 (1Ni0.5Co@NH2BDC) exhibited the lowest band gap (2.2 eV) and electron–hole recombination rate. The catalyst exhibits enhanced photocatalytic activity for hydrogen evolution reaction due to the absorption of photons by 2–amino benzene dicarboxylic acid and excitation of electrons from HOMO to LUMO of the organic linker. The excited electrons relay to the cluster of the framework and reduce the protons gather around the cluster to hydrogen. The holes in the HOMO state are occupied by the electrons from the sacrificial agents and it supports the photocatalytic hydrogen evolution by avoiding electron–hole recombination. The stability of MOF catalyst in water splitting medium even with sacrificial agents confirms its competency with the state–of–the–art photocatalytic materials.  相似文献   

18.
The present study involves numerical simulation of transient transport of hydrogen and heat within a metal–hydrogen reactor connected to a hydrogen tank during the hydriding process. This problem is of particular interest in the design of many installations in the field of energy technology (compressor, heat pumps, thermal or hydrogen storage systems). The reactor presents an expansion volume for hydrogen. The hydrogen flow is described by general momentum conservation equations instead of Darcy's law. The evolutions of the temperature, of the hydrogen concentration and of the hydrogen flow velocity are presented. The effects of the reactor dimensions, the inlet diameter, the volume of the expansion part, the tank volume, the initial pressure and the amount of hydrogen in the tank, on the heat and hydrogen transfer are determined.  相似文献   

19.
20.
The non-stoichiometric C15 Laves phase alloys namely Zr0.9Ti0.1Vx (x = 1.7, 1.8, 1.9, 2.1, 2.2, 2.3) are designed and expected to investigate the role of defect and microstructure on hydrogenation kinetics of AB2 type Zr-based alloys. The alloys are prepared by non-consumable arc melting in argon atmosphere and annealed at 1273 K for 168 h to ensure the homogeneity. The microstructure and phase constitute of these alloys are examined by SEM, TEM and XRD. The results indicate the homogenizing can reduce the minor phases α-Zr and abundant V solid solution originating from the non-equilibrium solidification of as-cast alloys. Twin defects with {111}<011 > orientation relationship are observed, and the role of defects on hydrogenation kinetics is discussed. Hydrogen absorption PCT characteristics and hydrogenation kinetics of Zr0.9Ti0.1Vx at 673–823 K are investigated by the pressure reduction method using a Sievert apparatus. The results show the hypo-stoichiometric alloys preserve faster hydrogenation kinetics than the hyper-stoichiometric ones due to the decrease of dendritic V. The excess content of Zr3V3O phase decreases the hydrogenation kinetics and the stability of hydrides. In addition, the different rate controlled mechanisms during hydrogen absorption are analyzed. The effects of non-stoichiometry on the crystal structure and hydrogen storage properties of Zr0.9Ti0.1Vx Laves alloys are discussed.  相似文献   

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