CN108855225B - Preparation method and application of alloy hydride material - Google Patents
Preparation method and application of alloy hydride material Download PDFInfo
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- Y02E60/30—Hydrogen technology
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Abstract
The invention discloses a preparation method of alloy hydride (rhodium-palladium hydride, ruthenium-palladium hydride and ruthenium-rhodium-palladium hydride) and application of the alloy hydride as an electrochemical hydrogen evolution catalyst. The invention mainly synthesizes rhodium-palladium hydride, ruthenium-palladium hydride and ruthenium-rhodium-palladium hydride materials by a one-step hydrothermal method. And modifying the obtained material on the surface of the glassy carbon electrode to obtain the alloy hydride material modified electrode. The invention is mainly applied to electrochemical hydrogen evolution, adopts a linear scanning curve (polarization curve) to detect the catalytic activity of the synthesized alloy hydride material, and uses a cyclic voltammetry curve to test the stability of the alloy hydride material. The invention fully utilizes the optimization of hydrogen atoms in the alloy hydride on the electronic structure and the coordination environment of metal atoms, and improves the catalytic efficiency of electrochemical hydrogen evolution.
Description
Technical Field
The invention belongs to the field of clean and sustainable novel energy preparation and application, and particularly relates to a preparation method and application of rhodium-palladium hydride, ruthenium-palladium hydride and ruthenium-rhodium-palladium hydride materials.
Background
With the rapid development of the world economy, the excessive consumption of traditional energy sources such as oil, natural gas and the like and the environmental problems caused by the use of the traditional energy sources restrict the rapid and effective further development of the current society. Therefore, it is important to solve the energy crisis to find an inexhaustible green clean energy to replace the traditional energy. As a renewable resource, the hydrogen has the characteristics of environmental friendliness, no pollution and the like, so that the hydrogen can be used as an ideal novel green energy to replace the traditional non-renewable resource. Among the various ways of producing hydrogen, alkaline electrolysis of water to produce hydrogen is of particular interest due to its high product purity, stable output, and safe operation. However, the difficulty of decomposing water in the first step of reaction in alkaline decomposed water into adsorbed hydrogen and hydroxyl makes the alkaline water decomposition efficiency lower than that in acidity by 2-3 orders of magnitude, so that the preparation of the high-efficiency alkaline hydrogen production catalyst is very important for basic scientific research and practical application.
Metal hydrides have received much attention due to their unique physicochemical properties and are widely used in hydrogen storage, as well as in superconducting applications. The conventional method for preparing metal hydride is to put the metal in a hydrogen atmosphere with a certain pressure, but the metal hydride obtained by this method is unstable, and hydrogen inside the metal hydride gradually escapes at room temperature. Metal hydrides are therefore rarely used in mildly conditioned electrochemical reactions. The hydride prepared by the hydrothermal synthesis method has certain stability, wherein the palladium hydride material can be prepared by the hydrothermal method and is applied to formic acid electrochemical oxidation reaction. However, a hydrided alloy material prepared by a hydrothermal method has not been reported, and the use of a hydrided alloy material in alkaline decomposed water has not been reported.
The invention aims to provide a method for preparing alloy hydrides (rhodium-palladium-hydrogen, ruthenium-palladium-hydrogen and ruthenium-rhodium-palladium-hydrogen) aiming at the defects of the prior art, and the method is applied to the field of electrochemical hydrogen evolution catalysis. The alloy hydride has the characteristics of high room temperature stability, high hydrogen production activity, high hydrogen production stability and the like.
Disclosure of Invention
The invention aims to provide a preparation method and application of rhodium-palladium hydride, ruthenium-palladium hydride and ruthenium-rhodium-palladium hydride materials aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a preparation method of a rhodium-palladium alloy hydride material comprises the following steps:
(1) uniformly dispersing palladium acetylacetonate, rhodium acetylacetonate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde according to the volume ratio of 1: 1; wherein the palladium acetylacetonate and the rhodium acetylacetonate have equal mass, and the concentration of the palladium acetylacetonate is 1 mg/mL-1.5 mg/mL; the mass ratio of the polyvinylpyrrolidone to the palladium acetylacetonate is 1/10-1/20.
(2) Stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, heating the mixed solution to 160-180 ℃ from room temperature within 30 minutes, and keeping the temperature for 5-8 hours to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol and cyclohexane according to the volume ratio of 1:1 for 3 times, and drying for 12 hours at 60 ℃ in vacuum to obtain the rhodium-palladium alloy hydride material.
A preparation method of a ruthenium palladium alloy hydride material comprises the following steps:
(1) uniformly dispersing palladium acetylacetonate, ruthenium acetylacetonate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde according to the volume ratio of 1: 1; wherein the palladium acetylacetonate and the rhodium acetylacetonate have equal mass, and the concentration of the palladium acetylacetonate is 1 mg/mL-1.5 mg/mL; the mass ratio of the polyvinylpyrrolidone to the palladium acetylacetonate is 1/10-1/20.
(2) Stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, heating the mixed solution to 160-180 ℃ from room temperature within 30 minutes, and keeping the temperature for 5-8 hours to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol and cyclohexane according to the volume ratio of 1:1 for 3 times, and drying for 12 hours at 60 ℃ in vacuum to obtain the rhodium-palladium alloy hydride material.
A preparation method of a ruthenium rhodium palladium alloy hydride material comprises the following steps:
(1) uniformly dispersing palladium acetylacetonate, rhodium acetylacetonate, ruthenium acetylacetonate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde according to the volume ratio of 1: 1; wherein the mass of the palladium acetylacetonate is 2 times of that of the rhodium acetylacetonate, the mass of the ruthenium acetylacetonate is equal to that of the rhodium acetylacetonate, and the concentration of the palladium acetylacetonate is 1 mg/mL-1.5 mg/mL; the mass ratio of the polyvinylpyrrolidone to the palladium acetylacetonate is 1/10-1/20.
(2) Stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, heating the mixed solution to 160-180 ℃ from room temperature within 30 minutes, and keeping the temperature for 5-8 hours to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol and cyclohexane according to the volume ratio of 1:1 for 3 times, and drying for 12 hours at 60 ℃ in vacuum to obtain the rhodium-palladium alloy hydride material.
The hydride material has the following applications: the material is applied to the preparation of an electrode, and the preparation method of the electrode comprises the following steps: 20 μ g of hydride was dissolved in 400 μ L cyclohexane and sonicated for 1 hour with 60 μ g carbon black (XC-72) in 1.2mL ethanol. Then, the mixture was collected by centrifugation and redissolved in a mixed solution of 3mL of ethanol and 1mL of acetic acid. And after continuing ultrasonic treatment for 30 minutes, centrifugally collecting, washing for 2 times by using ethanol, finally drying for 12 hours in vacuum at 60 ℃ to obtain a material with the alloy hydride loaded on the carbon black, dissolving the material in a mixed solution of 50 mu L of ethanol, water and naphthol (the volume ratio is 8.9: 1: 0.1), performing ultrasonic treatment for 1 hour, dripping 20 mu L of the solution on the surface of a glassy carbon electrode, and drying by using an infrared baking lamp to finally obtain the glassy carbon electrode modified by loading the alloy hydride on the carbon black.
The invention has the beneficial effects that: according to the invention, the rhodium-palladium-hydride compound, the ruthenium-palladium-hydride compound and the ruthenium-rhodium-palladium-hydride compound material are obtained by a simple one-step hydrothermal method, and the obtained hydrogenated alloy structure is very stable and is not changed after being kept at room temperature for 6 months. The electrode prepared by the material can be applied to alkaline electrochemical catalytic hydrogen evolution. In terms of catalytic activity, since H regulates the aggregate electronic structure and optimizes the coordination environment inside the alloy, it exhibits excellent hydrogen production performance and is far superior to commercial platinum carbon.
Drawings
FIG. 1 is a Transmission Electron Microscope (TEM) picture of a rhodium-palladium-hydride compound prepared by the invention.
FIG. 2 is a Transmission Electron Microscope (TEM) picture of the ruthenium palladium hydride prepared by the present invention.
Figure 3 is a Transmission Electron Microscope (TEM) picture of the ruthenium rhodium palladium hydride compound prepared by the present invention.
Figure 4 is an X-ray diffraction pattern (XRD) of the rhodium-palladium-hydrogen compounds, ruthenium-palladium-hydrogen compounds, and ruthenium-rhodium-palladium-hydrogen compounds prepared according to the present invention.
Figure 5 is an X-ray diffraction (XRD) of the rhodium-palladium-hydride compound prepared by the present invention initially and after 6 months of standing.
FIG. 6 is a Polarization curve (polization curves) of rhodium-palladium-hydride compounds prepared according to the invention in 1M potassium hydroxide for 1000 cycles of initial and cycling.
FIG. 7 is a plot of Polarization curves of electrochemical hydrogen evolution (Polarization curves) of rhodium-palladium-hydrogen compounds, ruthenium-rhodium-palladium-hydrogen compounds prepared according to the present invention in 1M potassium hydroxide solution, in comparison to commercial platinum carbon.
Detailed Description
The technical solution of the invention is further illustrated below with reference to examples, which are not to be construed as limiting the technical solution.
Example 1: the ruthenium rhodium palladium hydride compound material prepared by the embodiment specifically comprises the following steps:
(1) uniformly dispersing 8mg of palladium acetylacetonate, 4mg of rhodium acetylacetonate, 4mg of ruthenium acetylacetonate and 120mg of polyvinylpyrrolidone into 3mL of benzyl alcohol and 3mL of acetaldehyde solution;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, raising the temperature from room temperature to 180 ℃ through 30 minutes, and reacting for 5 hours at 180 ℃ to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol: the solution of cyclohexane (1: 1) is washed for 3 times and dried in vacuum at 60 ℃ for 12 hours to obtain the ruthenium rhodium palladium alloy hydride material.
Example 2: the rhodium-palladium hydride material prepared by the embodiment specifically comprises the following steps:
(1) uniformly dispersing 8mg of palladium acetylacetonate, 8mg of rhodium acetylacetonate and 120mg of polyvinylpyrrolidone into a mixed solution consisting of 3mL of benzyl alcohol and 3mL of acetaldehyde;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, raising the temperature from room temperature to 180 ℃ through 30 minutes, and reacting for 5 hours at 180 ℃ to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol: the solution of cyclohexane (1: 1) is washed for 3 times and dried in vacuum at 60 ℃ for 12 hours to obtain the rhodium-palladium alloy hydride material.
Example 3: the ruthenium palladium hydride material prepared in this embodiment specifically includes the following steps:
(1) uniformly dispersing 8mg of palladium acetylacetonate, 8mg of ruthenium acetylacetonate and 120mg of polyvinylpyrrolidone into a mixed solution consisting of 3mL of benzyl alcohol and 3mL of acetaldehyde;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, raising the temperature from room temperature to 180 ℃ through 30 minutes, and reacting for 5 hours at 180 ℃ to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol: and (3) cleaning with cyclohexane (1: 1) solution for 3 times, and vacuum-drying at 60 ℃ for 12 hours to obtain the ruthenium-palladium alloy hydride material.
Example 4: the ruthenium rhodium palladium hydride compound material prepared by the embodiment specifically comprises the following steps:
(1) uniformly dispersing 8mg of palladium acetylacetonate, 8mg of rhodium acetylacetonate and 120mg of polyvinylpyrrolidone into 3mL of benzyl alcohol and 3mL of acetaldehyde solution;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, then transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, raising the temperature from room temperature to 160 ℃ through 30 minutes, and reacting for 8 hours at 160 ℃ to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol: the solution of cyclohexane (1: 1) is washed for 3 times and dried in vacuum at 60 ℃ for 12 hours to obtain the ruthenium rhodium palladium alloy hydride material.
Example 5: the ruthenium rhodium palladium hydride compound material prepared by the embodiment specifically comprises the following steps:
(1) uniformly dispersing 8mg of palladium acetylacetonate, 4mg of rhodium acetylacetonate, 4mg of ruthenium acetylacetonate and 120mg of polyvinylpyrrolidone into 3mL of benzyl alcohol and 3mL of acetaldehyde solution;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, then transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, raising the temperature from room temperature to 160 ℃ through 30 minutes, and reacting for 5 hours at 160 ℃ to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol: the solution of cyclohexane (1: 1) is washed for 3 times and dried in vacuum at 60 ℃ for 12 hours to obtain the ruthenium rhodium palladium alloy hydride material.
Example 6: the ruthenium rhodium palladium hydride compound material prepared by the embodiment specifically comprises the following steps:
(1) uniformly dispersing 8mg of palladium acetylacetonate, 4mg of rhodium acetylacetonate, 4mg of ruthenium acetylacetonate and 120mg of polyvinylpyrrolidone into 3mL of benzyl alcohol and 3mL of acetaldehyde solution;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, then transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, raising the temperature from room temperature to 160 ℃ through 30 minutes, and reacting for 5 hours at 160 ℃ to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol: the solution of cyclohexane (1: 1) is washed for 3 times and dried in vacuum at 60 ℃ for 12 hours to obtain the ruthenium rhodium palladium alloy hydride material.
FIGS. 1, 2 and 3 are Transmission Electron Microscope (TEM) images of the rhodium-palladium-hydride compounds, the ruthenium-palladium-hydride compounds and the ruthenium-rhodium-palladium-hydride compounds prepared in examples 1 to 3, respectively, from which it is possible to show that 3 kinds of alloy hydrides are in the form of nanoparticles. Figure 2 is an X-ray diffraction pattern (XRD) of the rhodium-palladium-hydrogen compounds, ruthenium-palladium-hydrogen compounds, and ruthenium-rhodium-palladium-hydrogen compounds prepared according to the present invention. First, for the 3 materials, there is only one set of fcc diffraction peaks, which proves to be an alloy structure. And careful comparison with standard PDF cards, the peaks of rhodium-palladium hydride are to the left of the PDF card of rhodium, palladium alone, whereas the XRD peaks of typical rhodium-palladium alloys should be centered between rhodium and palladium, demonstrating that rhodium-palladium hydride has a lattice expansion characteristic, which is consistent with the hydride structure. Since ruthenium is generally hcp in structure, and ruthenium palladium hydride compound exhibits a diffraction peak of fcc structure, it is proved that the formation of ruthenium palladium hydride compound is mainly based on fcc crystal structure of palladium. Fig. 5 is an X-ray diffraction (XRD) pattern of the initial and 6 months of standing rhodium-palladium hydride prepared by the present invention, from which it can be seen that the XRD peaks of the rhodium-palladium hydride are not changed after 6 months of standing, which proves that the rhodium-palladium hydride is very stable. The products obtained in examples 4 to 6 also have the same characteristics.
The rhodium-palladium hydride, ruthenium-palladium hydride and ruthenium-rhodium-palladium hydride materials prepared in the embodiments 1 to 3 are respectively adopted to prepare glassy carbon electrodes, and the preparation method specifically comprises the following steps: a quantity of the hydride was dissolved in 400. mu.L cyclohexane and sonicated for 1 hour with 60. mu.g carbon black (XC-72) in 1.2mL ethanol. Then, the mixture was collected by centrifugation and redissolved in a mixed solution of 3mL of ethanol and 1mL of acetic acid. And after continuing ultrasonic treatment for 30 minutes, centrifugally collecting, washing for 2 times by using ethanol, finally drying for 12 hours in vacuum at 60 ℃ to obtain a material with the alloy hydride loaded on the carbon black, dissolving the material in a mixed solution of 50 mu L of ethanol, water and naphthol (the volume ratio is 8.9: 1: 0.1), performing ultrasonic treatment for 1 hour, dripping 20 mu L of the material on the surface of a glassy carbon electrode, and drying by using an infrared baking lamp to finally obtain the glassy carbon electrode modified by loading the alloy hydride on the carbon black.
The electrode is applied to electrochemical hydrogen evolution, and specifically comprises the following steps:
a three-electrode system is formed by taking a Glassy Carbon Electrode (GCE) modified by alloy hydride (rhodium-palladium-hydrogen, ruthenium-palladium-hydrogen and ruthenium-rhodium-palladium-hydrogen) as a Working Electrode (WE), a saturated calomel electrode as a Reference Electrode (RE) and a carbon rod as a Counter Electrode (CE), and 1M potassium hydroxide is taken as electrolyte. Before the electrochemical test, saturated nitrogen was introduced to remove oxygen from the solution. And the electrode was calibrated to positive SCE + 1.05V.
FIG. 6 shows Polarization curves (Polarization curves) of 1000 cycles of the rhodium-palladium hydride initial and cycling prepared by the present invention, and it can be seen from the graphs that when the current density is10mA/cm2When the overpotential is only 36mA/cm2And after 1000 cycles, the activity is not obviously changed, and higher stability is shown.
Fig. 7 is a polarization curve of alloy hydrides (rhodium-palladium hydride, ruthenium-palladium hydride and ruthenium-rhodium-palladium hydride) prepared by the invention and commercial platinum carbon, and it can be seen from the polarization curve that the alloy hydrides all show ultrahigh hydrogen production activity and are far superior to the commercial platinum carbon.
The products obtained in the embodiments 4-6 also show ultrahigh hydrogen production activity, which is far superior to commercial platinum carbon.
The alloy hydride (rhodium-palladium-hydrogen, ruthenium-palladium-hydrogen and ruthenium-rhodium-palladium-hydrogen) prepared by the method has the advantages of simple preparation method, high repeatability and strong operability. The catalyst is a novel electrochemical hydrogen evolution catalyst, and shows extremely high activity and catalytic stability.
Claims (2)
1. The application of the alloy hydride material is characterized in that the alloy hydride material is applied to the preparation of an electrochemical catalytic hydrogen evolution electrode; the alloy hydride material is a rhodium-palladium alloy hydride material, a ruthenium-palladium alloy hydride material or a ruthenium-rhodium-palladium alloy hydride material; wherein:
the rhodium-palladium alloy hydride material is prepared by the following steps:
(1) uniformly dispersing palladium acetylacetonate, rhodium acetylacetonate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde according to the volume ratio of 1: 1; wherein the mass of the palladium acetylacetonate and the mass of the rhodium acetylacetonate are equal, and the concentration of the palladium acetylacetonate is 1 mg/mL-1.5 mg/mL; the mass ratio of the polyvinylpyrrolidone to the palladium acetylacetonate is 1/10-1/20;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, heating the mixed solution to 160-180 ℃ from room temperature within 30 minutes, and keeping the temperature for 5-8 hours to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol and cyclohexane according to the volume ratio of 1:1 for 3 times, and drying the solution for 12 hours at the temperature of 60 ℃ in vacuum to obtain a rhodium-palladium alloy hydride material;
the ruthenium palladium alloy hydride material is prepared by the following steps:
(1) uniformly dispersing palladium acetylacetonate, ruthenium acetylacetonate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde according to the volume ratio of 1: 1; wherein the mass of the palladium acetylacetonate is equal to that of the ruthenium acetylacetonate, and the concentration of the palladium acetylacetonate is 1 mg/mL-1.5 mg/mL; the mass ratio of the polyvinylpyrrolidone to the palladium acetylacetonate is 1/10-1/20;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, heating the mixed solution to 160-180 ℃ from room temperature within 30 minutes, and keeping the temperature for 5-8 hours to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol and cyclohexane according to the volume ratio of 1:1 for 3 times, and drying the solution for 12 hours in vacuum at the temperature of 60 ℃ to obtain a ruthenium-palladium alloy hydride material;
the ruthenium rhodium palladium alloy hydride material is prepared by the following steps:
(1) uniformly dispersing palladium acetylacetonate, rhodium acetylacetonate, ruthenium acetylacetonate and polyvinylpyrrolidone into a mixed solution of benzyl alcohol and acetaldehyde according to the volume ratio of 1: 1; wherein the mass of palladium acetylacetonate is 2 times of that of rhodium acetylacetonate, the mass of ruthenium acetylacetonate and rhodium acetylacetonate are equal, and the concentration of palladium acetylacetonate is 1 mg/mL-1.5 mg/mL; the mass ratio of the polyvinylpyrrolidone to the palladium acetylacetonate is 1/10-1/20;
(2) stirring the mixed solution obtained in the step 1 for 1 hour, transferring the mixed solution into a reaction kettle, putting the reaction kettle into a muffle furnace, heating the mixed solution to 160-180 ℃ from room temperature within 30 minutes, and keeping the temperature for 5-8 hours to obtain a black product;
(3) and (3) carrying out reaction on the black product obtained in the step 2 by using ethanol and cyclohexane according to the volume ratio of 1:1 for 3 times, and drying for 12 hours at 60 ℃ in vacuum to obtain the ruthenium-rhodium-palladium alloy hydride material.
2. The use according to claim 1, wherein the electrode is prepared by a method comprising: dissolving 20 μ g of alloy hydride in 400 μ L of cyclohexane, and ultrasonically mixing with 60 μ g of carbon black dissolved in 1.2mL of ethanol for 1 hour; then centrifugally collecting and re-dissolving the mixture in a mixed solution of 3mL of ethanol and 1mL of acetic acid; after continuing the ultrasonic treatment for 30 minutes, centrifugally collecting and washing with ethanol for 2 times, and finally vacuum-drying at 60 ℃ for 12 hours to obtain a material with alloy hydride supported on carbon black, which is then dissolved in 50 μ L of a solvent with a volume ratio of 8.9: 1: 0.1 of mixed solution of ethanol, water and naphthol, performing ultrasonic treatment for 1 hour, dripping 20 mu L of mixed solution on the surface of a glassy carbon electrode, and drying by using an infrared baking lamp to finally obtain the glassy carbon electrode modified by alloy hydride loaded on carbon black.
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| Formaldehyde-assisted synthesis of ultrathin Rh nanosheets for applications in CO oxidation;Changping Hou，et al;《CrystEngComm》;20130603;第15卷;第6127-6130页 * |
| 纳米储氢合金制备方法的研究进展;张红兵等;《中国粉体技术》;20001231;第6卷(第6期);第21-25页 * |
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