CN112250582A - Preparation method of amino metal compound and application of amino metal compound - Google Patents
Preparation method of amino metal compound and application of amino metal compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/0005—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes
- C01B3/001—Reversible uptake of hydrogen by an appropriate medium, i.e. based on physical or chemical sorption phenomena or on reversible chemical reactions, e.g. for hydrogen storage purposes ; Reversible gettering of hydrogen; Reversible uptake of hydrogen by electrodes characterised by the uptaking medium; Treatment thereof
- C01B3/0015—Organic compounds; Solutions thereof
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
- C07C211/45—Monoamines
- C07C211/46—Aniline
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/82—Carbazoles; Hydrogenated carbazoles
- C07D209/86—Carbazoles; Hydrogenated carbazoles with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the ring system
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- C—CHEMISTRY; METALLURGY
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic System
- C07F1/005—Compounds containing elements of Groups 1 or 11 of the Periodic System without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/32—Hydrogen storage
Abstract
Disclosed is a method for producing an amino metal compound, which comprises contacting an amino compound with a metal source and reacting the two to obtain the amino metal compound. The preparation method has the advantages of simplicity, feasibility, thorough implementation, controllable reaction progress and easiness in amplification. The compound prepared by the method has the advantages of high hydrogen storage capacity, low cost, mild hydrogenation and dehydrogenation reaction and the like when being used as a hydrogen storage material.
Description
Technical Field
The invention relates to preparation of an organic-inorganic hybrid material, in particular to preparation of an amino metal compound and application of the prepared amino metal compound in the field of hydrogen storage, and belongs to the technical field of material preparation.
Background
The liquid organic matter stores hydrogen, has higher hydrogen storage capacity (6 to 8 percent), stable performance, high safety and recyclable use, can directly utilize the advantages of the prior gasoline conveying mode, the gas station framework and the like, and is more suitable for large-scale and long-distance hydrogen transportation. The traditional liquid organic matter dehydrogenation has high temperature, and low-temperature dehydrogenation is difficult to realize, so that the large-scale application and development of the traditional liquid organic matter are restricted. The discovery of unsaturated heteroaromatic organic compounds effectively lowers the reaction temperature for hydrogenation and dehydrogenation. However, the dehydrogenation enthalpy of the liquid organic hydride is still high, so that dehydrogenation at higher temperature is required, and the method is not suitable for practical application.
In recent years, the development of metal organic chemistry breaks the boundary of traditional organic chemistry and inorganic chemistry, and is also interwoven with theoretical chemistry, synthetic chemistry, catalytic chemistry, structural chemistry, bio-inorganic chemistry, polymer science, material science and the like, and becomes one of the leading fields of modern chemistry. [ Crabtree, Robert H.John Wiley & Sons,2009 ]
The amino metal compound is an important branch in metallorganics, and it originated in 1856 as the first amino metal organic compound-Zn (NEt)2)2The appearance of (D) is a mark. Due to the characteristics of electron arrangement, electronegativity and the like of the amino group, the compounds show many specificities and are therefore receiving wide attention.
Disclosure of Invention
The method provided by the application introduces metal elements into the cyclic amino compound to synthesize the organic-inorganic hybrid material. The metal modified amido compound provides a simple method for preparing the amido metal compound, and simultaneously reduces the dehydrogenation enthalpy value of the whole compound, thereby reducing the dehydrogenation temperature, and therefore, the method can be applied to the field of hydrogen storage materials. In order to achieve the above purpose, the present invention adopts preparation techniques based on a ball milling method (without solvent) and a solution method (with solvent).
Ball milling method: under the condition of no solvent, mixing a certain proportion of amino compound and corresponding metal source, and mechanically ball-milling to make them produce action. During the reaction, the reaction rate can be controlled by the method of ball milling temperature and ball milling rotating speed. The reaction progress can be judged by monitoring the pressure change in the ball mill tank.
Solution method: adding an amino compound and a corresponding metal source in a certain proportion into a solvent, stirring in a high-pressure reaction kettle for reaction until the mixture is balanced, and removing the solvent to obtain the corresponding amino metal compound. The reaction rate can be controlled by the reaction temperature. The reaction progress can be judged by monitoring the pressure change in the reaction kettle.
The materials used in the above preparation schemes are all deliquescent or oxidizable and therefore the procedure must be carried out under a dry inert atmosphere, such as in an Ar filled glove box.
One aspect of the present invention provides a method for preparing an amino metal compound, comprising contacting an amino compound with a metal source, and reacting the two to obtain the amino metal compound.
In a preferred embodiment, the reaction is carried out both with and without a solvent.
Under the condition of no solvent, mixing the amido compound and the metal source, and then carrying out solid-phase ball milling to react the amido compound and the metal source to obtain the amido metal compound.
Under the condition of solvent, adding the mixture of amino compound and metal source into the solution, stirring until the reaction is finished, and removing the solvent to obtain the amino metal compound.
In a preferred embodiment, the metal source includes at least one of a simple metal, a metal hydride, a metal amide, a metal imide, and a metal nitride.
In a preferred embodiment, the elemental metal is at least one of an alkali metal, an alkaline earth metal, and a transition metal.
Preferably, the alkali metal is selected from at least one of lithium, sodium, potassium, and the like.
Preferably, the alkaline earth metal is selected from at least one of magnesium, calcium, and the like.
Preferably, the transition metal is selected from at least one of titanium, zirconium, zinc, and the like.
The metal hydride is at least one of an alkali metal hydride, an alkaline earth metal hydride, and a transition metal hydride.
Preferably, the alkali metal hydride is selected from at least one of lithium hydride, sodium hydride, potassium hydride, and the like.
Preferably, the alkaline earth metal hydride is selected from at least one of magnesium hydride, calcium hydride, and the like.
Preferably, the transition metal hydride is selected from at least one of titanium hydride, zirconium hydride, zinc hydride, and the like.
Preferably, the metal amino compound is at least one of an alkali metal amino compound and an alkaline earth metal amino compound.
Preferably, the metal amino compound is at least one of lithium amide, sodium amide, potassium amide, magnesium amide, calcium amide, strontium amide, barium amide, and the like.
Preferably, the metal imide compound is at least one of an alkali metal imide compound and an alkaline earth metal imide compound.
Preferably, the metal imino compound is at least one of lithium imino, sodium imino, potassium imino, magnesium imino, calcium imino, strontium imino, barium imino, etc.
The metal nitride is at least one of lithium nitride, magnesium nitride, calcium nitride, strontium nitride and the like.
The amino compound is at least one selected from aromatic amines and derivatives thereof or cyclic aliphatic amines and derivatives thereof.
Preferably, the aromatic amines and derivatives thereof are selected from at least one of aniline, p-phenylenediamine, m-phenylenediamine, 1-naphthylamine, 2-naphthylamine, diphenylamine, benzidine, pyrrole, imidazole, pyrazole, indole, azaindole and carbazole.
Preferably, the cyclic aliphatic amine and the derivative thereof are selected from at least one of cyclohexylamine, p-cyclohexanediamine, m-cyclohexyldiamine, m-cyclohexyltriamine, 1-perhydronaphthylamine, 2-perhydronaphthylamine, dicyclohexylamine, pyrrolidine, imidazoline, pyrazolidine, indoline, perhydroindole, dihydroazaindole, perhydroazaindole, tetrahydrocarbazole, octahydrocarbazole, and dodecahydrocarbazole.
In a preferred embodiment, the ratio of the amine-based compound to the metal source is between 1:20 and 20: 1.
Preferably, the upper limit of the ratio of the amine-based compound to the metal source is selected from 20:1, 10:1, 5:1, 4: 1; preferably, the lower limit of the ratio of the amine-based compound to the metal source is selected from 1:20, 1:10, 1:5, 1: 4.
In a preferred embodiment, the ratio of the amine-based compound to the metal source is 1: 1.
In a preferred embodiment, the ball milling temperature is between-100 ℃ and 300 ℃, the ball milling speed is between 10 rpm and 500 rpm, and the ball milling time is between 1 hour and 300 hours in the absence of a solvent.
In a preferred embodiment, the reaction temperature is between-100 ℃ and 300 ℃, the stirring speed is between 10 rpm and 1000 rpm, and the reaction time is between 1 hour and 300 hours in the presence of a solvent.
In a preferred embodiment, the solvent is at least one of common organic solvents such as diethyl ether, tetrahydrofuran, cyclohexane, benzene, and the like.
The invention also provides the application of the amino metal compound prepared by the preparation method in hydrogen storage materials.
In a preferred embodiment, the amine-based metal compound effects hydrogen absorption and desorption from the hydrogen storage material catalyzed by the transition metal catalyst.
The active component in the transition metal catalyst comprises at least one of Pt, Pd, Ru, Rh, Fe, Co, Ni, Ir and Ag.
Preferably, the ratio of the amine metal compound to the catalyst is between 100000:1 and 1: 10.
The beneficial effects that this application can produce include:
1) the preparation method of the cyclic amino compound provided by the application has the characteristics of simplicity, easiness in implementation, thorough reaction, capability of monitoring the reaction progress degree and capability of easily amplifying the reaction to synthesize a product.
2) The cyclic amino compound prepared by the preparation method provided by the application has the advantages of high hydrogen storage capacity, low cost, mild hydrogenation and dehydrogenation reactions and the like.
Drawings
FIG. 1 shows the conversion of sodium aniline prepared by a solution process as a function of time;
FIG. 2 shows XRD spectra of sodium aniline and sodium hydride prepared by the ball milling method and the solution method;
FIG. 3 shows the preparation of sodium aniline and aniline in deuterated DMSO by ball milling and solution methods
1H-NMR spectrum;
FIG. 4 shows the reaction product of aniline sodium hydrogenation and aniline sodium and cyclohexylamine sodium dissolved in deuterated DMSO at 150 deg.C and 70bar hydrogen pressure using Pt/C as catalyst (molar ratio of aniline sodium to Pt is 30:1)1H-NMR spectrum;
FIG. 5 shows XRD spectra of prepared cyclohexylamine sodium sample and sodium hydride;
FIG. 6 shows the prepared cyclohexylamine sodium sample and the dissolution of cyclohexylamine in deuterated DMSO1H-NMR and13a C-NMR spectrum;
FIG. 7 shows the use of Rh/Al2O3Is a catalyst (the molar ratio of the cyclohexylamine sodium to the Rh is 10:1), and the product of the dehydrogenation reaction of the cyclohexylamine sodium, the aniline sodium and the cyclohexylamine sodium are dissolved in deuterated DMSO at the temperature of 150 ℃ under the vacuum condition1H-NMR spectrum;
figure 8 shows XRD spectra of the prepared carbazole sodium sample and carbazole, sodium hydride;
FIG. 9 shows prepared samples of sodium carbazole and carbazole dissolved in deuterated DMSO1H-NMR spectrum;
FIG. 10 shows in-situ reduction of metallic Ru catalyst (molar ratio of carbazole sodium to Ru is 5:1), carbazole sodium hydrogenation reaction product and carbazole hydrogenation product at 200 deg.C under 70bar hydrogen pressure, and dissolution of carbazole sodium in deuterated DMSO1H-NMR spectrum.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
Unless otherwise specified, the raw materials and catalysts in the examples of the present application were all purchased commercially.
Among these, Pt/C (5%) catalyst was purchased from Alfa Aesar.
Rh/Al2O3(5%) catalyst was purchased from Acros Organics.
In the embodiment of the application, a PANALYTICAL X' pert X-ray diffractometer is adopted for XRD analysis;
nuclear magnetic analysis was performed using a Bruker AVANCE 500MHz nuclear magnetic resonance spectrometer.
The conversion rate in the examples of the present application is calculated by hydrogen generation amount (synthesis of sodium aniline by a solution method, synthesis of sodium carbazole by heat treatment) and nuclear magnetic hydrogen spectrum integration (hydrogenation dehydrogenation reaction).
Example 1: preparation of sodium aniline by solution method
In the glove box, 0.920 ml of aniline liquid was pipetted using a pipette, 0.253 g of sodium hydride solid was weighed, both were placed in the same autoclave and 20 ml of ether was pipetted and added. After the reaction vessel was sealed, the reaction was carried out at room temperature for 48 hours at a stirring rate of 500 rpm. FIG. 1 is a graph showing the conversion of sodium aniline over time during the reaction. After equilibration the solvent ether was removed by rotary evaporation. The reaction progress can be realized by monitoring the pressure change in the kettle. FIG. 2 is an X-ray diffraction (XRD) spectrum of the prepared sample and the raw material sodium hydride, and FIG. 3 is an XRD spectrum of the prepared sample and the raw material aniline1H-NMR spectrogram, the nuclear magnetic hydrogen spectrum peaks of the sodium aniline prepared by the two methods are consistent and move to a high field compared with aniline, and the electron density on a benzene ring is increased due to the electron donating effect of alkali metal sodium, so that the solution method is proved to be used for synthesizing the sodium aniline.
Example 2: preparation of sodium aniline by ball milling method
In a glove box, 0.920 ml of aniline was pipetted using a pipette gun and 0.253 g of sodium hydride solid was weighed out and placed in the same ball mill jar. After the ball milling pot is sealed, the ball milling pot is carefully moved to a ball mill, and the ball milling is carried out for 10 hours at the room temperature and the rotating speed of 200 revolutions per minute. The reaction progress can be realized by monitoring the pressure change in the ball milling tank. FIG. 2 is an X-ray diffraction (XRD) spectrum of the prepared sample and the raw material sodium hydride, and FIG. 3 is an XRD spectrum of the prepared sample and the raw material aniline1The H-NMR spectrum is consistent with the hydrogen spectrum of the aniline sodium synthesized by the solution method, and the new substance is successfully synthesized and is the aniline sodium.
Example 3: hydrogenation experiment of sodium aniline
In a glove box, 58 mg of sodium aniline (solution process) and 65 mg of reduced Pt/C (5%) commercial catalyst were weighed, ground, mixed and placed in a high pressure reactor, after sealing, the gas in the apparatus was evacuated to 0psi, and then heated to 150 ℃ and hydrogenated at 70bar pressure, to carry out the hydrogenation reaction. FIG. 4 shows the equilibrium of the product obtained by reaction at 150 ℃ and 70bar under hydrogen pressure for 11 hours under Pt/C catalysis1And (4) an H-NMR spectrum shows that the hydrogenated product is consistent with the prepared sodium cyclohexylamine, and unhydrogenated reactant sodium aniline remains. Successful hydrogenation of sodium aniline to sodium cyclohexylamine was demonstrated with a conversion of 78%.
Example 4: preparation of sodium cyclohexylamine
In a glove box, 1.160 ml of cyclohexylamine liquid was pipetted using a pipette and 0.253 g of sodium hydride solid was weighed out and placed in the same ball mill pot. After the ball milling pot is sealed, the ball milling pot is carefully moved to a ball mill, and ball milling is carried out for 150 hours at the room temperature and the rotating speed of 200 revolutions per minute. The reaction progress can be realized by monitoring the pressure change in the ball milling tank. FIG. 5 is an X-ray diffraction (XRD) spectrum of the prepared sample and the raw material sodium hydride, and FIG. 6 is an XRD spectrum of the prepared sample and the raw material aniline1H-NMR spectrum and13and C-NMR spectrum shows that the carbon peak of the cyclohexylamine sodium is shifted compared with that of cyclohexylamine on a carbon spectrum, and the successful synthesis of the new substance is proved to be the cyclohexylamine sodium.
Example 5: dehydrogenation experiment of sodium cyclohexylamine
In a glove box, 61 mg of cyclohexylamine sodium and 103 mg of reduced Rh/Al were weighed2O3(5%) commercial catalyst, after grinding and mixing, was placed in a high pressure reactor, after sealing, the dehydrogenation reaction was carried out by evacuating the gas in the apparatus to 0psi and then heating to 150 ℃. FIG. 7 shows Rh/Al2O3The product is obtained after the reaction is carried out for 5 hours under the catalysis and the vacuum pressure at the temperature of 150 DEG C1H-NMR spectrum. The hydrogen peak of the dehydrogenation product is the same as that of the sodium aniline, and the remaining unreacted material is sodium cyclohexylamine, which proves that the sodium cyclohexylamine is dehydrogenated into the sodium aniline and the conversion rate is 72 percent according to the integration of a hydrogen spectrum.
Example 6: preparation of sodium carbazole
In a glove box, 1.760 g were weighedCarbazole solid, 0.253 g of sodium hydride solid (molar ratio of carbazole to sodium hydride is 1:1) was weighed and placed in the same ball mill pot. The ball milling pot is sealed and carefully moved to a ball mill, the ball milling is carried out for 4 hours at the room temperature and the rotation speed of 200 rpm, and the materials are uniformly mixed. Transferring the ball-milled carbazole sodium hydride mixed solid into a high-pressure closed reactor, heating to 243 ℃ by heat treatment, wherein the heating rate is 1 ℃ per minute. The extent of reaction progress can be achieved by monitoring the pressure change in the reactor. FIG. 8 is an X-ray diffraction (XRD) spectrum of the prepared sample and raw materials of sodium hydride and carbazole, and FIG. 9 is a spectrum of the prepared sample and carbazole1H-NMR spectrogram, hydrogen spectral peak arrangement of carbazole sodium is obviously different from carbazole, and N-H peak disappears, which proves that we successfully synthesize a new substance which is carbazole sodium.
Example 7: hydrogenation experiment of sodium carbazole
Hydrogenation experiments were performed using in situ reduction of metallic Ru catalysts. In a glove box, 0.01 mole of carbazole solid was weighed, 0.02 mole of sodium hydride solid was weighed, and both were placed in the same ball mill pot. The ball milling pot is sealed and carefully moved to a ball mill, the ball milling is carried out for 4 hours at the room temperature and the rotation speed of 200 rpm, and the materials are uniformly mixed. Transferring the ball-milled carbazole sodium hydride mixed solid into a high-pressure closed reactor, heating to 243 ℃ by heat treatment, wherein the heating rate is 1 ℃ per minute. The extent of reaction progress can be achieved by monitoring the pressure change in the reactor. In this case, a mixed solid having a molar ratio of sodium carbazole to sodium hydride of 1:1 was obtained.
0.426 g of the prepared mixed solid of sodium carbazole and sodium hydride (containing 2X 10 of sodium carbazole) is weighed-3Mol) is transferred into a ball milling pot, and 0.086 g of anhydrous ruthenium trichloride (containing 4 multiplied by 10 of ruthenium) is added into the ball milling pot-4Mole) and ball milling for 6 hours at the rotating speed of 150 rpm, wherein the ball milling tank is moved into a glove box and scraped once, and sodium hydride is used for in-situ reduction of ruthenium trichloride to synthesize the metal Ru catalyst.
Weighing 50 mg of mixed solid of in-situ reduction metal Ru and carbazole sodium, placing the mixed solid in a high-pressure reactor, sealing, pumping gas in the device to 0psi, heating to 200 ℃, and performing hydrogenation reaction at a hydrogenation pressure of 70 bar. FIG. 10 shows the in-situ reduction of a metal Ru catalyzed (the molar ratio of carbazole sodium to Ru is 1:1), 200 ℃, 70bar hydrogen pressure to reach equilibrium1H-NMR spectrum. The hydrogenation product of carbazole sodium is different from that of carbazole, so that carbazole sodium can be hydrogenated to generate sodium dodecahydrocarbazole.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A method for preparing an amino metal compound, comprising contacting an amino compound with a metal source and reacting the two to obtain the amino metal compound.
2. The preparation method according to claim 1, wherein the reaction is carried out in the presence or absence of a solvent, and specifically comprises:
under the condition of no solvent, mixing an amino compound with a metal source, and then carrying out solid-phase ball milling to react the amino compound with the metal source to obtain an amino metal compound; or
Under the condition of solvent, adding the mixture of amino compound and metal source into the solution, stirring until the reaction is finished, and removing the solvent to obtain the amino metal compound.
3. The method according to claim 1, wherein the amine-based compound is a cyclic amine-based compound;
the metal source includes at least one of a simple metal, a metal hydride, a metal amide, a metal imide, and a metal nitride.
4. The production method according to claim 3,
the metal simple substance is at least one of alkali metal, alkaline earth metal and transition metal;
the metal hydride is at least one of alkali metal hydride, alkaline earth metal hydride and transition metal hydride;
the metal amino compound is at least one of an alkali metal amino compound and an alkaline earth metal amino compound;
the imino compound is at least one of an alkali metal imino compound and an alkaline earth metal imino compound;
the metal nitride is selected from at least one of alkali metal nitride and alkaline earth metal nitride;
the amino compound is at least one of aromatic amine and derivatives thereof or cyclic aliphatic amine and derivatives thereof;
preferably, the aromatic amines and derivatives thereof are selected from at least one of aniline, p-phenylenediamine, m-phenylenediamine, 1-naphthylamine, 2-naphthylamine, diphenylamine, benzidine, pyrrole, imidazole, pyrazole, indole, azaindole and carbazole;
preferably, the cyclic aliphatic amine and the derivative thereof are selected from at least one of cyclohexylamine, p-cyclohexanediamine, m-cyclohexyldiamine, m-cyclohexyltriamine, 1-perhydronaphthylamine, 2-perhydronaphthylamine, dicyclohexylamine, pyrrolidine, imidazoline, pyrazolidine, indoline, perhydroindole, dihydroazaindole, perhydroazaindole, tetrahydrocarbazole, octahydrocarbazole and dodecahydrocarbazole;
preferably, the alkali metal hydride is selected from at least one of lithium hydride, sodium hydride, and potassium hydride;
preferably, the alkaline earth metal hydride is selected from at least one of magnesium hydride and calcium hydride;
preferably, the transition metal hydride is selected from at least one of titanium hydride, zirconium hydride, and zinc hydride;
preferably, the metal amino compound is selected from at least one of lithium amide, sodium amide, potassium amide, magnesium amide, calcium amide, strontium amide and barium amide;
preferably, the imino compound is at least one of lithium imino, sodium imino, potassium imino, magnesium imino, calcium imino, strontium imino and barium imino;
preferably, the metal nitride is at least one of lithium nitride, magnesium nitride, calcium nitride and strontium nitride.
5. The method of claim 1, wherein the molar ratio of the amine-based compound to the metal source is between 1:20 and 20: 1.
6. The method of claim 1 or 2, wherein the reaction temperature is between-100 ℃ and 300 ℃;
the reaction time is between 1 hour and 300 hours.
7. The method of claim 2, wherein the conditions of the method comprise:
in the absence of a solvent, the ball milling temperature is between-100 ℃ and 300 ℃, the ball milling rotating speed is between 10 revolutions per minute and 500 revolutions per minute, and the ball milling time is between 1 hour and 300 hours; or
In the presence of a solvent, the reaction temperature is between-100 ℃ and 300 ℃, the stirring speed is between 10 revolutions per minute and 1000 revolutions per minute, and the reaction time is between 1 hour and 300 hours.
8. The method according to claim 2 or 7, wherein the solvent is at least one of diethyl ether, tetrahydrofuran, cyclohexane, and benzene.
9. Use of the amino metal compound prepared according to the preparation method of any one of claims 1 to 8 in a hydrogen storage material.
10. The use according to claim 9, wherein the amine-based metal compound effects hydrogen sorption and desorption from the hydrogen storage material catalyzed by a transition metal catalyst.
The active component in the transition metal catalyst comprises at least one of Pt, Pd, Ru, Rh, Fe, Co, Ni, Ir and Ag.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112961097A (en) * | 2019-12-13 | 2021-06-15 | 中国科学院大连化学物理研究所 | Preparation method and application of organic metal compound |
| CN113292442A (en) * | 2020-02-21 | 2021-08-24 | 中国石油天然气股份有限公司 | Amino metal compound and preparation and application thereof |
| CN115215781A (en) * | 2021-04-21 | 2022-10-21 | 中国科学院大连化学物理研究所 | Amido metal compound indole lithium and preparation and application thereof |
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| CN113292442A (en) * | 2020-02-21 | 2021-08-24 | 中国石油天然气股份有限公司 | Amino metal compound and preparation and application thereof |
| CN115215781A (en) * | 2021-04-21 | 2022-10-21 | 中国科学院大连化学物理研究所 | Amido metal compound indole lithium and preparation and application thereof |
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