CN113292442A - Amino metal compound and preparation and application thereof - Google Patents
Amino metal compound and preparation and application thereof Download PDFInfo
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- CN113292442A CN113292442A CN202010107312.8A CN202010107312A CN113292442A CN 113292442 A CN113292442 A CN 113292442A CN 202010107312 A CN202010107312 A CN 202010107312A CN 113292442 A CN113292442 A CN 113292442A
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- aniline
- cyclohexylamine
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- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- -1 Amino metal compound Chemical class 0.000 title claims abstract description 15
- DAZLBCIMRZNCRV-UHFFFAOYSA-N aniline;sodium Chemical compound [Na].NC1=CC=CC=C1 DAZLBCIMRZNCRV-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000006243 chemical reaction Methods 0.000 claims abstract description 57
- UXHAUBHPFCNMCW-UHFFFAOYSA-N cyclohexanamine;sodium Chemical compound [Na].NC1CCCCC1 UXHAUBHPFCNMCW-UHFFFAOYSA-N 0.000 claims abstract description 51
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000001257 hydrogen Substances 0.000 claims abstract description 49
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 47
- 238000000498 ball milling Methods 0.000 claims abstract description 31
- 239000011232 storage material Substances 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 38
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 36
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 25
- 239000003054 catalyst Substances 0.000 claims description 25
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 24
- 239000012312 sodium hydride Substances 0.000 claims description 24
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 238000003795 desorption Methods 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 238000012544 monitoring process Methods 0.000 abstract description 9
- 238000003860 storage Methods 0.000 abstract description 5
- 230000003321 amplification Effects 0.000 abstract description 2
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 22
- 238000001228 spectrum Methods 0.000 description 19
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 238000006356 dehydrogenation reaction Methods 0.000 description 17
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 15
- 239000011734 sodium Substances 0.000 description 15
- 229910052708 sodium Inorganic materials 0.000 description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 229910001845 yogo sapphire Inorganic materials 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 230000010354 integration Effects 0.000 description 6
- 239000000376 reactant Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000012476 oxidizable substance Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 125000004436 sodium atom Chemical group 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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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
- C07C211/65—Metal complexes of amines
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses an amino metal compound and preparation and application thereof. The amido metal compound is aniline sodium or cyclohexylamine sodium, and the chemical formula is C6H6NNa or C6H12NNa. The preparation method comprises a ball milling method or a solution method, and has the advantages of simplicity, easiness in implementation, complete reaction, capability of monitoring the reaction progress, easiness in amplification of the reaction and the like. The aniline sodium and the cyclohexylamine sodium prepared by the method have the advantages of high hydrogen storage capacity, low cost, mild hydrogen storage operation temperature and the like when being used as hydrogen storage materials.
Description
Technical Field
The invention relates to the technical field of material preparation, in particular to an amino metal compound and preparation and application thereof.
Background
With the increasing shortage of oil and gas resources, the increasing energy demand of people and the increasing environmental problems, the development and use of efficient, clean and sustainable energy becomes the first problem facing the 21 st century. As a clean, safe, efficient and renewable energy source, the hydrogen is one of the most economical and effective alternative energy sources for people to get rid of dependence on the three major energy sources.
The organic liquid hydrogen storage technology is based on that unsaturated liquid organic matters are subjected to hydrogenation reaction under the action of a catalyst to generate a stable compound, and then dehydrogenation reaction is carried out when hydrogen is needed. The liquid organic matter stores hydrogen, has higher hydrogen storage density (6-8 percent), can realize the recycling of organic liquid through hydrogenation and dehydrogenation processes, has relatively lower cost, can realize the hydrogen storage by common materials at normal temperature and normal pressure, and has higher safety. Can directly utilize the advantages of the prior gasoline conveying mode, the gas station framework and the like, and is 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.
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
Based on the above background art, the invention provides an amino metal compound, and preparation and application thereof. The invention introduces metal element sodium into aniline and cyclohexylamine, designs and synthesizes organic-inorganic hybrid materials of aniline sodium and cyclohexylamine sodium, and researches the application of the two products in hydrogen storage materials.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides an amido metal compound, which is aniline sodium or cyclohexylamine sodium; having a chemical formula of C6H6NNa or C6H12NNa。
From the amount of hydrogen generated during the synthesis and the nuclear magnetic results, it was confirmed that metallic sodium substituted one hydrogen atom of the nitrogen atoms of aniline and cyclohexylamine to form new organic-inorganic hybrid material sodium aniline (C)6H6NNa) and sodium cyclohexylamine (C)6H12NNa)。
The present invention provides, in a second aspect, a process for producing the above sodium aniline or sodium cyclohexylamine, the process comprising: and contacting aniline or cyclohexylamine with sodium hydride to react to obtain sodium aniline or sodium cyclohexylamine.
The raw materials used in the preparation method are all deliquescent or oxidizable substances, so that the reaction is preferably carried out under anhydrous and anaerobic conditions; such as a glove box filled with Ar.
Further, the invention provides two specific preparation methods: ball milling (without solvent) or solution (with solvent); the reactants are contacted by ball milling or solution processes, where the positive hydrogen attached to the nitrogen atom is combined with the negative hydrogen attached to the sodium atom to form hydrogen gas, which drives the reaction to form sodium aniline and sodium cyclohexylamine.
Ball milling method: mixing aniline and sodium hydride or mixing cyclohexylamine and sodium hydride, and then carrying out solid-phase ball milling to react to obtain the aniline sodium or the cyclohexylamine sodium. In the reaction process, the reaction rate can be controlled by the ball milling temperature and the ball milling rotating speed; the reaction progress can be judged by monitoring the pressure change in the ball mill tank.
Solution method: adding aniline and sodium hydride or cyclohexylamine and sodium hydride into a solvent for reaction, and removing the solvent after the reaction is finished to obtain the aniline sodium or cyclohexylamine sodium. 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 preparation method has the advantages of simplicity, easiness in implementation, complete reaction, capability of monitoring the reaction progress, easiness in amplification of the reaction and the like.
Preferably, in the above ball milling method and solution method, the molar ratio of the aniline or cyclohexylamine to sodium hydride is 1:20 to 20: 1. Preferably, the upper limit of the molar ratio of the aniline or cyclohexylamine to the sodium hydride is selected from 20:1, 10:1, 5:1, 4: 1; preferably, the lower limit of the molar ratio of aniline or cyclohexylamine to sodium hydride is selected from 1:20, 1:10, 1:5, 1: 4.
Preferably, the reaction temperature in both the ball milling process and the solution process is from 0 ℃ to 300 ℃, preferably from 0 ℃ to 100 ℃, e.g., room temperature; the reaction time is 1-300 h, preferably 1-150 h; for example 10-48 h.
Preferably, the ball milling speed in the ball milling method is 10rpm to 500rpm, preferably 10rpm to 300 rpm; for example 200 to 500 rpm.
Preferably, the stirring speed for carrying out the reaction in the solution method is 10rpm to 1000rpm, preferably 10rpm to 500 rpm; for example 200 to 500 rpm.
Preferably, the solvent in the solution method is at least one of organic solvents such as diethyl ether, tetrahydrofuran, cyclohexane and benzene.
In a third aspect, the invention provides the use of the above sodium aniline or sodium cyclohexylamine in a hydrogen storage material. The sodium aniline and sodium cyclohexylamine of the present invention as hydrogen storing material has the advantages of high hydrogen storing amount, low cost, mild hydrogen storing temperature, etc.
Preferably, the aniline sodium or cyclohexylamine sodium realizes hydrogen absorption and desorption of the hydrogen storage material under the catalysis of a transition metal catalyst.
Preferably, the active component in the transition metal catalyst includes at least one of Pt, Pd, Ru, Rh, Fe, Co, Ni, Ir, and Ag.
Preferably, the molar ratio of the sodium aniline or sodium cyclohexylamine to the transition metal catalyst is 100000: 1-1: 10.
The invention introduces metal element sodium into aniline and cyclohexylamine, and designs and synthesizes organic-inorganic hybrid materials of aniline sodium and cyclohexylamine sodium; the preparation method is simple and easy to control, and simultaneously, the dehydrogenation enthalpy values of the amine sodium and the cyclohexylamine sodium are reduced by utilizing the metal modified amino compound, so that the dehydrogenation temperature is reduced, and the method can be applied to the field of hydrogen storage materials.
Drawings
FIG. 1 shows the conversion over time for the solution process (diethyl ether) for the preparation of sodium aniline.
FIG. 2 shows the conversion over time for the solution process (tetrahydrofuran) for the preparation of sodium aniline.
Figure 3 shows XRD patterns of sodium aniline and sodium hydride prepared by solution (ether) and ball milling.
FIG. 4 shows the preparation of sodium aniline and aniline in deuterated DMSO by ball milling and solution methods1H-NMR spectrum.
FIG. 5 shows the reaction product of aniline sodium hydrogenation and aniline sodium and cyclohexylamine sodium dissolved in deuterated DMSO at 150 deg.C under 70bar hydrogen pressure using Pt/C as catalyst (molar ratio of aniline sodium to Pt is 30:1)1H-NMR spectrum.
FIG. 6 shows the use of Ru/TiO2Na as catalyst (molar ratio of sodium aniline to Ru is 10:1), and the product of the hydrogenation reaction of sodium aniline, sodium aniline and sodium cyclohexylamine dissolved in deuterated DMSO at 150 ℃ and 70bar hydrogen pressure-1H-NMR spectrum.
FIG. 7 shows the use of Rh/Al2O3As a catalyst (molar ratio of sodium aniline to Rh 10:1), at 150 ℃ and 70baDissolving aniline sodium hydrogenation reaction product, aniline sodium and cyclohexylamine sodium in deuterated DMSO under hydrogen pressure condition1H-NMR spectrum.
FIG. 8 shows the use of Ru/Al2O3As catalyst (molar ratio of sodium aniline to Ru is 10:1), under the condition of 150 deg.C and 70bar hydrogen pressure making sodium aniline hydrogenation reaction product, sodium aniline and sodium cyclohexylamine dissolve in deuterated DMSO1H-NMR spectrum.
Fig. 9 shows XRD patterns of the prepared cyclohexylamine sodium sample and sodium hydride.
FIG. 10 shows the prepared sodium cyclohexylamine sample and the dissolution of cyclohexylamine in deuterated DMSO1H-NMR spectrum.
FIG. 11 shows the prepared sodium cyclohexylamine sample and the dissolution of cyclohexylamine in deuterated DMSO13C-NMR spectrum.
FIG. 12 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.
FIG. 13 shows the dehydrogenation reaction product of cyclohexylamine sodium with aniline sodium and cyclohexylamine sodium dissolved in deuterated DMSO at 180 deg.C under vacuum using Pt/C as catalyst (molar ratio of cyclohexylamine sodium to Pt is 30:1)1H-NMR spectrum.
Note: FIG. 5, FIG. 7, FIG. 8, FIG. 12 and FIG. 13 Nuclear magnetism1The number indicated in the H-NMR spectrum is the integrated area of the hydrogen peak.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
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.
Ru/Al2O3(5%) catalyst was purchased from Alfa Aesar.
Ru/TiO2the-Na (1%) catalyst is prepared by adopting an impregnation method (RuCl. xH with a certain proportion2O and TiO2Stirring in deionized water, evaporating, calcining at 300 deg.C for 4 hr, and reducing at 300 deg.C in hydrogen gas flow for 2 hr to obtain Ru/TiO2Then a certain proportion of Ru/TiO is added2And NaCO3Ru/TiO is prepared by the same steps2-Na catalyst).
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 in the examples of this application was calculated as:
conversion rate of sodium aniline synthesized by solution method: actual hydrogen production/theoretical hydrogen production
Conversion rate of dehydrogenation reaction: molar amount of product/(molar amount of remaining reactant + molar amount of product)
The hydrogen generation amount is obtained by monitoring a pressure gauge, and the residual reactant and the product molar amount are obtained by nuclear magnetic hydrogen spectrum integration.
Example 1
Preparation of sodium anilinate by solution method (diethyl ether)
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 change of the conversion of sodium aniline with time during the reaction; the reaction progress can be realized by monitoring the pressure change in the kettle, and the solvent diethyl ether is removed by rotary evaporation after the pressure reaches equilibrium. FIG. 3 shows X-ray diffraction (XRD) patterns of sodium aniline obtained from diethyl ether and sodium hydride as raw material in example 3, showing that a new phase different from sodium hydride appears, combined with FIG. 41The H-NMR spectrum can prove that the sodium aniline is synthesized.
Example 2
Preparation of sodium aniline by solution method (tetrahydrofuran)
In the glove box, 0.460 ml of aniline liquid was pipetted using a pipette gun, 0.126 g of sodium hydride solid was weighed, both were placed in the same autoclave and 20 ml of tetrahydrofuran was pipetted in. After the reaction vessel was sealed, the reaction was carried out at room temperature for 10 hours at a stirring rate of 500 rpm.
FIG. 2 is a graph showing the conversion of sodium aniline over time during the reaction. The reaction progress can be realized by monitoring the pressure change in the kettle, the tetrahydrofuran solvent is removed by rotary evaporation after the pressure reaches equilibrium, however, the tetrahydrofuran can not be completely removed due to certain interaction between the tetrahydrofuran and the product sodium aniline.
FIG. 4 shows the neutralization of sodium aniline in tetrahydrofuran with diethyl ether by ball milling1The nuclear magnetic hydrogen spectrum peaks of the sodium aniline prepared by an H-NMR spectrogram, a solvent method and a ball milling method 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 3
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. 3 is an X-ray diffraction (XRD) spectrum of the prepared sample and the raw material sodium hydride, and FIG. 4 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 4
Hydrogenation experiment of Pt/C catalytic aniline sodium
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. 5 shows the product obtained after 11 hours at 150 ℃ and 70bar hydrogen pressure, catalyzed by Pt/C1H-NMR spectrum, at which the pressure was about 68 bar. The hydrogenation product is consistent with the prepared sodium cyclohexylamine, and the unhydrogenated reactant sodium aniline remains. Successful hydrogenation of sodium aniline to sodium cyclohexylamine was demonstrated with a conversion of 78%. (conversion (16.59+17.37)/2 ÷ (16.59+17.37)/2+ 1.92+ 1.93) 78% calculated from the hydrogen spectrum integral.)
Example 5
Ru/TiO2Hydrogenation experiment of-Na-catalyzed sodium aniline
In a glove box, 6 mg of sodium anilinate (solution method) and 53 mg of the self-made catalyst Ru/TiO were weighed2And (4) grinding and mixing Na (1%), placing in a high-pressure reactor, sealing, pumping gas in the device to 0psi, heating to 150 ℃, and carrying out hydrogenation reaction at a hydrogenation pressure of 70 bar.
FIG. 6 shows Ru/TiO2Reaction under the catalysis of-Na at 150 ℃ and 70bar hydrogen pressure for 16 hours1H-NMR spectrum, at which the pressure was about 69 bar. In the figure, aniline sodium is completely converted (conversion rate is 100%) into target product cyclohexylamine sodium. Under appropriate conditions, the sodium aniline can be completely hydrogenated.
Example 6
Rh/Al2O3Hydrogenation experiment of catalytic sodium aniline
In a glove box, 58 mg of sodium anilinate (solution method) and 103 mg of reduced Rh/A were weighed2O3(5%) commercial catalyst, grind, mix, put in high-pressure reactor, after sealing, evacuate the gas in the apparatus to 0psi, then heat to 150 deg.C, hydrogenate the pressure 70bar, can carry on the hydrogenation.
FIG. 7 shows Rh/A2O3The product is obtained after the reaction is carried out for 24 hours under the catalysis and the hydrogen pressure of 70bar at the temperature of 150 DEG C1H-NMR spectrum, hydrogen pressure at equilibrium was kept constant and was about 68 bar.The hydrogenation product is consistent with the prepared sodium cyclohexylamine, and the unhydrogenated reactant sodium aniline remains. Successful hydrogenation of sodium aniline to sodium cyclohexylamine was demonstrated with a conversion of 49%. (conversion (4.44+4.95)/2 ÷ (4.44+4.95)/2+ 1.92+ 1.88) according to the hydrogen spectrum integral, 49%)
Example 7: Ru/Al2O3Hydrogenation experiment of catalytic sodium aniline
In a glove box, 58 mg of sodium anilinate (solution method) and 101 mg of reduced Ru/Al were weighed2O3(5%) commercial catalyst, grind, mix, put in high-pressure reactor, after sealing, evacuate the gas in the apparatus to 0psi, then heat to 150 deg.C, hydrogenate the pressure 70bar, can carry on the hydrogenation.
FIG. 8 shows Ru/Al2O3Catalytic reaction at 150 deg.C and 70bar hydrogen pressure for 90 hr1H-NMR spectrum, at which the pressure was about 67 bar. The hydrogenation product is consistent with the prepared sodium cyclohexylamine, and the unhydrogenated reactant sodium aniline remains. Successful hydrogenation of sodium aniline to sodium cyclohexylamine was demonstrated with a conversion of 84%. (conversion rate calculated from hydrogen spectrum integration (14.4+14.56)/2 ÷ (14.4+14.56)/2+ 1.09+ 0.59) = 84%)
Example 8
Preparation of cyclohexylamine sodium by ball milling method
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. 9 is an X-ray diffraction (XRD) spectrum of the prepared sample and a raw material sodium hydride, and FIGS. 10 and 11 are an X-ray diffraction (XRD) spectrum of the prepared sample and a raw material cyclohexylamine1H-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 9
Rh/Al2O3Catalyzed cyclohexylamineDehydrogenation experiment of sodium
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. 12 shows Rh/Al2O3The product is obtained after the reaction is carried out for 5 hours at 150 ℃ under vacuum pressure1H-NMR spectrum, at a pressure of about 8.8 psi. 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 80% according to the integration of a hydrogen spectrum. (conversion calculated from hydrogen spectrum integration (1.93+1.86+1) x2 ÷ [ 1.93+1.86+1) x2+1.19+1.25 ]: 80%)
Example 10
Pt/C catalyzed dehydrogenation experiment of cyclohexylamine sodium
In a glove box, 30 mg of cyclohexylamine sodium and 32 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 180 ℃ to effect dehydrogenation.
FIG. 13 shows the product obtained after reaction for 30 hours at 180 ℃ under vacuum pressure and under Pt/C catalysis1H-NMR spectrum, at a pressure of about 3 psi. The hydrogen peak of the dehydrogenation product was the same as that of sodium aniline, and the remaining unreacted material was a reaction intermediate product, demonstrating that sodium cyclohexylamine has been dehydrogenated to sodium aniline and that the conversion was 30% by integration according to the hydrogen spectrum. (conversion calculated from hydrogen spectrum integration (1.79+1.81+1) x2 ÷ [ 1.79+1.81+1) x2+10.61+10.66 ] - [ 30% ])
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (13)
1. An amino metal compound, characterized in that the amino metal compound is aniline sodium or cyclohexylamine sodium; having a chemical formula of C6H6NNa or C6H12NNa。
2. A process for preparing an amino metal compound according to claim 1, which comprises: and contacting aniline or cyclohexylamine with sodium hydride to react to obtain sodium aniline or sodium cyclohexylamine.
3. The method of claim 2, wherein the reaction is carried out under anhydrous and oxygen-free conditions.
4. The production method according to claim 2 or 3, characterized in that the production method comprises a ball milling method or a solution method;
ball milling method: mixing aniline and sodium hydride or mixing cyclohexylamine and sodium hydride, and then carrying out solid-phase ball milling to react to obtain aniline sodium or cyclohexylamine sodium;
solution method: adding aniline and sodium hydride or cyclohexylamine and sodium hydride into a solvent for reaction, and removing the solvent after the reaction is finished to obtain the aniline sodium or cyclohexylamine sodium.
5. The preparation method according to claim 4, wherein the molar ratio of the aniline or cyclohexylamine to the sodium hydride is 1:20 to 20: 1.
6. The preparation method according to claim 4, wherein the reaction temperature in the ball milling method and the reaction time in the solution method are both 0 ℃ to 300 ℃ and the reaction time is both 1h to 300 h.
7. The method according to claim 4, wherein the ball milling speed in the ball milling method is 10 to 500 rpm.
8. The production method according to claim 4, wherein the stirring speed at the time of the reaction in the solution method is 10 to 1000 rpm.
9. The method according to claim 4, wherein the solvent in the solution method is at least one of diethyl ether, tetrahydrofuran, cyclohexane and benzene.
10. Use of the metal amide compound of claim 1 in a hydrogen storage material.
11. The use according to claim 10, wherein the sodium aniline or sodium cyclohexylamine is catalyzed by a transition metal catalyst to effect hydrogen absorption and desorption from the hydrogen storage material.
12. Use according to claim 11, wherein the active component in the transition metal catalyst comprises at least one of Pt, Pd, Ru, Rh, Fe, Co, Ni, Ir and Ag.
13. The use according to claim 11, wherein the molar ratio of the sodium aniline or sodium cyclohexylamine to the transition metal catalyst is 100000:1 to 1: 10.
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| CN103879956A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Metal ion modified nitrogen-containing organic compound for storing hydrogen |
| CN112250582A (en) * | 2019-07-22 | 2021-01-22 | 中国科学院大连化学物理研究所 | Preparation method of amino metal compound and application of amino metal compound |
| 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 |
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| CN103879956A (en) * | 2012-12-20 | 2014-06-25 | 中国科学院大连化学物理研究所 | Metal ion modified nitrogen-containing organic compound for storing hydrogen |
| CN112250582A (en) * | 2019-07-22 | 2021-01-22 | 中国科学院大连化学物理研究所 | Preparation method of amino metal compound and application of amino metal compound |
| 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 |
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