CN116281854A - Method for catalyzing ammonia borane pyrolysis dehydrogenation by eutectic solvent - Google Patents
Method for catalyzing ammonia borane pyrolysis dehydrogenation by eutectic solvent Download PDFInfo
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- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000006356 dehydrogenation reaction Methods 0.000 title claims abstract description 42
- 239000002904 solvent Substances 0.000 title claims abstract description 31
- 230000005496 eutectics Effects 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 40
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 8
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 claims description 6
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical group Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 229940057054 1,3-dimethylurea Drugs 0.000 claims description 3
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000004064 recycling Methods 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 239000003054 catalyst Substances 0.000 description 22
- 239000000370 acceptor Substances 0.000 description 8
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 6
- JZGGZNWADMJJCC-UHFFFAOYSA-N 3-[6-(dimethylcarbamoylamino)hexyl]-1,1-dimethylurea Chemical compound CN(C)C(=O)NCCCCCCNC(=O)N(C)C JZGGZNWADMJJCC-UHFFFAOYSA-N 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical group 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
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- 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
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0247—Imides, amides or imidates (R-C=NR(OR))
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0245—Nitrogen containing compounds being derivatives of carboxylic or carbonic acids
- B01J31/0249—Ureas (R2N-C(=O)-NR2)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The scheme relates to a method for catalyzing ammonia borane to be pyrolyzed and dehydrogenated by using a eutectic solvent, which takes ammonia borane as a raw material, takes potassium tert-butoxide or potassium hydroxide as an additive, and carries out pyrolysis and dehydrogenation reaction on the ammonia borane in an organic solvent through the catalysis of the eutectic solvent; the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor in a mass ratio of 3:1-1:6. The invention provides a method for efficiently catalyzing pyrolytic dehydrogenation of ammonia borane by using a eutectic solvent, which has the advantages of simple preparation process, high catalytic efficiency, mild reaction condition, large hydrogen release amount and recycling, and a hydrogen bond donor-acceptor can play a role in synergistic catalysis.
Description
Technical Field
The invention relates to the field of dehydrogenation catalytic reaction, in particular to a method for catalyzing ammonia borane pyrolysis dehydrogenation by using a eutectic solvent.
Background
After twenty-first century, how to reasonably develop and utilize new energy gradually became a research hotspot. Ammonia borane (NH) 3 BH 3 ) The hydrogen content is extremely high (19.6 wt%) and has the characteristics of high stability, safety and no toxicity, thus being considered as a chemical hydrogen production material with great application prospect. The dehydrogenation mode of ammonia borane is generally classified into hydrolytic dehydrogenation and pyrolytic dehydrogenation. The hydrolytic dehydrogenation reaction condition is mild, the dehydrogenation rate is extremely fast, and the hydrogen release amount is large. Therefore, the current research is mostly focused on the aspect of hydrolytic dehydrogenation,a number of documents and patents have been reported, for example: applied Catalysis A General 595 (2020) 117511,ACS Sustainable Chem.Eng.2020,8,8256-8266, CN115608375A, CN115121271A.
However, hydrolytic dehydrogenation brings in oxygen atoms, the final product is borate, and the B-O bond in borate is required to be broken in order to regenerate ammonia borane, which is difficult to realize in practical operation. And the regenerated ammonia borane can be obtained by the boron nitrogen polymer generated by pyrolysis dehydrogenation only by a proper reducing agent, which is more beneficial to sustainable development. The ammonia borane pyrolysis dehydrogenation is divided into two conditions of existence of a solvent or non-existence, when no solvent exists, the first molecular hydrogen is released at 97 ℃ to 110 ℃, the second step occurs at 110 ℃ to 150 ℃, but the third step needs extremely high temperature to completely remove the last molecular hydrogen, and even reaches 1400 ℃. The pyrolytic dehydrogenation of ammonia borane in organic solutions (pyridine, diglyme, tetrahydrofuran, etc.) is relatively easy, but still requires a suitable catalyst to reduce the reaction activation energy. At present, relatively few researches on pyrolytic dehydrogenation of ammonia borane are still carried out, and the prior art still lacks an ammonia borane pyrolytic dehydrogenation method with mild reaction conditions and large hydrogen release amount.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method for efficiently catalyzing the pyrolytic dehydrogenation of ammonia borane by using a eutectic solvent, compared with the traditional catalyst, the invention avoids expensive organic ligands and complex manufacturing processes, stabilizes the metal center by utilizing the bond energy function between hydrogen bond acceptors, can achieve the function of synergistic catalysis, and has the advantages of simple preparation process, high catalytic efficiency, mild reaction condition, large hydrogen release amount and recycling.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the method for catalyzing ammonia borane pyrolysis dehydrogenation by using eutectic solvent is characterized by using ammonia borane as raw material, using potassium tert-butoxide or potassium hydroxide as additive, and making the ammonia borane undergo the process of pyrolysis dehydrogenation reaction in organic solvent by means of catalysis of eutectic solvent; the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor in a mass ratio of 3:1-1:6.
Further, the amount of the additive is 0.5-3 wt% of the mass of ammonia borane.
Further, the organic solvent is one or a mixture of tetrahydrofuran and diethylene glycol dimethyl ether.
Further, the organic solvent is a mixture of tetrahydrofuran and diethylene glycol dimethyl ether, and the mass ratio is 1:10-10:1.
Further, the mass ratio of the organic solvent to the ammonia borane is 20:1-80:1.
Further, the hydrogen bond acceptor of the eutectic solvent is iridium trichloride, and the hydrogen bond donor is one of acetamide, methyl urea and 1, 3-dimethyl urea.
Further, the usage amount of the eutectic solvent is 1-10 wt% of the ammonia borane.
Further, the pyrolysis dehydrogenation reaction temperature is 30-100 ℃, and the reaction time is 5-60 min.
In the pyrolytic catalysis process of ammonia borane, a B-H bond is firstly attacked through a metal active center M to form an active intermediate of M-H. Then the first molecule of hydrogen is removed, the process is continuously circulated, and all hydrogen is gradually removed, so that the efficient and stable formation of the metal hydrogen active intermediate is particularly critical. The eutectic solvent is used as a catalyst in the ammonia borane dehydrogenation reaction process, the bond energy between hydrogen bond acceptors is utilized to stabilize the metal center, noble metal iridium is used as an active center and the hydrogen bond acceptors, and meanwhile, the hydrogen bond donor can play a role in synergistic catalysis, so that the ammonia borane dehydrogenation catalyst has the advantages of simple preparation process, high catalysis efficiency, mild reaction condition, large hydrogen release amount and recycling.
Compared with the prior art, the invention has the beneficial effects that: the invention provides a method for efficiently catalyzing pyrolytic dehydrogenation of ammonia borane by using a eutectic solvent, which has the advantages of simple preparation process, high catalytic efficiency, mild reaction condition, large hydrogen release amount and recycling, and a hydrogen bond donor-acceptor can play a role in synergistic catalysis.
Drawings
FIG. 1 is the [ IrCl ] of example 1 3 ] 1 [ acetamide] 2 Nuclear magnetic hydrogen spectrogram.
FIG. 2 is the [ IrCl ] of example 1 3 ] 1 [ acetamide] 2 Nuclear magnetic carbon spectrogram.
FIG. 3 is the [ IrCl ] of example 1 3 ] 2 [ methyl urea ]] 1 Nuclear magnetic hydrogen spectrogram.
FIG. 4 is the [ IrCl ] of example 1 3 ] 2 [ methyl urea ]] 1 Nuclear magnetic carbon spectrogram.
FIG. 5 is the [ IrCl ] of example 1 3 ] 1 [1, 3-dimethylurea] 1 Nuclear magnetic hydrogen spectrogram.
FIG. 6 is the [ IrCl ] of example 1 3 ] 1 [1, 3-dimethylurea] 1 Nuclear magnetic carbon spectrogram.
FIG. 7 is a nuclear magnetic resonance boron spectrum of the product of pyrolytic dehydrogenation of ammonia borane in the present invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in connection with the embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical features of the different embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
Example 1 preparation of eutectic solvent catalyst the procedure is as follows
8.1g of iridium trichloride serving as a hydrogen bond acceptor and 3.3g of acetamide serving as a hydrogen bond donor are taken and placed in a 100mL single-neck flask, the mass ratio of the iridium trichloride to the acetamide is 1:2, the iridium trichloride is subjected to airtight stirring reaction at 80 ℃ for 6 hours, and a transparent homogeneous solution serving as a eutectic catalyst [ IrCl ] is formed after the reaction is finished 3 ] 1 [ acetamide] 2 Designated sample 1, no purification step was required. The nuclear magnetic hydrocarbon spectrogram of the catalyst in the embodiment is shown in figures 1-2.
Take upThe method comprises the following steps of: acetamide, methyl urea and 1, 3-dimethyl urea, and changing the molar ratio of hydrogen bond donor and acceptor, 7 eutectic solvent catalysts with different compositions can be prepared: [ IrCl ] 3 ] 3 [ acetamide] 1 、[IrCl 3 ] 1 [ acetamide] 1 、[IrCl 3 ] 1 [ acetamide] 6 、[IrCl 3 ] 2 [ methyl urea ]] 1 、[IrCl 3 ] 1 [ methyl urea ]] 4 、[IrCl 3 ] 1 [1, 3-dimethylurea] 1 、[IrCl 3 ] 1 [1, 3-dimethylurea] 5 (subscripts are mass ratios of substances), and are respectively designated as samples 2 to 8. Catalyst [ IrCl ] in this example 3 ] 2 [ methyl urea ]] 1 And [ IrCl ] 3 ] 1 [1, 3-dimethylurea] 1 The nuclear magnetic hydrocarbon spectrogram of (2) is shown in figures 3-6.
Example 2 pyrolytic dehydrogenation of ammonia borane, the procedure is as follows
0.5g ammonia borane is weighed and placed in a 50mL two-port pressure-resistant bottle, one port is sealed by a rubber plug, and the other port is connected with a leather hose for collecting hydrogen. Catalyst (5 wt%) and potassium t-butoxide (1 wt%) were weighed out and dispersed in a mixed solution of tetrahydrofuran and diethylene glycol dimethyl ether (20 g, mass ratio: 1:4). The mixture was injected into a reaction flask by a syringe, and the time was counted, and the mixture was heated and stirred at 50℃to record the volume of hydrogen collected after 5 minutes of reaction.
The invention adopts a drainage method to obtain the hydrogen quantity released by ammonia borane under normal pressure, and according to V H2 /V m Calculating nH 2 Complete reaction of each ammonia borane molecule can produce 3 hydrogen molecules, using n H2 /n AB The reaction progress was measured and when the ratio was 3, it was shown that the ammonia borane completely released all the hydrogen.
Wherein V is H2 Represents the volume of hydrogen collected in the experiment, unit L; v (V) m Represents the molar volume of the gas, V at 25 ℃ and normal pressure m About 24.5L/mol; n is n H2 Represents the amount of hydrogen species released, in mol, n AB Represents the amount of the initially charged ammonia borane per mole.
Example 2-1 influence of different eutectic solvents on pyrolytic dehydrogenation of Ammonia borane
TABLE 1
As can be seen from the above table, the catalyst selected sample 1, [ IrCl3]1[ acetamide ]2, gave excellent results as the catalyst, and the nuclear magnetic boron spectrum after the catalytic reaction is shown in FIG. 7, which shows that ammonia borane was successfully catalytically decomposed.
Examples 2-2 influence of catalyst and additive amounts on the pyrolytic dehydrogenation of Ammonia borane
The following conditions were changed using the procedure of example 2, the remainder being unchanged, and the results are shown in Table 2.
TABLE 2
It can be seen from table 2 that increasing the catalyst and additive amounts can accelerate the ammonia borane dehydrogenation reaction, wherein the catalyst amount has more remarkable effect on the result, and the potassium tert-butoxide has better effect as an additive. In view of product consumption, the effect is better when the catalyst is used in an amount of 5wt% and the additive is potassium t-butoxide in an amount of 1 wt%.
Examples 2 to 3, influence of solvent quantity and mixing ratio on pyrolytic dehydrogenation of Ammonia borane
Using the procedure of example 2, the catalyst was sample 1, and the mass ratio of organic solvent to ammonia borane (m 1 ) And the mass ratio (m 2 ) The remaining conditions were unchanged, and the results are shown in Table 3.
TABLE 3 Table 3
Examples 2-4, influence of reaction temperature and reaction time on pyrolytic dehydrogenation of Ammonia borane
The procedure of example 2 was used, the catalyst was sample 1, the corresponding conditions were changed, and the results are shown in Table 4.
TABLE 4 Table 4
As can be seen from Table 4, either increasing the reaction temperature or extending the reaction time is beneficial to the progress of the ammonia borane dehydrogenation reaction. In consideration of energy consumption cost, the reaction at 50 ℃ for 20min is a better result.
Examples 3-5, recycle of catalyst in ammonia borane dehydrogenation
In combination with examples 2-1 to 2-4, it was found that the method of example 2, in which the catalyst was sample 1, the reaction temperature was 50℃and the reaction time was 20 minutes, and the remaining conditions were unchanged, gave a preferable structure.
After the reaction is finished, filtering and collecting filtrate, and re-injecting the filtrate into new ammonia borane to perform catalyst circulation experiments, wherein the results are shown in table 5:
TABLE 5
As can be seen from Table 5, after multiple cycles of use, the catalyst showed a slight decrease in catalytic activity for the pyrolytic dehydrogenation of ammonia borane, but generally maintained a good catalytic effect.
Although embodiments of the present invention have been disclosed above, it is not limited to the use of the description and embodiments, it is well suited to various fields of use for the invention, and further modifications may be readily apparent to those skilled in the art, and accordingly, the invention is not limited to the particular details without departing from the general concepts defined in the claims and the equivalents thereof.
Claims (7)
1. A method for catalyzing ammonia borane to be pyrolyzed and dehydrogenated by using a eutectic solvent is characterized in that ammonia borane is taken as a raw material, potassium tert-butoxide or potassium hydroxide is taken as an additive, and the ammonia borane is pyrolyzed and dehydrogenated in an organic solvent through the catalysis of the eutectic solvent; the eutectic solvent comprises a hydrogen bond acceptor and a hydrogen bond donor in a mass ratio of 3:1-1:6; the hydrogen bond acceptor is iridium trichloride, and the hydrogen bond donor is one of acetamide, methyl urea and 1, 3-dimethyl urea.
2. A method of the eutectic solvent catalyzed pyrolytic dehydrogenation of ammonia borane according to claim 1, wherein the amount of the additive is 0.5wt% to 3wt% of the ammonia borane mass.
3. The method for the pyrolytic dehydrogenation of ammonia borane catalyzed by a eutectic solvent according to claim 1, wherein the organic solvent is one or a mixture of tetrahydrofuran and diethylene glycol dimethyl ether.
4. A method for the pyrolytic dehydrogenation of ammonia borane catalyzed by a eutectic solvent according to claim 3, wherein the organic solvent is a mixture of tetrahydrofuran and diethylene glycol dimethyl ether, and the mass ratio is 1:10-10:1.
5. The method for the pyrolytic dehydrogenation of ammonia borane catalyzed by a eutectic solvent according to claim 1, wherein the mass ratio of the organic solvent to ammonia borane is 20:1-80:1.
6. A method of ammonia borane pyrolysis dehydrogenation catalyzed by a eutectic solvent according to claim 1 wherein the eutectic solvent is used in an amount of 1wt% to 10wt% of ammonia borane mass.
7. The method for the pyrolytic dehydrogenation of ammonia borane catalyzed by the eutectic solvent according to claim 1, wherein the pyrolytic dehydrogenation reaction temperature is 30-100 ℃ and the reaction time is 5-60 min.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101730656A (en) * | 2007-05-18 | 2010-06-09 | 卡娜塔化学技术股份有限公司 | Method for the production of hydrogen from ammonia borane |
| US20110008693A1 (en) * | 2009-07-08 | 2011-01-13 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
| US20120201744A1 (en) * | 2011-02-08 | 2012-08-09 | University Of Southern California | Dehydrogenation of Ammonia-Borane by Bifunctional Catalysts |
| CN104891435A (en) * | 2015-05-14 | 2015-09-09 | 大连理工大学 | Hydrogen production method by using proton-responsive iridium complex for catalysis of ammonia borane hydrolysis |
| CN113546660A (en) * | 2021-07-05 | 2021-10-26 | 南京理工大学 | Alloy catalyst and application thereof in efficient hydrogen production of borane derivative |
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2023
- 2023-03-21 CN CN202310279778.XA patent/CN116281854A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101730656A (en) * | 2007-05-18 | 2010-06-09 | 卡娜塔化学技术股份有限公司 | Method for the production of hydrogen from ammonia borane |
| US20110008693A1 (en) * | 2009-07-08 | 2011-01-13 | Ford Motor Company | Hydrogen storage materials containing ammonia borane |
| US20120201744A1 (en) * | 2011-02-08 | 2012-08-09 | University Of Southern California | Dehydrogenation of Ammonia-Borane by Bifunctional Catalysts |
| CN104891435A (en) * | 2015-05-14 | 2015-09-09 | 大连理工大学 | Hydrogen production method by using proton-responsive iridium complex for catalysis of ammonia borane hydrolysis |
| CN113546660A (en) * | 2021-07-05 | 2021-10-26 | 南京理工大学 | Alloy catalyst and application thereof in efficient hydrogen production of borane derivative |
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