CN113731465A - Pd/N-CNTs catalyst, and preparation method and application thereof - Google Patents
Pd/N-CNTs catalyst, and preparation method and application thereof Download PDFInfo
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- CN113731465A CN113731465A CN202111008978.9A CN202111008978A CN113731465A CN 113731465 A CN113731465 A CN 113731465A CN 202111008978 A CN202111008978 A CN 202111008978A CN 113731465 A CN113731465 A CN 113731465A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 85
- 150000002940 palladium Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 20
- 238000006264 debenzylation reaction Methods 0.000 claims abstract description 19
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000012716 precipitator Substances 0.000 claims abstract description 4
- IUKZSMGVHPBEHK-UHFFFAOYSA-N hexabenzilisovyurtsitan Chemical compound C=1C=CC=CC=1CN(C1C(N(CC=2C=CC=CC=2)C(N2CC=3C=CC=CC=3)C3N1CC=1C=CC=CC=1)N1CC=4C=CC=CC=4)C1C2N3CC1=CC=CC=C1 IUKZSMGVHPBEHK-UHFFFAOYSA-N 0.000 claims description 45
- 229910052763 palladium Inorganic materials 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 26
- NINQAYBICGTGQD-UHFFFAOYSA-N 1-(6,8,12-triacetyl-4,10-dibenzyl-2,4,6,8,10,12-hexazatetracyclo[5.5.0.03,11.05,9]dodecan-2-yl)ethanone Chemical compound CC(=O)N1C2C(N3CC=4C=CC=CC=4)N(C(=O)C)C1C(N1C(C)=O)N(C(C)=O)C3C1N2CC1=CC=CC=C1 NINQAYBICGTGQD-UHFFFAOYSA-N 0.000 claims description 17
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- INIOZDBICVTGEO-UHFFFAOYSA-L palladium(ii) bromide Chemical compound Br[Pd]Br INIOZDBICVTGEO-UHFFFAOYSA-L 0.000 claims description 2
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011736 potassium bicarbonate Substances 0.000 claims description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000011148 porous material Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 239000000047 product Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000006640 acetylation reaction Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- NDYLCHGXSQOGMS-UHFFFAOYSA-N CL-20 Chemical compound [O-][N+](=O)N1C2N([N+]([O-])=O)C3N([N+](=O)[O-])C2N([N+]([O-])=O)C2N([N+]([O-])=O)C3N([N+]([O-])=O)C21 NDYLCHGXSQOGMS-UHFFFAOYSA-N 0.000 description 2
- 230000021736 acetylation Effects 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000003367 polycyclic group Chemical group 0.000 description 2
- 238000002390 rotary evaporation Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- POCJOGNVFHPZNS-ZJUUUORDSA-N (6S,7R)-2-azaspiro[5.5]undecan-7-ol Chemical compound O[C@@H]1CCCC[C@]11CNCCC1 POCJOGNVFHPZNS-ZJUUUORDSA-N 0.000 description 1
- BSPUVYFGURDFHE-UHFFFAOYSA-N Nitramine Natural products CC1C(O)CCC2CCCNC12 BSPUVYFGURDFHE-UHFFFAOYSA-N 0.000 description 1
- 229910002666 PdCl2 Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- POCJOGNVFHPZNS-UHFFFAOYSA-N isonitramine Natural products OC1CCCCC11CNCCC1 POCJOGNVFHPZNS-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/399—
-
- B01J35/60—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
- C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
Abstract
The invention provides a Pd/N-CNTs catalyst, which is prepared by the following method: dispersing an N-CNTs carrier into water, stirring uniformly at room temperature, dropwise adding a palladium salt water solution, stirring for 2-4 h, adding a precipitator to adjust the pH to 10-12, heating to 40-80 ℃, keeping the temperature for 2-4 h, adding a reducing agent to reduce for 0.5-1.5 h, and carrying out aftertreatment A on the obtained reaction liquid A to obtain the Pd/N-CNTs catalyst; the Pd/N-CNTs catalyst provided by the invention realizes higher catalytic efficiency in the hydrogenolysis debenzylation reaction of HBIW. The carrier has larger pore channels, is beneficial to the adsorption and desorption of reactant and product molecules with larger volume on the catalyst, reduces the probability of the blockage of the pore channels of the catalyst, reduces the possibility of activity reduction caused by the blockage, and has good application prospect.
Description
(I) technical field
The invention relates to a high-efficiency Pd/N-CNTs catalyst, a preparation method thereof and application thereof in a reaction of generating Tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) through hydrogenolysis, debenzylation and acetylation of Hexabenzylhexaazaisowurtzitane (HBIW).
(II) technical background
Hexamethylhexaazaisowurtzitane (HBIW) is a polycyclic caged organic compound, contains six N-benzylated groups, is an important chemical intermediate for synthesizing polycyclic nitramine hexanitrohexaazaisowurtzitane (CL-20), and has attracted wide attention in the field of high-energy material chemistry.
It is well known that reductive debenzylation of HBIW is a key step in the overall synthesis. This step is a simultaneous hydrodebenzylation-acetylation process, in which the C-N bond is subjected to hydrogenolysis over a catalyst, followed by acetylation of the amine formed with acetic anhydride. The hydrogenolytic debenzylation of HBIW is a typical representation of the deprotection of complex organic molecules due to their complex structure and harsh reaction conditions. For the hydrogenolysis debenzylation reaction of HBIW, a Pd/C catalyst loading of 10 wt.% is typically used. However, low atom utilization, loss and aggregation of Pd inhibit the catalytic reaction. The development of a novel high-efficiency HBIW debenzylation catalyst has important significance in the field of high-energy materials.
Based on the background, the invention provides a Pd/N-CNTs catalyst which can be used for HBIW hydrogenolysis debenzylation so as to improve the yield of a TADBIW product.
Disclosure of the invention
In order to solve the problem of low catalyst efficiency in the prior art, the invention provides a Pd/N-CNTs catalyst, a preparation method thereof and application thereof in HBIW hydrogenolysis debenzylation reaction.
The invention realizes the purpose through the following technical scheme:
in a first aspect, the invention provides a Pd/N-CNTs catalyst, which is prepared by the following method: dispersing an N-CNTs carrier into water, uniformly stirring at room temperature, dropwise adding a palladium salt water solution, stirring for 2-4 h (preferably 3h), adding a precipitator to adjust the pH to 10-12, heating to 40-80 ℃, keeping the temperature for 2-4 h (preferably 60 ℃, keeping the temperature for 3h), adding a reducing agent to reduce for 0.5-1.5 h (preferably 1h), and carrying out aftertreatment A on the obtained reaction liquid A to obtain the Pd/N-CNTs catalyst; the mass of the palladium salt contained in the aqueous solution of the palladium salt is 5-10 wt.% (preferably 10 wt.%) of the total mass of the N-CNTs carrier, calculated as palladium; the ratio of the amount of palladium salt substance contained in the aqueous solution of palladium salt, calculated as palladium, to the amount of reducing agent substance is 1: 5-30 (preferably 1: 30).
The Pd/N-CNTs catalyst comprises palladium as an active component, and is loaded on a carrier in an elementary substance form.
Preferably, the palladium salt in the aqueous solution of palladium salt is one or a mixture of more than two of palladium chloride acid, palladium acetate, palladium nitrate and palladium bromide. Further, the concentration of the palladium salt contained in the aqueous solution of the palladium salt is 0.01 to 0.05g/mL (preferably 0.05g/mL) in terms of palladium.
Preferably, the precipitant may be one or a mixture of two or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate. Preferably the precipitant is added in the form of an aqueous solution at a concentration of 5 wt.% to 20 wt.% (preferably 10 wt.% aqueous sodium carbonate solution).
Further, the reducing agent is a reducing agent commonly used in the art, and preferably is one or a mixture of two or more of formaldehyde, formic acid, hydrazine hydrate, sodium borohydride and oxalic acid.
Furthermore, the volume of the water is 100-250 mL/g (preferably 200mL/g) based on the mass of the N-CNTs carrier.
Further, the post-treatment A comprises the following steps: and filtering the obtained reaction solution A, washing the reaction solution A to be neutral by deionized water, and drying the reaction solution A in vacuum (drying the reaction solution in a vacuum oven at the temperature of 80 ℃ for 12 hours) to obtain the Pd/N-CNTs catalyst.
The invention particularly recommends that the Pd/N-CNTs catalyst is prepared by the following method: dispersing an N-CNTs carrier into water, uniformly stirring at room temperature, dropwise adding a palladium salt water solution, stirring for 3 hours, adding a precipitator to adjust the pH to 10-12, heating to 60 ℃, keeping the temperature for 3 hours, adding a reducing agent to reduce for 1 hour, and carrying out aftertreatment A on the obtained reaction liquid A to obtain the Pd/N-CNTs catalyst; the mass of the palladium salt contained in the aqueous solution of the palladium salt is 10 wt.% of the total mass of the N-CNTs carrier, calculated by palladium; the ratio of the amount of palladium salt substances contained in the aqueous solution of palladium salt to the amount of reducing agent substances is 1: 30; the water solution of the palladium salt is 0.094mol/L chloropalladate acid water solution; the precipitant is a 10 wt.% aqueous solution of sodium carbonate; the reducing agent is sodium borohydride.
The invention adopts nitrogen-doped carbon nanotubes (N-CNTs) as a carrier of metal palladium (Pd), and the carrier has stable structure and is acid and alkali resistant; the existence of nitrogen element can generate stronger interaction with palladium, so that the metal palladium can be uniformly distributed on the carrier N-CNTs. The N-CNTs carrier has larger pore channels, which is beneficial to the transfer and reaction of a macromolecular substrate HBIW in the catalyst, and the high transfer efficiency is beneficial to the easy removal of impurities adsorbed on the catalyst, thereby prolonging the service life of the catalyst.
In a second aspect, the invention also provides an application of the Pd/N-CNTs catalyst in the hydrogenolysis debenzylation reaction of Hexabenzylhexaazaisowurtzitane (HBIW).
Specifically, the application is as follows: in the hydrogen atmosphere, generating tetraacetyldibenzylhexaazaisowurtzitane in N, N-dimethylformamide by hexabenzylhexaazaisowurtzitane, acetic anhydride and bromobenzene under the action of the Pd/N-CNTs catalyst.
Further, the application is as follows: hexabenzylhexaazaisowurtzitane, acetic anhydride (Ac) in a hydrogen atmosphere2O) and bromobenzene (PhBr) are subjected to a first reaction in N, N-Dimethylformamide (DMF) for 4-6 h (preferably 19 ℃ and 5h) at 16-20 ℃ under the action of the Pd/N-CNTs catalyst, and then subjected to a second reaction for 8-12 h (preferably 40 ℃ and 10h) at 35-45 ℃, and the obtained reaction solution B is subjected to post-treatment B to obtain Tetraacetyldibenzylhexaazaisowurtzitane (TADBIW); said acetic anhydride (Ac)2O) in a volume of 0.8 to 2mL/g (preferably 1.4mL/g) based on the mass of the hexabenzylhexaazaisowurtzitane, and bromobenzene (PhBr) in a volume of 0.01 to 0.04mL/g (preferably 0.02mL/g) based on the mass of the hexabenzylhexaazaisowurtzitane; the hexabenzylhexaazaisowurtzitsThe mass ratio of the alkane to the Pd/N-CNTs catalyst is 1: 0.05 to 0.2 (preferably 1: 0.08 to 0.15, particularly preferably 1: 0.1).
Further, the volume of the N, N-dimethylformamide is 6 to 14mL/g (preferably 10mL/g) based on the mass of the hexabenzylhexaazaisowurtzitane.
Further, the post-treatment B is as follows: and filtering the reaction solution B, washing with absolute ethyl alcohol, drying, dissolving with acetic acid, filtering to remove the catalyst, and performing rotary evaporation on the filtrate to remove the acetic acid to obtain the tetraacetyldibenzylhexaazaisowurtzitane.
The letters in the reaction solution A, B and post-treatment A, B in the present invention are only for distinguishing the reaction solution and post-treatment in different reactions, and have no other special meanings.
Wherein the catalytic hydrogenolysis reaction comprises the following steps:
preferably, the hydrogen pressure in the hydrogen atmosphere is 0.3-0.5MPa, preferably 0.4 MPa. The above pressure may be achieved by methods conventional in the art.
The N-CNTs carrier is of a multi-wall structure, the nitrogen doping amount is more than 2.5 wt.% (preferably 10 wt.%), the outer diameter is 30-80 nm, and the specific surface area is 200-400 m2A pore volume of 0.15 to 0.20cm3/g。
Compared with the prior art, the invention has the beneficial effects that:
1. the Pd/N-CNTs catalyst provided by the invention realizes higher catalytic efficiency in the hydrogenolysis debenzylation reaction of HBIW. The carrier has larger pore channels, is beneficial to the adsorption and desorption of reactant and product molecules with larger volume on the catalyst, reduces the probability of the blockage of the pore channels of the catalyst, reduces the possibility of activity reduction caused by the blockage, and has good application prospect.
2. The existence of nitrogen element can generate stronger interaction with palladium, so that the metal palladium can be uniformly distributed on the carrier N-CNTs. The catalyst has good activity and stability, the activity of the catalyst is well maintained after simple treatment, the catalyst can be recycled, the cost is reduced, and the catalyst has good application prospect.
(IV) detailed description of the preferred embodiments
The invention is illustrated by the following specific examples. It should be noted that the examples are only intended to illustrate the invention further, but should not be construed as limiting the scope of the invention. The experimental methods not specifically mentioned in the following examples were selected in accordance with conventional methods and conditions, and the starting materials and reagents involved in the present invention were all commercially available.
The present invention will be further described with reference to the following examples.
Example 1
Preparation of 5 wt.% Pd/N-CNTs catalyst:
N-CNTs (purchased from Xiancheng nano material science and technology Co., Ltd., product number 101741) with the content of 0.95g N of 10 wt.% are accurately weighed and evenly dispersed into 200ml of deionized water, stirred for 30min, then 5ml of chloropalladite solution (0.094mol/L) with the concentration of 0.01g/ml (recorded by palladium) is dropwise added, and stirred for 2 h. Then 10 wt.% sodium carbonate solution was added dropwise to slowly increase the pH to 11-13, after which the temperature was raised to 60 ℃ and held for 3 h. Then 0.50g of sodium borohydride (0.013mol) was added and reduced for 1 h. And finally, filtering, washing the solution to be neutral by deionized water, and drying the solution in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain 0.93g of Pd/N-CNTs with the theoretical loading capacity of 5 wt.%.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
5.0g of HBIW, 50ml of DMF, 0.1ml of PhBr, 0.50g of palladium supported 5 wt.% Pd/N-CNTs (mass ratio of catalyst to reactant HBIW 1: 10) and 7ml of Ac2Sequentially adding O into a reaction vessel and introducing H2The air in the reactor was discharged five times to make the hydrogen pressure 0.4 MPa. The first stage was carried out at 19 ℃ for 5h, and the second stage was carried out at 40 ℃ for 10 h. After the reaction is finished, naturally cooling to room temperature, and filtering to obtain a mixture of a product Tetraacetyldibenzylhexaazaisowurtzitane (TADBIW) and the catalyst. TADBIW in the mixture was dissolved in 50ml of acetic acid, and the catalyst and the acetic acid solution in which TADBIW was dissolved were separated by filtration. Tong (Chinese character of 'tong')The mass of the product TADBIW obtained by removing acetic acid through over-rotary evaporation is 2.7038g, the product is white crystal, the measured melting point is 321-323 ℃, and the product conforms to the literature, so that the target product can be proved to be generated. The catalyst is washed by ethanol and deionized water in sequence until the catalyst is neutral, and then the catalyst is put into a vacuum oven at 80 ℃ for drying for 12 hours and is recovered.
Example 2
Preparation of 10 wt.% Pd/N-CNTs catalyst:
N-CNTs with the content of 0.90g N being 10 wt.% are accurately weighed and evenly dispersed into 200ml of deionized water, stirred for 30min, then 10ml of chloropalladate solution (0.094mol/L) with the concentration of 0.01g/ml (in terms of palladium) is dropwise added, and stirred for 2 h. Then 10 wt.% sodium carbonate solution was added dropwise to slowly increase the PH to 11-13, after which the temperature was raised to 60 ℃ and held for 3 h. Then, 1.00g of sodium borohydride (0.026mol) was added to reduce for 1 h. And finally, filtering, washing the solution to be neutral by deionized water, and drying the solution in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain 0.91g of Pd/N-CNTs with the theoretical loading capacity of 10 wt.%.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
the catalyst was changed to only 10 wt.% Pd/N-CNTs (0.5g), the remaining conditions were the same as in example 1, and the yield was 3.2273 g.
Example 3
The Pd/N-CNTs catalyst used in this example was 10 wt.% Pd/N-CNTs recovered from example 2.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
the same procedure as in example 1 was repeated except for using only the catalyst in the hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW) as the catalyst, and 10 wt.% Pd/N-CNTs (0.5g) was recovered. The yield was 3.0685g
Comparative example 1
Preparation of 10 wt.% Pd/N-C catalyst:
the operation and parameters for the preparation of the 10 wt.% Pd/N-C catalyst of this example were the same as in example 2. Only the carrier was changed to activated carbon (0.9g, available from national pharmaceutical group chemical agents limited, cat # 10006618) having a N content of 10 wt.%.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
the catalyst was changed to only 10 wt.% Pd/N-C (0.5g), and the remaining conditions were the same as in example 2. The yield was 2.8910 g.
Comparative example 2
The Pd/N-C catalyst used in this comparative example was 10 wt.% Pd/N-C (0.5g) recovered in comparative example 1.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
the catalyst was replaced with only 10 wt.% Pd/N-C (0.5g) recovered in comparative example 1, and the remaining conditions were the same as in example 1. The yield was 0 g.
Comparative example 3
Preparation of 10 wt.% Pd/N-CNTs (not precipitated) catalyst:
no precipitant was added during the preparation of the catalyst, and the rest of the conditions were the same as in example 2.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
the catalyst was changed to only 10 wt.% Pd/N-CNTs (not precipitated), and the rest of the conditions were the same as in example 1. The yield was 2.3795 g.
Comparative example 4
Preparation of 10 wt.% Pd @ N-CNTs catalyst:
accurately weigh 0.167g of PdCl2(Pd content 0.10g) and 0.90g N-CNTs, mixed and ground thoroughly using a pestle and mortar. The resulting mixture was transferred to a stainless steel MOCVD reactor. The MOCVD reactor was evacuated by means of a vacuum pump for 40 min. The MOCVD reactor was then inserted into a CVD muffle furnace and heated at 120 ℃ for 30 min. The temperature was then adjusted at 2 ℃/min-1The rate of (2) was increased to 300 ℃ and then held at 300 ℃ for 45min to give 0.90g of 10 wt% Pd @ N-CNTs.
Hydrogenolysis debenzylation of Hexabenzylhexaazaisowurtzitane (HBIW):
the catalyst was changed to only 10 wt.% Pd @ N-CNTs, and the remaining conditions were the same as in example 1. The yield was 1.9000 g.
The yields and purities of the HBIW hydrogenolysis products in the examples and comparative examples are shown in Table 1:
wherein, regarding the calculation of the yield, it is obtained by the following formula: yield is the amount of TADBIW substance/amount of HBIW substance. And the product purity data is obtained by analyzing and testing through a high performance liquid chromatograph.
Wherein, the amount of product TADBIW substance is (mass of solid product-mass of catalyst)/relative molecular mass of TADBIW, and the amount of reactant HBIW substance is (mass of HBIW)/relative molecular mass of HBIW.
Wherein the relative molecular mass of TADBIW is 516.60g/mol, and the relative molecular mass of HBIW is 709.85 g/mol.
Table 1: yield and purity of HBIW hydrogenolysis product in each example and comparative example
Claims (10)
1. A Pd/N-CNTs catalyst is characterized in that the Pd/N-CNTs catalyst is prepared by the following method: dispersing an N-CNTs carrier into water, stirring uniformly at room temperature, dropwise adding a palladium salt water solution, stirring for 2-4 h, adding a precipitator to adjust the pH to 10-12, heating to 40-80 ℃, keeping the temperature for 2-4 h, adding a reducing agent to reduce for 0.5-1.5 h, and carrying out aftertreatment A on the obtained reaction liquid A to obtain the Pd/N-CNTs catalyst; the mass of the palladium salt contained in the water solution of the palladium salt is 5-10 wt% of the total mass of the N-CNTs carrier, calculated as palladium; the ratio of the amount of palladium salt substance contained in the aqueous solution of palladium salt, calculated as palladium, to the amount of reducing agent substance is 1: 5 to 30.
2. The Pd/N-CNTs catalyst of claim 1, wherein: the palladium salt in the water solution of the palladium salt is one or a mixture of more than two of palladium chloride acid, palladium acetate, palladium nitrate and palladium bromide.
3. The Pd/N-CNTs catalyst of claim 1, wherein: the concentration of the palladium salt contained in the water solution of the palladium salt is 0.01-0.05 g/mL calculated by palladium.
4. The Pd/N-CNTs catalyst of claim 1, wherein: the precipitant is one or a mixture of more than two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate.
5. The Pd/N-CNTs catalyst of claim 1, wherein: the precipitant is added in the form of aqueous solution, and the concentration is 5 wt.% to 20 wt.%.
6. The Pd/N-CNTs catalyst of claim 1, wherein: the reducing agent is one or a mixture of more than two of formaldehyde, formic acid, hydrazine hydrate, sodium borohydride and oxalic acid.
7. The Pd/N-CNTs catalyst of claim 1, wherein: the volume of the water is 100-250 mL/g based on the mass of the N-CNTs carrier.
8. The Pd/N-CNTs catalyst according to claim 1, characterised in that the post-treatment a is: and filtering the obtained reaction liquid A, washing the reaction liquid A to be neutral by deionized water, and drying the reaction liquid A in vacuum to obtain the Pd/N-CNTs catalyst.
9. The use of the Pd/N-CNTs catalyst as defined in claim 1 for the hydrogenolysis debenzylation of hexabenzylhexaazaisowurtzitane.
10. The use according to claim 9, characterized in that the use is: in the hydrogen atmosphere, generating tetraacetyldibenzylhexaazaisowurtzitane in N, N-dimethylformamide by hexabenzylhexaazaisowurtzitane, acetic anhydride and bromobenzene under the action of the Pd/N-CNTs catalyst.
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