CN109928898A - A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green - Google Patents
A kind of method that the derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green Download PDFInfo
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- CN109928898A CN109928898A CN201910278343.7A CN201910278343A CN109928898A CN 109928898 A CN109928898 A CN 109928898A CN 201910278343 A CN201910278343 A CN 201910278343A CN 109928898 A CN109928898 A CN 109928898A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- -1 azoxy compound Chemical class 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 21
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 19
- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 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 abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 7
- DMLAVOWQYNRWNQ-UHFFFAOYSA-N azobenzene Chemical compound C1=CC=CC=C1N=NC1=CC=CC=C1 DMLAVOWQYNRWNQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 230000000694 effects Effects 0.000 claims abstract description 3
- 238000006479 redox reaction Methods 0.000 claims abstract description 3
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 238000003763 carbonization Methods 0.000 claims description 6
- CZGCEKJOLUNIFY-UHFFFAOYSA-N 4-Chloronitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C=C1 CZGCEKJOLUNIFY-UHFFFAOYSA-N 0.000 claims description 5
- ORPVVAKYSXQCJI-UHFFFAOYSA-N 1-bromo-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Br ORPVVAKYSXQCJI-UHFFFAOYSA-N 0.000 claims description 3
- FWIROFMBWVMWLB-UHFFFAOYSA-N 1-bromo-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Br)=C1 FWIROFMBWVMWLB-UHFFFAOYSA-N 0.000 claims description 2
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 claims description 2
- KMAQZIILEGKYQZ-UHFFFAOYSA-N 1-chloro-3-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC(Cl)=C1 KMAQZIILEGKYQZ-UHFFFAOYSA-N 0.000 claims description 2
- QZYHIOPPLUPUJF-UHFFFAOYSA-N 3-nitrotoluene Chemical compound CC1=CC=CC([N+]([O-])=O)=C1 QZYHIOPPLUPUJF-UHFFFAOYSA-N 0.000 claims description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 2
- ZPTVNYMJQHSSEA-UHFFFAOYSA-N 4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1 ZPTVNYMJQHSSEA-UHFFFAOYSA-N 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 239000002114 nanocomposite Substances 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- ZDFBKZUDCQQKAC-UHFFFAOYSA-N 1-bromo-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(Br)C=C1 ZDFBKZUDCQQKAC-UHFFFAOYSA-N 0.000 claims 1
- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical compound [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 230000001476 alcoholic effect Effects 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000007809 chemical reaction catalyst Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 238000011084 recovery Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000003480 eluent Substances 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- YUCNDEWLRLACNP-UHFFFAOYSA-N (4,4-dichlorocyclohexa-1,5-dien-1-yl)-oxido-phenyliminoazanium Chemical compound C=1CC(Cl)(Cl)C=CC=1[N+]([O-])=NC1=CC=CC=C1 YUCNDEWLRLACNP-UHFFFAOYSA-N 0.000 description 1
- PLAZTCDQAHEYBI-UHFFFAOYSA-N 2-nitrotoluene Chemical compound CC1=CC=CC=C1[N+]([O-])=O PLAZTCDQAHEYBI-UHFFFAOYSA-N 0.000 description 1
- PEXGTUZWTLMFID-UHFFFAOYSA-N 2-phenyldiazenylphenol Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1 PEXGTUZWTLMFID-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 1
- 238000006531 Wallach Azoxybenzene rearrangement reaction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 description 1
- 229910010277 boron hydride Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005691 oxidative coupling reaction Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The method that the derivative magnetic nanoparticle of a kind of MOFs disclosed by the invention prepares azoxy compound as recyclable catalyst green, it is characterized in that, aromatic nitro compound and reducing agent are under the effect of magnetic nano-catalyst containing Co, redox reaction occurs, obtain azobenzene oxide compound, using Co@C-N as catalyst, aromatic hydrocarbon nitro compound is raw material, hydrazine hydrate is reducing agent in alcoholic solution synthesis azobenzene oxide compound, participate in reaction catalyst can magnetic recovery be recycled, reduce production cost, it is environmentally protective, reaction condition is simple, yield is high.
Description
Technical field
The present invention relates to azoxy compound fields, and in particular to a kind of derivative magnetic nanoparticle of MOFs is as can return
Receive the method that catalyst green prepares azoxy compound.
Background technique
In recent years, azoxy compound is received more and more attention due to its special construction, can be widely applied to contaminate
Material, pigment, reducing agent, analytical reagent, chemical stabilizer and polymerization inhibitor and organic synthesis intermediate etc. such as aoxidize even
Pyridine is the presoma of Wallach rearrangement reaction, it provides a kind of straightforward procedure for preparing hydroxyazobenzene.
Currently, the conventional method of synthesis azoxy compound is under alkaline condition with zinc, glucose, NaBH4Deng also
Former agent p-nitrophenyl compound reduction, the method can generate a large amount of alkali wasteliquid, will cause destruction to environment, while also need to compare
Harsher reaction condition, high process cost do not meet environmental-friendly and green syt requirement；Azoxy compound is another
One common synthetic method is that aniline compound is carried out oxidative coupling with oxidant, however, most of oxidant is to meeting to environment
It damages, is also unfavorable for sustainable development.
Current environmentally friendly Green Chemistry is increasingly paid close attention to, since the environmental requirement whole world includes that the country has all existed
Constantly eliminate all kinds of heavy environmental pollution techniques (including substituting original iron powder Zinc powder process with palladium carbon hydro-reduction technique).So
The use that the metallic catalyst of environmentally friendly nonhazardous how is designed in Green Chemistry becomes key, metal organic framework
(MOFs) material is due to having the characteristics that orderly regular structure, higher specific surface area and adjustability of structure have obtained people
Extensive concern and research, before there is more tempting application compared with conventional porous materials as the emerging porous material grown rapidly
Scape, however, practical application and development are limited by very large since MOFs has relatively poor stability.
Summary of the invention
To solve the above problems, the present invention provides a kind of recyclable catalyst green of MOFs derivative magnetic nanoparticle conduct
The method for preparing azoxy compound, yield is high, catalyst is recyclable, green non-pollution, reaction cost are low.
It is green as recyclable catalyst that the technical solution that the present invention solves is to provide a kind of derivative magnetic nanoparticle of MOFs
The method that color prepares azoxy compound, aromatic nitro compound and reducing agent magnetic nano-catalyst containing Co effect under,
Redox reaction occurs, obtains azobenzene oxide compound.
Preferably, the aromatic nitro compound be nitrobenzene, it is parachloronitrobenzene, m-chloro-nitrobenzene, o-chloronitrobenzene, right
Bromo nitrobenzene, m-bromonitrobenzene, o-bromonitrobenzene, ortho-methylnitrobenzene, meta-nitrotoluene, para-nitrotoluene, p-nitrobenzonitfile,
One of p-nitrophenol is several.
Preferably, the reducing agent is hydrazine hydrate.
Preferably, the magnetic nano-catalyst containing Co is with zeolite imidazole skeleton structural material (ZIF-67) for raw material,
Cobalt obtained from carbonization-carbon nano-composite material Co@C-N.
Preferably, further include purification step: the product that reaction terminates is dissolved with ethyl acetate, recycle magnetic containing Co with magnet
Property nanocatalyst.
Preferably, the molar ratio of the aromatic nitro compound and reducing agent is 1:1-10.
Preferably, the mass ratio of the aromatic nitro compound and Co@C-N are 100:0.1-5.
Preferably, the temperature of the carbonization is 500-800 DEG C, carbonization time 2-5h.
The coordination preparation simple aspect of MOFs material is carried out with cobalt ions and 2-methylimidazole molecule, cobalt metal can highly divide
Cloth is between 2-methylimidazole molecule.When by MOFs high temperature cabonization at Co@C-N material, 2-methylimidazole be directly carbonized as C and
Two kinds of elements of N, and cobalt ions is then reduced to cobalt simple substance.Since cobalt ions is separated by C and N, cobalt simple substance will not reunite after carbonization,
And will form Co nanoparticle is kernel, the core-shell catalyst Co@C-N that N doped graphite carbon is shell.It is urged in Co/C-N
In agent, C-N is provided preferably by the catalyst surface that Co active nano cluster is dispersed and between catalyst and reaction medium
Chemical interface, it is suppressed that the aggregation of active nano cluster.Meanwhile C-N structure can accumulate interaction absorption nitro by p-p
Benzene substrate improves contact of the reactant with catalyst surface, electronics is promoted to move to Co active nano cluster from C-N.These because
Element causes the nitroaromatic of high concentration to accumulate in active Co/C-N catalyst surface, and is effectively reduced into corresponding
Azoxy compound.In addition, the electronic structure of Co simple substance makes Co@C-N show stronger magnetism, so that the catalyst
It can be recycled with magnet, improve the utilization of resources.
The preferred hydrazine hydrate of the present invention is reducing agent, is primarily due to the product of hydrazine hydrate after the reaction and there was only water and hydrogen,
There are no pollution to the environment, meets green reaction direction.In addition, the reproducibility of hydrazine hydrate is weaker than boron hydride, it will not be by nitro
Benzene compound is reduced directly to amino-compound.
Beneficial effects of the present invention are, using Co@C-N as catalyst, aromatic hydrocarbon nitro compound is raw material, and hydrazine hydrate is also
Former agent alcoholic solution synthesize azobenzene oxide compound, participate in reaction catalyst can magnetic recovery be recycled, reduce production
Cost, environmentally protective, reaction condition is simple, and yield is high.
Detailed description of the invention
The SEM figure that Fig. 1 is ZIF-67 in embodiment 1；
The SEM figure that Fig. 2 is Co@C-N in embodiment 1；
The TEM figure that Fig. 3 is Co@C-N in embodiment 1；
Fig. 4 is the EDS analysis chart of Co@C-N in embodiment 1.
Specific embodiment
In order to make content of the present invention easily facilitate understanding, With reference to embodiment to of the present invention
Technical solution is described further, but the present invention is not limited only to this.
Raw material used in the present invention be unless otherwise specified it is common commercially available, AR is pure.
Embodiment 1
A. ZIF-67 synthesize: by 0.6g cabaltous nitrate hexahydrate and 7.31g 2-methylimidazole be dissolved in respectively 4ml and 26 ml go from
In sub- water, second part solution is slowly added in the first solution, the rapid purpling of color stirs 3h under the conditions of being stirred at room temperature,
After the reaction was completed, blue solid is collected by centrifugation with 8000 rpm, is centrifuged 4 min, then with ethanol washing 3 times, the crystal being collected into
After being dried in vacuo 5h, yield reaches 61%.ZIF-67 structure is as shown in Figure 1, be the faceted particles that diameter is about 400nm.
B. the preparation of Co@C-N catalyst: under the conditions of nitrogen atmosphere, placing 0.8g ZIF-67 in Muffle furnace,
It is carbonized at 800 DEG C, heating rate is respectively 10 DEG C/min, keeps the temperature 2h, is naturally cooling to room temperature and obtains Co@C-N catalyst.
The structure of Co@C-N is about the particle (as shown in Fig. 2 SEM figure) of 100nm, and wherein the partial size of cobalt simple substance particle is about
25nm, and there is no very serious reunion occurs for cobalt nanometer particle (as shown in Fig. 3 TEM figure).Co@C-N is further surveyed by EDS
Examination carries out constituent analysis, as shown in figure 4, EDS is the result shows that Co@C-N contains a large amount of Co, C and a small amount of N element.
C. Catalysis experiments: nitrobenzene (0.5g, 10 mmol) and Co/C-N (0.006-0.024g) are mixed in circular base bottle
In, 5-25ml ethyl alcohol is added, stirs to 50 DEG C, until nitrobenzene is completely dissolved.Then 0.2- is added in said mixture
80% hydrazine hydrate of 1.5g.Reaction temperature is maintained at 50 DEG C, is characterized with thin-layered chromatography.After the reaction was completed, 5- is added
25ml ethyl acetate, with magnet adsorbing separation Co/C-N.Filtrate decompression concentration, remaining fluid column chromatography (eluent is petroleum ether,
60-90 DEG C) it is purified, obtain azoxybenzene, yield 78%.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that the deionized water in step (a) is changed to methanol or second
Alcohol, the ethyl alcohol in step (c) are changed to methanol.Equally successfully synthesize target product.
Embodiment 3
Embodiment 4 is substantially the same manner as Example 1, the difference is that the nitrobenzene in step (c) is changed to methyl nitrobenzene.
Similarly successfully synthesize target product.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that the nitrobenzene in step (c) is changed to parachloronitrobenzene.
Similarly successfully synthesize target product.
Embodiment 4
Parachloronitrobenzene (62.8g, 1mol) and Co/C-N (0.1g) are mixed in circular base bottle, 500ml methanol are added, stirring is extremely
50 DEG C, until parachloronitrobenzene is completely dissolved.Then 80% hydrazine hydrate of 100g is added in said mixture.Reaction temperature is kept
At 50 DEG C, reaction is monitored with thin-layered chromatography.After the reaction was completed, 300ml ethyl acetate is added, with magnet adsorbing separation
Co/C-N catalyst.Filtrate decompression concentration, remaining fluid column chromatography (eluent be petroleum ether, 60-90 DEG C) are purified, and obtain 4,
4- dichloroazoxybenzene, yield 82%.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 4, the difference is that Co/C-N catalyst is not added in reaction system.As the result is shown
Do not obtain target product.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, is all covered by the present invention.
Claims (8)
1. the method that a kind of derivative magnetic nanoparticle of MOFs prepares azoxy compound as recyclable catalyst green,
It is characterized in that, aromatic nitro compound and reducing agent occur redox reaction, obtain under the effect of magnetic nano-catalyst containing Co
To azobenzene oxide compound.
2. the derivative magnetic nanoparticle of a kind of MOFs according to claim 1 is as recyclable catalyst green preparation oxidation
The method of azo-compound, which is characterized in that the aromatic nitro compound be nitrobenzene, parachloronitrobenzene, m-chloro-nitrobenzene,
O-chloronitrobenzene, p-Nitrobromobenzene, m-bromonitrobenzene, o-bromonitrobenzene, ortho-methylnitrobenzene, meta-nitrotoluene, para-nitrotoluene,
One of p-nitrobenzonitfile, p-nitrophenol are several.
3. the derivative magnetic nanoparticle of a kind of MOFs according to claim 1 is as recyclable catalyst green preparation oxidation
The method of azo-compound, which is characterized in that the reducing agent is hydrazine hydrate.
4. the derivative magnetic nanoparticle of a kind of MOFs according to claim 1 is as recyclable catalyst green preparation oxidation
The method of azo-compound, the magnetic nano-catalyst containing Co be using zeolite imidazole skeleton structural material as raw material, carbonization and
Obtained cobalt-carbon nano-composite material Co@C-N.
5. the derivative magnetic nanoparticle of a kind of MOFs according to claim 1 is as recyclable catalyst green preparation oxidation
The method of azo-compound, which is characterized in that further include purification step: the product that reaction terminates is dissolved with ethyl acetate, is used
Magnet recycles magnetic nano-catalyst containing Co.
6. the derivative magnetic nanoparticle of a kind of MOFs according to claim 1 is as recyclable catalyst green preparation oxidation
The method of azo-compound, which is characterized in that the molar ratio of the aromatic nitro compound and reducing agent is 1:1-10.
7. the derivative magnetic nanoparticle of a kind of MOFs according to claim 3 is as recyclable catalyst green preparation oxidation
The method of azo-compound, which is characterized in that the mass ratio of the aromatic nitro compound and Co@C-N are 100:0.1-5.
8. the derivative magnetic nanoparticle of a kind of MOFs according to claim 3 is as recyclable catalyst green preparation oxidation
The method of azo-compound, which is characterized in that the temperature of the carbonization is 500-800 DEG C, carbonization time 2-5h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910278343.7A CN109928898B (en) | 2019-04-09 | 2019-04-09 | Green preparation method of azoxy compound by taking MOFs derived magnetic nanoparticles as recyclable catalyst |
Applications Claiming Priority (1)
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| CN115318324A (en) * | 2022-08-04 | 2022-11-11 | 浙江工业大学 | Application of porous FeCo-N/C carbon nano material in selective reduction of p-nitrophenol |
| CN115569661A (en) * | 2022-04-29 | 2023-01-06 | 武汉工程大学 | Magnetic Ag-Co @ C-N recoverable catalyst, and preparation method and application thereof |
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