CN104437566B - A kind of Fe of core shell structure3o4@SiO2nanometer particle load type Cu catalyst and its preparation method and application - Google Patents
A kind of Fe of core shell structure3o4@SiO2nanometer particle load type Cu catalyst and its preparation method and application Download PDFInfo
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- CN104437566B CN104437566B CN201410733593.2A CN201410733593A CN104437566B CN 104437566 B CN104437566 B CN 104437566B CN 201410733593 A CN201410733593 A CN 201410733593A CN 104437566 B CN104437566 B CN 104437566B
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Abstract
The present invention relates to a kind of Fe using core shell structure3O4@SiO2Nano particle parcel CuCl2Preparation XL Cu (II) Fe3O4@SiO2The method of loaded catalyst.It is characterized in that the magnetic nano-particle stable in properties of core shell structure, good dispersion, surface texture interconnection, stronger constraint ability is had to being involved in copper catalyst therein, huge specific surface area provides abundant activated centre, generating β carbonyl nitrile compounds for catalysis aromatic alcohol and acetonitrile and have significant catalytic effect, magnetic properties out can be reused by delamination, and activity the most significantly reduces.
Description
Technical field
The present invention relates to a kind of Fe using core shell structure3O4@SiO2Nano particle parcel CuCl2Preparation XL-Cu (II) Fe3O4@SiO2The method of loaded catalyst, belongs to nanocatalyst technical field.
Background technology
β-carbonyl nitrile compounds has consequence in the compound field of synthesizing heterocyclic structure, such as synthesizing amino pyrazoles, imidazoles, furans, thiophene and 2-pyridine compounds.Additionally, they can also be as synthesising biological and the precursor of pharmacological active substance, such as anti-HCV medicament, NHE-1 inhibitor etc..Synthesis β-carbonyl nitrile compounds has some common methods, the displacement reaction etc. of coupled reaction, alpha-brominated ketone compound and the nitrile compound under highly basic participates in including alkyl nitrile and ester.There is certain weak point in these synthetic methods, participates in than if desired for highly basic, uses the nitrile compound of severe toxicity, and metallic catalyst is expensive, seriously polluted, and synthesis step is various.From the point of view of sustainable development, it is the most economical and the most practical that we are badly in need of finding one, the synthetic method of clean environment firendly again.Liu seminar (Org.Lett.2014,16,350-353) proposition CuCl in 20142The method that catalysis aromatic alcohol synthesizes β-carbonyl nitrile compounds with acetonitrile.The method is homogeneous catalytic reaction, and catalyst can not recycle and reuse, however it remains certain wastes and pollution.
Summary of the invention
In order to solve the problems referred to above of the prior art, We conducted substantial amounts of research, it is proposed that a kind of novel magnetic Nano supported copper catalyst.
Magnetic nano-catalyst advantage compared with conventional catalyst system is
1, magnetic nano-catalyst size is little, has great specific surface area.
2, that catalyst activity component is contacted with reactant is more abundant for big specific surface area, and its catalytic effect can match in excellence or beauty homogeneous catalysis.
3, easily controllable size shape makes the material for specific catalytic reaction is reasonable in design be possibly realized, and nano metal can be catalyzed under its macrostate the reaction that cannot be catalyzed.
4, can isolate magnetic nano-catalyst easily with externally-applied magnetic field, catalyst can be reused.
In recent years, the nano particle of core shell structure becomes the focus of a research.We use SiO2Parcel Fe3O4, on the one hand can improve dispersiveness and the stability of nano particle, on the other hand be beneficial to follow-up nanoparticle surface modified carrying out.Additionally, we are by CuCl2It is involved in core shell structure, and outside is made the form that intersection combines, greatly reduce the expulsion rate of metal.
Described XL-Cu (II) Fe3O4@SiO2Loaded catalyst preparation method, comprises the steps:
(1) SiO is prepared2Nano particle.The SiO that we prepare2It is the features such as six side's ordered arrangements, size is uniform, aperture can continuously adjust in the range of 2-10nm, specific surface area is big that nano particle has duct.Weigh 1.37g cetyl trimethylammonium bromide (CTAB) to be dissolved in 30mL deionized water, use NH3·H2O regulates PH=10, drips 5.2g TEOS, has white precipitate to generate, and proceeds to 105 DEG C of crystallization 24h in reactor after continuing stirring 3h.Reaction filters out solid after terminating, vacuum drying, and gained solid is placed in 550 DEG C of high-temperature calcination 6h in Muffle furnace and removes template agent, obtains the SiO that duct is hexahedron2Nano particle.
(2) SiO is prepared2-NH2Nano particle.The coordination of subsequent metal is conducive to after surface is carried out ammoniated treatment.Weigh 300mg SiO2In crucible, it is placed in Muffle furnace and at 115 DEG C, activates 4h, the SiO that will activate2Add in 50mL there-necked flask, add 30mL toluene solvant, drip 0.5mLAPTES, N2The lower 117 DEG C of backflow 24h of environment.Toluene solvant is spin-dried for after terminating by reaction, is cleaned three times by solid with absolute ethyl alcohol, and filtration under diminished pressure goes out solid, 50 DEG C of dried in vacuum overnight.
(3) cross-linked (XL)-SiO is prepared2Nano particle.By making outside nano particle, to intersect the form combined higher to the constraint ability of coordinating metal, makes the metal can more stable existence.Weigh 50mg SiO2-NH2In 25mL round-bottomed flask, addition 10mL dichloroethane solvent, severalDrip 200 μ L triethylamines, after magnetic agitation 30min, be slowly added dropwise 100 μ L oxalyl chlorides, continue stirring 4h.Solvent is spin-dried for after terminating by reaction, 50 DEG C of dried in vacuum overnight after solid being cleaned three times with absolute ethyl alcohol.
(4) cross-linked (XL)-Cu (II) SiO is prepared2Nano particle.By CuCl2It is involved in carrier, forms effective catalytic active center.Weigh 50mg cross-linked (XL)-SiO2In 50mL there-necked flask, add 10mL toluene solvant, then weigh 20mg CuCl2It is dissolved in 5mL methanol solvate, methanol solution is injected in toluene solution, N2The lower 64 DEG C of backflow 24h of environment.Solvent is spin-dried for after terminating by reaction, and with washes of absolute alcohol solid three times, filtration under diminished pressure goes out 50 DEG C of dried in vacuum overnight of solid product.
(5) Fe is prepared3O4Nano particle.3.3g FeCl3、2.0g FeCl2·4H2O adds in 50mL alcohol solvent, adds 10mLNH3·H2O (28wt%), is stirred 5h and obtains black solid, separated by black solid by externally-applied magnetic field, 50 DEG C of dried in vacuum overnight after cleaning three times by deionized water at 78 DEG C.
(6) XL-Cu (II) Fe is prepared3O4@SiO2Nano particle.At SiO2Fe is inserted inside duct3O4Make magnetic material, it is simple to the separation of catalyst.Weigh 50mg XL-Cu (II) SiO2In 50mL round-bottomed flask, add 20mL toluene solvant, add 5mgFe3O4, stir 5h.Solvent is spin-dried for after terminating by reaction, gained solid dried in vacuum overnight.
The invention has the beneficial effects as follows:
XL-Cu (II) Fe prepared by the present invention3O4@SiO2Nano particle catalysis aromatic alcohol and acetonitrile generate β-carbonyl nitrile compounds outstanding effect, and catalyst can recycle and reuse, and activity the most significantly reduces.
Detailed description of the invention
Present invention following example illustrate, but the present invention is not limited to following embodiment, and on the premise of without departing from the most described objective, change is included in the technical scope of the present invention.
Embodiment 1
Being analyzed product, result is as follows:1H NMR (400MHz, CDCl3): 3.97 (s, 2H), 7.56 (t, J=7.6Hz, 2H), 7.64 (t, J=7.2Hz, 1H), 7.94 (d, J=7.6Hz, 2H).13C NMR(100Hz,CDCl3): 134.1,128.8,128.6133.1,187.1,134.4,29.3. data above proves that purpose product is successfully prepared.
Catalyst is recycled five products therefrom productivity as follows:
| Run NO. | 1 | 2 | 3 | 4 | 5 |
| Yield (%) | 85 | 85 | 83 | 81 | 78 |
Embodiment 2
Being analyzed product, result is as follows:1H NMR (400MHz, CDCl3): 4.03 (s, 2H), 7.52 (t, J=8.4Hz, 2H), 7.90 (d, J=8.4Hz, 2H).13C NMR(100Hz,CDCl3): 134.9,128.8,128.6,135.1,186.1,139.4,29.4. data above proves that purpose product is successfully prepared.
Embodiment 3～9
Claims (4)
1. the Fe of a core shell structure3O4@SiO2Nanometer particle load type Cu catalyst-, it is characterised in that with Fe3O4@SiO2
For carrier, with APTES to SiO2Surface is involved in metallic catalyst CuCl after carrying out ammoniated treatment2, and the side combined by intersection
Method makes the metal of parcel can more stable existence.
The Fe of a kind of core shell structure the most according to claim 13O4@SiO2The preparation of nanometer particle load type Cu catalyst
Method, it is characterised in that:
Preparation Fe3O4Nano particle, 3.3g FeCl3、2.0g FeCl2·4H2O adds in 50ml alcohol solvent, adds
10mlNH3·H2O, is stirred 5h and obtains black solid, separated by black solid by externally-applied magnetic field, use deionization at 78 DEG C
Water cleans 50 DEG C of dried in vacuum overnight after three times；
Preparation hexagon SiO2Nano particle, weighs 1.37g cetyl trimethylammonium bromide (CTAB) and is dissolved in 30ml deionization
In water, use NH3·H2O regulates PH=10, drips 5.2g TEOS, has white precipitate to generate, and proceeds to after continuing stirring 3h
105 DEG C of crystallization 24h in reactor, reaction filters out solid after terminating, and vacuum drying, gained solid is placed in Muffle furnace
550 DEG C of high-temperature calcination 6h remove template agent, obtain the SiO that duct is hexahedron2Nano particle；
Preparation SiO2-NH2Nano particle, weighs 300mg SiO2In crucible, it is placed in Muffle furnace and at 115 DEG C, activates 4h,
The SiO that will activate2Add in 50ml there-necked flask, add 30ml toluene solvant, drip 0.5ml APTES, N2Under environment
117 DEG C of backflow 24h, toluene solvant is spin-dried for after terminating by reaction, is cleaned three times by solid with absolute ethyl alcohol, and filtration under diminished pressure goes out solid,
50 DEG C of dried in vacuum overnight；
Preparation cross-linked (XL)-SiO2Nano particle, weighs 50mg SiO2-NH2In 25ml round-bottomed flask, add 10ml
Dichloroethane solvent, several 4AMS drip 200 μ l triethylamines, are slowly added dropwise 100 μ l oxalyl chlorides after magnetic agitation 30min,
Continuing stirring 4h, solvent is spin-dried for after terminating by reaction, 50 DEG C of dried in vacuum overnight after solid being cleaned three times with absolute ethyl alcohol；
Preparation cross-linked (XL)-Cu (II) SiO2Nano particle, weighs 50mg cross-linked (XL)-SiO2In 50ml
In there-necked flask, add 10ml toluene solvant, then weigh 20mg CuCl2It is dissolved in 5ml methanol solvate, methanol solution is noted
Enter in toluene solution, N2The lower 64 DEG C of backflow 24h of environment, solvent is spin-dried for after terminating by reaction, with washes of absolute alcohol solid three times,
Filtration under diminished pressure goes out 50 DEG C of dried in vacuum overnight of solid product；
Preparation XL-Cu (II) Fe3O4@SiO2Nano particle, weighs 50mg XL-Cu (II) SiO2In 50ml round-bottomed flask
In, add 20ml toluene solvant, add 5mg Fe3O4, stirring 5h, solvent is spin-dried for after terminating by reaction, gained solid vacuum
It is dried overnight.
The Fe of a kind of core shell structure the most according to claim 13O4@SiO2The application of nanometer particle load type Cu catalyst,
It is characterized in that: generate β-carbonyl nitrile compounds with this catalyst aromatic alcohol with acetonitrile, obtain higher productivity.
The Fe of a kind of core shell structure the most according to claim 13O4@SiO2The application of nanometer particle load type Cu catalyst,
It is characterized in that: this catalyst is heterogeneous magnetic catalyst, it is easy to separate, stable in properties, recycling rate of waterused is high.
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| CN106902887B (en) * | 2017-03-14 | 2019-06-14 | 山东管理学院 | It is a kind of can magnetic force recycling copper complex catalyst and the preparation method and application thereof |
| CN116178595A (en) * | 2021-11-26 | 2023-05-30 | 中国石油天然气股份有限公司 | Supported metallocene catalyst for olefin polymerization and preparation method and application thereof |
| CN116178594A (en) * | 2021-11-26 | 2023-05-30 | 中国石油天然气股份有限公司 | In-situ supported metallocene catalyst for olefin polymerization and preparation method and application thereof |
Citations (4)
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| WO2003090927A1 (en) * | 2002-04-24 | 2003-11-06 | Beijing University Of Chemical Technology | Magnetic superfine solid acid catalyst with double shell structure and process for preparing |
| KR20070004228A (en) * | 2005-07-04 | 2007-01-09 | 최성우 | Adsorbent for recovering volatile organic compound and manufacturing method the same of |
| CN101205420A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
| CN102688760A (en) * | 2012-06-07 | 2012-09-26 | 北京科技大学 | Fe3O4/CuO/pSiO2 catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003090927A1 (en) * | 2002-04-24 | 2003-11-06 | Beijing University Of Chemical Technology | Magnetic superfine solid acid catalyst with double shell structure and process for preparing |
| KR20070004228A (en) * | 2005-07-04 | 2007-01-09 | 최성우 | Adsorbent for recovering volatile organic compound and manufacturing method the same of |
| CN101205420A (en) * | 2007-12-06 | 2008-06-25 | 复旦大学 | Magnetic inorganic nano-particle/ordered meso-porous silica core-shell microspheres and preparation thereof |
| CN102688760A (en) * | 2012-06-07 | 2012-09-26 | 北京科技大学 | Fe3O4/CuO/pSiO2 catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
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| Salen complex of Cu(II) supported on superparamagnetic Fe3O4@SiO2 nanoparticles: An efficient and recyclable catalyst for synthesis of 1- and 5-substituted 1H-tetrazoles;Farzaneh Dehghani等;《Journal of Organometallic Chemistry》;20131015;第743卷;全文 * |
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