CN102527407A - Preparation and application of amphiphilic magnetic palladium-loaded nano-ferric oxide and emulsion thereof - Google Patents
Preparation and application of amphiphilic magnetic palladium-loaded nano-ferric oxide and emulsion thereof Download PDFInfo
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- CN102527407A CN102527407A CN2010105780586A CN201010578058A CN102527407A CN 102527407 A CN102527407 A CN 102527407A CN 2010105780586 A CN2010105780586 A CN 2010105780586A CN 201010578058 A CN201010578058 A CN 201010578058A CN 102527407 A CN102527407 A CN 102527407A
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Abstract
The invention discloses a preparation method of a Pickering emulsion by utilizing amphiphilic magnetic palladium-loaded nano Fe3O4 particles, and a method of carrying out an organic synthetic reaction in the Pickering emulsion. The preparation method is characterized by comprising the following steps: modifying nano Fe3O4 particles by using alkyl carboxylic acid and salts thereof to enable the particles to have amphiphilic property; loading palladium to the particles, thus preparing amphiphilic palladium-loaded nano FeO4 particles with catalytic activity; preparing the Pickering emulsion in oil-water phase, and applying the Pickering emulsion to a Suzuki reaction; adsorbing all magnetic nano-particles by using a magnet after the reaction is completed; and automatically separating the emulsion into an oil phase and a water phase to facilitate the separation and reclamation of a catalyst. According to the preparation method, a complicated process of removing a surfactant in a conventional emulsion is avoided, and a process of reclaiming nano-particles by adopting a filter mode is avoided, so that breaking emulsion separation, catalyst reclamation and other operations are simplified.
Description
Technical field
The present invention relates to a kind of nanometer Fe with amphipathic supported palladium
3O
4The preparation method of particle is particularly carried the method that the palladium nanocatalyst particles prepares the Pickering emulsion with this amphiphilic, and the application in organic synthesis in this Pickering emulsion.
Background technology
Emulsion (emulsions) has been represented one type of important self assembly parents system, is the dispersion that two kinds of immiscible liquid (like oil and water) form under the effect of surfactant molecule interfacial film.Emulsion has had extensive studies in fields such as washing agent, fuel, extraction, environmental protection, organic synthesis, polymer chemistry, biochemistry and nano material preparation.
Similar with phase transfer catalysis (PTC); Emulsion ubiquity surfactant in organic synthesis separates from product thoroughly, emulsion components and catalyst recovery are utilized problems such as difficulty again, has therefore seriously limited the application of surfactant aggregates such as emulsion in organic synthesis.
If can embody the advantage of emulsion in organic synthesis, can simplify the breakdown of emulsion lock out operation again, solve a separation of emulsions difficult problem, realize component (oil, water, catalyst etc.) recovery, will be to oil/water heterogeneous catalysis, widen field such as emulsion applications important meaning is arranged.
The phenomenon of solid granulates stable emulsion is at first found at the beginning of last century by Britain scientist Ramsden and Pickering.Therefore people's emulsion that solid particle is stable is called Pickering emulsion [Pickering S U.J Chem Soc.1907,91,2001-2021].Compare with the emulsion that conventional surfactant is stable, the Pickering emulsion has the advantage of himself: (1) reduces amount of surfactant greatly, even can be without surfactant.System only needs filter operation just can realize separating, and has both practiced thrift cost, simplifies the breakdown of emulsion lock out operation again; (2) stability is strong.The stable emulsion of conventional surfactants molecule is thermodynamic unstable system.Surfactant granules can form layer protecting film in oil/water termination, so the Pickering emulsion has superstability; And the Pickering emulsion is difficult for receiving the influence of factors such as system pH, salinity, temperature and oil phase composition.Therefore the Pickering emulsion is expected to embody the advantage of emulsion system, can solves separation, the recovery difficult problem of conventional emulsions in organic synthesis again.
Summary of the invention
The objective of the invention is to adopt nanometer Fe with amphipathic supported palladium in order to solve separation, the recovery difficult problem of conventional emulsions in organic synthesis
3O
4Particle is that solid particle comes stable emulsion, and is applied in the organic synthesis.Particles with superparamagnetism does not have magnetic when no external magnetic field; When externally-applied magnetic field is arranged, show stronger magnetic, the therefore general externally-applied magnetic field that only needs magnet to provide just can be with all magnetic nano-particles absorption, and the separation that make things convenient for catalyst is used with reclaiming again.The present invention has avoided removal surfactant process loaded down with trivial details in the conventional emulsions, also avoids adopting filter type to reclaim the nano particle process, has therefore simplified breakdown of emulsion and has separated and reclaim operations such as catalyst.
Scheme of the present invention is earlier through alkyl carboxylic acid and salt pair superparamagnetism Fe thereof
3O
4Nano particle surface modifying makes particle surface become amphipathic from strongly hydrophilic.Superparamagnetism Fe wherein
3O
4The nano particle average grain diameter is chosen in the particle of 20nm-500nm, and the molecular formula of alkyl carboxylic acid and salt thereof is following:
R-COOX
R is the straight or branched alkyl of 4 to 12 carbon atoms in the molecular formula of alkyl carboxylic acid and salt thereof; X is alkyl carboxylic acid and salt form thereof, and promptly X is H, sodium or potassium.Specifically can be selected from the following material one or more: n-pentyl acid, two amyl groups acid, n-hexyl acid, two hexyls acid; N-octyl acid, two octyl group acid, pelargonic acid, two n-nonanoic acids; N-capric acid, two capric acid, positive dodecoic acid, two dodecoic acid, n-hexyl acid sodium; N-octyl acid sodium, positive sodium laurate, n-hexyl acid potassium.
Through the amphiphilic magnetic Nano Fe after the modification
3O
4Particle immerses Na
2PdCl
4In the aqueous solution, with hydrogen, NaBH
4, one or more reducing agents reduction palladiums such as ascorbic acid, obtain the amphiphilic magnetic Nano Fe of supported palladium
3O
4Particle.
With the non-polar solven is oil phase, specifically can be selected from the following material one or more: toluene, n-hexane, normal heptane.Amphiphilic magnetic Nano Fe with supported palladium
3O
4Particle is put into oil/water two-phase system, makes the Pickering emulsion, and the type of emulsion is following a kind of: water-in-oil type (W/O), oil-in-water type (O/W), profit co-continuous phase (bicontinuous).
The present invention is carried the palladium nanometer Fe with amphiphilic magnetic
3O
4The emulsion applications that particle constitutes is in the Suzuki of bromobenzene and phenyl boric acid reaction, and reaction finishes the back and uses the magnet attracts nanometer Fe
3O
4Particle, the automatic breakdown of emulsion layering of emulsion is collected oil phase and is obtained product.The nanometer Fe that reclaims
3O
4Particle can make the Pickering emulsion again.The present invention is expected to solve a separation of emulsions difficult problem, and it is multi-field to be applied in organic synthesis, extraction, agricultural chemicals etc.
Advantage of the present invention is:
(1) the present invention is carried the palladium nanometer Fe with amphiphilic magnetic
3O
4The emulsion applications that particle constitutes is in the Suzuki of bromobenzene and phenyl boric acid reaction, and reaction finishes the back and separates nanometer Fe through magnet
3O
4Particle, removal surfactant process loaded down with trivial details in the conventional emulsions has been avoided in emulsion automatic breakdown of emulsion layering, also avoids adopting filter type to reclaim the nano particle process, has therefore simplified breakdown of emulsion and has separated and reclaim operations such as catalyst.
(2) the amphiphilic magnetic of the present invention's preparation is carried the palladium nanometer Fe
3O
4Particle plays the emulsifying agent effect, can stablize the Pickering emulsion.
(3) the amphiphilic magnetic of the present invention's preparation is carried the palladium nanometer Fe
3O
4Particle also plays catalyst action, can efficient catalytic Suzuki reaction in the Pickering emulsion.
Description of drawings
Fig. 1 is that the specific embodiment 1 synthetic amphiphilic magnetic is carried the palladium nanometer Fe
3O
4The transmission electron microscope picture of particle (TEM).
The specific embodiment
Through specific embodiment the present invention is done further description below, but the present invention should not only limit to these embodiment.Superparamagnetism Fe
3O
4Nano particle and alkyl carboxylic acid and salt thereof are available from Sigma-Aldrich company, and other reagent are available from Shanghai traditional Chinese medicines reagent group.
Embodiment 1
This embodiment is according to following steps: with magnetic Nano Fe
3O
4Particle is placed in the deionized water, and concentration of solid particles is 5-50g/L, and regulator solution pH to 4-6 stirs adding n-octyl acid down, and the consumption of n-octyl acid is Fe
3O
4The 10%-50% of particle reacts regulator solution pH to 7 after 30-60 minute, and magnet separates Fe
3O
4With washing with alcohol 2-3 time, obtain amphipathic magnetic Nano Fe after the drying behind the particle
3O
4Particle; This particle is put into the Na that concentration is 3-10mmol/L
2PdCl
4In the aqueous solution, control Fe
3O
4The mass ratio 1-10% of particle and palladium stirs down and feeds hydrogen, finishes the back and separates Fe with magnet
3O
4Particle obtains amphiphilic and carries palladium magnetic Nano Fe
3O
4Particle, accompanying drawing 1 are the TEM figure of this particle.
Get the 0.1-1.5g amphiphilic and carry palladium magnetic Nano Fe
3O
4Particle joins in 10mL toluene (toluene and water volume ratio 1: the 1) solution, at 5000 rev/mins of following emulsification 3-10 minutes, makes oil-in-water type (O/W) Pickering emulsion with the high-shear emulsifying agent.Solubilising 10mmol bromobenzene in the Pickering emulsion, 10mmol phenyl boric acid and 15mmolNaOH reacted 2 hours down at 80 ℃, and reaction finishes the back and separates Fe with magnet
3O
4Particle, emulsion are divided into profit two phases automatically, in oil phase, collect product, yield 90%.Carry the amphipathic magnetic Nano Fe of palladium
3O
4Particle is used deionized water, reuses after the washing with alcohol.
Embodiment 2
This embodiment prepares amphiphilic and carries palladium magnetic Nano Fe
3O
4Particle is got 0.1-1.5g and is carried the amphipathic magnetic Nano Fe of palladium with embodiment 1
3O
4Particle joins in 10mL normal heptane/water (normal heptane and water volume ratio 1: 1) solution, at 5000 rev/mins of following emulsification 3-10 minutes, makes water-in-oil type (W/O) Pickering emulsion with the high-shear emulsifying agent.Solubilising 10mmol bromobenzene in the Pickering emulsion, 10mmol phenyl boric acid and 15mmolNaOH reacted 2 hours down at 80 ℃, and reaction finishes the back and separates Fe with magnet
3O
4Particle, emulsion are divided into profit two phases automatically, in oil phase, collect product, yield 82%.Carry the amphipathic magnetic Nano Fe of palladium
3O
4Particle is used deionized water, reuses after the washing with alcohol.
Embodiment 3
This embodiment is according to following steps: with magnetic Nano Fe
3O
4Particle is placed in the deionized water, and concentration of solid particles is 5-50g/L, and regulator solution pH to 4-6 stirs adding n-hexyl acid down, and the consumption of n-hexyl acid is Fe
3O
4The 10%-50% of particle reacts regulator solution pH to 7 after 30-60 minute, and magnet separates Fe
3O
4With washing with alcohol 2-3 time, obtain amphipathic magnetic Nano Fe after the drying behind the particle
3O
4Particle; This particle is put into the Na that concentration is 3-10mmol/L
2PdCl
4In the aqueous solution, control Fe
3O
4The mass ratio 1-10% of particle and palladium stirs the NaBH that adds 2-10mmol/L down
4Aqueous solution 10mL finishes the back and separates Fe with magnet
3O
4Particle obtains amphiphilic and carries palladium magnetic Nano Fe
3O
4Particle.
This embodiment prepares Pickering emulsion and catalysis Suzuki reactions step with embodiment 1, Suzuki reaction yield 86%.
Embodiment 4
This embodiment is according to following steps: with magnetic Nano Fe
3O
4Particle is placed in the deionized water, and concentration of solid particles is 5-50g/L, and regulator solution pH to 4-6 stirs the positive sodium laurate of adding down, and the consumption of positive sodium laurate is Fe
3O
4The 10%-50% of particle reacts regulator solution pH to 7 after 30-60 minute, and magnet separates Fe
3O
4With washing with alcohol 2-3 time, obtain amphipathic magnetic Nano Fe after the drying behind the particle
3O
4Particle; This particle is put into the Na that concentration is 3-10mmol/L
2PdCl
4In the aqueous solution, control Fe
3O
4The mass ratio 1-10% of particle and palladium stirs the NaBH that adds 2-10mmol/L down
4Aqueous solution 10mL finishes the back and separates Fe with magnet
3O
4Particle obtains amphiphilic and carries palladium magnetic Nano Fe
3O
4Particle.
This embodiment prepares Pickering emulsion and catalysis Suzuki reactions step with embodiment 1, Suzuki reaction yield 88%.
Claims (5)
1. amphiphilic magnetic is carried the preparation and the application of palladium nano-sized iron oxide and emulsion thereof, it is characterized in that carrying out according to the following steps: one, earlier through alkyl carboxylic acid and salt pair superparamagnetism Fe thereof
3O
4Nano particle surface modifying makes particle surface become amphipathic from strongly hydrophilic; With amphiphilic magnetic Nano Fe
3O
4Particle immerses Na
2PdCl
4In the aqueous solution, with hydrogen, NaBH
4, one or more reducing agents reduction palladiums such as ascorbic acid, obtain the amphiphilic magnetic Nano Fe of supported palladium
3O
4Particle; Amphiphilic magnetic Nano Fe with supported palladium
3O
4Particle is put into oil/water two-phase system, makes the Pickering emulsion; In the Suzuki of bromobenzene and phenyl boric acid reaction, reaction finishes the back with magnet attracts magnetic Nano Fe with this emulsion applications
3O
4Particle, the automatic breakdown of emulsion layering of emulsion is collected oil phase and is obtained product.
2. according to claim 1 is the straight or branched alkyl of 4 to 12 carbon atoms with alkyl R among alkyl carboxylic acid and the salt RCOOX thereof; X is H, sodium or potassium, and the consumption of alkyl carboxylic acid and salt thereof is Fe
3O
4The 10%-50% of particle, the amphiphilic magnetic Nano Fe that makes
3O
4Particle is put into the Na that concentration is 3-10mmol/L
2PdCl
4In the aqueous solution, control Fe
3O
4The mass ratio 1-10% of particle and palladium stirs adding reducing agent hydrogen down, NaBH
4Or ascorbic acid, finish the back and separate Fe with magnet
3O
4Particle obtains amphiphilic magnetic and carries the palladium nanometer Fe
3O
4Particle.
3. according to claim 1,2 is said, and 0.1-1.5g amphiphilic magnetic is carried the palladium nanometer Fe
3O
4Particle joins in 10mL oil/water (oil and water volume ratio 1: 1) solution, at 5000 rev/mins of following emulsification 3-10 minutes, makes oil-in-water type with the high-shear emulsifying agent, water-in-oil type and profit doubly-linked ideotype Pickering emulsion, and oil is toluene or normal heptane.
4. according to Suzuki reaction in the said Pickering emulsion of claim 1, be solubilising 10mmol bromobenzene in the Pickering emulsion, 10mmol phenyl boric acid and 15mmolNaOH reacted 2 hours down at 80 ℃.
5. according to after the Suzuki reaction finishes in claim 1 and the 5 said Pickering emulsions, external magnetic field is provided, holds magnetic Nano Fe with magnet
3O
4Particle, the automatic breakdown of emulsion of emulsion is layered as profit two phases, collect oil phase and obtain product, and recovery amphiphilic magnetic is carried the palladium nanometer Fe
3O
4Particle.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525061A (en) * | 2014-11-07 | 2015-04-22 | 陕西师范大学 | Magnetic-responsive Pickering emulsion based on ionic liquid and amphiphilic Fe3O4 nano-particles |
| CN110613960A (en) * | 2019-09-17 | 2019-12-27 | 杭州电子科技大学 | Preparation method and application of magnetic demulsifier capable of simultaneously realizing efficient oil-water separation of O/W and W/O emulsions |
| CN111203230A (en) * | 2020-01-23 | 2020-05-29 | 陕西师范大学 | Pd/FeOOH @ RGO Pickering emulsion and application thereof in catalyzing carbon-carbon coupling reaction |
| CN114653398A (en) * | 2022-03-21 | 2022-06-24 | 中节能工程技术研究院有限公司 | Pickering emulsion acetalization reaction of surface-modified magnetic nanoparticles |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104525061A (en) * | 2014-11-07 | 2015-04-22 | 陕西师范大学 | Magnetic-responsive Pickering emulsion based on ionic liquid and amphiphilic Fe3O4 nano-particles |
| CN104525061B (en) * | 2014-11-07 | 2016-08-24 | 陕西师范大学 | Based on ionic liquid and the magnetic responsiveness pickering emulsion of amphipathic Fe3O4 nano particle |
| CN110613960A (en) * | 2019-09-17 | 2019-12-27 | 杭州电子科技大学 | Preparation method and application of magnetic demulsifier capable of simultaneously realizing efficient oil-water separation of O/W and W/O emulsions |
| CN110613960B (en) * | 2019-09-17 | 2022-07-26 | 杭州电子科技大学 | Preparation method and application of magnetic demulsifier capable of simultaneously realizing efficient oil-water separation of O/W and W/O emulsions |
| CN111203230A (en) * | 2020-01-23 | 2020-05-29 | 陕西师范大学 | Pd/FeOOH @ RGO Pickering emulsion and application thereof in catalyzing carbon-carbon coupling reaction |
| CN111203230B (en) * | 2020-01-23 | 2022-08-23 | 陕西师范大学 | Pd/FeOOH @ RGO Pickering emulsion and application thereof in catalyzing carbon-carbon coupling reaction |
| CN114653398A (en) * | 2022-03-21 | 2022-06-24 | 中节能工程技术研究院有限公司 | Pickering emulsion acetalization reaction of surface-modified magnetic nanoparticles |
| CN114653398B (en) * | 2022-03-21 | 2024-02-13 | 中节能工程技术研究院有限公司 | Pickering emulsion acetal reaction of surface-modified magnetic nanoparticles |
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Application publication date: 20120704 |