CN105879881A - Preparation method of PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and application thereof in HECK reaction - Google Patents
Preparation method of PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and application thereof in HECK reaction Download PDFInfo
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- CN105879881A CN105879881A CN201610284060.XA CN201610284060A CN105879881A CN 105879881 A CN105879881 A CN 105879881A CN 201610284060 A CN201610284060 A CN 201610284060A CN 105879881 A CN105879881 A CN 105879881A
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000011943 nanocatalyst Substances 0.000 title claims abstract description 22
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 20
- 238000007341 Heck reaction Methods 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- 229910018879 Pt—Pd Inorganic materials 0.000 claims abstract description 35
- 239000002105 nanoparticle Substances 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 15
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000004140 cleaning Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000000460 chlorine Substances 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229940069328 povidone Drugs 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 3
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 claims 2
- 229940074391 gallic acid Drugs 0.000 claims 1
- 235000004515 gallic acid Nutrition 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract 2
- 238000001035 drying Methods 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 10
- YCOXTKKNXUZSKD-UHFFFAOYSA-N as-o-xylenol Natural products CC1=CC=C(O)C=C1C YCOXTKKNXUZSKD-UHFFFAOYSA-N 0.000 description 8
- SNHMUERNLJLMHN-UHFFFAOYSA-N iodobenzene Chemical compound IC1=CC=CC=C1 SNHMUERNLJLMHN-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 239000008187 granular material Substances 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 6
- 239000004202 carbamide Substances 0.000 description 5
- 235000013877 carbamide Nutrition 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000010485 C−C bond formation reaction Methods 0.000 description 1
- GSNUFIFRDBKVIE-UHFFFAOYSA-N DMF Natural products CC1=CC=C(C)O1 GSNUFIFRDBKVIE-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002896 organic halogen compounds Chemical class 0.000 description 1
- RPGWZZNNEUHDAQ-UHFFFAOYSA-N phenylphosphine Chemical compound PC1=CC=CC=C1 RPGWZZNNEUHDAQ-UHFFFAOYSA-N 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8906—Iron and noble metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/86—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon
- C07C2/861—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation between a hydrocarbon and a non-hydrocarbon the non-hydrocarbon contains only halogen as hetero-atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
- C07C2523/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper
- C07C2523/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of the iron group metals or copper combined with noble metals
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a preparation method of a PtPd/Fe3O4 (platinum-palladium/ferroferric oxide) nanocatalyst and an application thereof in HECK reaction, and belongs to the technical field of nanocatalysts. The preparation method is characterized in that a catalyst carrier is magnetic Fe3O4 nanoparticles, and the average particle size is 18nm; the active components are Pt and Pd nanoparticles, and the average particle sizes are respectively 12nm and 10nm; the average mass percentages of Pt and Pd in the catalyst are respectively about 0.39% and 0.75%; the balance is Fe3O4 nanoparticles. The preparation method comprises the following steps of oxidizing and reducing FeCl3 6H2O into the Fe3O4 nanoparticles by a hydrothermal method; cleaning, and metering volume for use; using polymers of polyvinylpyrrolidone and the like as stabilizers, and reducing a certain ratio of chloroplatinic acid and chloropalladic acid by a reducing agent, so as to prepare a Pt-Pd sol; adding the treated Fe3O4 nanoparticles into the Pt-Pd sol, stirring, filtering, and drying, so as to finally prepare the Pt-Pd magnetic nanometer-supported catalyst. The catalyst prepared by the preparation method has higher catalytic activity in the Heck reaction.
Description
Technical field
The present invention relates to PtPd/Fe3O4The preparation of nanocatalyst and the application in HECK reacts thereof, belong to nanocatalyst
Technical field.
Background technology
Heck reaction is the coupling reaction that organohalogen compounds and alkene generate substituted olefine under highly basic and palladium chtalyst, is transition metal
Being catalyzed most important is also one of reaction applying the most promising C-C bond formation, at organic intermediate, organic functional material, medicine
Thing, natural product etc. is widely used in synthesizing.Then the preparation of precious metals palladium catalyst causes the concern of more people.
Some scientists, by using coordination compound to prepare palladium catalyst, wherein belong to Phenylphosphine coordination compound best results, the most significantly
Improve catalytic performance but also make the response time be substantially reduced, but this part brings harm to environment, do not meet green ring
The requirement protected.Along with the development of nanotechnology, Technique of Nano Pd has been applied in Heck reaction by more people.Because of nano material specific surface
Long-pending increasing considerably is readily available the advantage such as avtive spot of nano grain surface with the reactant in solution, and Technique of Nano Pd is at Heck
Reaction shows splendid catalysis activity.But Technique of Nano Pd the most easily forms palladium black and loses activity, and causes
Cyclic utilization rate is low, and practical value is the highest.Again sight line is transferred to supported catalyst to solve problem above researchers
Field, the use of heterogeneous catalysis makes Technique of Nano Pd cycle utilization rate significantly promote, but such nano Pd catalyst is difficult
To separate, economy is bad.
Summary of the invention
In order to solve the problems referred to above, one clean environment firendly of the present invention and easily catalyst, by loading platinum-palladium nanoparticle
On magnetic carrier, the most effectively prevent reunion, and more effectively the catalyst of preparation is separated and recovered, and carry
The catalysis activity of high catalyst and utilization rate.The present invention by magnetic being incorporated in the middle of the preparation of Nano type loaded palladium catalyst,
Being easy to be separated by Magneto separate Technique of Nano Pd, the present invention is mixed with noble metal also by during preparing Technique of Nano Pd in addition
Platinum prepares magnetic Nano Pd-Pt catalyst, improves the catalysis activity of Technique of Nano Pd further and reduces at Heck to a certain extent
Harsh conditions during reaction.
First purpose of the present invention is to provide the bimetallic PtPd/Fe of a kind of magnetic loading3O4Nanocatalyst, described catalyst
Carrier be Fe3O4Nano-particle, active component is Pt and Pd nanoparticle.
In one embodiment of the invention, described PtPd/Fe3O4In nanocatalyst, in catalyst, Pt's and Pd is average
Mass fraction respectively may be about 0.39% and 0.75%, and remaining is Fe3O4Nano-particle.
In one embodiment of the invention, described Fe3O4The mean diameter of nano-particle is 18 nanometers, active component Pt
It is respectively 12 nanometers and 10 nanometers with the mean diameter of Pd.
Second object of the present invention is to provide a kind of described bimetallic PtPd/Fe3O4The preparation method of nanocatalyst.
Described preparation method is as follows: (1) prepares Fe3O4Nano-particle；(2) preparation of Pt-Pd colloidal sol: exist at stabilizer
Under the conditions of, obtain Pt-Pd colloidal sol with the reducing agent a certain proportion of chloroplatinic acid of reduction and chlorine palladium processed with acid；(3) by the Fe of step (1)3O4
Nano-particle joins in Pt-Pd colloidal sol, stirs, filters, dries, and finally prepares the bimetallic PtPd/Fe of magnetic loading3O4
Nanocatalyst.
In one embodiment of the invention, the stabilizer of described step (2) can be polyvinylpyrrolidone, Polyethylene Glycol,
Ionic liquid, lignin etc..Please supplement as far as possible many can stabilizer, to ensure relatively large protection domain.
In one embodiment of the invention, the reducing agent of described step (2) can be sodium borohydride, metagallic acid, first
Alcohol, hydrogen, propylene glycol etc..Can be supplemented with as far as possible many can reducing agent.
In one embodiment of the invention, it is also possible to be applied in the coupling reactions such as Suzuki, Sonogashira, Stille.
In one embodiment of the invention, described step (1) is specifically: take FeCl3·6H2O, carbamide, polyvinyl pyrrole
Alkanone, is subsequently added 1,2-PD, stirs, mixes to obtaining clear solution, transfers in reactor, after sealing
14-18h is reacted at 180-200 DEG C；After reaction terminates, it is cooled to room temperature, product deionized water, ethanol is repeatedly washed,
Black precipitate granule after washing is scattered in ethanol and obtains Fe3O4Nanomagnets granule.
In one embodiment of the invention, described preparation method is specific as follows:
(1) preparation of carrier and pretreatment thereof
By hydro-thermal method by FeCl3·6H2The Fe that O oxidoreduction becomes3O4Nano-particle, uses deionized water, dehydrated alcohol to carry out
Clean, until supernatant liquid is transparent, then used dehydrated alcohol constant volume, standby；By ferromagnet to Fe in cleaning process3O4
Nano-particle separates；
(2) preparation of Pt-Pd colloidal sol
A small amount of aqueous povidone solution is added, after stirring in a certain proportion of chloroplatinic acid and chlorine palladium acid mixed liquor
Drip appropriate reductant solution, continue stirring certain time, prepare and stablize Pt-Pd colloidal sol；
(3) preparation of Pt-Pd magnetic Nano supported catalyst
Accurately measure a certain amount of Fe3O4Nano-particle, in above-mentioned prepared Pt-Pd colloidal sol, stands a period of time after stirring, makes
It is isolated with ferromagnet, dries to obtain Pt-Pd magnetic Nano supported catalyst.
In one embodiment of the invention, preparation Fe in described step (1)3O4Reducing agent used by nano-particle be methanol,
1,2-PD, metagallic acid etc., optimal with 1,2-PD.
In one embodiment of the invention, described method is specifically:
(1) preparation of carrier and pretreatment thereof
FeCl according to every 0.2125g3·6H2O, weighs the polyvinylpyrrolidone of the carbamide of 0.1432g, 0.1663g, subsequently
Add the 1,2-PD of 8.5ml, stir, mix to obtaining clear solution, transfer in reactor, at 190 DEG C after sealing
Lower reaction 16h；Reaction terminate after, be cooled to room temperature, product deionized water, ethanol repeatedly washed, will washing after black
Color precipitation granule is scattered in ethanol and obtains Fe3O4Nanomagnets material；
(2) preparation of Pt-Pd colloidal sol
Accurately weigh the polyvinylpyrrolidone of 0.0789g, measure 3.86 × 10-3The chloroplatinic acid aqueous solution 1.15ml of mol/L mol/L,
1.13×10-3The chlorine palladium aqueous acid 4.35ml of mol/L mol/L, stirring, until being completely dissolved, is subsequently added 0.0373g hydroboration
Sodium, prepares Pt-Pd colloidal sol；
(3) preparation of Pt-Pd magnetic Nano supported catalyst
By the Fe of preparation in (1)3O4Nano-particle is in above-mentioned prepared Pt-Pd colloidal sol, and mechanical agitation stands 1 after 8 hours little
Time, use ferromagnet to be isolated, dry to obtain Pt-Pd magnetic Nano supported catalyst.
Third object of the present invention is to provide the application of described Pt-Pd magnetic Nano supported catalyst.
In one embodiment of the invention, described application is to react for Heck.
In one embodiment of the invention, described application, specifically comprise the following steps that
In there-necked flask, add iodobenzene, styrene, DMF, add a certain amount of Pt-Pd magnetic Nano supported catalyst,
After stirring, put in water-bath and react；After reaction terminates, being separated in product by catalyst, catalyst remains circulation
Use.
Beneficial effects of the present invention:
(1) PtPd/Fe that the present invention prepares3O4Nanocatalyst is a kind of tool effectively and easily reclaimed in Heck reacts
Having the catalyst of excellent catalytic performance, the conversion ratio of iodobenzene is about 100%, after catalyst recycles 7 times, conversion ratio still can be protected
Hold more than 91%.
(2) catalyst of the present invention, use magnetic-particle is carrier, and it is convenient to recycle, and does not results in environmental pollution.
(3) catalyst of the present invention, preparation technology is simply, easily operate.
Accompanying drawing explanation
The transmission electron microscope photo of Fig. 1: Pt-Pd magnetic Nano supported catalyst.
Detailed description of the invention
The following is the example of the present invention, but be not limited to following method and consumption, any process similarly, method, change
It it is all protection scope of the present invention.
Embodiment 1:PtPd/Fe3O4The preparation of nanocatalyst
(1) preparation of carrier and pretreatment thereof
In 50ml beaker, accurately weigh the FeCl of 0.2125g3·6H2The carbamide of O, 0.1432g, the polyethylene of 0.1663g
Ketopyrrolidine, is subsequently added the 1,2-PD of 8.5ml, and mixture stirs on magnetic stirring apparatus until solution mix homogeneously obtains
Transfer to after yellow transparent solution in reactor, at 190 DEG C, after sealing, react 16h.After reaction terminates, it is cooled to room temperature,
Product is transferred in wide mouth glass bottle, repeatedly wash with deionized water, ethanol, and pour out the supernatant in wide mouthed bottle with Magneto separate
Liquid.The ethanol that black precipitate granule after washing is scattered in 10mL is obtained Fe3O4Nanomagnets material.
(2) preparation of Pt-Pd colloidal sol
In 50ml beaker, accurately weigh the polyvinylpyrrolidone of 0.0789g, measure 3.86 × 10-3The chloroplatinic acid water of mol/L
Solution 1.15ml, 1.13 × 10-3The chlorine palladium aqueous acid 4.35ml of mol/L, mixture stirs on magnetic stirring apparatus, until complete
CL.It is subsequently added 0.0373g sodium borohydride, prepares Pt-Pd colloidal sol.
(3) preparation of Pt-Pd magnetic Nano supported catalyst
By the Fe of preparation in (1)3O4Nano-particle is in above-mentioned prepared Pt-Pd colloidal sol, and mechanical agitation stands 1 after 8 hours little
Time, use ferromagnet to be isolated, dry to obtain Pt-Pd magnetic Nano supported catalyst.
Embodiment 2:PtPd/Fe3O4The application of nanocatalyst
The application in Heck reacts of the Pt-Pd magnetic Nano supported catalyst
The styrene of DMF, 0.20mL of the iodobenzene of 0.16mL, 3mL, above-mentioned system is added in 100ml there-necked flask
Obtain Pt-Pd magnetic Nano supported catalyst, after stirring, add the K of 0.2764g2CO3, electric stirring 9h at 90 DEG C.
After reaction terminates, being separated in product by catalyst, catalyst remains to recycle, and result is as shown in table 1.As shown in Table 1,
PtPd/Fe3O4Nanocatalyst is about 100% to the conversion ratio of iodobenzene, catalyst recycle 4 times after conversion ratio the most significantly under
Fall.
Wherein conversion ratio is by reactant iodobenzene gas phase calculated by peak area: iodobenzene initial peak area S1, reacted iodobenzene peak area
S2, then conversion ratio is: (S1-S2)/S1。
Table 1 PtPd/Fe3O4The nanocatalyst conversion ratio to iodobenzene
| Cycle-index | 1 | 2 | 3 | 4 |
| Conversion ratio (%) | 99.98 | 91.26 | 75.26 | 56.62 |
Additionally, inventor finds, the present invention's: the catalytic effect of Pt-Pd magnetic Nano supported catalyst is than independent Pd nanometer
Nanocatalyst after grain and Pd load to be got well, and corresponding data are as shown in table 2.
The catalytic effect of the different nanocatalyst of table 2
Additionally, the present invention uses hydro-thermal method to prepare Fe3O4Granule, the Fe prepared3O4Granule does not has unnecessary Fe2+And Fe3+'s
Interference；And use 1,2-PD as reducing agent, this reducing agent environmental protection and there is amphiphilic (hydrophilic, oleophylic) property；In addition
Have employed the alkalescence relatively low carbamide of ratio, in preparation, carbamide release ratio is relatively slow, the nanometer Fe obtained3O4Granule ratio is more uniform.
Although the present invention is open the most as above with preferred embodiment, but it is not limited to the present invention, any person skilled in the art,
Without departing from the spirit and scope of the present invention, all can do various changes and modification, therefore protection scope of the present invention should be with
What claims were defined is as the criterion.
Claims (9)
1. the bimetallic PtPd/Fe of a magnetic loading3O4Nanocatalyst, it is characterised in that described PtPd/Fe3O4Nanometer is urged
The carrier of agent is Fe3O4Nano-particle, active component is Pt and Pd nanoparticle.
PtPd/Fe the most according to claim 13O4Nanocatalyst, it is characterised in that described PtPd/Fe3O4Nanometer is urged
In agent, the average mass fraction of Pt and Pd respectively may be about 0.39% and 0.75%, and remaining is Fe3O4Nano-particle.
PtPd/Fe the most according to claim 13O4Nanocatalyst, it is characterised in that described Fe3O4Nano-particle
Mean diameter is that the mean diameter of 18 nanometers, active component Pt and Pd is respectively 12 nanometers and 10 nanometers.
4. bimetallic PtPd/Fe described in a claim 13O4The preparation method of nanocatalyst, it is characterised in that described system
Preparation Method is as follows: (1) prepares Fe3O4Nano-particle；(2) preparation of Pt-Pd colloidal sol: under conditions of stabilizer exists, uses
The reducing agent a certain proportion of chloroplatinic acid of reduction and chlorine palladium processed with acid obtain Pt-Pd colloidal sol；(3) by the Fe of step (1)3O4Nano-particle
Join in Pt-Pd colloidal sol, stir, filter, dry, finally prepare the bimetallic PtPd/Fe of magnetic loading3O4Nano-catalytic
Agent.
Method the most according to claim 4, it is characterised in that the stabilizer of described step (2) is polyvinylpyrrolidine
Ketone, Polyethylene Glycol, ionic liquid.
Method the most according to claim 4, it is characterised in that the reducing agent of described step (2) is sodium borohydride, Jiao
Gallic acid.
Method the most according to claim 4, it is characterised in that described preparation method is specific as follows:
(1) preparation of carrier and pretreatment thereof
By hydro-thermal method by FeCl3·6H2The Fe that O oxidoreduction becomes3O4Nano-particle, uses deionized water, dehydrated alcohol to carry out
Clean, until supernatant liquid is transparent, then used dehydrated alcohol constant volume, standby；By ferromagnet to Fe in cleaning process3O4
Nano-particle separates；
(2) preparation of Pt-Pd colloidal sol
A small amount of aqueous povidone solution is added, after stirring in a certain proportion of chloroplatinic acid and chlorine palladium acid mixed liquor
Drip appropriate reductant solution, continue stirring certain time, prepare and stablize Pt-Pd colloidal sol；
(3) preparation of Pt-Pd magnetic Nano supported catalyst
Accurately measure a certain amount of Fe3O4Nano-particle, in above-mentioned prepared Pt-Pd colloidal sol, stands a period of time after stirring, makes
It is isolated with ferromagnet, dries to obtain Pt-Pd magnetic Nano supported catalyst.
Method the most according to claim 7, it is characterised in that preparation Fe in described step (1)3O4Nano-particle institute
Reducing agent be methanol, 1,2-PD or metagallic acid.
9. the arbitrary described PtPd/Fe of claim 1-33O4Nanocatalyst application in Heck reacts.
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