CN106423290A - Preparation method of magnetic nanoparticle supported precious metal catalyst - Google Patents
Preparation method of magnetic nanoparticle supported precious metal catalyst Download PDFInfo
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- CN106423290A CN106423290A CN201610868444.6A CN201610868444A CN106423290A CN 106423290 A CN106423290 A CN 106423290A CN 201610868444 A CN201610868444 A CN 201610868444A CN 106423290 A CN106423290 A CN 106423290A
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- precious metal
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- metal catalyst
- catalyst
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- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 62
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 239000010970 precious metal Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 22
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 17
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 239000000725 suspension Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 229910052763 palladium Inorganic materials 0.000 claims description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- AJVBXLXLODZUME-UHFFFAOYSA-N ethenyl(diphenyl)phosphane Chemical compound C=1C=CC=CC=1P(C=C)C1=CC=CC=C1 AJVBXLXLODZUME-UHFFFAOYSA-N 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- 239000007822 coupling agent Substances 0.000 claims description 4
- 229960004756 ethanol Drugs 0.000 claims description 4
- 230000005415 magnetization Effects 0.000 claims description 4
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 229910003771 Gold(I) chloride Inorganic materials 0.000 claims description 3
- KGXCHACLIFYNOP-VOTSOKGWSA-N [(e)-2-phenylethenyl]phosphane Chemical compound P\C=C\C1=CC=CC=C1 KGXCHACLIFYNOP-VOTSOKGWSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 125000006267 biphenyl group Chemical group 0.000 claims description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 2
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- GQWAOUOHRMHSHL-UHFFFAOYSA-N 4-ethenyl-n,n-dimethylaniline Chemical compound CN(C)C1=CC=C(C=C)C=C1 GQWAOUOHRMHSHL-UHFFFAOYSA-N 0.000 claims description 2
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 6
- 239000003446 ligand Substances 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 238000012650 click reaction Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 2
- 150000003573 thiols Chemical class 0.000 abstract 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 238000007259 addition reaction Methods 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000009835 boiling Methods 0.000 description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- -1 salt Palladous chloride Chemical class 0.000 description 4
- 125000003396 thiol group Chemical group [H]S* 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 229910052703 rhodium Inorganic materials 0.000 description 3
- 239000010948 rhodium Substances 0.000 description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000002539 nanocarrier Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/10—Complexes comprising metals of Group I (IA or IB) as the central metal
- B01J2531/18—Gold
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- 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
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/828—Platinum
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The preparation method of a magnetic nanoparticle supported precious metal catalyst comprises the following steps: grafting the silane coupling agent containing thiol to the surface of magnetic ferriferrous oxide nanoparticles, using the thiols on the surface to conduct the click reaction with vinyl organic ligand compound to form magnetic nanoparticle supporting complex, complexing with precious metal salt to acquire the magnetic nanoparticle supported precious metal catalyst. According to the method, the click chemical reaction is used to combine the magnetic nanoparticle surface and the vinyl organic ligand compound by covalent bonds, and solidly bind the ligand to the magnetic nanoparticle. At the same time the method can guarantee that the ligand is far from the supporter, and can coordinate with the precious metal in a better way to achieve the effect of homogeneous catalysis. Moreover under the external magnetic field, the catalyst is easy to be magnetized, and has the advantage of fast separation, fast recycling and reusable features. The method can lower the production cost, and enhance the production efficiency. The catalyst prepared by the method can be used in the coupling reaction and addition reaction of metal catalytic reaction.
Description
Technical field
The present invention relates to a kind of method that magnetic nano-particle supported precious metal catalyst is prepared based on click chemistry method, belong to
Catalyst technical field.
Background technology
Precious metal catalyst reaction is one of organic chemical synthesis method important means, but these noble metal catalysts exist
It is difficult to from reaction system classification and reclaims, increase reaction cost, or even metal organic catalysis such as palladium metal can palladium in course of reaction
Black, not only reduce the activity of catalyst, but also product can be polluted, be very restricted in actual applications.Cause
This, increasing researcher, by solving these problems to the research of loaded catalyst, makes every effort to both keep homogeneous
The high efficiency of catalyst, can solve the recycling of catalyst again, realize the targets such as the minimum consumption of noble metal.A lot of documents at present
Report different types of carrier such as high molecular polymer, molecular sieve, silica gel, activated carbon etc., be all applied to precious metal catalyst
The supported research of agent.But either adopt organic polymer carrier or inorganic carrier, its catalysis activity, stability and recovery
Reusability can need to improve further, and its range of application is fairly limited.In recent years, magnetic nano-particle is as catalyst carrier
Receive significant attention, its technological means is in magnetic Fe3O4Nanoparticle surface coats a thin layer silica gel, using the hydroxyl on surface
Connect various organic ligands, but it is low also to deposit bullion content, lead to usage amount to increase, and when recycling due to part
Insecure its activity is led to be gradually lowered.Therefore it provides the preparation method of supported precious metal catalyst, there is very strong theoretical meaning
Justice and using value.
Content of the invention
The purpose of the present invention is, in order to overcome the deficiencies in the prior art, provides one kind to prepare magnetic nano-particle load expensive
The method of metallic catalyst.
Technical program of the present invention lies in, drawn by carrying out the light between sulfydryl-vinyl on magnetic nano-particle surface
Send out click-reaction, vinyl organic ligand is grafted on magnetic nano-particle, with precious metal salt complexation.
A kind of method preparing magnetic nano-particle supported precious metal catalyst of the present invention comprises the following steps：
（1）2 ~ 4 weight portion nano ferriferrous oxides are scattered in 10 ~ 50 weight parts organic solvent, add 2 ~ 8 parts of weight portions to go
Ionized water, 4 ~ 10 weight portion dehydrated alcohol, 50 ~ 100 weight portion mercaptosilane coupling agents, regulation system pH value is 5 ~ 7,60 ~
6 ~ 8h is stirred, product is through filtering, washing, be dried to obtain the magnetic nano-particle that surface is sulfydryl at 80 DEG C；
（2）By step（1）3 ~ 5 weight portion surfaces of preparation are the magnetic nano-particle ultrasonic disperse of sulfydryl in 10 ~ 30 weight portions
Organic solvent, adds 10 ~ 100 parts by weight of ethylene base organic ligand compound and 0.01 ~ 0.05 weight portion light trigger, in ultraviolet
6 ~ 10h is reacted, after reaction terminates, suspension separates, washs, being dried to obtain magnetic nano-particle load through Magnet under light irradiation
Part product；
（3）By step（2）2 ~ 4 parts by weight of magnetic nanometer particle load parts of preparation are scattered in the anhydrous of 50 ~ 150 weight portions to be had
In machine solvent, add the precious metal salt of 0.02 ~ 0.05 weight portion, after adding backflow 12 ~ 48h in a nitrogen atmosphere, suspension
It is vacuum dried after Magnet separation, washing and obtain target product magnetic nano-particle supported precious metal catalyst again.
Its tenor of described catalyst is the 0.1 ~ 5.0% of catalyst total amount.
Described magnetic nano-particle supported precious metal catalyst has superparamagnetism at room temperature, and saturation magnetization is 10
~30.0emu/g.
Described mercaptosilane coupling agents are gamma-mercaptopropyltriethoxysilane or γ-mercaptopropyl trimethoxysilane.
Described organic solvent is one or more of toluene, dimethylbenzene, isopropanol, ethanol, methanol, acetone.
Described vinyl organic ligand is diphenyl to styryl phosphine, vinyldiphenylphosphine, 4- dimethylamino benzene
One of ethylene.
Described light trigger benzophenone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketone
One or more of.
Described precious metal salt is one of Palladous chloride., palladium, aurous chloride, chloroplatinic acid or rhodium chloride.
The beneficial effects of the present invention is, the magnetic Nano supported precious metal catalyst prepared by the present invention, its carrier selects
With magnetic nanoparticle, pass through to introduce sulfydryl on nano-carrier surface, by the strategy of " click chemistry " by nano-carrier and second
Alkenyl ligand is combined with chemical bond form so that load ligand compound is firm, and away from carrier, can effectively join with metal
Position, its carrier has higher specific surface area simultaneously, has excellent point of dispersion and mechanical performance, reaches the effect of homogeneous catalysis.
There is superparamagnetism at room temperature, be easily magnetized under additional the action of a magnetic field, after removing magnetic field, then magnetic disappears, it is easy to accomplish expensive
The sharp separation of metallic catalyst and the purpose that recycles it is adaptable to the coupling of precious metal catalyst and additive reaction, such
In reaction, supported catalyst can be reused many times, activity is basically unchanged, and is effectively reduced synthesis cost, it is to avoid noble metal
Run off.
Specific embodiment
Embodiment 1
The preparation method of magnetic nano-particle loaded palladium catalyst is as follows：
1. 2g nano ferriferrous oxide and 30g first are added in equipped with thermometer, agitator, the 250ml four-hole boiling flask of condensing tube
Benzene, after ultrasonic disperse 2h, adds 5g deionized water, 6g dehydrated alcohol, 60g γ-mercapto propyl-triethoxysilicane under stirring
Alkane, the pH value using acetic acid regulation system is 5, stirs 8h at 60 DEG C, and product is mercapto through filtering, washing, be dried to obtain surface
The magnetic nano-particle of base；
2. the 5g surface 1. prepared step is the magnetic nano-particle of sulfydryl and 30g toluene is added in 250ml four-hole boiling flask
Ultrasonic disperse 2h, adds 20g diphenyl to styryl phosphine and 0.02g light trigger benzophenone, under ultraviolet light
Reaction 10h, after reaction terminates, suspension separates, washs, being dried to obtain magnetic nano-particle load part product through Magnet；
3. the 4g magnetic nano-particle that 2. step is prepared is loaded part and 80g anhydrous propanone is added in 250ml four-hole boiling flask
Ultrasonic disperse 2h, adds 0.02g precious metal salt Palladous chloride., and after adding backflow 48h in a nitrogen atmosphere, suspension divides through Magnet
It is vacuum dried and obtains target product magnetic nano-particle loaded palladium catalyst after, washing.Its palladium content is 5.0%, saturation magnetic
Change intensity is 20emu/g.
Embodiment 2
The preparation method of magnetic nano-particle load platinum catalyst is as follows：
1. 4g nano ferriferrous oxide and 50g bis- are added in equipped with thermometer, agitator, the 250ml four-hole boiling flask of condensing tube
Toluene, after ultrasonic disperse 4h, adds 8g deionized water, 10g dehydrated alcohol, 100g γ-mercapto propyl group trimethoxy under stirring
Base silane, the pH value using acetic acid regulation system is 7, stirs 6h, product is through filtering, washing, be dried to obtain surface at 80 DEG C
Magnetic nano-particle for sulfydryl；
2. magnetic nano-particle and the 10g dimethylbenzene being sulfydryl by the 3g surface that 1. step is prepared, is added to 250ml four-hole boiling flask
Middle ultrasonic disperse 1h, adds 100g 4- dimethylaminostyrene and 0.05g light trigger 1- hydroxycyclohexylphenyl first
Ketone, reacts 6h, after reaction terminates, suspension separates, washs, is dried to obtain magnetic nano particle through Magnet under ultraviolet light
Son load part product；
3. the 2g magnetic nano-particle that 2. step is prepared is loaded part and 80g absolute methanol is added in 250ml four-hole boiling flask
Ultrasonic disperse 4h, adds 0.05g precious metal salt chloroplatinic acid, and after adding backflow 24h in a nitrogen atmosphere, suspension divides through Magnet
It is vacuum dried and obtains target product magnetic nano-particle load platinum catalyst after, washing.Its platinum content is 4.0%, saturation magnetic
Change intensity is 18.0emu/g.
Embodiment 3
The preparation method of magnetic nano-particle load gold catalyst is as follows：
1. 3g nano ferriferrous oxide and 40g first are added in equipped with thermometer, agitator, the 250ml four-hole boiling flask of condensing tube
Benzene, after ultrasonic disperse 2h, adds 6g deionized water, 8g dehydrated alcohol, 60g γ-mercapto propyl trimethoxy silicon under stirring
Alkane, the pH value using acetic acid regulation system is 6, stirs 8h at 70 DEG C, and product is mercapto through filtering, washing, be dried to obtain surface
The magnetic nano-particle of base；
2. the 5g surface 1. prepared step is the magnetic nano-particle of sulfydryl and 30g isopropanol is added to 250ml four-hole boiling flask
Middle ultrasonic disperse 2h, adds 80g vinyldiphenylphosphine and 0.04g light trigger 2- hydroxy-2-methyl -1- phenyl -1- third
Ketone, reacts 8h, after reaction terminates, suspension separates, washs, is dried to obtain magnetic nano particle through Magnet under ultraviolet light
Son load part product；
3. the 3g magnetic nano-particle that 2. step is prepared is loaded part and 50g anhydrous propanone is added in 250ml four-hole boiling flask
Ultrasonic disperse 6h, adds 0.04g precious metal salt aurous chloride, and after adding backflow 48h in a nitrogen atmosphere, suspension is through Magnet
It is vacuum dried after separation, washing and obtain target product magnetic nano-particle load gold catalyst again.Its gold content is 2.0%, saturation
The intensity of magnetization is 25.0emu/g.
Embodiment 4
The preparation method of magnetic nano-particle supported rhodium catalyst is as follows：
1. 2g nano ferriferrous oxide and 10g first are added in equipped with thermometer, agitator, the 250ml four-hole boiling flask of condensing tube
Benzene, after ultrasonic disperse 4h, adds 2g deionized water, 4g dehydrated alcohol, 40g γ-mercapto propyl-triethoxysilicane under stirring
Alkane, the pH value using acetic acid regulation system is 5, stirs 6h at 80 DEG C, and product is mercapto through filtering, washing, be dried to obtain surface
The magnetic nano-particle of base；
2. the 3g surface 1. prepared step is the magnetic nano-particle of sulfydryl and 10g ethanol is added in 250ml four-hole boiling flask
Ultrasonic disperse 4h, adds 10g vinyldiphenylphosphine and 0.01g light trigger benzophenone, reacts under ultraviolet light
6h, after reaction terminates, suspension separates, washs, being dried to obtain magnetic nano-particle load part product through Magnet；
3. the 2g magnetic nano-particle that 2. step is prepared is loaded part and 150g anhydrous propanone is added in 250ml four-hole boiling flask
Ultrasonic disperse 4h, adds 0.02g precious metal salt rhodium chloride, and after adding backflow 12h in a nitrogen atmosphere, suspension is through Magnet
It is vacuum dried after separation, washing and obtain target product magnetic nano-particle supported rhodium catalyst again.Its rhodium content is 3.0%, saturation
The intensity of magnetization is 18.0emu/g.
Embodiment 5
The preparation method of magnetic nano-particle loaded palladium catalyst is as follows：
1. 3g nano ferriferrous oxide and 40g first are added in equipped with thermometer, agitator, the 250ml four-hole boiling flask of condensing tube
Benzene, after ultrasonic disperse 4h, adds 6g deionized water, 8g dehydrated alcohol, 60g γ-mercapto propyl trimethoxy silicon under stirring
Alkane, the pH value using acetic acid regulation system is 6, stirs 8h at 70 DEG C, and product is mercapto through filtering, washing, be dried to obtain surface
The magnetic nano-particle of base；
2. the 5g surface 1. prepared step is the magnetic nano-particle of sulfydryl and 30g ethanol is added in 250ml four-hole boiling flask
Ultrasonic disperse 4h, adds 80g vinyldiphenylphosphine and 0.04g light trigger 2- hydroxy-2-methyl -1- phenyl -1- acetone,
React 8h under ultraviolet light, after reaction terminates, suspension separates, washs, is dried to obtain magnetic nano-particle through Magnet
Load part product；
3. the 3g magnetic nano-particle that 2. step is prepared is loaded part and 50g dry toluene is added in 250ml four-hole boiling flask
Ultrasonic disperse 4h, adds 0.04g precious metal salt palladium, and after adding backflow 24h in a nitrogen atmosphere, suspension divides through Magnet
It is vacuum dried and obtains target product magnetic nano-particle loaded palladium catalyst after, washing.Its palladium content is 4.0%, saturation magnetic
Change intensity is 30.0emu/g.
Claims (8)
1. a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that methods described include following
Step：
（1）2 ~ 4 weight portion nano ferriferrous oxides are scattered in 10 ~ 50 weight parts organic solvent, add 2 ~ 8 parts of weight portions to go
Ionized water, 4 ~ 10 weight portion dehydrated alcohol, 50 ~ 100 weight portion mercaptosilane coupling agents, regulation system pH value is 5 ~ 7,60 ~
6 ~ 8h is stirred, product is through filtering, washing, be dried to obtain the magnetic nano-particle that surface is sulfydryl at 80 DEG C；
（2）By step（1）3 ~ 5 weight portion surfaces of preparation are the magnetic nano-particle ultrasonic disperse of sulfydryl in 10 ~ 30 weight portions
Organic solvent, adds 10 ~ 100 parts by weight of ethylene base organic ligand compound and 0.01 ~ 0.05 weight portion light trigger, in ultraviolet
6 ~ 10h is reacted, after reaction terminates, suspension separates, washs, being dried to obtain magnetic nano-particle load through Magnet under light irradiation
Part product；
（3）By step（2）2 ~ 4 parts by weight of magnetic nanometer particle load parts of preparation are scattered in the anhydrous of 50 ~ 150 weight portions to be had
In machine solvent, add the precious metal salt of 0.02 ~ 0.05 weight portion, after adding backflow 12 ~ 48h in a nitrogen atmosphere, suspension
It is vacuum dried after Magnet separation, washing and obtain target product magnetic nano-particle supported precious metal catalyst again.
2. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
The tenor of described catalyst is the 0.1 ~ 5.0% of catalyst total amount.
3. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
Described magnetic nano-particle supported precious metal catalyst has superparamagnetism at room temperature, saturation magnetization be 10 ~
30.0emu/g.
4. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
Described mercaptosilane coupling agents are gamma-mercaptopropyltriethoxysilane or γ-mercaptopropyl trimethoxysilane.
5. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
Described organic solvent is one or more of toluene, dimethylbenzene, isopropanol, ethanol, methanol, acetone.
6. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
Described vinyl organic ligand is diphenyl in styryl phosphine, vinyldiphenylphosphine, 4- dimethylaminostyrene
A kind of.
7. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
One of described light trigger benzophenone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketone
Or it is several.
8. according to claim 1 a kind of method preparing magnetic nano-particle supported precious metal catalyst it is characterised in that
Described precious metal salt is one of Palladous chloride., palladium, aurous chloride, chloroplatinic acid or rhodium chloride.
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