CN106423290B - A method of preparing magnetic nano-particle supported precious metal catalyst - Google Patents
A method of preparing magnetic nano-particle supported precious metal catalyst Download PDFInfo
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- CN106423290B CN106423290B CN201610868444.6A CN201610868444A CN106423290B CN 106423290 B CN106423290 B CN 106423290B CN 201610868444 A CN201610868444 A CN 201610868444A CN 106423290 B CN106423290 B CN 106423290B
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- 239000002122 magnetic nanoparticle Substances 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 46
- 239000010970 precious metal Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 16
- 239000003446 ligand Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 6
- 150000001875 compounds Chemical group 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 239000000725 suspension Substances 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 230000005415 magnetization Effects 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound 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
- 235000019441 ethanol Nutrition 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
- 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
- 239000002245 particle Substances 0.000 claims description 4
- TXDNPSYEJHXKMK-UHFFFAOYSA-N sulfanylsilane Chemical compound S[SiH3] TXDNPSYEJHXKMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- 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
- 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 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
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical compound CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 claims description 2
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-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
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 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
- 239000006228 supernatant Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 229910000510 noble metal Inorganic materials 0.000 abstract description 4
- 238000004064 recycling Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000007259 addition reaction Methods 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000012650 click reaction Methods 0.000 abstract description 2
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 238000007172 homogeneous catalysis Methods 0.000 abstract description 2
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract description 2
- 239000006087 Silane Coupling Agent Substances 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 15
- 238000003756 stirring Methods 0.000 description 10
- -1 mercapto propyl Chemical group 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 3
- 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
- 229910052742 iron 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
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 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
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000009566 rice Nutrition 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
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 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
A method of preparing magnetic nano-particle supported precious metal catalyst, it is that the silane coupling agent for containing sulfydryl is grafted to Nanometer Magnetite surface, click-reaction, which is carried out, using its surface sulfydryl and vinyl organic ligand compound forms magnetic nano-particle supported complex, it is further complexed with precious metal salt, obtains magnetic nano-particle supported precious metal catalyst.Catalyst prepared by this method is to be combined on magnetic nano-particle surface and vinyl organic ligand compound in the form of chemical bond click chemistry reaction, so that ligand is secured with magnetic nano-particle, it can guarantee ligand far from carrier again simultaneously, it is preferably coordinated with noble metal, can achieve the effect of homogeneous catalysis.In addition adding the such catalyst of magnetic fields to be easily magnetized outside, having the advantages that quick separating recycling, be recycled, production cost can be reduced, improve production efficiency.In the coupling of prepared magnetic nano-particle supported catalyst suitable metal catalysis, addition reaction.
Description
Technical field
The present invention relates to a kind of methods for preparing magnetic nano-particle supported precious metal catalyst based on click chemistry method, belong to
Catalyst technical field.
Background technique
Precious metal catalyst reaction is one of organic chemical synthesis method important means, but these noble metal catalysts exist
It is difficult to classify from reaction system and recycle, increases reaction cost or even metal organic catalysis such as palladium metal in reaction process meeting palladium
It is black, the activity of catalyst is not only reduced, but also reaction product can be polluted, is very restricted in practical applications.Cause
This, more and more researchers are solved these problems by the research to loaded catalyst, make every effort to both keep homogeneous
The high efficiency of catalyst, and can solve the recycling of catalyst, realize the targets such as the minimum consumption of noble metal.Current many documents
Different types of carrier such as high molecular polymer, molecular sieve, silica gel, active carbon etc. is reported, precious metal catalyst is all applied to
The supported research of agent.But either use organic polymer carrier or inorganic carrier, catalytic activity, stability and recycling
Reusability can it still needs further improvement, and application range is fairly limited.In recent years, magnetic nano-particle is as catalyst carrier
It receives significant attention, technological means is in magnetic Fe3O4Nanoparticle surface coats a thin layer silica gel, utilizes the hydroxyl on surface
Various organic ligands are connected, but it is low also to deposit bullion content, and usage amount is caused to increase, and when being recycled due to ligand
It is insecure that its activity is caused to gradually decrease.Therefore it provides the preparation method of supported precious metal catalyst, has very strong theoretical meaning
Justice and application value.
Summary of the invention
The object of the present invention is to for overcome the deficiencies in the prior art, provide that a kind of 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
Click-reaction is sent out, vinyl organic ligand is grafted on magnetic nano-particle, is complexed with precious metal salt.
A kind of method for preparing magnetic nano-particle supported precious metal catalyst of the present invention the following steps are included:
(1) it disperses 2 ~ 4 parts by weight nano ferriferrous oxides in 10 ~ 50 weight parts organic solvents, 2 ~ 8 parts of weight is added
Part deionized water, 4 ~ 10 parts by weight dehydrated alcohols, 50 ~ 100 parts by weight mercaptosilane coupling agents, regulation system pH value are 5 ~ 7,
6 ~ 8h is stirred at 60 ~ 80 DEG C, product is filtered, washed, is dried to obtain the magnetic nano-particle that surface is sulfydryl；
It (2) is the magnetic nano-particle ultrasonic disperse of sulfydryl in 10 ~ 30 weights by 3 ~ 5 parts by weight surfaces of step (1) preparation
Part organic solvent is measured, 10 ~ 100 parts by weight of ethylene base organic ligand compounds and 0.01 ~ 0.05 parts by weight photoinitiator is added,
6 ~ 10h is reacted under ultraviolet light, after reaction, suspension separates, washs, is dried to obtain magnetic nano-particle by magnet
Load ligand product；
(3) 2 ~ 4 parts by weight of magnetic nanometer particle load ligands prepared by step (2) are dispersed in the nothing of 50 ~ 150 parts by weight
In aqueous organic solvent, the precious metal salt of 0.02 ~ 0.05 parts by weight is added, after 12 ~ 48h of reflux is added in a nitrogen atmosphere, is hanged
Supernatant liquid separates through magnet, is dried in vacuo to obtain target product magnetic nano-particle supported precious metal catalyst again after washing.
Its tenor of the catalyst is the 0.1 ~ 5.0% of catalyst total amount.
The magnetic nano-particle supported precious metal catalyst has superparamagnetism, saturation magnetization 10 at room temperature
~30.0emu/g。
The mercaptosilane coupling agents are gamma-mercaptopropyltriethoxysilane or γ-mercaptopropyl trimethoxysilane.
The organic solvent is one or more of toluene, dimethylbenzene, isopropanol, ethyl alcohol, methanol, acetone.
The vinyl organic ligand is diphenyl to styryl phosphine, vinyldiphenylphosphine, 4- dimethylamino benzene
One of ethylene.
The photoinitiator benzophenone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketone
One or more of.
The precious metal salt is one of palladium chloride, palladium acetate, aurous chloride, chloroplatinic acid or rhodium chloride.
The beneficial effects of the present invention are, magnetic Nano supported precious metal catalyst prepared by the present invention, carrier choosing
Pass through the tactful by nano-carrier and second of " click chemistry " on nano-carrier surface by introducing sulfydryl with magnetic nanoparticle
Alkenyl ligand is combined with chemical bond form, so that load ligand compound is secured, and far from carrier, can effectively be matched with metal
Position, while its carrier specific surface area with higher have excellent point of dispersion and mechanical performance, achieve the effect that homogeneous catalysis.
There is superparamagnetism at room temperature, be easily magnetized under the action of an external magnetic field, remove then magnetic disappearance behind magnetic field, it is easy to accomplish expensive
The quick separating of metallic catalyst and the purpose of recycling, suitable for the coupling and addition reaction of precious metal catalyst, such
In reaction, supported catalyst may be reused it is multiple, active be basically unchanged, be effectively reduced synthesis cost, avoid noble metal
It is lost.
Specific embodiment
Embodiment 1
Magnetic nano-particle loaded palladium catalyst the preparation method is as follows:
1. equipped with thermometer, blender, condenser pipe 250ml four-hole boiling flask in be added 2g nano ferriferrous oxide and
After ultrasonic disperse 2h, 5g deionized water, 6g dehydrated alcohol, 60g γ-three second of mercapto propyl is added in 30g toluene under stirring
Oxysilane uses the pH value of acetic acid regulation system to stir 8h at 60 DEG C, product is filtered, washed, is dried to obtain table for 5
Face is the magnetic nano-particle of sulfydryl；
2. being that the magnetic nano-particle of sulfydryl and 30g toluene are added to tetra- mouthfuls of 250ml burnings by the 1. surface 5g that step is prepared
Ultrasonic disperse 2h in bottle, adds 20g diphenyl to styryl phosphine and 0.02g photoinitiator benzophenone, in ultraviolet lighting
Lower reaction 10h is penetrated, after reaction, suspension is separated, washed by magnet, being dried to obtain magnetic nano-particle load ligand production
Object；
3. 2. 4g magnetic nano-particle load ligand and 80g anhydrous propanone that step is prepared is added to tetra- mouthfuls of 250ml burnings
Ultrasonic disperse 2h in bottle, adds 0.02g precious metal salt palladium chloride, and after reflux 48h is added in a nitrogen atmosphere, suspension is through magnetic
It is dried in vacuo to obtain target product magnetic nano-particle loaded palladium catalyst again after iron separation, washing.Its palladium content is 5.0%, is satisfied
It is 20emu/g with the intensity of magnetization.
Embodiment 2
Magnetic nano-particle load platinum catalyst the preparation method is as follows:
1. equipped with thermometer, blender, condenser pipe 250ml four-hole boiling flask in be added 4g nano ferriferrous oxide and
After ultrasonic disperse 4h, 8g deionized water, 10g dehydrated alcohol, 100g γ-mercapto propyl is added in 50g dimethylbenzene under stirring
Trimethoxy silane uses the pH value of acetic acid regulation system to stir 6h at 80 DEG C, product is filtered, washed, is dried for 7
It is the magnetic nano-particle of sulfydryl to surface；
2. the 1. surface 3g that step is prepared is the magnetic nano-particle and 10g dimethylbenzene of sulfydryl, it is added to tetra- mouthfuls of 250ml
Ultrasonic disperse 1h in flask adds 100g 4- dimethylaminostyrene and 0.05g photoinitiator 1- hydroxycyclohexylphenyl
Ketone reacts 6h under ultraviolet light, and after reaction, suspension separates, washs, is dried to obtain magnetic Nano by magnet
Particle loads ligand product；
3. 2. 2g magnetic nano-particle load ligand and 80g anhydrous methanol that step is prepared is added to tetra- mouthfuls of 250ml burnings
Ultrasonic disperse 4h in bottle, adds 0.05g precious metal salt chloroplatinic acid, and after reflux for 24 hours is added in a nitrogen atmosphere, suspension is through magnetic
It is dried in vacuo to obtain target product magnetic nano-particle load platinum catalyst again after iron separation, washing.Its platinum content is 4.0%, is satisfied
It is 18.0emu/g with the intensity of magnetization.
Embodiment 3
Magnetic nano-particle load gold catalyst the preparation method is as follows:
1. equipped with thermometer, blender, condenser pipe 250ml four-hole boiling flask in be added 3g nano ferriferrous oxide and
After ultrasonic disperse 2h, 6g deionized water, 8g dehydrated alcohol, 60g γ-mercapto propyl front three is added in 40g toluene under stirring
Oxysilane uses the pH value of acetic acid regulation system to stir 8h at 70 DEG C, product is filtered, washed, is dried to obtain table for 6
Face is the magnetic nano-particle of sulfydryl；
2. being that the magnetic nano-particle of sulfydryl and 30g isopropanol are added to tetra- mouthfuls of 250ml by the 1. surface 5g that step is prepared
Ultrasonic disperse 2h in flask adds 80g vinyldiphenylphosphine and 0.04g photoinitiator 2- hydroxy-2-methyl -1- phenyl -
1- acetone reacts 8h under ultraviolet light, and after reaction, suspension, which separated, washed by magnet, is dried to obtain magnetism receives
Rice corpuscles loads ligand product；
3. 2. 3g magnetic nano-particle load ligand and 50g anhydrous propanone that step is prepared is added to tetra- mouthfuls of 250ml burnings
Ultrasonic disperse 6h in bottle, adds 0.04g precious metal salt aurous chloride, after reflux 48h is added in a nitrogen atmosphere, suspension warp
It is dried in vacuo to obtain target product magnetic nano-particle load gold catalyst again after magnet separation, washing.Its gold content is 2.0%,
Saturation magnetization is 25.0emu/g.
Embodiment 4
Magnetic nano-particle supported rhodium catalyst the preparation method is as follows:
1. equipped with thermometer, blender, condenser pipe 250ml four-hole boiling flask in be added 2g nano ferriferrous oxide and
After ultrasonic disperse 4h, 2g deionized water, 4g dehydrated alcohol, 40g γ-three second of mercapto propyl is added in 10g toluene under stirring
Oxysilane uses the pH value of acetic acid regulation system to stir 6h at 80 DEG C, product is filtered, washed, is dried to obtain table for 5
Face is the magnetic nano-particle of sulfydryl；
2. being that the magnetic nano-particle of sulfydryl and 10g ethyl alcohol are added to tetra- mouthfuls of 250ml burnings by the 1. surface 3g that step is prepared
Ultrasonic disperse 4h in bottle, adds 10g vinyldiphenylphosphine and 0.01g photoinitiator benzophenone, under ultraviolet light
6h is reacted, after reaction, suspension is separated, washed by magnet, being dried to obtain magnetic nano-particle load ligand product；
3. 2. 2g magnetic nano-particle load ligand and 150g anhydrous propanone that step is prepared is added to tetra- mouthfuls of 250ml burnings
Ultrasonic disperse 4h in bottle, adds 0.02g precious metal salt rhodium chloride, after reflux 12h is added in a nitrogen atmosphere, suspension warp
It is dried in vacuo to obtain target product magnetic nano-particle supported rhodium catalyst again after magnet separation, washing.Its rhodium content is 3.0%,
Saturation magnetization is 18.0emu/g.
Embodiment 5
Magnetic nano-particle loaded palladium catalyst the preparation method is as follows:
1. equipped with thermometer, blender, condenser pipe 250ml four-hole boiling flask in be added 3g nano ferriferrous oxide and
After ultrasonic disperse 4h, 6g deionized water, 8g dehydrated alcohol, 60g γ-mercapto propyl front three is added in 40g toluene under stirring
Oxysilane uses the pH value of acetic acid regulation system to stir 8h at 70 DEG C, product is filtered, washed, is dried to obtain table for 6
Face is the magnetic nano-particle of sulfydryl；
2. being that the magnetic nano-particle of sulfydryl and 30g ethyl alcohol are added to tetra- mouthfuls of 250ml burnings by the 1. surface 5g that step is prepared
Ultrasonic disperse 4h in bottle, adds 80g vinyldiphenylphosphine and 0.04g photoinitiator 2- hydroxy-2-methyl -1- phenyl -1-
Acetone reacts 8h under ultraviolet light, and after reaction, suspension separates, washs, is dried to obtain magnetic Nano by magnet
Particle loads ligand product；
3. 2. 3g magnetic nano-particle load ligand and 50g dry toluene that step is prepared is added to tetra- mouthfuls of 250ml burnings
Ultrasonic disperse 4h in bottle, adds 0.04g precious metal salt palladium acetate, and after reflux for 24 hours is added in a nitrogen atmosphere, suspension is through magnetic
It is dried in vacuo to obtain target product magnetic nano-particle loaded palladium catalyst again after iron separation, washing.Its palladium content is 4.0%, is satisfied
It is 30.0emu/g with the intensity of magnetization.
Claims (6)
1. a kind of method for preparing magnetic nano-particle supported precious metal catalyst, which is characterized in that the method includes following
Step:
(1) it disperses 2~4 parts by weight nano ferriferrous oxides in 10~50 weight parts organic solvents, 2~8 parts of weight is added
Part deionized water, 4~10 parts by weight dehydrated alcohols, 50~100 parts by weight mercaptosilane coupling agents, regulation system pH value is 5~
7,6~8h is stirred at 60~80 DEG C, product is filtered, washed, is dried to obtain the magnetic nano-particle that surface is sulfydryl；
It (2) is the magnetic nano-particle ultrasonic disperse of sulfydryl in 10~30 weight by 3~5 parts by weight surfaces of step (1) preparation
Part organic solvent, is added 10~100 parts by weight of ethylene base organic ligand compounds and 0.01~0.05 parts by weight photoinitiator,
6~10h is reacted under ultraviolet light, after reaction, suspension separates, washs, is dried to obtain magnetic nano particle by magnet
Son load ligand product；
(3) the anhydrous of 50~150 parts by weight is dispersed by 2~4 parts by weight of magnetic nanometer particle load ligands prepared by step (2)
In organic solvent, the precious metal salt of 0.02~0.05 parts by weight is added, after 12~48h of reflux is added in a nitrogen atmosphere, is hanged
Supernatant liquid separates through magnet, is dried in vacuo to obtain target product magnetic nano-particle supported precious metal catalyst again after washing；
The mercaptosilane coupling agents are gamma-mercaptopropyltriethoxysilane or γ-mercaptopropyl trimethoxysilane；
The vinyl organic ligand is diphenyl to styryl phosphine, vinyldiphenylphosphine, 4- dimethylaminostyrene
One of.
2. a kind of method for preparing magnetic nano-particle supported precious metal catalyst according to claim 1, which is characterized in that
The tenor of the catalyst is the 0.1~5.0% of catalyst total amount.
3. a kind of method for preparing magnetic nano-particle supported precious metal catalyst according to claim 1, which is characterized in that
The magnetic nano-particle supported precious metal catalyst has a superparamagnetism at room temperature, and saturation magnetization is 10~
30.0emu/g。
4. a kind of method for preparing magnetic nano-particle supported precious metal catalyst according to claim 1, which is characterized in that
The organic solvent is one or more of toluene, dimethylbenzene, isopropanol, ethyl alcohol, methanol, acetone.
5. a kind of method for preparing magnetic nano-particle supported precious metal catalyst according to claim 1, which is characterized in that
One of the photoinitiator benzophenone, 2- hydroxy-2-methyl -1- phenyl -1- acetone, 1- hydroxycyclohexyl phenyl ketone
Or it is several.
6. a kind of method for preparing magnetic nano-particle supported precious metal catalyst according to claim 1, which is characterized in that
The precious metal salt is one of palladium chloride, palladium acetate, aurous chloride, chloroplatinic acid or rhodium chloride.
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| US20160083526A1 (en) * | 2014-09-23 | 2016-03-24 | Korea Institute Of Science And Technology | Mercapto-based polysilsesquioxane and method for preparing functional polysilsesquioxane using the same |
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