CN107913741A - A kind of preparation method of 199 load nano particle composite materials of MOF - Google Patents
A kind of preparation method of 199 load nano particle composite materials of MOF Download PDFInfo
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- CN107913741A CN107913741A CN201610881932.0A CN201610881932A CN107913741A CN 107913741 A CN107913741 A CN 107913741A CN 201610881932 A CN201610881932 A CN 201610881932A CN 107913741 A CN107913741 A CN 107913741A
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- 239000002131 composite material Substances 0.000 title claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 238000005253 cladding Methods 0.000 claims abstract description 21
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 21
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 16
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 14
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 5
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 5
- 239000013148 Cu-BTC MOF Substances 0.000 claims description 41
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 38
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 38
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 38
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 30
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 28
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 13
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000010949 copper Substances 0.000 claims description 8
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 235000009566 rice Nutrition 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 4
- 241000209094 Oryza Species 0.000 claims 2
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 102000004190 Enzymes Human genes 0.000 abstract description 4
- 108090000790 Enzymes Proteins 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000009977 dual effect Effects 0.000 abstract description 3
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 229920002994 synthetic fiber Polymers 0.000 abstract 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 102000003992 Peroxidases Human genes 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 108040007629 peroxidase activity proteins Proteins 0.000 description 2
- -1 polytetrafluoroethylene Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 150000003462 sulfoxides Chemical class 0.000 description 2
- 150000003639 trimesic acids Chemical class 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 241000549556 Nanos Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 102000004316 Oxidoreductases Human genes 0.000 description 1
- 108090000854 Oxidoreductases Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000013259 porous coordination polymer Substances 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- ORZHVTYKPFFVMG-UHFFFAOYSA-N xylenol orange Chemical compound OC(=O)CN(CC(O)=O)CC1=C(O)C(C)=CC(C2(C3=CC=CC=C3S(=O)(=O)O2)C=2C=C(CN(CC(O)=O)CC(O)=O)C(O)=C(C)C=2)=C1 ORZHVTYKPFFVMG-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
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
A kind of preparation method of 199 load nano particle composite materials of MOF, the MOFs composite materials load Fe for MOF 1993O4Or noble metal nano particles composite material, step are as follows：The magnetic nano-particle and noble metal nano particles of PVP claddings are prepared first, are then dispersed in the precursor solution of MOF 199, with the composite material of traditional 199 load nano particles of hydro-thermal method in-situ one-step synthesis MOF.It is an advantage of the invention that：The preparation method of 199 load nano particles of MOF is simple, easy to implement.The synthetic material, which has concurrently, to be magnetic or the dual excellent specific property of noble metal and MOF 199, and the organic pollutant in catalytic degradation ambient water can be carried out as biosimulation enzyme.
Description
【Technical field】
The present invention relates to a kind of preparation method of MOF-199 load nano particles, particularly MOF-199 loads Fe3O4It is or expensive
The preparation method of metal nano particle composite material.
【Background technology】
Metal-organic framework materials (MOFs), also known as Porous coordination polymer, are a kind of new organic-inorganic porosity
Material, is organic ligand and the coordination work of metal ion or metal cluster as center between the two by the use of rigid polyhedral structure
With the porous material with periodicity mesh skeleton structure by being self-assembly of.It has high specific surface area and hole
Degree, diversified skeleton structure and good chemical stability.Compared with traditional inorganic porous material, its application field is more
Add extensively, such as：The fields such as adsorbing separation, gas storage, catalysis, medicament transport and bio-imaging.
Recent decades, China's process of industrialization are persistently accelerated, and promote the rapid growth of economy.It is but various complicated
Environmental problem is on the rise, a large amount of waste water for including organic matter that especially industrial processes produce, this has become maximum
Society and economic problems.For the more efficient pollution problem solved in environment, the MOFs composite materials of load nano particle due to
Become most promising candidate with catalysis and degradation effect.
MOF-199 is as a kind of new organic framework material, the three-dimensional MOFs materials being made of copper and trimesic acid
Material, has excellent characteristic, such as peroxidase activity, oxidase active, superpower absorption property.And Fe3O4, noble metal receives
Rice corpuscles (such as Pt, Au, Pd) is respectively provided with peroxidase activity.MOF-199 loads Fe3O4Or noble metal nano particles are answered
Condensation material has MOF-199 and nano-particle double grading concurrently, can be efficiently in catalytic degradation ambient water as biosimulation enzyme
The organic pollutions such as methylene blue, xylenol orange.
The present invention is to synthesize the magnetic nano-particle and noble metal nano particles of morphology controllable first, is then dispersed in
In the precursor synthetic solvent of MOF-199, without adding other solvents, born with traditional hydro-thermal method in-situ one-step synthesis MOF-199
Carry the composite material of nano-particle.
【The content of the invention】
The present invention provides a kind of preparation method of MOF-199 load nano particles composite material, easy to operate, be easy to control
System.The composite material of synthesis has the magnetic or dual excellent specific property of noble metal and MOF-199 concurrently, can be used as biosimulation enzyme
Carry out the organic pollutant in catalytic degradation ambient water.
Technical scheme：
A kind of preparation method of MOF-199 load nano particles composite material is as follows：
1) Fe of PVP claddings3O4The preparation of magnetic nano-particle
By 1.08g FeCl3·6H2O is dissolved in 40mL ethylene glycol and diethylene glycol (volume ratio 1: 19) in the mixed solvent, surpasses
Sound 30min, adds anhydrous sodium acetate 3g stirrings and is allowed to dissolve, add polyvinylpyrrolidone (PVP) and dissolve completely, then
Uniform suspension is transferred in the reaction kettle equipped with polytetrafluoroethyllining lining, reacts 12h at 200 DEG C.Magneto separate is consolidated after reaction
Body product, 60 DEG C of vacuum drying 12h after cleaning 3 times with water and ethanol respectively, is made the Fe that PVP is coated3O4Magnetic nano-particle；
2) preparation of the Pt metal nanoparticles of PVP claddings
Pt seed-solutions are prepared first：By chloroplatinic acid (H2PtCl6·6H2O) it is dissolved in the mixed solution of first alcohol and water, adds
Enter PVP stirrings to be allowed to dissolve, 3h is refluxed at 70 DEG C, be cooled to room temperature i.e. acquisition Pt seed-solutions；
Pt seed-solutions 1mL is taken to be added to 10mL concentration as in 1mM platinum acid chloride solutions, it is molten to add 0.1M ascorbic acid
Liquid, is stirred at room temperature until solution colour becomes black, centrifugation PVP cladding Pt metallic nanoparticles, are dispersed in dimethyl
In sulfoxide；
3) a kind of preparation of MOF-199 load nano particles composite material
By Cu (NO3)2·3H2O, trimesic acid is dissolved in dimethyl sulfoxide (DMSO), and fully ultrasound is until dissolving, then adds
The Fe of the PVP claddings prepared3O4Nano-particle or noble metal nano particles, are transferred to equipped with polytetrafluoroethylene (PTFE) after being uniformly dispersed
In the reaction kettle of liner, 65 DEG C of reaction 12h.After being cooled to room temperature, reaction product is added to the 50mL first containing 0.5g PVP
In alcoholic solution, 55 DEG C of mechanical agitation 90min, are cooled to room temperature, and by external magnet or product is collected by centrifugation, is washed with methanol
3 times, 40 DEG C of vacuum drying 12h, the composite material of MOF-199 load nano particles is made.
The FeCl3·6H2The molar ratio of O and PVP is 1: 1-10；
The H2PtCl6·6H2O, PVP, methanol, the amount ratio of ultra-pure water are 1 μm ol: 0.5-2 μm ol: 800-2000 μ L:
100-500μL；H2PtCl6·6H2The molar ratio of O and ascorbic acid is 1: 5-15
Cu (the NO3)2·3H2O, trimesic acid and dimethyl sulfoxide (DMSO) molar ratio are 1: 0.1-0.5: 2-10；Cu
(NO3)23H2The amount ratio of O and nano-particle is 1mol: 2-20mg；
The noble metal nano particles include Pt, Au and Pd metal nanoparticle
Advantages of the present invention and application effect：The synthesis prepares a kind of MOF-199 using easily operated solvent-thermal method
The composite material of load nano particle, the composite material have the magnetic or dual excellent specific property of noble metal and MOF-199 concurrently, can
To carry out the organic pollutant in catalytic degradation ambient water as biosimulation enzyme.
【Brief description of the drawings】
Fig. 1 is the transmission electron microscope picture of nano-particle and the MOF-199 load nano particle composite materials of PVP claddings, in figure：
(A) Fe of PVP claddings3O4Magnetic nano-particle；(B) MOF-199 loads Fe3O4Magnetic nano-particle composite material；(C) PVP bags
Cover Pt metal nanoparticles；(D) MOF-199 supporting Pts metal nano particle composite material.
【Embodiment】
Technical scheme is further described below by way of several specific embodiments.
Embodiment 1：
A kind of preparation method of MOF-199 load nano particles, the MOF-199 load nano particles composite material are
MOF-199 loads Fe3O4Magnetic nano-particle composite material, step are as follows：
1) Fe of PVP claddings3O4The preparation of magnetic nano-particle
By 1.08g FeCl3·6H2O is dissolved in 40mL ethylene glycol and diethylene glycol (volume ratio 1: 19) in the mixed solvent, surpasses
Sound 30min, adds anhydrous sodium acetate 3g stirrings and is allowed to dissolve, and adds PVP 4g and dissolves completely, then turns uniform suspension
Enter in the reaction kettle equipped with polytetrafluoroethyllining lining, react 12h at 200 DEG C.Magneto separate solid product after reaction, is used respectively
60 DEG C of vacuum drying 12h after water and ethanol clean 3 times, are made the Fe of PVP claddings3O4Magnetic nano-particle；
The Fe of Fig. 1 (A) PVP claddings3O4Magnetic nano-particle, shows in figure：The magnetic nano particle of synthesized PVP claddings
Son is that spherical and particle diameter distribution is uniform, pattern is neat.
2) preparation of MOF-199 carried magnetic nanos particle composite material
By 2.44g Cu (NO3)2·3H2O, 0.58g trimesic acids are dissolved in 4mL dimethyl sulfoxide (DMSO)s, fully ultrasound until
Dissolving, then adds the Fe of the PVP claddings prepared3O4Nano-particle 10mg, is transferred to equipped with polytetrafluoroethylene (PTFE) after being uniformly dispersed
In the reaction kettle of lining, 65 DEG C of reaction 12h.After being cooled to room temperature, solution is added to the 50mL methanol solutions containing 0.5g PVP
In, 55 DEG C of mechanical agitation 90min, are cooled to room temperature, collect product by external magnet, are washed 3 times with methanol, 40 DEG C of vacuum are done
Dry 12h, is made the composite material of MOF-199 carried magnetic nano particles.
Fig. 1 (B) MOF-199 carried magnetic nano particle composite material electron microscopes, show in figure：The magnetic particles of PVP claddings
Son is irregular to be embedded in inside MOF-199, and MOF-199 is regular octahedron, and pattern is uniformly regular.
Embodiment 2：
A kind of preparation method of MOF-199 load nano particles, the MOF-199 load nano particles composite material are
MOF-199 supporting Pt metal nano particle composite materials, step are as follows：
1) preparation of the Pt nano-particles of PVP claddings
Pt seed-solutions are prepared first：By H2PtCl6·6H230 μm of ol of O are dissolved in the mixed solution of 45mL first alcohol and waters
(volume ratio 9: 1), adds 30 μm of ol stirrings of PVP and is allowed to dissolve, be refluxed 3h at 70 DEG C, be cooled to room temperature and obtain
Pt seed-solutions；
Pt seed-solutions 5mL is taken to be added to 50mL concentration in 1mM platinum acid chloride solutions, to add 0.6mmol ascorbic acid,
It is stirred at room temperature until solution colour becomes black, centrifugation PVP cladding Pt metallic nanoparticles, are dispersed in 15mL dimethyl
In sulfoxide；
Display in Fig. 1 (C)：Synthesized Pt metal nanoparticles are solid spheroidal particle, and particle diameter distribution is uniform.
2) preparation of MOF-199 supporting Pts metal nano particle composite material
By 2.44g Cu (NO3)2·3H2O, 0.58g trimesic acids are dissolved in 4mL dimethyl sulfoxide (DMSO)s, fully ultrasound until
Dissolving, then adds the Pt metal nanoparticle solution 1mL of the PVP claddings prepared, is transferred to after being uniformly dispersed equipped with polytetrafluoro
In the reaction kettle of ethene liner, 65 DEG C of reaction 12h.After being cooled to room temperature, solution is added to the 50mL first containing 0.5g PVP
In alcoholic solution, 55 DEG C of mechanical agitation 90min, are cooled to room temperature, collect product by external magnet, are washed 3 times, 40 DEG C with methanol
12h is dried in vacuo, the composite material of MOF-199 carried magnetic nano particles is made.
Display in Fig. 1 (D)：The Pt metal nanoparticles of PVP claddings are embedded in inside MOFs, high-visible, octahedral
MOFs does not have big change after the insertion of noble metal.
Claims (5)
- A kind of 1. MOF-199 load nano particles composite material and preparation method thereof, it is characterised in that：The MOF-199 loads are received Rice corpuscles composite material loads Fe for MOF-1993O4Or noble metal nano particles composite material, wherein MOF-199 be by metal from Sub- copper and the built-up metal-organic framework materials of trimesic acid, synthesis step are as follows：1) Fe of PVP claddings3O4The preparation of magnetic nano-particleBy 1.08g FeCl3·6H2O is dissolved in 40mL ethylene glycol and diethylene glycol (volume ratio 1: 19) in the mixed solvent, ultrasound 30min, adds anhydrous sodium acetate 3g stirrings and is allowed to dissolve, and adds polyvinylpyrrolidone (PVP) and dissolves completely, then will Uniform suspension is transferred in the reaction kettle equipped with polytetrafluoroethyllining lining, reacts 12h at 200 DEG C.Magneto separate solid after reaction Product, 60 DEG C of vacuum drying 12h after cleaning 3 times with water and ethanol respectively, is made the Fe that PVP is coated3O4Magnetic nano-particle；2) preparation of the Pt metal nanoparticles of PVP claddingsPt seed-solutions are prepared first：By chloroplatinic acid (H2PtCl6·6H2O) it is dissolved in the mixed solution of first alcohol and water, adds PVP Stirring is allowed to dissolve, and 3h is refluxed at 70 DEG C, is cooled to room temperature i.e. acquisition Pt seed-solutions；Pt seed-solutions 1mL is taken to be added to 10mL concentration in 1mM platinum acid chloride solutions, to add 0.1M ascorbic acid solutions, room Until solution colour becomes black, centrifugation PVP cladding Pt metallic nanoparticles, are dispersed in dimethyl sulfoxide (DMSO) for temperature stirring In；3) a kind of preparation of MOF-199 load nano particles composite materialBy Cu (NO3)2·3H2O, trimesic acid is dissolved in dimethyl sulfoxide (DMSO), and fully ultrasound is until dissolving, then adds and prepare The Fe of good PVP claddings3O4Nano-particle or noble metal nano particles, are transferred to equipped with polytetrafluoroethyllining lining after being uniformly dispersed Reaction kettle in, 65 DEG C reaction 12h.After being cooled to room temperature, it is molten that reaction product is added to the 50mL methanol containing 0.5g PVP In liquid, 55 DEG C of mechanical agitation 90min, are cooled to room temperature, and by external magnet or product is collected by centrifugation, and are washed 3 times with methanol, 40 DEG C of vacuum drying 12h, are made the composite material of MOF-199 load nano particles.
- 2. the composite material and preparation method thereof of MOF-199 load nano particles according to claim 1, it is characterised in that： FeCl3·6H2The molar ratio of O and PVP is 1: 1-10.
- 3. the composite material and preparation method thereof of the MOF-199 load nano particles according to claim 1, it is characterised in that： H2PtCl6·6H2O, PVP, methanol, the amount ratio of ultra-pure water are 1 μm of L: 100-500 μ L of ol: 0.5-2 μm of ol: 800-2000 μ； H2PtCl6·6H2The molar ratio of O and ascorbic acid is 1: 5-15.
- 4. the composite material and preparation method thereof of the MOF-199 load nano particles according to claim 1, it is characterised in that： Cu(NO3)2·3H2O, trimesic acid and dimethyl sulfoxide (DMSO) molar ratio are 1: 0.1-0.5: 2-10；Cu(NO3)2·3H2O is with receiving The amount ratio of rice corpuscles is 1mol: 2-20mg.
- 5. the composite material and preparation method thereof of the MOF-199 load nano particles according to claim 1, it is characterised in that： The noble metal nano particles include Pt, Au and Pd metal nanoparticle.
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Cited By (8)
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|---|---|---|---|---|
| CN109503858A (en) * | 2019-01-17 | 2019-03-22 | 南京大学 | A kind of magnetism sandwich structure metal-organic framework materials and preparation method |
| CN110470840A (en) * | 2019-09-06 | 2019-11-19 | 齐鲁工业大学 | A method of detection vibrio parahemolyticus |
| CN112397736A (en) * | 2020-12-10 | 2021-02-23 | 福州大学 | FePt @ C composite nano material prepared based on MOF and application thereof |
| CN112718010A (en) * | 2021-01-06 | 2021-04-30 | 中国船舶重工集团公司第七一九研究所 | Preparation method of Pd/MOF catalyst for catalytic hydrogenation upgrading of caprylic acid |
| CN114480321A (en) * | 2022-01-21 | 2022-05-13 | 商洛学院 | Magnetic Zr-MOF @ PVP @ Fe3O4Immobilized enzyme reactor and application thereof |
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| CN115282792A (en) * | 2022-01-21 | 2022-11-04 | 浙江师范大学 | Preparation method of polymer-magnetic organic metal framework compound composite separation membrane |
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| CN115228440B (en) * | 2022-08-09 | 2024-03-08 | 国家能源集团科学技术研究院有限公司 | Sulfhydryl functional magnetic metal organic framework material and preparation method and application thereof |
| CN116444809A (en) * | 2023-03-23 | 2023-07-18 | 河南大学 | Hollow nano flower-like double MOF-based heterojunction material and preparation method and application thereof |
| CN116444809B (en) * | 2023-03-23 | 2023-12-08 | 河南大学 | Hollow nano flower-like double MOF-based heterojunction material and preparation method and application thereof |
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