CN113353994A - Controllable preparation and modification method of nickel ferrite nanoparticles - Google Patents
Controllable preparation and modification method of nickel ferrite nanoparticles Download PDFInfo
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- CN113353994A CN113353994A CN202110705248.8A CN202110705248A CN113353994A CN 113353994 A CN113353994 A CN 113353994A CN 202110705248 A CN202110705248 A CN 202110705248A CN 113353994 A CN113353994 A CN 113353994A
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 90
- NQNBVCBUOCNRFZ-UHFFFAOYSA-N nickel ferrite Chemical compound [Ni]=O.O=[Fe]O[Fe]=O NQNBVCBUOCNRFZ-UHFFFAOYSA-N 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000002715 modification method Methods 0.000 title claims abstract description 20
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 38
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims abstract description 28
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims abstract description 24
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims abstract description 24
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims abstract description 24
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000005642 Oleic acid Substances 0.000 claims abstract description 24
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims abstract description 24
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 22
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000000376 reactant Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052742 iron Inorganic materials 0.000 claims abstract description 5
- 238000005119 centrifugation Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 20
- 238000000926 separation method Methods 0.000 claims description 16
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 239000003446 ligand Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000013543 active substance Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000010355 oscillation Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 8
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 abstract description 7
- 239000004793 Polystyrene Substances 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 4
- 229920002223 polystyrene Polymers 0.000 abstract description 4
- -1 oleic acid modified nickel ferrite Chemical class 0.000 abstract description 3
- 238000013500 data storage Methods 0.000 abstract description 2
- 238000002595 magnetic resonance imaging Methods 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000000015 thermotherapy Methods 0.000 abstract description 2
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 12
- 229910017604 nitric acid Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 12
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004627 transmission electron microscopy Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000001000 micrograph Methods 0.000 description 5
- 229910000859 α-Fe Inorganic materials 0.000 description 4
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical group [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 3
- 239000002122 magnetic nanoparticle Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 206010020843 Hyperthermia Diseases 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000036031 hyperthermia Effects 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
- 238000013421 nuclear magnetic resonance imaging Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WHRNULOCNSKMGB-UHFFFAOYSA-N tetrahydrofuran thf Chemical compound C1CCOC1.C1CCOC1 WHRNULOCNSKMGB-UHFFFAOYSA-N 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/88—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by thermal analysis data, e.g. TGA, DTA, DSC
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/42—Magnetic properties
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- Chemical & Material Sciences (AREA)
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- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Soft Magnetic Materials (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention provides a controllable preparation and modification method of nickel ferrite nano-particles, which comprises the steps of taking iron acetylacetonate, nickel acetylacetonate, oleic acid, sodium oleate and benzyl ether as raw materials, heating and reacting under the protection of nitrogen or inert gas to obtain the oleic acid modified nickel ferrite nano-particles, wherein the atomic ratio of nickel and iron in the nano-particles can be regulated and controlled by adjusting the proportion of reactants. Further, the nickel ferrite nano-particles with the surfaces modified by polystyrene are obtained by reaction in tetrahydrofuran solution dissolved with polystyrene after alcohol centrifugation is carried out to remove surface oleic acid. The nickel ferrite nano particles prepared by the method have good monodispersity, good dispersibility in water and superparamagnetism, and are expected to be applied to the fields of magnetic data storage, thermotherapy treatment, magnetic resonance imaging and the like. In addition, the modified nickel ferrite nano-particles can be kept dispersed in tetrahydrofuran solution for a long time, so that the aim of converting water phase into oil phase is fulfilled, and the modified nickel ferrite nano-particles are convenient to store and further use.
Description
Technical Field
The invention belongs to the field of materials, and particularly relates to a controllable preparation and modification method of nickel ferrite nanoparticles with good dispersibility in Tetrahydrofuran (THF).
Technical Field
The ferrite magnetic nanoparticles have high application value in the fields of magnetic data storage, thermotherapy treatment, Magnetic Resonance Imaging (MRI) and the like, and attract wide attention of people. Nickel ferrite nanoparticles of the formula NixFe3-xO4And is one kind of ferrite magnetic nanoparticles. At present, with respect to CoxFe3-xO4，MnxFe3-xO4，Fe3O4Relatively mature research on Ni SynthesisxFe3-xO4Relatively few studies. The nickel ferrite nano-particles show good performance in soft magnets and low-loss materials, and particularly have good application prospects in a high-frequency range, so that an efficient controllable preparation method is needed to be developed to obtain the nickel ferrite nano-materials with different magnetic properties. In addition, considering that the nickel ferrite magnetic nanoparticles are easily oxidized in an aqueous solution and easily agglomerated and settled in an organic solvent, it causes difficulties in the use and storage of the nanoparticles in various occasions. In view of the above problems, there is a need in the art for a method for preparing a nickel ferrite nanomaterial with high efficiency and controllability and a modification method for uniformly dispersing the nickel ferrite nanomaterial in an organic solvent (such as THF).
Disclosure of Invention
Therefore, the present invention aims to provide a simple preparation and modification method, which can realize the controllable preparation of nickel ferrite nanoparticles containing different nickel iron atom ratios, and obtain nickel ferrite nanoparticles uniformly dispersed in an organic solvent (such as THF), so as to avoid the agglomeration and sedimentation of the nickel ferrite nanoparticles, and facilitate the storage and further use.
The purpose of the invention is realized by the following technical scheme.
The invention provides a controllable preparation and modification method of nickel ferrite nanoparticles with high dispersion in tetrahydrofuran THF, which comprises the following steps;
1) pyrolyzing organic complex of iron and nickel in surfactant and benzyl ether to obtain nickel ferrite nanoparticles;
2) removing unreacted substances by using the nickel ferrite nano-particles obtained in the centrifugal separation step 1) and then using a solvent adding and centrifugal separation mode, and repeating the cleaning for four to five times to prepare a nickel ferrite nano-particle solution;
3) further adding C into the nickel ferrite nanoparticle solution obtained in the step 2)1～4And then washing away the active agent coated on the surface of the nickel ferrite nano-particle by centrifugation, adding the washed active agent into a THF solution dissolved with a ligand, and successfully modifying to obtain the nickel ferrite nano-particle with high dispersion in THF.
Further, in the step 1), the organic complex of iron and nickel is iron (III) acetylacetonate and nickel (II) acetylacetonate.
Furthermore, in the step 1), the mass ratio of the nickel element to the iron element is 1: 1. 1: 3. 1: 5. 1: 7. 1: 9, reacting to obtain nickel ferrite with different atomic ratios.
Further, in step 1), the mass/volume ratio of the iron (III) acetylacetonate to the benzyl ether is in the range of g: and ml is 0.025-0.1: 1, preferably 0.025: 1.
further, in the step 1), the pyrolysis is carried out in a nitrogen/inert gas protective atmosphere, the temperature is increased to 250-290 ℃ at a speed of 3-10 ℃/min, preferably to 295 ℃ at a speed of 6 ℃/min, the stirring reaction is carried out for 1-2 h, and according to an experimental result, the stirring reaction is preferably carried out for 1 h.
Further, in step 2), before solvent cleaning of the ferronickel nano-particles, firstly, the ferronickel nano-particles obtained in step 1) and the incompletely reacted reactants such as benzyl ether and oleic acid are centrifuged (11000rpm, 10min) to remove the unreacted reactants such as benzyl ether.
Furthermore, the solvent added in the step 2) is n-hexane. Adding a proper amount of n-hexane into the nickel ferrite nanoparticles without unreacted reactants such as benzyl ether, performing ultrasonic treatment or oscillation at room temperature for 5-10 min, and then performing centrifugation (11000rpm for 10min) to remove the unreacted reactants in the step 1), thereby finally obtaining the nickel ferrite nanoparticles coated with the oleic acid, wherein the size of the nickel ferrite nanoparticles is 10-20 nm.
Further, in step 3), C1～4The alcohol of (a) is preferably ethanol, butanol, propanol or methanol. Ethanol is more preferred for reasons of cost and environmental protection. In addition, a large number of experiments prove that the nickel ferrite nano-particles washed by ethanol are easier to directly carry out surface modification in the next step because the atomic surfaces with high surface energy are exposed.
Further, in step 3), the ligand in THF is PS-COOH. Adding dissolved mass-to-volume ratio g: ml is not less than 0.02: 1, performing ultrasonic treatment or oscillation on a THF solution of PS-COOH with the molecular weight of 2000-5000-.
The preparation method disclosed by the invention is short in reaction time and simple in process, and compared with the nickel ferrite nano-particles in the prior art, the proportion of nickel iron atoms in the nickel ferrite nano-particles can be effectively regulated and controlled.
The modification method disclosed by the invention is simple in preparation process flow, and compared with the nickel ferrite nano-particles modified by the prior art, the modification method fully utilizes the electrostatic interaction and steric hindrance, so that the obtained nickel ferrite is more fully modified, and has better stability and dispersibility in THF. For example, the oleic acid-coated nickel ferrite nanoparticles obtained in step 2) showed particle settling within several hours in THF solution, whereas the nickel ferrite nanoparticles modified with PS-COOH in the present invention were stably and uniformly dispersed in THF solution for at least three months.
The invention provides a controllable preparation and modification method of nickel ferrite nano particles, which has the following beneficial effects: the preparation method provided by the invention has the advantages of simple process flow, mild conditions, simple required equipment and capability of realizing batch production. The nano nickel ferrite obtained by the preparation method and the modification method has few surface ligands, uniform particle size, good crystallinity and stable performance, the particle size is between 10 and 20nm, the proportion of nickel iron atoms is adjustable, and the nano nickel ferrite has superparamagnetism, can keep dispersion for a long time in a THF solution without sedimentation or agglomeration, and has wide application prospects in the biomedical fields of nuclear magnetic resonance imaging, magnetic hyperthermia, catalysis and the like.
Drawings
FIG. 1 is a basic flow diagram of an embodiment;
FIG. 2 is an X-ray diffraction pattern (XRD) of the samples of examples 1-6;
FIG. 3 is a Transmission Electron Micrograph (TEM) of the samples of examples 1-6; wherein the content of the first and second substances,
panel (a) is a transmission electron microscope image of nanoparticles prepared in example 1;
panel (b) is a transmission electron microscope photograph of nanoparticles prepared in example 2;
panel (c) is a transmission electron microscopy image of the magnetic nickel ferrite nanoparticle body prepared in example 3;
panel (d) is a transmission electron microscopy image of the magnetic nickel ferrite nanoparticle body prepared in example 4;
panel (e) is a transmission electron microscopy image of the magnetic nickel ferrite nanoparticle body prepared in example 5;
panel (f) is a transmission electron microscopy image of the magnetic nickel ferrite nanoparticle body prepared in example 6.
FIG. 4 is an inductively coupled atomic emission spectrum (ICP-AES) of the samples of examples 1-6;
FIG. 5 is a hysteresis loop diagram of samples of examples 1-6;
FIG. 6 is a thermogravimetric plot (TG) of the sample of example 6;
FIG. 7 is a Fourier transform Infrared Spectroscopy (FTIR) of the sample of example 6.
Detailed Description
The present invention is described in further detail below with reference to specific examples and with reference to the data. It will be understood that these examples are intended to illustrate the invention and are not intended to limit the scope of the invention in any way.
The first embodiment is as follows:
1) a100 mL three-necked reaction flask was charged with 0.78g of iron (III) acetylacetonate, 0.56g of nickel (II) acetylacetonate, 0.9g of sodium oleate, 6mL of oleic acid, and 30mL of a benzyl ether solution, and the mixture was dissolved by stirring in N2Under the protection ofRaising the temperature to 295 ℃ at the speed of 6 ℃/min, and reacting for 1h to prepare black nickel ferrite granular crystals with the mass of about 0.42 g.
2) And (3) taking the reaction product, performing centrifugal separation, adding a proper amount of n-hexane for washing, performing centrifugal separation again, and repeating the steps for five times to obtain the nickel ferrite nano-particles coated with the oleic acid.
As shown in fig. 2, the X-ray diffraction pattern indicates that the black solid prepared in this example is nickel ferrite nanoparticles; the transmission electron microscopy image for preparing the nanoparticles is shown in FIG. 3(a), and it is clear that the size distribution of the nanoparticles is relatively uniform, with a diameter of about 19.4 nm.
FIG. 4 is a diagram showing the results of ICP-AES tests on a sample of example one, wherein a small amount of sample is dissolved by concentrated nitric acid, deionized water is added after the sample is sufficiently dissolved, the temperature is maintained at 100 ℃ for half an hour to sufficiently decompose and volatilize the nitric acid, and then a proper amount of sample is placed in a centrifuge tube and is sent to a sample for detection. From the test results, the sample prepared in example one was oleic acid-modified Ni1.27Fe1.73O4。
Fig. 5 is a hysteresis loop of a sample whose magnetic properties were measured at room temperature with a Vibrating Sample Magnetometer (VSM), demonstrating that the sample, example, is superparamagnetic at room temperature.
Example two:
1) a100 mL three-necked reaction flask was charged with 1.162g of iron (III) acetylacetonate, 0.283g of nickel (II) acetylacetonate, 0.9g of sodium oleate, 6mL of oleic acid, and 30mL of a benzyl ether solution, and the mixture was dissolved by stirring in N2Under protection, raising the temperature to 295 ℃ at the speed of 6 ℃/min, and reacting for 1h to prepare black nickel ferrite granular crystals with the mass of about 0.42 g.
2) Taking 1mL of nickel ferrite nanoparticles (about 10mg) wrapped by oleic acid, performing centrifugal separation, adding a proper amount of n-hexane for washing, performing centrifugal separation again, and repeating five times.
As shown in fig. 2, the X-ray diffraction pattern indicates that the black solid prepared in this example is nickel ferrite nanoparticles; the transmission electron microscopy image for preparing the nanoparticles is shown in FIG. 3(b), from which it can be seen that the size distribution of the nanoparticles is relatively uniform, with a diameter of about 19.1 nm.
FIG. 4 is an ICP-AES test chart of a second sample of the example, a small amount of the sample is taken and dissolved by concentrated nitric acid, deionized water is added after the sample is fully dissolved, the temperature is kept at 100 ℃ for half an hour to fully decompose and volatilize the nitric acid, and then a proper amount of the sample is taken and placed in a centrifuge tube to be sent for detection. From the test results, the sample prepared in example two was oleic acid-modified Ni0.55Fe2.45O4。
Fig. 5 is a hysteresis loop of the sample of example two, whose magnetic properties were measured at room temperature with a Vibrating Sample Magnetometer (VSM), the picture demonstrating that example two is superparamagnetic at room temperature.
Example three:
1) a100 mL three-necked reaction flask was charged with 1.27g of iron (III) acetylacetonate, 0.19g of nickel (II) acetylacetonate, 0.9g of sodium oleate, 6mL of oleic acid, and 30mL of a benzyl ether solution, and the mixture was dissolved by stirring in N2Under protection, raising the temperature to 295 ℃ at the speed of 6 ℃/min, and reacting for 1h to prepare black nickel ferrite granular crystals with the mass of about 0.42 g.
2) Taking 1mL of nickel ferrite nanoparticles (about 10mg) wrapped by oleic acid, performing centrifugal separation, adding a proper amount of n-hexane for washing, performing centrifugal separation again, and repeating five times.
As shown in fig. 2, the X-ray diffraction pattern indicates that the black solid prepared in this example is nickel ferrite nanoparticles; the transmission electron microscope image of the prepared magnetic nickel ferrite nanoparticle body is shown in fig. 3(c), and it can be known from the image that the size distribution of the nanoparticle body is relatively uniform, and the diameter is about 18.3 nm.
FIG. 4 is an ICP-AES test chart of three samples of the example, a small amount of the sample is taken and dissolved by concentrated nitric acid, deionized water is added after the sample is fully dissolved, the temperature is kept for half an hour after the sample is heated to 100 ℃, the nitric acid is fully decomposed and volatilized, and then a proper amount of the sample is taken and placed in a centrifuge tube to be sent for detection. As can be seen from the test results, the sample prepared in example III was oleic acid-modified Ni0.5Fe2.5O4。
Fig. 5 is a hysteresis loop of the three samples of example whose magnetic properties were measured at room temperature with a Vibrating Sample Magnetometer (VSM), the picture demonstrating that the three samples of example are superparamagnetic at room temperature.
Example four:
1) a100 mL three-necked reaction flask was charged with 1.36g of iron (III) acetylacetonate, 0.14g of nickel (II) acetylacetonate, 0.9g of sodium oleate, 6mL of oleic acid, and 30mL of a benzyl ether solution, and the mixture was dissolved by stirring in N2Under protection, raising the temperature to 295 ℃ at the speed of 6 ℃/min, and reacting for 1h to prepare black nickel ferrite granular crystals with the mass of about 0.42 g.
2) Taking 1mL of nickel ferrite nanoparticles (about 10mg) wrapped by oleic acid, performing centrifugal separation, adding a proper amount of n-hexane for washing, performing centrifugal separation again, and repeating five times.
As shown in fig. 2, the X-ray diffraction pattern indicates that the black solid prepared in this example is nickel ferrite nanoparticles; the transmission electron microscope image of the prepared magnetic nickel ferrite nanoparticle body is shown in fig. 3(d), and it can be known from the image that the size distribution of the nanoparticle body is relatively uniform, and the diameter is about 18.1 nm.
FIG. 4 is an ICP-AES test chart of four samples of the example, a small amount of the sample is taken and dissolved by concentrated nitric acid, deionized water is added after the sample is fully dissolved, the temperature is kept for half an hour after the sample is heated to 100 ℃, the nitric acid is fully decomposed and volatilized, and then a proper amount of the sample is taken and placed in a centrifuge tube to be sent for detection. From the test results, the sample prepared in example four was oleic acid-modified Ni0.35Fe2.65O4。
Fig. 5 is a hysteresis loop of the four samples of example whose magnetic properties were measured at room temperature with a Vibrating Sample Magnetometer (VSM), which demonstrates that the four samples of example are superparamagnetic at room temperature.
Example five:
1) a100 mL three-necked reaction flask was charged with 1.40g of iron (III) acetylacetonate, 0.11g of nickel (II) acetylacetonate, 0.9g of sodium oleate, 6mL of oleic acid, and 30mL of a benzyl ether solution, and the mixture was dissolved by stirring in N2Under protection, raising the temperature to 295 ℃ at the speed of 6 ℃/min, and reacting for 1h to prepare black nickel ferrite granular crystals with the mass of about 0.42 g.
2) Taking 1mL of nickel ferrite nanoparticles (about 10mg) wrapped by oleic acid, performing centrifugal separation, adding a proper amount of n-hexane for washing, performing centrifugal separation again, and repeating five times.
As shown in fig. 2, the X-ray diffraction pattern indicates that the black solid prepared in this example is nickel ferrite nanoparticles; fig. 3(e) shows a transmission electron microscope image of the prepared magnetic nickel ferrite nanoparticles, which shows that the nanoparticles have uniform size distribution and good dispersibility, and the diameter of the nanoparticles is about 18.2 nm.
FIG. 4 is an ICP-AES test chart of five samples of the example, a small amount of the sample is taken and dissolved by concentrated nitric acid, deionized water is added after the sample is fully dissolved, the temperature is kept for half an hour after the sample is heated to 100 ℃, the nitric acid is fully decomposed and volatilized, and then a proper amount of the sample is taken and placed in a centrifuge tube to be sent for detection. From the test results, the sample prepared in example five was oleic acid modified Ni0.27Fe2.73O4。
Fig. 5 is a hysteresis loop of the five samples of example whose magnetic properties were measured at room temperature with a Vibrating Sample Magnetometer (VSM), the pictures demonstrating that the five samples were superparamagnetic at room temperature.
Example six:
1) a100 mL three-necked reaction flask was charged with 1.40g of iron (III) acetylacetonate, 0.11g of nickel (II) acetylacetonate, 0.9g of sodium oleate, 6mL of oleic acid, and 30mL of a benzyl ether solution, and the mixture was dissolved by stirring in N2Under protection, raising the temperature to 295 ℃ at the speed of 6 ℃/min, and reacting for 1h to prepare black nickel ferrite granular crystals with the mass of about 0.42 g.
2) Taking 1mL of nickel ferrite nanoparticles (about 10mg) wrapped by oleic acid, performing centrifugal separation, adding a proper amount of n-hexane for washing, performing centrifugal separation again, and repeating five times.
3) Taking 5mg of nickel ferrite nanoparticles modified by oleic acid, centrifuging by using alcohol to remove the oleic acid, adding the oleic acid into 1ml of Tetrahydrofuran (THF) solution containing 20mg/ml of PS-COOH, carrying out ultrasonic treatment for 5min, and standing for 24h to obtain the nickel ferrite nanoparticles modified by PS and uniformly dispersed in the THF.
As shown in fig. 2, the X-ray diffraction pattern indicates that the black solid prepared in this example is nickel ferrite nanoparticles; the transmission electron microscope image of the prepared magnetic nickel ferrite nanoparticle body is shown in fig. 3(f), and it can be known from the image that the size distribution of the nanoparticle body is uniform and the dispersibility is good, and the diameter is about 18.2 nm.
FIG. 4 is an ICP-AES test chart of six samples in an example, a small amount of sample is taken and dissolved by concentrated nitric acid, deionized water is added after the sample is fully dissolved, the temperature is kept for half an hour after the sample is heated to 100 ℃, the nitric acid is fully decomposed and volatilized, and then a proper amount of sample is taken and placed in a centrifuge tube to be sent for detection. As can be seen from the test results, the sample prepared in example six was oleic acid-modified Ni0.27Fe2.73O4。
FIG. 5 is a hysteresis loop of the six samples of example, which is the same as the characterization results of the five samples of example, and illustrates that the modification does not affect the magnetic properties of the nanoparticles themselves.
FIG. 6 is a thermogravimetric analysis diagram of six samples of the example, a proper amount of PS-COOH with a molecular weight of 5000, oleic acid-modified nickel ferrite and PS-modified nickel ferrite are respectively taken for sample sending detection, and the grafting density of the PS-modified nickel ferrite is calculated to be about 0.22 (chain/nm) according to the diagram2)。
FIG. 7 is a Fourier transform spectrum of six samples of the example, in which a proper amount of oleic acid-modified nickel ferrite and PS-modified nickel ferrite are respectively sampled and detected, and we can see that 1600cm is observed-1The absorption peaks at (A) are from the C ═ C elongation of the aromatic ring of polystyrene, 1494 and 1453cm-1The absorption peak is the C-H bending mode of the aromatic ring of the polystyrene, and PS-COOH is proved to successfully modify the nickel ferrite nano-particles.
Claims (9)
1. A controllable preparation and modification method of nickel ferrite nano-particles is characterized by comprising the following steps;
1) pyrolyzing organic complex of iron and nickel in surfactant and benzyl ether to obtain nickel ferrite nanoparticles;
2) removing unreacted substances by using the nickel ferrite nano-particles obtained in the centrifugal separation step 1) and then using a solvent adding and centrifugal separation mode, and repeating the cleaning for four to five times to prepare a nickel ferrite nano-particle solution;
3) adding C into the nickel ferrite nanoparticle solution obtained in the step 2)1～4Then alcohol ofWashing away the active agent coated on the surface of the nickel ferrite nano-particle by centrifugation, adding the washed active agent into THF solution dissolved with ligand, and successfully modifying to obtain the nickel ferrite nano-particle with high dispersion in THF.
2. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 1, characterized in that: in the step 1), the organic complex of iron and nickel is iron (III) acetylacetonate and nickel (II) acetylacetonate.
3. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 2, characterized in that: in the step 1), the mass/volume ratio of the iron (III) acetylacetonate to the benzyl ether is as follows: and ml is 0.025-0.1: 1.
4. the controllable preparation and modification method of nickel ferrite nanoparticles according to claim 1 or 2, characterized in that: in the step 1), the mass ratio of the nickel element to the iron element is 1: 1. 1: 3. 1: 5. 1: 7. 1: 9, reacting to respectively obtain nickel ferrite with different atomic ratios.
5. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 1, characterized in that: in the step 1), the pyrolysis is carried out in a nitrogen/inert gas protective atmosphere, the temperature is raised to 250-290 ℃ at the speed of 3-10 ℃/min, and the stirring reaction is carried out for 1-2 h.
6. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 1, characterized in that: in the step 2), before solvent cleaning is carried out on the ferronickel oxide nanoparticles, firstly, the ferronickel oxide nanoparticles obtained in the step 1) and the benzyl ether and the oleic acid reactant which are not completely reacted are centrifuged at 11000rpm for 10min to remove the unreacted benzyl ether reactant.
7. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 1, characterized in that: the solvent added in the step 2) is n-hexane; adding a proper amount of n-hexane into the nickel ferrite nanoparticles without the benzyl ether unreacted substances, performing ultrasonic treatment or oscillation at room temperature for 5-10 min, and then centrifuging at 11000rpm for 10min to remove the unreacted substances in the step 1), thereby finally obtaining the nickel ferrite nanoparticles coated with the oleic acid, wherein the size of the nickel ferrite nanoparticles is 10-20 nm.
8. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 1, characterized in that: in step 3), C1～4The alcohol of (a) is ethanol, butanol, propanol or methanol.
9. The controllable preparation and modification method of nickel ferrite nanoparticles as claimed in claim 1, characterized in that: in the step 3), the ligand in the THF is PS-COOH; adding dissolved mass-to-volume ratio g: ml is not less than 0.02: 1, performing ultrasonic treatment or oscillation on a THF solution of PS-COOH with the molecular weight of 2000-5000-.
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