CN115255360B - High-performance FePt@Fe shell-core structure magnetic nanocrystalline and preparation method thereof - Google Patents
High-performance FePt@Fe shell-core structure magnetic nanocrystalline and preparation method thereof Download PDFInfo
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- 229910005335 FePt Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000002159 nanocrystal Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 23
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- 239000000463 material Substances 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 12
- 150000002367 halogens Chemical class 0.000 claims abstract description 12
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 12
- 239000000523 sample Substances 0.000 claims abstract description 7
- 238000002595 magnetic resonance imaging Methods 0.000 claims abstract description 6
- 239000002923 metal particle Substances 0.000 claims abstract description 6
- 239000002872 contrast media Substances 0.000 claims abstract description 4
- 238000003384 imaging method Methods 0.000 claims abstract description 4
- CCCMONHAUSKTEQ-UHFFFAOYSA-N octadecene Natural products CCCCCCCCCCCCCCCCC=C CCCMONHAUSKTEQ-UHFFFAOYSA-N 0.000 claims description 14
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002243 precursor Substances 0.000 claims description 12
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 10
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical group CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims description 10
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 10
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 10
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005642 Oleic acid Substances 0.000 claims description 10
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 10
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims description 8
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical group CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000012071 phase Substances 0.000 claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- BTOOAFQCTJZDRC-UHFFFAOYSA-N 1,2-hexadecanediol Chemical group CCCCCCCCCCCCCCC(O)CO BTOOAFQCTJZDRC-UHFFFAOYSA-N 0.000 claims description 5
- GQEZCXVZFLOKMC-UHFFFAOYSA-N 1-hexadecene Chemical compound CCCCCCCCCCCCCCC=C GQEZCXVZFLOKMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 claims description 4
- MHDVGSVTJDSBDK-UHFFFAOYSA-N dibenzyl ether Chemical compound C=1C=CC=CC=1COCC1=CC=CC=C1 MHDVGSVTJDSBDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000000197 pyrolysis Methods 0.000 claims description 4
- PRAKJMSDJKAYCZ-UHFFFAOYSA-N squalane Chemical compound CC(C)CCCC(C)CCCC(C)CCCCC(C)CCCC(C)CCCC(C)C PRAKJMSDJKAYCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003381 stabilizer Substances 0.000 claims description 4
- CMHKGULXIWIGBU-UHFFFAOYSA-N [Fe].[Pt] Chemical compound [Fe].[Pt] CMHKGULXIWIGBU-UHFFFAOYSA-N 0.000 claims description 2
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- JXTPJDDICSTXJX-UHFFFAOYSA-N n-Triacontane Natural products CCCCCCCCCCCCCCCCCCCCCCCCCCCCCC JXTPJDDICSTXJX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 229940032094 squalane Drugs 0.000 claims description 2
- 239000011232 storage material Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 5
- 229910000640 Fe alloy Inorganic materials 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 230000005415 magnetization Effects 0.000 abstract description 6
- 238000005580 one pot reaction Methods 0.000 abstract description 3
- 239000011162 core material Substances 0.000 description 39
- 239000002105 nanoparticle Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 9
- 239000011258 core-shell material Substances 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011257 shell material Substances 0.000 description 8
- 230000005540 biological transmission Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000000634 powder X-ray diffraction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- -1 2-hexadecanediol Chemical compound 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 230000008878 coupling Effects 0.000 description 3
- 238000010168 coupling process Methods 0.000 description 3
- 238000005859 coupling reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000012869 ethanol precipitation Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- 239000002122 magnetic nanoparticle Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 230000001404 mediated effect Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000005086 pumping Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/17—Metallic particles coated with metal
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01R—MEASURING ELECTRIC VARIABLES; MEASURING MAGNETIC VARIABLES
- G01R33/00—Arrangements or instruments for measuring magnetic variables
- G01R33/20—Arrangements or instruments for measuring magnetic variables involving magnetic resonance
- G01R33/44—Arrangements or instruments for measuring magnetic variables involving magnetic resonance using nuclear magnetic resonance [NMR]
Abstract
The invention discloses a high-performance FePt@Fe shell-core structure magnetic nanocrystal and a preparation method thereof. The metal alloy-metal particle shell-core structure nanocrystalline comprises a core region and a shell region; the material constituting the core region is a metal alloy and the material constituting the shell region is a metal atom. The metal alloy-metal atom shell-core structure nanocrystalline prepared by the invention has small size and wide magnetic property regulation and control, and can be used for structural elements of magnetic devices such as magnetic recording, magnetic storage and the like. The metal alloy-metal shell-core structure nanocrystalline prepared by the method has wide magnetic property regulation and control, can be used for contrast agents or magnetic probes for MRI (magnetic resonance imaging), ultra-low field imaging and the like, and has adjustable saturation magnetization and adjustable low saturation magnetization. The invention provides a simple, efficient and low-cost halogen one-pot synthesis method, which can prepare metal alloy-metal atom shell-core structure nanocrystalline which is synthesized in a large scale, has good monodispersity and controllable magnetic property.
Description
Technical Field
The invention relates to a high-performance FePt@Fe shell-core structure magnetic nanocrystal and a preparation method thereof, and belongs to the field of nanomaterials.
Background
The exchange coupled nanocomposite with the shell/core phase is promising as a next generation magnetic memory material. Because of the magnetic coupling exchange interaction between the core shells, the regulation and control of the magnetic coupling effect can be realized by regulating and controlling the size, the crystallinity and the interface, and further, the basic magnetic properties such as the saturation magnetization, the residual magnetic property and the blocking temperature of the material are optimized, so that the magnetic coupling magnetic material can be applied to the fields of medicine, aviation, biology, materials and the like.
However, the preparation of the core-shell structure magnetic material is mostly carried out by adopting a seed-mediated growth method, the methods are complex to operate and require a high-temperature calcination process, so that the preparation method not only consumes time and reagents, but also has poor monodispersity of the prepared core-shell material, and the morphology and properties of the particles are difficult to regulate. And further limit the magnetic performance and application research of the shell-core particles. In view of the above, a simple and efficient method is designed, and the preparation of the shell-core material with good monodispersity and controllable crystal forms has important scientific significance and value.
Disclosure of Invention
The invention aims to provide a metal alloy-metal atom shell-core structure nanocrystalline, which is synthesized by adopting a halogen-mediated one-pot method, so that the shell-core structure can be regulated in size, and the crystal form of the shell-core double-magnetic nanocrystalline can be regulated; the method has the characteristics of simplicity, high efficiency and low cost, and can prepare large-scale synthesized metal alloy-metal particle shell-core structure nanocrystals with good monodispersity and super-controllable magnetic performance.
The invention provides a metal alloy-metal particle shell-core structure nanocrystalline, which comprises a core region and a shell region;
the material constituting the nuclear region is a metal alloy;
the material comprising the shell region is a metal atom.
Preferably, the metal alloy is a face-centered tetragonal type iron-platinized alloy (formula FePt), wherein the atomic number ratio of platinum to iron is 1:1;
the metal atoms are iron atoms, and can be expanded to other metal atoms according to the needs.
The metal alloy-metal particle shell-core structure nanocrystalline provided by the invention is preferably FePt@Fe shell-core nanocrystalline;
wherein the diameter of the nuclear region is 3-10 nm;
the grain diameter of the shell-core structure nanocrystalline is 3-11 nm.
The invention also provides a preparation method of the shell-core structure nanocrystalline, which comprises the following steps:
mixing the precursor of the metal alloy and the precursor of the metal atom in the same closed reaction container under the protection of inert atmosphere, adding an organic phase and a halogen source, and adopting an oil phase high-temperature thermal decomposition method to react.
In the preparation method, the precursor of the metal alloy is a mixture of platinum acetylacetonate and iron acetylacetonate;
the precursor of the metal atom is ferric acetylacetonate;
the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
In the preparation method, the organic phase is a mixture of a stabilizer, a reducing agent and a solvent;
the stabilizer is oleylamine and oleic acid;
the reducing agent is 1, 2-hexadecane diol;
the solvent is at least one of octadecene, hexadecene, dibenzyl ether and squalane;
the halogen source is ammonium chloride or sodium chloride.
In the preparation method, the oil phase high-temperature thermal decomposition method is carried out for 30 min-2 h, and the temperature is 180-300 ℃.
In the above preparation method, the molar ratio of the precursor of the metal alloy, the reducing agent, the precursor of the metal atom, the halogen source, the oleylamine, the oleic acid and the solvent is: 1: 1-20: 1:1 to 9:2 to 50:2 to 50:30 to 320, preferably 1:3:6: 6-10: 6-10: 3:62.5, 1:3:6:6:6:3:62.5 or 1:3:6:6:6:3:62.5.
after the oil phase high temperature pyrolysis method is reacted, the method further comprises the following steps: centrifugal washing, collecting solid products, and then re-suspending in a good solvent to obtain a solution of the magnetic nanocrystalline with a shell-core structure, wherein the solution can be stored in a refrigerating way;
the conditions of the centrifugal washing may be: adding a precipitator, wherein the rotating speed is 3000-8000 r/min, and the centrifugation time is 5-20 min; specifically, ethanol solvent is added, 5000r/min, and the mixture is centrifuged for 10min and repeated for 5 times.
The shell-core structure nanocrystalline provided by the invention can be used for at least one of the following 1) -5):
1) Preparing a catalytic material;
2) Preparing a magnetic storage material;
3) Cell magnetic imaging detection;
4) Preparing an ultralow field probe;
5) A contrast agent for magnetic resonance imaging is prepared.
The invention has the following advantages:
1. the preparation method can obtain the core-shell structure magnetic nano material without multi-pot synthesis, avoids the defects of complicated steps for synthesizing the core-shell structure by a seed method, waste of experiment consumable reagents and waste of time, and is simple, efficient, low in cost and time-saving.
2. The core-shell structure magnetic nanocrystalline prepared by the invention is nano-scale, good in monodispersity and uniform in size.
3. The core-shell structure magnetic nanocrystalline shell and core prepared by the invention has controllable crystal forms, and the crystal forms of the whole nanomaterial can be controlled by adjusting the proportion of the halogen source participating in the reaction.
4. The magnetic property of the core-shell structure magnetic nanocrystalline prepared by the invention is controllable, and the magnetic property of the whole nanomaterial is adjusted by adjusting the nanocrystalline form.
5. The material related by the invention can be purchased, and meanwhile, the method is novel, the process is simple, the equipment is common, the operability is good, the function is strong, and a large amount of double-magnetic functional nano magnetic materials with shell-core structures can be prepared at one time.
6. The metal alloy-metal atom shell-core structure nanocrystalline prepared by the invention has small size and wide magnetic property regulation and control, and can be used for structural elements of magnetic devices such as magnetic recording, magnetic storage and the like.
7. The metal alloy-metal shell-core structure nanocrystalline prepared by the method has wide magnetic property regulation and control, can be used for contrast agents or magnetic probes for MRI (magnetic resonance imaging), ultra-low field imaging and the like, and has adjustable saturation magnetization and adjustable low saturation magnetization.
In conclusion, the invention provides a simple, efficient and low-cost halogen one-pot synthesis method, which can prepare metal alloy-metal atom shell-core structure nanocrystals which are synthesized in a large scale, have good monodispersity and controllable magnetic performance.
Drawings
FIG. 1 is a schematic diagram of a device and nanocrystals of FePt@Fe shell-core magnetic nanocrystals prepared in example 1 of the present invention.
FIG. 2 is a high resolution transmission electron microscope (HTEM) image and an elemental scanning image of FePt@Fe shell-core magnetic nanocrystals prepared in example 1 of the present invention; fig. 2a is a high-resolution transmission electron microscope (HTEM) diagram of the fept@fe shell-core magnetic nanocrystal, and fig. 2b, fig. 2c and fig. 2d are diagrams of a platinum element scan, an iron element scan and a platinum-iron element scan, respectively.
Fig. 3 is a Transmission Electron Microscope (TEM) image of FePt nanoparticles prepared in example 2 of the present invention.
FIG. 4 is a Transmission Electron Microscope (TEM) image of FePt@Fe shell-core structure nanocrystals prepared in example 3 of the present invention.
Fig. 5 is a graph showing the X-ray powder diffraction (XRD) test results of the fept@fe core-shell magnetic nanocrystal prepared in example 1 of the present invention and the FePt nanoparticle prepared in example 2.
FIG. 6 is a graph of magnetic properties (H-M) of FePt@Fe shell-core magnetic nanocrystals prepared in example 1 and FePt nanoparticles prepared in example 2, 5K according to the present invention.
FIG. 7 is a graph showing the FC-ZFC curve measured for FePt@Fe shell core magnetic nanocrystals prepared in example 1 of the present invention.
FIG. 8 is a graph showing the FC-ZFC measured for FePt nanoparticles prepared in example 2 of the present invention.
Detailed Description
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of tetragonal FePt@Fe core-shell Structure nanocrystalline
The preparation was carried out in the apparatus shown in fig. 1, and the specific procedure was as follows:
0.5mmol of platinum acetylacetonate, 1.5mmol of 1, 2-hexadecanediol and 20mL of 1-octadecene are added into a 150mL three-necked flask, the mixture is stirred and mixed uniformly by magnetic force at 1600rpm/min, the vacuum is pumped at 40 ℃ for 30min, nitrogen is introduced, 1.6mL of oleic acid, 1.7mL of oleylamine, 1.5mmol of ammonium chloride and 3mmol of ferric acetylacetonate are added (platinum acetylacetonate, 2-hexadecanediol, ferric acetylacetonate, oleic acid, oleylamine, ammonium chloride, 1-octadecene in a ratio of 1:3:6:10:10:3:62.5), the mixture is pumped at 80 ℃ for 30min, the nitrogen is introduced, and the temperature is raised to 300 ℃ and the mixture is refluxed for 30min. Removing heat source, cooling to room temperature, adding appropriate amount of ethanol, centrifuging at 6000r/min for 10min, collecting precipitate, adding appropriate amount of cyclohexane, dissolving the product, centrifuging at 6000r/min for 10min again, collecting supernatant, repeating ethanol precipitation/cyclohexane dispersion process for 3 times, and finally directly using the prepared magnetic nanoparticle for next experiment, or dispersing in cyclohexane, storing in sample bottle, and placing in refrigerator at 4deg.C.
High resolution transmission electron microscope (HTEM) pictures of FePt@Fe shell-core structured nanocrystals prepared in example 1 of the present invention are shown in FIG. 2. XRD characterization of FePt@Fe shell-core structure nanocrystals prepared in example 1 of the present invention is shown in FIG. 5. The magnetic properties of the FePt@Fe shell-core structure nanocrystals prepared in example 1 of the present invention are shown in FIGS. 6 and 7.
As can be seen from FIG. 2, the nanocrystals prepared in the present invention have a shell-core structure, the entire nanocrystal has a pea shape and uniform size, the average size of the core is about 7.4nm, and the average thickness of the shell layer is about 0.46nm. As can be seen from fig. 5, the diffraction peaks measured for the fept@fe shell-core structure nanocrystals prepared according to the present invention correspond to the off-peak positions of the face-centered tetragonal FePt nanoparticles and pure Fe particles, respectively.
Example 2: preparation of FePt nanocrystals vs example 1
0.5mmol of platinum acetylacetonate, 1.5mmol of 1, 2-hexadecanediol and 20mL of 1-octadecene are added into a 150mL three-necked flask, the mixture is stirred and mixed uniformly by magnetic force at 1600rpm/min, the vacuum is pumped at 40 ℃ for 30min, nitrogen is introduced, 1.6mL of oleic acid, 1.7mL of oleylamine and 3mmol of ferric acetylacetonate (platinum acetylacetonate, 2-hexadecanediol, ferric acetylacetonate, oleic acid, oleylamine and 1-octadecene are in a ratio of 1:3:6:10:10:62.5) are added, the vacuum is pumped at 80 ℃ for 30min, the nitrogen is introduced, and the temperature is raised to 300 ℃ and the reflux is carried out for 30min. Removing heat source, cooling to room temperature, adding appropriate amount of ethanol, centrifuging at 6000r/min for 10min, collecting precipitate, adding appropriate amount of cyclohexane, dissolving the product, centrifuging at 6000r/min for 10min again, collecting supernatant, repeating ethanol precipitation/cyclohexane dispersion process for 3 times, and finally directly using the prepared magnetic nanoparticle for next experiment, or dispersing in cyclohexane, storing in sample bottle, and placing in refrigerator at 4deg.C.
A Transmission Electron Microscope (TEM) picture of the FePt nanocrystals prepared from this example 2 is shown in fig. 3. XRD characterization of FePt nanoparticles prepared from example 2 is shown in section 5. The magnetic properties of the FePt nanoparticles prepared from example 2 are characterized in figures 6 and 8.
As can be seen from fig. 3, the prepared nanoparticles have an oval shape and a uniform size, and the average size is about 5nm. As can be seen from fig. 5, the diffraction peak measured by the prepared FePt nanoparticles corresponds to the peak position of the cubic FCC structure of the pure FePt nanoparticles, which indicates that the FCT face-centered square crystal form peak of the FePt nanoparticles appears after the halogen source is added in the preparation process, but the FCT face-centered square crystal form peak does not appear when the halogen source is not added. Comparing fig. 6, fig. 7, and fig. 8, it can be seen that the fept@fe shell-core structure nanocrystal prepared in example 1 has higher saturation magnetization and blocking temperature due to the magnetic coupling exchange interaction between the core and the shell.
Example 3: preparation of FePt@Fe shell-core structure nanocrystals with different sizes
0.5mmol of platinum acetylacetonate, 1.5mmol of 1, 2-hexadecanediol and 20mL of 1-octadecene are added into a 150mL three-necked bottle, the mixture is stirred and mixed uniformly by magnetic force at 1600rpm/min, vacuum pumping is carried out at 40 ℃ for 30min, nitrogen is introduced, 1mL of oleic acid, 1mL of oleylamine, 1.5mmol of ammonium chloride and 3mmol of ferric acetylacetonate (platinum acetylacetonate, 2-hexadecanediol, ferric acetylacetonate, oleic acid, oleylamine, ammonium chloride, 1-octadecene are in a ratio of 1:3:6:6:6:3:62.5) are added, vacuum pumping is carried out at 80 ℃ for 30min, nitrogen is introduced, the temperature is raised to 300 ℃, and reflux is carried out for 30min. Removing heat source, cooling to room temperature, adding appropriate amount of ethanol, centrifuging at 6000r/min for 10min, collecting precipitate, adding appropriate amount of cyclohexane, dissolving the product, centrifuging at 6000r/min for 10min again, collecting supernatant, repeating ethanol precipitation/cyclohexane dispersion process for 3 times, and finally directly using the prepared magnetic nanoparticle for next experiment, or dispersing in cyclohexane, storing in sample bottle, and placing in refrigerator at 4deg.C.
A Transmission Electron Microscope (TEM) image of the FePt@Fe shell-core structure nanocrystal prepared in this example 3 is shown in FIG. 4. As can be seen from FIG. 4, the prepared nanoparticles have an oval shape and a uniform size, the average size of the core is about 6nm, and the average thickness of the shell is about 0.3nm. As can be seen from comparative examples 1 and 3, the size of the product nanoparticles becomes smaller when the surface ligand is at a low concentration. It was demonstrated that the size of the nanoparticles can be regulated by surface ligands.
Claims (8)
1. A preparation method of metal alloy-metal particle shell-core structure nanocrystalline comprises the following steps:
mixing a precursor of a metal alloy and a precursor of a metal atom in the same closed reaction container under the protection of inert atmosphere, adding an organic phase and a halogen source, and reacting by adopting an oil phase high-temperature pyrolysis method to obtain the metal alloy;
the halogen source is ammonium chloride;
the metal alloy-metal particle shell-core structure nanocrystalline comprises a core region and a shell region;
the material constituting the nuclear region is a metal alloy; the metal alloy is a face-centered tetragonal platinum iron alloy;
the material comprising the shell region is a metal atom; the metal atom is an iron atom;
the temperature of the oil phase high temperature pyrolysis reaction is 180-300 ℃.
2. The method of manufacturing according to claim 1, characterized in that: the shell-core structure nanocrystalline is FePt@Fe shell-core structure nanocrystalline.
3. The preparation method according to claim 1 or 2, characterized in that: the diameter of the nuclear region is 3-10 nm;
the grain diameter of the shell-core structure nanocrystalline is 3-11 nm.
4. The method of manufacturing according to claim 1, characterized in that: the precursor of the metal alloy is a mixture of platinum acetylacetonate and iron acetylacetonate;
the precursor of the metal atom is ferric acetylacetonate;
the inert atmosphere comprises a nitrogen atmosphere and/or an argon atmosphere.
5. The method of manufacturing according to claim 1, characterized in that: the organic phase is a mixture of a stabilizer, a reducing agent and a solvent;
the stabilizer is oleylamine and oleic acid;
the reducing agent is 1, 2-hexadecane diol;
the solvent is at least one of octadecene, hexadecene, dibenzyl ether and squalane.
6. The method of manufacturing according to claim 1, characterized in that: the oil phase high temperature pyrolysis reaction time is 30 min-2 h.
7. The method of manufacturing according to claim 5, wherein: the molar ratio of the precursor of the metal alloy, the reducing agent, the precursor of the metal atom, the halogen source, the oleylamine, the oleic acid and the solvent is 1: 1-20: 1:1 to 9:2 to 50: 30-320.
8. Use of the shell-core structure nanocrystals prepared by the method of any one of claims 1 to 7 in at least one of the following 1) to 5):
1) Preparing a catalytic material;
2) Preparing a magnetic storage material;
3) Cell magnetic imaging detection;
4) Preparing an ultralow field probe;
5) A contrast agent for magnetic resonance imaging is prepared.
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