CN106830094B - A kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle - Google Patents
A kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle Download PDFInfo
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- 239000002105 nanoparticle Substances 0.000 title claims abstract description 67
- 230000005307 ferromagnetism Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 claims abstract description 32
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 229910002902 BiFeO3 Inorganic materials 0.000 claims abstract description 27
- 229920000962 poly(amidoamine) Polymers 0.000 claims abstract description 27
- 239000000412 dendrimer Substances 0.000 claims abstract description 26
- 229920000736 dendritic polymer Polymers 0.000 claims abstract description 20
- 230000005291 magnetic effect Effects 0.000 claims abstract description 20
- SENLDUJVTGGYIH-UHFFFAOYSA-N n-(2-aminoethyl)-3-[[3-(2-aminoethylamino)-3-oxopropyl]-[2-[bis[3-(2-aminoethylamino)-3-oxopropyl]amino]ethyl]amino]propanamide Chemical compound NCCNC(=O)CCN(CCC(=O)NCCN)CCN(CCC(=O)NCCN)CCC(=O)NCCN SENLDUJVTGGYIH-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 claims abstract description 13
- 239000013049 sediment Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 31
- 238000003756 stirring Methods 0.000 claims description 25
- 239000007864 aqueous solution Substances 0.000 claims description 24
- 239000000126 substance Substances 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 13
- 229910021641 deionized water Inorganic materials 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 12
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 125000004185 ester group Chemical group 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 claims description 6
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 125000003368 amide group Chemical group 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 239000000428 dust Substances 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000013589 supplement Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 claims 1
- 230000003111 delayed effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000005415 magnetization Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 230000005389 magnetism Effects 0.000 abstract 1
- 238000002955 isolation Methods 0.000 description 5
- 230000005294 ferromagnetic effect Effects 0.000 description 4
- 229920002472 Starch Polymers 0.000 description 3
- 238000002242 deionisation method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 235000019698 starch Nutrition 0.000 description 3
- 239000008107 starch Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003519 biomedical and dental material Substances 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 230000005621 ferroelectricity Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000005690 magnetoelectric effect Effects 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002277 temperature effect Effects 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Classifications
-
- 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
- C01G49/0081—Mixed oxides or hydroxides containing iron in unusual valence state [IV, V, VI]
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/843—Arsenic, antimony or bismuth
- B01J23/8437—Bismuth
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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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
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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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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- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Catalysts (AREA)
- Hard Magnetic Materials (AREA)
Abstract
The present invention relates to a kind of ferromagnetism BiFeO3‑γ‑Fe2O3The preparation method of nuclear shell structured nano particle, it is characterised in that：First with polyamide-amide（PAMAM）Dendrimer is template, and ferromagnetism BiFeO is made using solvent-thermal method3Nano particle, then with suitable pamam dendrimer molecule to BiFeO3Nano particle is coated, and FeCl is then added dropwise3·6H2O or Fe (NO3)3·9H2O solution, makes Fe3+It is coordinated with dendrimer, reaction solution pH is adjusted to 7~9, gained magnetism sediment is placed in Muffle furnace, 2h is calcined at 300 DEG C, obtains ferromagnetism BiFeO3‑γ‑Fe2O3Nuclear shell structured nano particle.Nano particle photochemical catalyst good dispersion prepared by the present invention, saturation magnetization is high, and photocatalytic activity is high, can be used as the fields such as magnetic recovery visible light catalyst and sensor material, has broad application prospects.
Description
Technical field
The present invention relates to a kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle belongs to material
Preparing technical field.
Background technology
BiFeO3It is the multiferroic semi-conducting material that a kind of band gap is about 2.2eV, can fully absorbs using can
It is light-exposed, there is ferroelectricity and weak ferromagnetism at room temperature, and magnetoelectric effect can be generated.BiFeO3Pattern and microcosmic knot
Structure influences very big, the BiFeO of small size to its performance3Nano particle has the specific surface area of bigger, stronger quantum size effect
It answers, small-size effect and macro quanta tunnel effect, stronger adsorption capacity and photocatalyst activity can be shown.In addition,
BiFeO3Magnetic structure long period be 62nm, when the macro-size of bismuth ferrite be less than this length when, spiral magnetic structure quilt
It destroys, ferromagnetism improves, and therefore, prepares that size is as small as possible, BiFeO of pure phase3, try to promote its photocatalytic activity and saturation
The intensity of magnetization becomes one of research hotspot.γ-Fe2O3Nano-particle has superparamagnetism, and cost of material is less expensive, in magnetic
The fields such as fluid, magnetic storage, magnetic-optic devices, catalyst, bio-medical material have wide practical use, if be made
BiFeO3-γ-Fe2O3Nuclear shell structured nano particle can obtain saturation magnetization ratio BiFeO3It is higher, have ferromagnetism
, more excellent performance of nanocomposite, but related report is also seldom.
Currently, we using pamam dendrimer molecule as template, use solvent-thermal method prepared diameter 10 nm with
Under pure phase BiFeO3Nano particle, good dispersion have high catalytic activity under visible light illumination, have ferromagnetism, saturation
The intensity of magnetization has prepared ferromagnetism BiFeO up to 24.6 emu/g, the present invention i.e. as core3-γ-Fe2O3Nucleocapsid structure
Nano particle has very in fields such as magnetic recovery visible light catalyst, emr fluid material, sensor and storage materials
Strong theory significance and application value.
Invention content
The object of the present invention is to provide a kind of ferromagnetism BiFeO that can prepare high saturation and magnetic intensity3-γ-Fe2O3
The method of nuclear shell structured nano particle makes gained BiFeO3-γ-Fe2O3Nuclear shell structured nano particle has high magnetic recovery
Rate, high absorption capacity and photocatalytic activity.Its technology contents is：
A kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is characterised in that：
Include the following steps：
（1）Ferromagnetism pure phase BiFeO3It is prepared by nano particle：
The ferromagnetism pure phase BiFeO3Nano particle prepare preparation process be：By the Fe of the amount of equal substances
(NO3)3·9H2O and Bi (NO3)3·5H2O is added in organic solvent, and a concentration of 8~10% dilute nitre is slowly added dropwise while stirring
Acid is to Fe (NO3)3·9H2O and Bi (NO3)3·5H2O is completely dissolved, and adds pamam dendrimer molecular solution, use power for
After the supersonic wave cleaning machine concussion 5min of 50W, it is placed in 2~4h of stirring at room temperature, makes Fe3+And Bi3+Fully match with dendrimer
Mixing speed is adjusted to 800 r/min or more by position, and concentrated alkali solution, which is added, makes the pH value of reaction system be 13~14, stirs at room temperature
After mixing reaction 1h, reaction solution is transferred in hydrothermal reaction kettle, supplement organic solvent or deionized water make compactedness be 70%~
80%, concentrated alkali solution, which is added, makes the pH value of reaction system be 13~14, and reaction kettle is placed in 130~140 DEG C of baking oven after sealing
In, it takes out, centrifuges after keeping the temperature 12~18h, it is neutral, centrifuged deposit object to be washed sediment to pH value with deionized water
As ferromagnetism pure phase BiFeO3Nano particle.
（2）Ferromagnetism BiFeO3-γ-Fe2O3The preparation of nuclear shell structured nano particle：
The ferromagnetism BiFeO3-γ-Fe2O3The preparation process of nuclear shell structured nano particle is：By step（1）Gained
Ferromagnetism pure phase BiFeO3Nano particle is distributed in water, after using power to shake 30min for the supersonic wave cleaning machine of 50W, drop
Add a concentration of 1 × 10-4~1 × 10-2The pamam dendrimer molecule aqueous solution of mol/L stirs 2h or more, obtains surface and coat
The BiFeO of dendrimer3- PAMAM nano particles, are then added dropwise FeCl3·6H2O or Fe (NO3)3·9H2O aqueous solutions, at room temperature
Stirring coordination 2h or more, is adjusted to 800 r/min or more by mixing speed, is warming up to 40~60 DEG C, be added 0.01 mol/L's
The pH value of reaction system is adjusted to 7~9 by NaOH aqueous solutions, after being stirred to react 1h, sediment is carried out Magnetic Isolation, uses deionization
Water cleans magnetic product 3 time or more, dries, is placed in Muffle furnace at 60 DEG C or less, is warming up to 300 DEG C, calcining 2h, naturally cold
But up to ferromagnetism BiFeO3-γ-Fe2O3Nuclear shell structured nano particle.
A kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is characterised in that：
The step（1）In pamam dendrimer molecule algebraically be 4~6 generations, end group be ester group, hydroxyl or carboxyl, addition with
Fe3+Or Bi3+Amount ratio with the substance of dendrimer is 100:1~10:1 is standard, and the solvent of dendrimer solution is water or second
Alcohol, a concentration of 1 × 10-4~1 × 10-2mol/L；The step（2）In pamam dendrimer molecule end group be amido or
Ester group, algebraically were 5~6 generations, and addition is step（1）In 10~50 times of amount of substance of added dendrimer.
A kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is characterised in that：
Organic solvent is ethyl alcohol or acetone, and the volume ratio of organic solvent and water is 1 in reaction kettle:4~1:1, Fe (NO3)3·9H2O、Bi
(NO3)3·5H2O or FeCl3·6H2A concentration of 0.01~0.1 mol/L of O, step（2）Middle Fe (NO3)3·9H2O or
FeCl3·6H2The addition of O is step（1）In added Fe (NO3)3·9H21~5 times of the amount of O substances.
A kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is characterised in that：
Step（1）Middle aqueous slkali is the aqueous solution of the NaOH or KOH of a concentration of 4~8 mol/L, and aqueous slkali is added portionwise, first adds
Enter amount and is no less than reactant Fe (NO in system3)3·9H2O、Bi(NO3)3·5H2The summation of the amount of the substance of O and nitric acid, then
It is added dropwise to regulation pH value.
Compared with prior art, the present invention having the following advantages that：
1, the present invention use the coefficient of dispersion close to 1 spherical shape pamam dendrimer molecule for template, using solvent heat side
BiFeO is first made in method3Then nano particle adsorbs one layer of pamam dendrimer molecule of cladding in particle surface, and tree-like with these
Molecule is that Fe (OH) has been prepared in situ in template3Nano particle is coated on BiFeO3Shell is formed around nano particle, is forged through 300 DEG C
Burning obtains BiFeO3-γ-Fe2O3Nuclear shell structured nano particle, this particle have high absorption capacity, have under visible light illumination
There are high catalytic activity, saturation magnetization to reach 32.99 emu/g；
2, the present invention prepares BiFeO using solvent-thermal method and low temperature calcination method3-γ-Fe2O3Nuclear shell structured nano particle,
It is simple for process, it can be used for the fields such as magnetic recovery visible light catalyst and sensor material.
Specific implementation mode
Embodiment 1：
Step（1）：Ferromagnetism pure phase BiFeO3It is prepared by nano particle：By the Fe (NO of the amount of equal substances3)3·9H2O and Bi
(NO3)3·5H2O is added in acetone, and a concentration of 10% dust technology is slowly added dropwise while stirring to Fe (NO3)3·9H2O and Bi
(NO3)3·5H2O is completely dissolved, Fe3+Or Bi3+A concentration of 0.01 mol/L, add end group be ester group 4 generations
Pamam dendrimer molecule aqueous solution, a concentration of the 1 × 10 of dendrimer-2Mol/L, addition is with Fe3+Or Bi3+With dendrimer
Substance amount ratio be 10:1 is standard, after using power to shake 5min for the supersonic wave cleaning machine of 50W, is placed in and stirs at room temperature
2 h, make Fe3+And Bi3+After being fully coordinated with dendrimer, mixing speed is adjusted to 800 r/min or more, 6 mol/L are added
KOH aqueous solutions make reaction system pH value be 13, after being stirred to react 1h at room temperature, reaction solution is transferred to hydrothermal reaction kettle
In, acetone or deionized water are supplemented, it is 75% to make compactedness, and the volume ratio of acetone and water is 1:2, KOH solution, which is added, makes reactant
The pH value of system is 13, and reaction kettle is placed in 140 DEG C of baking oven after sealing, is taken out after keeping the temperature 12h, centrifuges, uses deionization
It is neutrality that water, which washs sediment to pH value, and centrifuged deposit object is ferromagnetism pure phase BiFeO3Nano particle.
Step（2）：Ferromagnetism BiFeO3-γ-Fe2O3The preparation of nuclear shell structured nano particle：By step（1）Gained is ferromagnetic
Property pure phase BiFeO3Nano particle is distributed in water, after using power to shake 30min for the supersonic wave cleaning machine of 50W, is added dropwise dense
Degree is 1 × 10-2The end group of mol/L is 5 generation pamam dendrimer molecule aqueous solutions of amido, and addition is step（1）In
50 times of the amount of the substance of added dendrimer stir 2h or more, obtain the BiFeO that surface has coated dendrimer3-PAMAM
Then Fe (the NO of a concentration of 0.01 mol/L are added dropwise in nano particle3)3·9H2O aqueous solutions, addition are step（1）In it is added
Fe(NO3)3·9H25 times of the amount of O substances, stirring coordination 2h or more, 800 r/min or more are adjusted to by mixing speed at room temperature,
40 DEG C are warming up to, the pH value of reaction system is adjusted to 7 by the NaOH aqueous solutions that 0.01 mol/L is added, and after being stirred to react 1h, will be sunk
Starch carries out Magnetic Isolation, is cleaned magnetic product 3 times or more with deionized water, dries, is placed in Muffle furnace at 60 DEG C or less,
300 DEG C are warming up to, calcines 2h, natural cooling is up to ferromagnetism BiFeO3-γ-Fe2O3Nuclear shell structured nano particle.
Embodiment 2：
Step（1）：Ferromagnetism pure phase BiFeO3It is prepared by nano particle：By the Fe (NO of the amount of equal substances3)3·9H2O and Bi
(NO3)3·5H2O is added in acetone, and a concentration of 10% dust technology is slowly added dropwise while stirring to Fe (NO3)3·9H2O and Bi
(NO3)3·5H2O is completely dissolved, Fe3+Or Bi3+A concentration of 0.05 mol/L, add end group be carboxyl 5 generations
Pamam dendrimer molecule aqueous solution, a concentration of the 1 × 10 of dendrimer-3Mol/L, addition is with Fe3+Or Bi3+With dendrimer
Molar ratio be 50:1 is standard, after using power to shake 5min for the supersonic wave cleaning machine of 50W, is placed in and stirs 3 h at room temperature,
Make Fe3+And Bi3+After being fully coordinated with dendrimer, mixing speed is adjusted to 800 r/min or more, the KOH of 6 mol/L is added
Aqueous solution makes the pH value of reaction system be 13, and after being stirred to react 1h at room temperature, reaction solution is transferred in hydrothermal reaction kettle, is supplemented
Acetone or deionized water, it is 80% to make compactedness, and the volume ratio of acetone and water is 1:4, KOH solution, which is added, makes the pH of reaction system
Value is 14, and reaction kettle is placed in 140 DEG C of baking oven after sealing, is taken out after keeping the temperature 12h, centrifuges, will be sunk with deionized water
It is neutrality that starch, which is washed to pH value, and centrifuged deposit object is ferromagnetism pure phase BiFeO3Nano particle.
Step（2）：Ferromagnetism BiFeO3-γ-Fe2O3The preparation of nuclear shell structured nano particle：By step（1）Gained is ferromagnetic
Property pure phase BiFeO3Nano particle is distributed in water, after using power to shake 30min for the supersonic wave cleaning machine of 50W, is added dropwise dense
Degree is 1 × 10-3The end group of mol/L is 6 generation pamam dendrimer molecule aqueous solutions of amido, and addition is step（1）In
20 times of the amount of the substance of added dendrimer stir 2h or more, obtain the BiFeO that surface has coated dendrimer3-PAMAM
Then Fe (the NO of a concentration of 0.05 mol/L are added dropwise in nano particle3)3·9H2O aqueous solutions, addition are step（1）In it is added
Fe(NO3)3·9H22 times of the amount of O substances, stirring coordination 2h or more, 800 r/min or more are adjusted to by mixing speed at room temperature,
50 DEG C are warming up to, the pH value of reaction system is adjusted to 7 by the NaOH aqueous solutions that 0.01 mol/L is added, and after being stirred to react 1h, will be sunk
Starch carries out Magnetic Isolation, is cleaned magnetic product 3 times or more with deionized water, dries, is placed in Muffle furnace at 60 DEG C or less,
300 DEG C are warming up to, calcines 2h, natural cooling is up to ferromagnetism BiFeO3-γ-Fe2O3Nuclear shell structured nano particle.
Embodiment 3：
Step（1）：Ferromagnetism pure phase BiFeO3It is prepared by nano particle：By the Fe (NO of the amount of equal substances3)3·9H2O and Bi
(NO3)3·5H2O is added in ethyl alcohol, and a concentration of 8% dust technology is slowly added dropwise while stirring to Fe (NO3)3·9H2O and Bi
(NO3)3·5H2O is completely dissolved, Fe3+Or Bi3+A concentration of 0.1 mol/L, add end group be ester group 6 generation PAMAM
Dendrimer ethanol solution, a concentration of the 1 × 10 of dendrimer-4Mol/L, addition is with Fe3+Or Bi3+With the object of dendrimer
The amount ratio of matter is 100:1 is standard, after using power to shake 5min for the supersonic wave cleaning machine of 50W, is placed in and stirs 4 at room temperature
H makes Fe3+And Bi3+After being fully coordinated with dendrimer, mixing speed is adjusted to 800 r/min or more, is added 8 mol/L's
NaOH aqueous solutions make the pH value of reaction system be 13, and after being stirred to react 1h at room temperature, reaction solution is transferred in hydrothermal reaction kettle,
Ethyl alcohol or deionized water are supplemented, it is 70% to make compactedness, and the volume ratio of ethyl alcohol and water is 1:1, and NaOH solution is added makes reactant
The pH value of system is 13, and reaction kettle is placed in 130 DEG C of baking oven after sealing, is taken out after keeping the temperature 18h, centrifuges, uses deionization
It is neutrality that water, which washs sediment to pH value, and centrifuged deposit object is ferromagnetism pure phase BiFeO3Nano particle.
Step（2）：Ferromagnetism BiFeO3-γ-Fe2O3The preparation of nuclear shell structured nano particle：By step（1）Gained is ferromagnetic
Property pure phase BiFeO3Nano particle is distributed in water, after using power to shake 30min for the supersonic wave cleaning machine of 50W, is added dropwise dense
Degree is 1 × 10-4The end group of mol/L is 6 generation pamam dendrimer molecule aqueous solutions of amido, and addition is step（1）In
10 times of the amount of the substance of added dendrimer stir 2h or more, obtain the BiFeO that surface has coated dendrimer3-PAMAM
Then the FeCl of a concentration of 0.1 mol/L is added dropwise in nano particle3·6H2O aqueous solutions, addition are step（1）In added Fe
(NO3)3·9H21 times of the amount of O substances, stirring coordination 2h or more, 800 r/min or more are adjusted to by mixing speed at room temperature, are risen
For temperature to 60 DEG C, the pH value of reaction system is adjusted to 9 by the NaOH aqueous solutions that 0.01 mol/L is added, and after being stirred to react 1h, will be precipitated
Object carries out Magnetic Isolation, is cleaned magnetic product 3 times or more with deionized water, dries, is placed in Muffle furnace at 60 DEG C or less, is risen
Temperature calcines 2h, natural cooling is up to ferromagnetism BiFeO to 300 DEG C3-γ-Fe2O3Nuclear shell structured nano particle.
Embodiment 4：
Step（1）：Ferromagnetism pure phase BiFeO3It is prepared by nano particle：By the Fe (NO of the amount of equal substances3)3·9H2O and Bi
(NO3)3·5H2O is added in ethyl alcohol, and a concentration of 8% dust technology is slowly added dropwise while stirring to Fe (NO3)3·9H2O and Bi
(NO3)3·5H2O is completely dissolved, Fe3+Or Bi3+A concentration of 0.05 mol/L, add end group be hydroxyl 5 generations
Pamam dendrimer molecules of ethanol solution, a concentration of the 1 × 10 of dendrimer-3Mol/L, addition is with Fe3+Or Bi3+With tree-like point
The amount ratio of the substance of son is 50:1 is standard, after using power to shake 5min for the supersonic wave cleaning machine of 50W, is placed in and stirs at room temperature
3 h are mixed, Fe is made3+And Bi3+After being fully coordinated with dendrimer, mixing speed is adjusted to 800 r/min or more, 4 mol/L are added
NaOH aqueous solutions make reaction system pH value be 14, after being stirred to react 1h at room temperature, reaction solution is transferred to hydrothermal reaction kettle
In, ethyl alcohol or deionized water are supplemented, it is 75% to make compactedness, and the volume ratio of ethyl alcohol and water is 1:2, and NaOH solution is added makes instead
It is 14 to answer the pH value of system, and reaction kettle is placed in 130 DEG C of baking oven after sealing, is taken out after keeping the temperature 18h, centrifuges, spends
It is neutrality that ionized water, which washs sediment to pH value, and centrifuged deposit object is ferromagnetism pure phase BiFeO3Nano particle.
Step（2）：Ferromagnetism BiFeO3-γ-Fe2O3The preparation of nuclear shell structured nano particle：By step（1）Gained is ferromagnetic
Property pure phase BiFeO3Nano particle is distributed in water, after using power to shake 30min for the supersonic wave cleaning machine of 50W, is added dropwise dense
Degree is 1 × 10-3The end group of mol/L is 6 generation pamam dendrimer molecular solution of ester group, and addition is step（1）Middle institute
Add 50 times of the amount of the substance of dendrimer, stirs 2h or more, obtain the BiFeO that surface has coated dendrimer3- PAMAM receives
Then the FeCl of a concentration of 0.05 mol/L is added dropwise in rice grain3·6H2O aqueous solutions, addition are step（1）In added Fe
(NO3)3·9H25 times of the amount of O substances, stirring coordination 2h or more, 800 r/min or more are adjusted to by mixing speed at room temperature, are risen
For temperature to 50 DEG C, the pH value of reaction system is adjusted to 9 by the NaOH aqueous solutions that 0.01 mol/L is added, and after being stirred to react 1h, will be precipitated
Object carries out Magnetic Isolation, is cleaned magnetic product 3 times or more with deionized water, dries, is placed in Muffle furnace at 60 DEG C or less, is risen
Temperature calcines 2h, natural cooling is up to ferromagnetism BiFeO to 300 DEG C3-γ-Fe2O3Nuclear shell structured nano particle.
Claims (4)
1. a kind of ferromagnetism BiFeO3-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is characterised in that：Including following
Step：（1）Ferromagnetism pure phase BiFeO3It is prepared by nano particle：The ferromagnetism pure phase BiFeO3Preparation prepared by nano particle
Step is：By the Fe (NO of the amount of equal substances3)3·9H2O and Bi (NO3)3·5H2O is added in organic solvent, is delayed while stirring
Slowly a concentration of 8~10% dust technology is added dropwise to Fe (NO3)3·9H2O and Bi (NO3)3·5H2O is completely dissolved, and adds PAMAM
Dendrimer solution after using power to shake 5min for the supersonic wave cleaning machine of 50W, is placed in 2~4h of stirring at room temperature, makes Fe3+
And Bi3+It is fully coordinated with dendrimer, mixing speed is adjusted to 800 r/min or more, concentrated alkali solution, which is added, makes reaction system
PH value be 13~14, after being stirred to react 1h at room temperature, reaction solution is transferred in hydrothermal reaction kettle, supplement organic solvent or go from
Sub- water makes compactedness be 70%~80%, and concentrated alkali solution, which is added, makes the pH value of reaction system be 13~14, sets reaction kettle after sealing
It in 130~140 DEG C of baking oven, is taken out after keeping the temperature 12~18h, centrifuges, washed sediment to pH values with deionized water
For neutrality, centrifuged deposit object is ferromagnetism pure phase BiFeO3Nano particle；（2）Ferromagnetism BiFeO3-γ-Fe2O3Core-shell structure copolymer
The preparation of structure nano particles:The ferromagnetism BiFeO3-γ-Fe2O3The preparation process of nuclear shell structured nano particle is：It will
Step（1）Gained ferromagnetism pure phase BiFeO3Nano particle is distributed in water, and power is used to be shaken for the supersonic wave cleaning machine of 50W
After 30min, it is added dropwise a concentration of 1 × 10-4~1 × 10-2The pamam dendrimer molecule aqueous solution of mol/L stirs 2h or more, obtains
Surface has coated the BiFeO of dendrimer3- PAMAM nano particles, are then added dropwise FeCl3·6H2O or Fe (NO3)3·9H2O water
Solution, stirring coordination 2h or more, 800 r/min or more are adjusted to by mixing speed at room temperature, are warming up to 40~60 DEG C, are added
The pH value of reaction system is adjusted to 7~9 by the NaOH aqueous solutions of 0.01mol/L, and after being stirred to react 1h, sediment is carried out magnetic point
From, magnetic product is cleaned 3 times or more with deionized water, at 60 DEG C or less dry, be placed in Muffle furnace, be warming up to 300 DEG C, forge
2h is burnt, natural cooling is up to ferromagnetism BiFeO3-γ-Fe2O3Nuclear shell structured nano particle.
2. a kind of ferromagnetism BiFeO as described in claim 13-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is special
Sign is：The step（1）In pamam dendrimer molecule algebraically be 4~6 generations, end group be ester group, hydroxyl or carboxyl,
Addition is with Fe3+Or Bi3+Amount ratio with the substance of dendrimer is 100:1~10:1 is standard, the solvent of dendrimer solution
For water or ethyl alcohol, a concentration of 1 × 10-4~1 × 10-2mol/L；The step（2）In pamam dendrimer molecule end group
For amido or ester group, algebraically was 5~6 generations, and addition is step（1）In added dendrimer substance amount 10~50
Times.
3. a kind of ferromagnetism BiFeO as described in claim 13-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is special
Sign is：Organic solvent is ethyl alcohol or acetone, and the volume ratio of organic solvent and water is 1 in reaction kettle:4~1:1, Fe (NO3)3·
9H2O、Bi(NO3)3·5H2O or FeCl3·6H2A concentration of 0.01~0.1 mol/L of O, step（2）Middle Fe (NO3)3·9H2O
Or FeCl3·6H2The addition of O is step（1）In added Fe (NO3)3·9H21~5 times of the amount of O substances.
4. a kind of ferromagnetism BiFeO as described in claim 13-γ-Fe2O3The preparation method of nuclear shell structured nano particle, it is special
Sign is：Step（1）Middle aqueous slkali is the aqueous solution of the NaOH or KOH of a concentration of 4~8 mol/L, and aqueous slkali is added portionwise, the
A collection of addition is no less than reactant Fe (NO in system3)3·9H2O、Bi(NO3)3·5H2The amount of the substance of O and nitric acid it is total
Be then added dropwise to regulation pH value.
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