CN107162064B - A kind of method that high-temperature decomposition prepares ferrous fluoride nano material - Google Patents
A kind of method that high-temperature decomposition prepares ferrous fluoride nano material Download PDFInfo
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Abstract
The present invention provides a kind of methods that high-temperature decomposition prepares ferrous fluoride nano material.In high boiling solvent and surfactant system; using the organic coordination compound of iron for presoma, fluoride is ion source; 190 DEG C~340 DEG C are heated under inert protective gas atmosphere; keep the temperature 0.25~4h; end system Temperature fall is reacted, the good ferrous fluoride nano particle of size uniformity, pattern is obtained after centrifuge washing.This preparation method has many advantages, such as simple, controllable, reproducible.
Description
Technical field
The present invention relates to a kind of preparation methods of anti-ferromagnetism ferrous fluoride nano particle, and in particular to a kind of high warm point
Solution prepares the preparation method of the uniform ferrous fluoride nano particle of favorable dispersibility, particle size.
Background technique
Ferrous fluoride has comparatively ideal application as functional nano material, in new energy and field of biomedicine.
The existing method for preparing ferrous fluoride nano particle mainly has solvent-thermal method, coprecipitation, high temperature thermal decomposition method etc., wherein
High temperature thermal decomposition method has the characteristic of good control nanoparticle size and pattern.But high temperature thermal decomposition method General reactions condition compared with
For harshness, there is different requirements for different presomas.
Summary of the invention
In place of existing technical deficiency, the invention proposes a kind of high temperature thermal decompositions to prepare ferrous fluoride nanometer
The method of material, the method have the characteristics that reaction condition is simple, repeatability is high, product morphology is excellent.
A kind of method that high-temperature decomposition prepares ferrous fluoride nano material, steps are as follows:
(1) source of iron presoma and fluoride are placed in high boiling solvent and are completely dissolved, then with higher boiling surfactant
It is mixed to get mixed system；The source of iron presoma is ferric acetyl acetonade, iron oleate, carbonyl iron or ferrocene, the higher boiling
Solvent is oleyl amine, octadecylene or benzyl ether；
(2) step (1) mixed system is warming up to 80 DEG C~120 DEG C, keeps 40~60min, mixed system is made to be in nothing
Water anaerobic state；
(3) continue to heat up, be warming up to 190~340 DEG C with the speed of 15 DEG C~20 DEG C/min, and 0.25~4h is kept to obtain instead
Answer product；
(4) 20~60 DEG C are naturally cooling to, the reaction product is sufficiently cleaned with organic solvent, is obtained well dispersed
Ferrous fluoride nano material；
Further, fluoride of the present invention is ammonium fluoride or sodium fluoride.
Further, the mass ratio of the material of source of iron presoma and fluoride of the present invention is 1:2~8.
Further, high boiling solvent dosage of the present invention is completely dissolved source of iron presoma and fluoride.
Further, the volume ratio of higher boiling surfactant and high boiling solvent of the present invention is 1:1~9.
Further, the dosage of higher boiling surfactant of the present invention be calculated as 2 with the amount of the substance of source of iron presoma~
20mL/mmol。
Further, higher boiling surfactant of the present invention is oleyl amine, cetylamine, octadecylamine or oleic acid.
Further, organic solvent described in step (4) of the present invention is ethyl alcohol, methanol, acetone, n-hexane, one in chloroform
Kind or two kinds.
Further, ferrous fluoride nano material made from step (4) of the present invention, which need to be deposited in n-hexane or chloroform, saves.
The invention has the advantages that:
(1) preparation method is simple, and condition is not so harsh relatively；
(2) product purity is high, does not occur miscellaneous phase；
(3) favorable dispersibility has repeatability well.
Detailed description of the invention
Fig. 1: the XRD of ferric acetyl acetonade and the ferrous fluoride nano material of cubic structure made from ammonium fluoride in embodiment 1
Characterization
Fig. 2: the TEM of ferric acetyl acetonade and the ferrous fluoride nano material of cubic structure made from ammonium fluoride in embodiment 1
Figure
Fig. 3: the XRD diagram of ferric acetyl acetonade and ferrous fluoride flower pattern nanocluster made from sodium fluoride in embodiment 2
Fig. 4: the TEM of ferric acetyl acetonade and ferrous fluoride flower pattern nanocluster made from sodium fluoride schemes in embodiment 2
Fig. 5: the XRD diagram of iron oleate and spherical shape ferrous fluoride nano material made from ammonium fluoride in embodiment 4
Fig. 6: iron oleate and the TEM of spherical shape ferrous fluoride nano material made from ammonium fluoride scheme in embodiment 4
Fig. 7: the XRD diagram of carbonyl iron and the ferrous fluoride nano material of club shaped structure made from ammonium fluoride in embodiment 6
Fig. 8: carbonyl iron and the TEM of the ferrous fluoride nano material of club shaped structure made from ammonium fluoride scheme in embodiment 6
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1: pyrolytic ferric acetyl acetonade prepares cubic structure nanoparticle
It disperses 20mL oleyl amine for 1mmol ferric acetyl acetonade, 2mmol ammonium fluoride to be added in four-hole boiling flask, under magnetic agitation
Obtain brown solution.It vacuumizes and is warming up to 95 DEG C, keep 60min, nitrogen atmosphere is filled with, then with the heating rate of 20 DEG C/min
190 DEG C are risen to, 4h is kept.It is down to room temperature to the end of reacting, pours out product, the mixing for being 1:3 with n-hexane and ethyl alcohol volume ratio
Solvent wash products 3 times, obtained nano particle, which is dispersed in n-hexane, to be saved.Fig. 1 gives to be stood according to what embodiment 1 obtained
The XRD characterization of square structure ferrous fluoride nanoparticle, as can be seen from the figure material crystalline is complete and free from foreign meter.Fig. 2 can be with
It will become apparent from the whole pattern of cubic structure nanocluster.
Embodiment 2: pyrolytic ferric acetyl acetonade prepares flower pattern nanocluster
Four-hole boiling flask is added after dispersing 15mL octadecylene, 5mL octadecylamine for 1mmol ferric acetyl acetonade, 2mmol sodium fluoride
In, brown solution is obtained under magnetic agitation.Vacuumize and be warming up to 80 DEG C, keep 60min, be filled with argon atmosphere, then with 20 DEG C/
The heating rate of min rises to 260 DEG C, keeps 1h.It is down to room temperature to the end of reacting, pours out product, with acetone and ethyl alcohol volume ratio
It is mixed solvent wash products 3 times of 1:3, obtained nano particle, which is dispersed in chloroform, to be saved.Product such as Fig. 3, receives for flower pattern
Rice cluster.
Embodiment 3: thermal decomposition ferric acetyl acetonade prepares flower pattern nanocluster
Four-hole boiling flask is added after dispersing 15mL benzyl ether, 5mL cetylamine for 1mmol ferric acetyl acetonade, 8mmol ammonium fluoride
In, brown solution is obtained under magnetic agitation.Vacuumize and be warming up to 95 DEG C, keep 40min, be filled with argon atmosphere, then with 20 DEG C/
The heating rate of min rises to 340 DEG C, keeps 0.25h.It is down to room temperature to the end of reacting, pours out product, with n-hexane and ethyl alcohol body
Than mixed solvent wash products 3 times for 1:3, obtained nano particle is dispersed in n-hexane to be saved product.Product is received for flower pattern
Rice cluster, pattern are similar to Example 2.
Embodiment 4: pyrolytic iron oleate prepares spherical nanoparticle
20mL oleyl amine is dispersed by 1mmol iron oleate, 2mmol ammonium fluoride to be added in four-hole boiling flask, is obtained under magnetic agitation
Brown solution.It vacuumizes and is warming up to 120 DEG C, keep 60min, then rise to 300 DEG C with the heating rate of 15 DEG C/min, keep
0.5h.It is down to room temperature to the end of reacting, pours out product, the mixed solvent wash products 3 for being 1:3 with chloroform and ethyl alcohol volume ratio
Secondary, obtained nano particle, which is dispersed in chloroform, to be saved.Fig. 4 this it appears that spherical ferrous fluoride nano particle whole shape
Looks.
Embodiment 5: pyrolytic ferric acetyl acetonade prepares nano spherical particle
It is added in four-hole boiling flask after dispersing 18mL oleyl amine, 2mL oleic acid for 1mmol ferric acetyl acetonade, 2mmol ammonium fluoride,
Brown solution is obtained under magnetic agitation.It vacuumizes and is warming up to 85 DEG C, 60min is kept, then with the heating rate liter of 15 DEG C/min
To 220 DEG C, 1h is kept.It is down to 60 DEG C to the end of reacting, pours out product, the mixed solvent for being 1:3 with chloroform and ethyl alcohol volume ratio
Wash products 3 times, obtained nano particle, which is dispersed in chloroform, to be saved.Product is spherical nanoparticle, pattern and 4 class of embodiment
Seemingly.
Embodiment 6: pyrolytic carbonyl iron prepares rod-like nano particle
2mmol ammonium fluoride is scattered in 20mL oleyl amine and is added in four-hole boiling flask, vacuumizes and is warming up to 90 DEG C, keeps 60min.So
Rise to 170 DEG C afterwards with the heating rate of 20 DEG C/min, injection 1mmol carbonyl iron keeps 0.5h, after with identical speed be warming up to 240
DEG C, keep the temperature 0.5h.It is down to room temperature to the end of reacting, pours out product, the mixed solvent for being 1:3 with n-hexane and ethyl alcohol volume ratio is clear
It washes product 3 times, obtained nano particle, which is dispersed in n-hexane, to be saved.Fig. 5 is this it appears that rodlike ferrous fluoride nanometer material
The whole pattern of material.
Embodiment 7: pyrolytic ferrocene prepares flower pattern nanocluster
1mmol ferrocene, 2mmol ammonium fluoride are added in four-hole boiling flask after being scattered in 20mL oleyl amine, obtain under magnetic agitation
Brown solution.It vacuumizes and is warming up to 85 DEG C, keep 60min, then rise to 320 DEG C with the heating rate of 20 DEG C/min, keep 1h.
It is down to room temperature to the end of reacting, pours out product, mixed solvent wash products 3 times for being 1:3 with chloroform and ethyl alcohol volume ratio obtain
Nano particle be dispersed in chloroform and save.Product is flower pattern nanocluster, and pattern is similar to Example 2.
Claims (8)
1. a kind of method that high-temperature decomposition prepares ferrous fluoride nano material, it is characterised in that the method comprises the following steps:
(1) source of iron presoma and fluoride are placed in high boiling solvent and are completely dissolved, then mixed with higher boiling surfactant
Obtain mixed system；The source of iron presoma is ferric acetyl acetonade, iron oleate, carbonyl iron or ferrocene, the high boiling solvent
For oleyl amine, octadecylene or benzyl ether；
(2) step (1) mixed system is warming up to 80 DEG C~120 DEG C, keeps 40~60min, mixed system is made to be in anhydrous nothing
Oxygen condition；
(3) continue to heat up, be warming up to 190~340 DEG C with the speed of 15 DEG C~20 DEG C/min, and keep 0.25~4h that must react production
Object；
(4) 20~60 DEG C are naturally cooling to, the reaction product is sufficiently cleaned with organic solvent, obtains well dispersed fluorination
Ferrous iron nanometer material.
2. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: the fluorine
Compound is ammonium fluoride or sodium fluoride.
3. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: the height
Boiling point surfactant is oleyl amine, cetylamine, octadecylamine or oleic acid.
4. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: the iron
The mass ratio of the material of source presoma and fluoride is 1:2~8.
5. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: the height
The volume ratio of boiling point surfactant and high boiling solvent is 1:1~9.
6. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: the height
The dosage of boiling point surfactant is calculated as 2~20mL/mmol with the amount of the substance of source of iron presoma.
7. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: step
(4) organic solvent described in is one of ethyl alcohol, methanol, acetone, n-hexane, chloroform or two kinds.
8. the method that high-temperature decomposition as described in claim 1 prepares ferrous fluoride nano material, it is characterised in that: step
(4) ferrous fluoride nano material made from need to be deposited in n-hexane or chloroform and be saved.
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| CN111850389B (en) * | 2019-04-29 | 2021-12-21 | 中国科学院金属研究所 | Method for preparing iron nitride nanorod material |
| CN110589771B (en) * | 2019-09-10 | 2021-01-08 | 华南师范大学 | Preparation method of flower-shaped metal fluoride nano material |
| WO2021072635A1 (en) * | 2019-10-15 | 2021-04-22 | 诸暨易联众创企业管理服务有限公司 | Method for preparing rod-shaped ferrous chloride nano-material |
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| CN104445373A (en) * | 2014-12-05 | 2015-03-25 | 合肥工业大学 | Preparation method of sub-10-nanometer NaGdF4 nanocrystal |
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| CN103682340A (en) * | 2013-12-26 | 2014-03-26 | 中国科学院上海硅酸盐研究所 | Iron-based fluoride nano material with hierarchical structure, preparation method and application thereof |
| CN104445373A (en) * | 2014-12-05 | 2015-03-25 | 合肥工业大学 | Preparation method of sub-10-nanometer NaGdF4 nanocrystal |
| CN105623663A (en) * | 2016-01-04 | 2016-06-01 | 哈尔滨工程大学 | Red up-conversion luminous nano-carrier and preparation method |
| CN106207116A (en) * | 2016-07-22 | 2016-12-07 | 昆明理工大学 | A kind of method of one-step synthesis method ferrous fluoride/C positive electrode material |
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