CN103771536B - A kind of Z 250 rhombic dodecahedron particle and preparation method thereof - Google Patents
A kind of Z 250 rhombic dodecahedron particle and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of Z 250 rhombic dodecahedron particle and preparation method thereof, step comprises: add in organic solvent by pyrrolidone stablizer, source of iron, add DMF (DMF) solution containing hydrazine hydrate after stirring, stir to obtain precursor solution; Precursor solution is incubated at 140 ~ 240 DEG C, growth magnetic ferroferric oxide rhombic dodecahedron particle; Afterwards solution is carried out aftertreatment and obtain magnetic ferroferric oxide rhombic dodecahedron particle.The exposure that the present invention's solvent-thermal method has obtained more difficult synthesis is at present the Z 250 rhombic dodecahedron particle of high surface energy; preparation process is simple to operate; do not need protection of inert gas; reproducible; be easy to control, gained ferriferrous oxide particles pattern is regular, intact, even size distribution, and particle surface is smooth; there is superpower magnetic and good superparamagnetism, in raising catalytic activity and magnetic recovery utilize, there is huge potential application.
Description
Technical field
The present invention relates to the pattern that a kind of Z 250 is new---the preparation method of rhombic dodecahedron particle, be specifically related to a kind of utilize solvent-thermal method to prepare SPIO rhombic dodecahedron particle method and products obtained therefrom, belong to magneticsubstance preparing technical field.
Background technology
Because the magnetic ferroferric oxide particle of different-shape exists potential application in all respects such as magnetic fluid, drug loading, medical diagnosis, data storage, catalysis, the pattern rationally and accurately controlling ferriferrous oxide particles is the focus of research always.Up to the present, scientists has successfully synthesized the ferriferrous oxide particles of a series of different-shape, and main pattern comprises irregular particle, cubic block, line, pipe, rod, sheet, ring, octahedron etc.But not yet there is the report about preparing magnetic ferroferric oxide rhombic dodecahedron particle.This is because the face of this polyhedral Z 250 exposure is high surface energy face, is easy to disappear, therefore synthesizes dodecahedral Z 250 very difficult in building-up process.From performance, the magnetic ferroferric oxide in this exposure high surface energy face has excellent catalytic activity and there is special application in optics, electricity, magnetic devices.Therefore, the method for research synthesis topographic profile uniform magnetic ferroferric oxide rhombic dodecahedron particle remains a very important challenge.
Summary of the invention
For in prior art lack prepare the technology of Z 250 rhombic dodecahedron particle and the deficiency of rhombic dodecahedron evanescence in building-up process, the invention provides a kind of adopt solvent-thermal method to prepare SPIO rhombic dodecahedron method and products obtained therefrom.The method is simple to operate, controllability is strong, reproducible, do not need protection of inert gas can obtain the homogeneous SPIO rhombic dodecahedron particle of pattern rule.
The concrete technical scheme of the present invention is as follows:
A kind of ferriferrous oxide particles, it is characterized in that: described ferriferrous oxide particles has superparamagnetism, pattern is rhombic dodecahedron, and particle surface is smooth, and the rhombus length of side is 100-500 nm.
A preparation method for Z 250 rhombic dodecahedron particle, is characterized in that comprising the following steps:
(1) pyrrolidone stablizer, source of iron are added in organic solvent, stir and obtain uniform solution A; Hydrazine hydrate is added in DMF (DMF), stir and obtain solution B;
(2) solution B prepared by step (1) is slowly added drop-wise in solution A, stirring reaction certain hour, obtains uniform precursor solution;
(3) precursor solution of step (2) is incubated at 140 ~ 240 DEG C, growth magnetic ferroferric oxide rhombic dodecahedron particle; Afterwards solution is naturally cooled to room temperature, magnetic resolution collects black product, and black product, after water and washing with alcohol, obtains magnetic ferroferric oxide rhombic dodecahedron particle.
In above-mentioned preparation method, described pyrrolidone stablizer is polyvinylpyrrolidone, N-Methyl pyrrolidone, vinyl pyrrolidone or 2-Pyrrolidone.
In above-mentioned preparation method, described source of iron is ferric soluble salt, or mol ratio is ferrous soluble salt of 1:1 and the mixture of ferric soluble salt.Described ferric soluble salt is containing crystal water or not containing the iron(ic) chloride of crystal water, ferric sulfate, iron nitrate or ferric acetyl acetonade, and described ferrous soluble salt is containing crystal water or the iron protochloride or the ferrous sulfate that do not contain crystal water.
In above-mentioned preparation method, described organic solvent is DMF (DMF) or oleyl amine.
In above-mentioned preparation method, described solution B is that 80wt% hydrazine hydrate is dissolved in the solution formed in DMF (DMF), and the volume ratio of 80wt% hydrazine hydrate and DMF is 0.01-1:1, preferred 0.1-0.2:1.
In above-mentioned preparation method, in step (3), precursor solution is insulation reaction under closed environment.
When preparing precursor solution, add each composition according to following relation, thus form required pattern:
the volume ratio of solution A and solution B is 0.5-1.5:1, and preferred ratio is 0.9-1.1:1.
in solution A, pyrrolidone stablizer and source of iron are according to pyrrolidone stablizer: the mol ratio of source of iron is that the relation of 0.5 ~ 20:1 is added, most preferably 2-8:1.Wherein, when pyrrolidone stablizer is high molecular polymer, the mole number of pyrrolidone stablizer refers to the mole number of polymer monomer, such as, when pyrrolidone stablizer is polyvinylpyrrolidone, the mole number that the mole number of pyrrolidone stablizer refers to polyvinylpyrrolidone is multiplied by the number of monomer.
in solution A, the concentration of pyrrolidone stablizer is preferably 20 ~ 120 mM, more preferably 50-70mM.Wherein, when pyrrolidone stablizer is high molecular polymer, the concentration of pyrrolidone stablizer refers to the concentration of polymer monomer, such as, when pyrrolidone stablizer is polyvinylpyrrolidone, the concentration that the concentration of pyrrolidone stablizer refers to polyvinylpyrrolidone is multiplied by the number of monomer.
in solution A, the concentration of source of iron is preferably 10 ~ 900mM, most preferably 150-250 mM.
the rate of addition of hydrazine hydrate can not be too fast, product pattern can be made too soon to be formed or size dimension uneven, the injection speed of general solution B is less than 1 mL/min, preferred 100-300 μ L/min.
In above-mentioned preparation method, in step (2), after dripping off solution B, react 30-60min, preferred 40min.
In above-mentioned preparation method, in step (3), temperature of reaction is preferably 200 DEG C, the insulation reaction time at 2 ~ 40 hours, preferred 20h.
The invention provides a kind of method of synthesizing ferromagnetic ferriferrous oxide rhombic dodecahedron particle, the method is by controlling stablizer, source of iron, the consumption of hydrazine hydrate and concentration, obtained suitable precursor solution, then precursor solution is incubated under high temperature, closed environment, rhombic dodecahedron can well be grown.In precursor, the consumption of each composition and the rate of addition of hydrazine hydrate have very important impact to the formation of product pattern and quality, if can not reasonably control these conditions, and can not the rhombic dodecahedron of formation rule.
Precursor solution grows rhombic dodecahedron particle under the environment of airtight, high temperature, because the volatilization of composition can make system have certain pressure in high temperature and system under closed environment, facilitates the growth of rhombic dodecahedron particle.
The exposure that the present invention's solvent-thermal method has obtained more difficult synthesis is at present the Z 250 rhombic dodecahedron particle of high surface energy; preparation process is simple to operate; do not need protection of inert gas; reproducible; be easy to control; gained granule-morphology is regular, intact, even size distribution, has superpower magnetic and good superparamagnetism, in raising catalytic activity and magnetic recovery utilize, there is huge potential application.
Accompanying drawing explanation
Fig. 1 is scanning electron microscope (SEM) picture of the magnetic ferroferric oxide rhombic dodecahedron particle that the embodiment of the present invention 1 is synthesized.
Fig. 2 is the room temperature magnetic hysteresis loop of the magnetic ferroferric oxide rhombic dodecahedron particle that the embodiment of the present invention 1 is synthesized.
Fig. 3 is scanning electron microscope (SEM) picture of the magnetic ferroferric oxide rhombic dodecahedron particle of the 2-in-1 one-tenth of the embodiment of the present invention.
Fig. 4 is scanning electron microscope (SEM) picture of the magnetic ferroferric oxide rhombic dodecahedron particle that the embodiment of the present invention 3 is synthesized.
Fig. 5 is scanning electron microscope (SEM) picture of the magnetic ferroferric oxide rhombic dodecahedron particle that the embodiment of the present invention 22 is synthesized.
Embodiment
Below in conjunction with embodiment, the invention will be further described, and following embodiment is the further explanation to technical solution of the present invention, but protection scope of the present invention is not limited to following embodiment.
embodiment 1
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.067 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 1.1, stir 20 minutes.
9 mL DMF mix with 1.5 mL80wt% hydrazine hydrates by 1.2, and then in the solution described in embodiment 1.1, slowly drip this mixed solution, rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 1.2 is sealed in autoclave by 1.3, at 200 DEG C, be incubated 20 hours, after reaction terminates, naturally cool to room temperature, after reaction, product is black, can pass through magnetic resolution (such as using magnet) and collect, illustrating that product magnetic is comparatively strong, is Z 250.Product after separation is through water and washing with alcohol 3 times, obtain ferriferrous oxide particles, electron-microscope scanning is carried out to it, gained stereoscan photograph as shown in Figure 1, as can be seen from the figure, gained Z 250 pattern is the rhombic dodecahedron of very standard, and particle surface is smooth, and the rhombus length of side is 400-500nm.
As shown in Figure 2, as can be seen from the figure: this sample has good superparamagnetism, and magnetic saturation intensity is 80emu/g to the room temperature magnetic hysteresis loop of gained particle, and compared with nano ferriferrous oxide, the Z 250 magnetic property of pattern of the present invention improves a lot.
embodiment 2
2.1 by 0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and and 0.067 g polyvinylpyrrolidone be dissolved in 10 mL DMF, stir 20 minutes.
2.2 drip solution B (the 1.5 mL hydrazine hydrates diluted by 8 mL DMF) in the solution described in embodiment 2.1, and rate of addition is 1mL/min, stirs 60 minutes.
Mixing solutions described in embodiment 2.2 is sealed in autoclave by 2.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, its stereoscan photograph is shown in Fig. 3, rhombic dodecahedron pattern standard, smooth surface, and the rhombus length of side is 200-400nm.
embodiment 3
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.13 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 3.1, stir 20 minutes.
3.2 slowly drip solution B (the 1.5 mL hydrazine hydrates diluted by 10 mL DMF) in the solution described in embodiment 3.1, and rate of addition is 0.2 mL/min, stirs 30 minutes.
Mixing solutions described in embodiment 3.2 is sealed in autoclave by 3.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, its stereoscan photograph is shown in Fig. 4, rhombic dodecahedron pattern standard, smooth surface, and the rhombus length of side is 200-400nm.
embodiment 4
0.216 g iron(ic) chloride and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 4.1, stir 20 minutes.
4.2 drip solution B (the 1.5 mL hydrazine hydrates diluted by 10 mL DMF) in the solution described in embodiment 4.1, and rate of addition is 0.5mL/min, stirs 50 minutes.
Mixing solutions described in embodiment 4.2 is sealed in autoclave by 4.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 5
0.323 g iron nitrate and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL oleyl amines by 5.1, stir 20 minutes.
5.2 drip solution B (the 1.5 mL hydrazine hydrates diluted by 10 mL oleyl amines) in the solution described in embodiment 5.1, and rate of addition is 0.1 mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 5.2 is sealed in autoclave by 5.3, at 200 DEG C, be incubated 30 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 6
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 6.1, stir 20 minutes.
6.2 drip solution B (the 0.7 mL hydrazine hydrate diluted by 10 mL DMF) in the solution described in embodiment 6.1, and rate of addition is 0.1 mL/min, stirs 30 minutes.
Mixing solutions described in embodiment 6.2 is sealed in autoclave by 6.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 7
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 7.1, stir 20 minutes.
7.2 slowly drip solution B (the 1.5 mL hydrazine hydrates diluted by 10 mL DMF) in the solution described in embodiment 7.1, and rate of addition is 0.2mL/min, stirs 30 minutes.
Mixing solutions described in embodiment 7.2 is sealed in autoclave by 7.3, at 180 DEG C, be incubated 10 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 8
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667 g N-Methyl pyrrolidone are dissolved in 10 mL DMF by 8.1, stir 20 minutes.
8.2 slowly drip solution B (the 1.5 mL hydrazine hydrates diluted by 5 mL DMF) in the solution described in embodiment 8.1, and rate of addition is 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 8.2 is sealed in autoclave by 8.3, at 180 DEG C, be incubated 10 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 9
0.323 g iron nitrate, 0.278 g ferrous sulfate and 0.667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 9.1, stir 10 minutes.
9.2 slowly drip solution B (the 1.5 mL hydrazine hydrates diluted by 10 mL DMF) in the solution described in embodiment 9.1, and rate of addition is 0.2mL/min, stirs 30 minutes.
Mixing solutions described in embodiment 9.2 is sealed in autoclave by 9.3, at 180 DEG C, be incubated 10 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 10
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.06 g N-Methyl pyrrolidone are dissolved in 10 mL DMF by 10.1, stir 20 minutes.
10.2 slowly drip the 5 mL hydrazine hydrates diluted by 5 mL DMF in the solution described in embodiment 10.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 10.2 is sealed in autoclave by 10.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 11
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.03g V-Pyrol RC are dissolved in 10 mL DMF by 11.1, stir 20 minutes.
11.2 slowly drip the 0.2 mL hydrazine hydrate diluted by 14 mL DMF in the solution described in embodiment 11.1, and rate of addition 0.2 mL/min, stirs 30 minutes.
Mixing solutions described in embodiment 11.2 is sealed in autoclave by 11.3, at 240 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 12
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667g vinyl pyrrolidone are dissolved in 5 mL DMF by 12.1, stir 20 minutes.
12.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 8 mL DMF in the solution described in embodiment 12.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 12.2 is sealed in autoclave by 12.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 13
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 13.1, stir 20 minutes.
13.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 13.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 13.2 is sealed in autoclave by 13.3, at 140 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 14
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 14.1, stir 20 minutes.
14.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 14.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 14.2 is sealed in autoclave by 14.3, at 240 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 15
0.3 g ferric sulfate, 0.1325 g iron protochloride and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 15.1, stir 20 minutes.
15.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 15.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 15.2 is sealed in autoclave by 15.3, at 200 DEG C, be incubated 2 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 16
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 16.1, stir 20 minutes.
16.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 16.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 16.2 is sealed in autoclave by 16.3, at 200 DEG C, be incubated 40 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 17
0.354g ferric acetyl acetonade and 0.08g polyvinylpyrrolidone are dissolved in 10 mL DMF by 17.1, stir 20 minutes.
17.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 17.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 17.2 is sealed in autoclave by 17.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 18
0.162 g iron(ic) chloride (anhydrous), 0.127 g iron protochloride (anhydrous) and 0.1 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 18.1, stir 20 minutes.
18.2 inject the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 18.1, and rate of addition 180mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 18.2 is sealed in autoclave by 18.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 19
0.08g iron nitrate and 0.07 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 19.1, stir 20 minutes.
19.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 19.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 19.2 is sealed in autoclave by 19.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 20
0.162 g iron(ic) chloride (not calculating the amount of water), 0.106 ferrous sulfate (not calculating the amount of water) and 0.08 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 20.1, stir 20 minutes.
20.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 20.1, and rate of addition 0.2mL/min, stirs 40 minutes.
Mixing solutions described in embodiment 20.2 is sealed in autoclave by 20.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
embodiment 21
0.216 g iron(ic) chloride, 0.1325 g iron protochloride and 0.0667 g polyvinylpyrrolidone are dissolved in 10 mL oleyl amines by 21.1, stir 20 minutes.
21.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 10 mL DMF in the solution described in embodiment 21.1, and rate of addition 0.2mL/min, stirs 50 minutes.
Mixing solutions described in embodiment 21.2 is sealed in autoclave by 21.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution (such as using magnet) collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle, grain particle surface is smooth, and the rhombus length of side is 100-500 nm.
comparative example
0.5 g iron(ic) chloride, 0.1 g iron protochloride and 0.01 g polyvinylpyrrolidone are dissolved in 10 mL DMF by 22.1, stir 20 minutes.
22.2 slowly drip the 1.5 mL hydrazine hydrates diluted by 1 mL DMF in the solution described in enforcement 22.1, and rate of addition 1.2mL/min, stirs 10 minutes.
Mixing solutions described in embodiment 22.2 is sealed in autoclave by 22.3, at 200 DEG C, be incubated 20 hours, and after reaction terminates, naturally cool to room temperature, magnetic resolution collects black product.Through water and washing with alcohol 3 times, obtain magnetic ferroferric oxide rhombic dodecahedron particle.Its stereoscan photograph is shown in Fig. 5.As can be seen from the figure do not obtain the rhombic dodecahedron of rule, have the tired octahedra shape of some displays, also have some irregular particles, it is very uneven that size becomes, and some particles also have cavity.
Claims (12)
1. a preparation method for Z 250 rhombic dodecahedron particle, is characterized in that comprising the following steps:
(1) pyrrolidone stablizer, source of iron are added in organic solvent, stir and obtain uniform solution A; Hydrazine hydrate is added in DMF to stir and obtain solution B;
(2) solution B prepared by step (1) is slowly added drop-wise in solution A, stirring reaction certain hour, obtains uniform precursor solution;
(3) precursor solution of step (2) is incubated at 140 ~ 240 DEG C, growth magnetic ferroferric oxide rhombic dodecahedron particle; Afterwards solution is naturally cooled to room temperature, magnetic resolution collects black product, and black product, after water and washing with alcohol, obtains magnetic ferroferric oxide rhombic dodecahedron particle;
In solution A, pyrrolidone stablizer: the mol ratio of source of iron is 0.5 ~ 20:1, when wherein pyrrolidone stablizer is high molecular polymer, its mole number is the mole number of high molecular polymer monomer;
In solution A, the concentration of pyrrolidone stablizer is 20 ~ 120 mM, and when wherein pyrrolidone stablizer is high molecular polymer, its concentration is the concentration of high molecular polymer monomer;
In solution A, the concentration of source of iron is 10 ~ 900mM;
The volume ratio of solution A and solution B is 0.5-1.5:1;
In step (2), the injection speed of solution B is less than 1 mL/min.
2. preparation method according to claim 1, is characterized in that: gained ferriferrous oxide particles has superparamagnetism, and pattern is rhombic dodecahedron, and particle surface is smooth, and the rhombus length of side is 100-500 nm.
3. preparation method according to claim 1, is characterized in that: described pyrrolidone stablizer is polyvinylpyrrolidone, N-Methyl pyrrolidone, vinyl pyrrolidone or 2-Pyrrolidone; Described source of iron is ferric soluble salt, or mol ratio is ferrous soluble salt of 1:1 and the mixture of ferric soluble salt; Described organic solvent is DMF or oleyl amine; Solution B is that 80wt% hydrazine hydrate is dissolved in the solution formed in DMF, and the volume ratio of 80wt% hydrazine hydrate and DMF is 0.01-1:1.
4. preparation method according to claim 3, is characterized in that: the volume ratio of 80wt% hydrazine hydrate and DMF is 0.1-0.2:1.
5. preparation method according to claim 3, it is characterized in that: described ferric soluble salt is containing crystal water or not containing the iron(ic) chloride of crystal water, ferric sulfate, iron nitrate or ferric acetyl acetonade, described ferrous soluble salt is containing crystal water or the iron protochloride or the ferrous sulfate that do not contain crystal water.
6. the preparation method according to claim 1,2,3 or 4, is characterized in that: in step (3), precursor solution is insulation reaction under closed environment.
7. the preparation method according to claim 1,2,3 or 4, is characterized in that: the volume ratio of solution A and solution B is 0.9-1.1:1; In solution A, pyrrolidone stablizer: the mol ratio of source of iron is 2-8:1.
8. the preparation method according to claim 1,2,3 or 4, is characterized in that: in step (2), and the injection speed of solution B is 100-300 μ L/min.
9. preparation method according to claim 1, is characterized in that: in step (2), react 30-60min after dripping off solution B; In step (3), insulation reaction 2 ~ 40 hours.
10. preparation method according to claim 9, is characterized in that: in step (2), react 40min after dripping off solution B; In step (3), insulation reaction 20h.
11. preparation methods according to claim 1,2,3 or 4, it is characterized in that: in step (3), temperature of reaction is 200 DEG C.
12. preparation methods according to claim 1,2,3 or 4, it is characterized in that: in solution A, the concentration of pyrrolidone stablizer is 50-70mM, and when wherein pyrrolidone stablizer is high molecular polymer, its concentration is the concentration of high molecular polymer monomer; In solution A, the concentration of source of iron is 150-250 mM.
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