CN102633307A - Method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles - Google Patents
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Abstract
The invention relates to a method for hydrothermally preparing mono-dispersed hollow magnetic nanometer particles. The method comprises the following steps of: firstly, mixing a divalent metal salt solution with a urea solution; secondly, adding an organic dispersant and a divalent metal oxidation inhibitor; thirdly, slowly adding an alkali precipitant solution into the solution; fourthly, adjusting the pH (Potential of Hydrogen) value of the mixed solution to 10-12; and finally, adding a surface radical modifier, and carrying out hydrothermal reaction for 5-15 hours at the temperature of 150-250 DEG C, so as to prepare the magnetic nanometer particles having a hollow structure. Compared with the prior art, the method provided by the invention has the advantages of simple technique step, low cost and the like, and is easy to be large-scale.
Description
Technical field
The invention belongs to inorganic superfine powder and field of nanometer technology, be specifically related to a kind of hydrothermal preparing process of hollow structure magnetic Nano material.
Background technology
Magnetic nano-particle with hollow structure is a kind of novel materials with wide application prospect, at albumen and separate nucleic acid, target medicine carrier, zeugmatography, catalytic field important use is arranged owing to have magnetic response characteristic and hollow structure.
The hollow structure nanoparticle forms mechanism and mainly comprises Ke Kendaer effect and Ostwald ripening mechanism, and the preparation method mainly comprises hard template method and soft template method.Hard template method mainly comprises four main processes: the preparation that at first is hard template; Next is that template surface is carried out functional modification; Obtain surface of good; Be that template after adopting metal-salt to modification coats once more, make up the housing of imporosity, obtain the hollow structure nanoparticle through the selective removal template at last.The hard template method main drawback is that the hollow nano-material preparation cost is high, the complicated loaded down with trivial details and productive rate of process is low etc.Soft template method normally adopts tensio-active agent and other super molecular compounds, for nanoparticle provides growing environment, through the decomposition reaction of metal-salt, prepares the hollow Nano particle through vesica, bubble or emulsion droplet etc. then.Back one class methods are mainly utilized self-assembly layer by layer, through coulombic interaction and complexing absorption etc., from atom, molecule rank nanoparticle are constructed step by step, obtain hollow nanostructured material.The advantage of these class methods is that the diameter of hollow magnetic nanoparticle can be controlled through regulating template capsule size; Simultaneously to the magnetic saturation intensity of magnetic nano-particle with shell is thick also can effectively regulate and control, yet this method main drawback is that the synthesis technique complicacy is loaded down with trivial details, cost is high, unsuitable scale operation etc.
In recent years, more existing synthetic reports about the hollow magnetic nanoparticle.Caruso etc. (F.Caruso, M.Spasova, A.Susha, M.Giersig, R.A.Caruso, Chem.Mater., 2001,13,109-116) scholar adopts physics and chemofacies combining method with Fe
3O
4Nanoparticle is adsorbed on polymer microsphere surface, obtains the hollow structure magnetic particle through high temperature sintering then, and the problem that this method mainly exists is that preparation process is loaded down with trivial details, and the hollow magnetic diameter of nano particles of preparation is big, the size distribution broad.People such as Cheng (Kai Chen, Sheng Peng, Chenjie Xu; Shouheng Sun, J.Am.Chem.Soc., 2009; 131,10637-10644), prepare the hollow magnetic nanoparticle through the acid attack method then at first at 250 ℃ of following Oxidation of Fe nanoparticles of high temperature; The nanoparticle that obtains can stable existence under neutral and alkaline condition, and lung cancer SK-BR-3 tumour cell is had good Targeting Performance.First (the Deng Yonghui of seminar in Zhao east; Liu Jia; Liu's Chong, Zhao Dongyuan, CN 101345112A) adopt the solvent evaporates method to make magnetic nano-particle and polymer microsphere generation co-precipitation; Nano-particles filled in the slit of polymer microsphere, is filled inorganic oxide sol through " nanometer casting " method again in polymer microsphere.Through the inorganic oxide sol hydrolysis, magnetic nano-particle is covered around the polymer microsphere, remove polymer microsphere through high-temperature calcination again, obtain the hollow structure magnetic microsphere.People such as Sun Kang (Sun Kang, Dou Hongjing, Ma Wuwei, CN 101183588A) are shell with the magnetic nano-particle, and the surface has the polymer microsphere of negative charge as template, at microsphere surface parcel one deck SiO
2, remove organic formwork through high temperature sintering then, obtain the hollow structure magnetic nano-balls.People such as Li Chunzhong (Li Chunzhong, Wang Shufen, Cao Hongming; Gu Feng, Hu Yanjie, CN 101318709A) iron trichloride and ferric sulfate are added in the X 2073 liquid solution; Stir the back and add urea, 95～105 ℃ of refluxed, obtain precursor through washing, alcohol is washed and dry processing after; Handle through the differing temps section calcining again, prepare hollow structure γ-Fe
2O
3Oldly build fixed people (Chen Jianding, Zhang Xiaojun, the Xuan Zhaofeng of waiting; Huang Guangjian, Ma Xinsheng, Wu Qiufang; CN101086911A) adopt raw materials such as polystyrene microsphere, manganous salt, divalent iron salt, nucleator and precipitation agent; Preparation PS-including Mn-Fe oxidation nucleocapsid composite particles falls PS high-temperature calcination under nitrogen protection then under certain temperature and whipped state, and preparation has the including Mn-Fe magnetic microsphere of central hole structure.Old build peak seminar (not big, Shen Shuling, Guo Kai; Chen Jianfeng CN101195085A) adopts the intermediate processing magnetic oxygenated nanoparticle of preparation earlier, mixes with ionogen suspension-s then; Again the silicon source is added in the emulsion; Through control pH value of solution value, make silicon-dioxide precursor hydrolytic reactions, preparation magnetic silica hollow granule.(Wu Huixia, Shi Jianlin CN101966344A) adopt hydrothermal method to prepare β-FeOOH nanoparticle to people such as Wu Huixia, wrap silicon at particle surface then and handle, and remove pore-forming material through thermal treatment, make kernel change Fe into through reductive agent
3O
4Capsules at last at finishing luminous organic material and biocompatible compound, obtains the hollow structure magnetic nano-particle.People such as Marvin's wise man (the Marvin's wise man, Hou Pingjuan, the money snowy peak, Zhu Zikang CN1528675A) adopts the polyoxyethylene-poly-oxypropylene polyoxyethylene triblock copolymer as template, adopts coprecipitation method to prepare hollow superparamagnetism Fe
3O
4Nanoparticle, prepared nano particle diameter is controlled, and the pattern homogeneous is about the thick about 5nm of shell.
Though the researcher does a lot of work aspect preparing at the hollow magnetic nanoparticle; But problems such as the subject matter that exists at present is that complex process is loaded down with trivial details, cost is high, pattern heterogeneity and unsuitable scale operation have seriously restricted the industrialized development of hollow magnetic nanoparticle.How prepare and introduce technology of preparing fast in the hollow magnetic nanoparticle, solve present hollow magnetic nanoparticle and prepare the difficult problem in the process, the increment utilization that promotes China's fe source is had great importance in traditional template.
Summary of the invention
The object of the invention is exactly to provide in order to overcome the defective that above-mentioned prior art exists that a kind of process step is simple, cost is low and the method for the hydrothermal preparation monodisperse hollow magnetic nano-particle of easy scale operation.
The object of the invention can be realized through following technical scheme: a kind of method of hydrothermal preparation monodisperse hollow magnetic nano-particle; It is characterized in that; This method is that the divalent metal salts solution is mixed with urea soln, adds organic dispersing agent and divalent metal oxidation co-inhibitor then, slowly adds the alkaline sedimentation agent solution in the above-mentioned solution; Then mixing solutions pH value is adjusted to 10-12; Add the surface group modifier again, then at 150-250 ℃ of hydro-thermal reaction 5-15 hour, preparation hollow structure magnetic nano-particle;
The mol ratio of described divalent metal salt and urea, organic dispersing agent, alkaline precipitating agent is (20-2): (1-7): (0.25-0.5): (3-9); TV in all raw materials; The add-on of described divalent metal oxidation co-inhibitor is (0.2-2) g/L, and the add-on of described surface group modifier is (0.001-0.01) mol/L.
Described method specifically may further comprise the steps:
(1) configuration concentration is the urea soln of (0.05-0.2) mol/L, (0.2-0.6) mol/L divalent metal salts solution, (0.2-0.5) the alkaline sedimentation agent solution of mol/L, (0.2-0.4) the NaOH solution of mol/L;
(2) at ambient temperature; The divalent metal salts solution is added in the urea soln with (2-3) ml/min speed; Stir after 10-15 minute, stirring velocity is controlled at (600-800) rev/min, adds organic dispersing agent in the mixing solutions that obtains; Continue to stir (20-40) min, add divalent metal oxidation co-inhibitor then;
(3) alkaline precipitating agent is added in the above-mentioned solution with the speed of (0.5-1) ml/min; The reinforced continued that finishes stirred 20-30 minute; With NaOH solution the pH value is regulated and control between 10-12, obtained divalent metal salt sol deposition slurries, add the surface group modifier then;
(4) change step (3) synthetic colloidal sol shape suspension-s over to the high pressure water heating kettle, with heat-up rate (2.5-5) ℃/min, in (150-250) ℃ hydro-thermal reaction (5-15) hour;
(5) with obtain black solid product washing after the hydro-thermal reaction, magnet separates and lyophilize after 24 hours, prepare the pattern homogeneous, particle diameter is controlled and is the hollow structure magnetic nano-particle of single dispersing characteristic.
Described divalent metal salt is one or more in ferrous sulfate, iron protochloride, Iron nitrate, rose vitriol, single nickel salt, manganous sulfate and the zinc sulfate.
Described dispersion agent is any in cetyl trimethylammonium bromide, X 2073, Vinylpyrrolidone polymer, the polyoxyethylene glycol.
Described divalent metal oxidation co-inhibitor is any in glucose, xitix and the formaldehyde.
Described alkaline precipitating agent is any in sodium hydrogencarbonate, yellow soda ash and the ammoniacal liquor.
Described surface group modifier is any in morphine quinoline, sodium oleate, Trisodium Citrate, quadrol, the propylamine.
Described hollow structure magnetic nano-particle is Fe
3O
4, Co
3O
4, NiO, γ-Fe
2O
3, CoFe
2O
4, MnFe
2O
4, ZnFe
2O
4In one or more.
The thick 10-50nm of the shell of described hollow structure magnetic nano-particle, diameter are adjustable continuously between 80-200nm, and magnetic saturation intensity is at 20-80emu/g, and the surface has amido or carboxyl functional group.
The present invention is the Hydrothermal Preparation hollow magnetic nanoparticle novel method of template with the organic dispersing agent, through avtive spot complexing divalent-metal ion in the dispersion agent, solves reunion and particle diameter control problem that the hollow magnetic nanometer occurs in the preparation process.The present invention uses cheaply, and dispersion agent and inorganic divalent metal salt are raw material; The hollow magnetic nanoparticle that directly synthesizes single dispersing characteristic through a step hydro-thermal reaction; Adopt expensive divalent metal raw material to compare with tradition, have that process step is simple, cost is low and advantage such as easy scale operation.Through adjusting organic coating materials, can make synthetic hollow magnetic nanoparticle surface have amido or carboxyl functional group.The hollow structure magnetic nano-particle of the present invention's preparation can be widely used in fields such as medical science, biology, information storing device and transductor amplifier.
Compared with prior art, the present invention has the following advantages:
1. employed raw material sources are extensive, cost is low, working method is simple, is convenient to suitability for industrialized production, for the rich increment utilization of producing resource of China provides a new way;
2. adopting cheaply, organic dispersing agent is a template; With reactive group in the organic molecule (like groups such as O, N or C=C) complexing divalent-metal ion; The agglomeration traits that the regulation and control nanoparticle occurs in nucleation, process of growth; Through control control hydro-thermal reaction parameter (reactant composition, temperature, time and pH value of solution value etc.), preparation monodisperse hollow magnetic nano-particle;
3. adopt organic coating materials to regulate and control hollow magnetic nanoparticle surface functional group kind, make it have amido or carboxyl functional group, be convenient to application in fields such as biology, medical science.
In a word; The hollow magnetic nanoparticle method that the present invention proposes has that working method is simple, cost is low; And controlled, the good dispersibility of nano particle diameter pattern of preparation with fine butt joint of existing hydrometallurgical processes ability, is easy to the large-scale promotion of China powder metallurgy enterprise.
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Fig. 2 is for preparing the hollow magnetic nanoparticle (with Fe
3O
4Be example) X-ray powder diffraction spectrogram (XRD); Among the figure X-coordinate be diffraction angle 2 θ (°), ordinate zou is diffraction peak relative intensity value Intensity (a.u.);
Fig. 3 is for preparing the hollow magnetic nanoparticle (with Fe
3O
4Be example) magnetic hysteresis loop (VSM) figure;
Fig. 4 is that the hollow magnetic nanoparticle is (with Fe
3O
4Be example) shape appearance figure of AFM (AFM);
Fig. 5 hollow magnetic nanoparticle is (with Fe
3O
4Be example) phasor of AFM (AFM);
Fig. 6 is that hollow magnetic nanoparticle of the present invention is (with Fe
3O
4Be example) ESEM (SEM);
Fig. 7 is that hollow magnetic nanoparticle of the present invention is (with Fe
3O
4Be example) transmission electron microscope (TEM) shape appearance figure;
Fig. 8 is that hollow magnetic nanoparticle of the present invention is (with Fe
3O
4Be example) high-resolution-ration transmission electric-lens (HRTEM) figure;
Fig. 9 is that hollow magnetic nanoparticle of the present invention is (with Fe
3O
4Be example) choose electron diffraction (SAED) analysis.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is elaborated.
Embodiment 1
As shown in Figure 1, the technical process of preparation hollow magnetic nanoparticle is specially: dispose 20 milliliter of 0.15 mol urea soln, under 25 ℃ and 750 rev/mins of agitation conditions, add the FeSO of 50 milliliter of 0.4 mol successively
4The polyvinylpyrrolidonesolution solution of solution and 5 milliliter of 0.05 mol is dosed 0.05 gram solid ascorbic acid then, treat that it dissolves fully after, in above-mentioned hybrid sol solution, add the sodium carbonate solution of 40 milliliter of 0.2 mol.Behind above-mentioned solution thorough mixing, with 0.2 mol sodium hydroxide solution the pH value is adjusted to 10.5, add 0.001 mole quadrol then, mix to stir after 30 minutes, change the hydro-thermal device over to, 200 ℃ of hydro-thermals 10 hours.The product that obtains after the hydro-thermal through magnet separation, washing, alcohol wash with lyophilize after, obtain the hollow magnetic Fe that a large amount of black are single dispersing characteristic
3O
4Nanoparticle, the about 100nm of particle diameter, the thick 30nm of shell.
Shown in Fig. 2-9, products obtained therefrom is formed and standard Fe
3O
4JCPDS card No.19-629 corresponding, grain size about 100nm, the thick about 30nm of shell, magnetic saturation intensity is 78.2emu/g, synthetic Fe
3O
4Nanoparticle presents the monocrystalline characteristic.
Embodiment 2
Dispose 20 milliliter of 0.2 mol urea soln, under 25 ℃ and 750 rev/mins of agitation conditions, add the FeSO of 30 milliliter of 0.4 mol successively
4The CoSO of solution and 20 milliliter of 0.4 mol
4Solution adds 3 milliliters of Z 150PH-200 (PEG-200) dispersion agent then, mixes the back and adds 0.1 gram solid ascorbic acid to above-mentioned solution; After treating that it dissolves fully, in above-mentioned hybrid sol solution, add the sodium carbonate solution of 30 milliliter of 0.25 mol, the pH value is adjusted to 11.0 with 0.2 mol sodium hydroxide solution; Add 0.0001 mole of trisodium citrate then; Thorough mixing stirred after 30 minutes, changed the hydro-thermal device over to, 220 ℃ of hydro-thermals 10 hours.The black product that obtains after the hydro-thermal through magnet separation, washing, alcohol wash with lyophilize after, obtain being the hollow magnetic CoFe of single dispersing characteristic
2O
4Nanoparticle, the about 150nm of particle diameter, the thick 40nm of shell.
Dispose 20 milliliter of 0.05 mol urea soln, under 25 ℃ and 750 rev/mins of agitation conditions, add the CoSO of 40 milliliter of 0.35 mol successively
4The cetyl trimethylammonium bromide solution of solution and 3 milliliter of 0.1 mol is dosed 0.02 gram solid ascorbic acid then, treat that it dissolves fully after, in above-mentioned hybrid sol solution, add the sodium carbonate solution of 30 milliliter of 0.3 mol.Behind above-mentioned solution thorough mixing, with 0.2 mol sodium hydroxide solution the pH value is adjusted to 10.0, add 0.001 mole quadrol then, mix to stir after 30 minutes, change the hydro-thermal device over to, 235 ℃ of hydro-thermals 8 hours.The product that obtains after the hydro-thermal through magnet separation, washing, alcohol wash with lyophilize after, be the hollow magnetic Co of single dispersing characteristic in a large number
3O
4Nanoparticle, the about 80nm of particle diameter, the thick 20nm of shell.
Embodiment 4
Dispose 20 milliliter of 0.1 mol urea soln, under 25 ℃ and 750 rev/mins of agitation conditions, add the FeSO of 20 milliliter of 0.2 mol successively
4The ZnSO of solution and 15 milliliter of 0.2 mol
4Solution adds the X 2073 of 5 milliliter of 0.1 mol then, mixes the back and adds 0.15 gram solid ascorbic acid to above-mentioned solution; After treating that it dissolves fully, in above-mentioned hybrid sol solution, add the sodium carbonate solution of 20 milliliter of 0.15 mol, the pH value is adjusted to 11.5 with 0.2 mol sodium hydroxide solution; Add 0.0001 mole of oleic acid sodium then; Thorough mixing stirred after 30 minutes, changed the hydro-thermal device over to, 180 ℃ of hydro-thermals 10 hours.The product that obtains after the hydro-thermal through magnet separation, washing, alcohol wash with lyophilize after, obtain being the hollow magnetic ZnFe of single dispersing characteristic
2O
4Nanoparticle, the about 100nm of particle diameter, the thick 30nm of shell.
Embodiment 5
A kind of method of hydrothermal preparation monodisperse hollow magnetic nano-particle, this method specifically may further comprise the steps:
(1) configuration concentration is the urea soln of 0.05mol/L, 0.2mol/L divalent metal salt nickel sulfate solution, the sodium hydrogen carbonate solution of 0.2mol/L, the NaOH solution of 0.2mol/L; Get the raw materials ready; The mol ratio that makes divalent metal salt single nickel salt and urea, organic dispersing agent cetyl trimethylammonium bromide, sodium hydrogen carbonate solution is 20: 1: 0.25: 3; TV in all raw materials; The add-on of described divalent metal oxidation co-inhibitor glucose is 0.2g/L, and the add-on of described surface group modifier is 0.001mol/L;
(2) at ambient temperature, nickel sulfate solution is added in the urea soln with 2ml/min speed, stir after 10 minutes; Stirring velocity is controlled at 600 rev/mins; Add cetyl trimethylammonium bromide in the mixing solutions that obtains, continue to stir 20min, add glucose then;
(3) sodium hydrogen carbonate solution is added in the above-mentioned solution with the speed of 0.5ml/min, the reinforced continued that finishes stirred 20 minutes, with NaOH solution the pH value was regulated and control between 10-12, obtained divalent metal salt sol deposition slurries, added the surface group modifier then;
(4) change step (3) synthetic colloidal sol shape suspension-s over to the high pressure water heating kettle, with 2.5 ℃/min of heat-up rate, 150 ℃ of hydro-thermal reactions 5 hours;
(5) with obtain black solid product washing after the hydro-thermal reaction, magnet separates and lyophilize after 24 hours, prepare the pattern homogeneous, particle diameter is controlled and is the hollow structure magnetic nano-particle of single dispersing characteristic.
The thick 10nm of shell of gained hollow structure magnetic nano-particle, the about 80nm of particle diameter, magnetic saturation intensity are 20emu/g, the surface has amido or carboxyl functional group.
Embodiment 6
A kind of method of hydrothermal preparation monodisperse hollow magnetic nano-particle, this method specifically may further comprise the steps:
(1) configuration concentration is the urea soln of 0.2mol/L, 0.6mol/L manganese sulfate solution, the sodium carbonate solution of 0.5mol/L, the NaOH solution of 0.4mol/L; Get the raw materials ready; The mol ratio that makes divalent metal salt and urea, organic dispersing agent X 2073, alkaline precipitating agent ammoniacal liquor is 2: 7: 0.5: 9; TV in all raw materials; The add-on of described divalent metal oxidation co-inhibitor formaldehyde is 2g/L, and the add-on of described surface group modifier morphine quinoline is 0.01mol/L;
(2) at ambient temperature, manganese sulfate solution is added in the urea soln with (2-3) ml/min speed, stir after 15 minutes; Stirring velocity is controlled at 800 rev/mins; Add X 2073 in the mixing solutions that obtains, continue to stir 40min, add formaldehyde then;
(3) ammoniacal liquor is added in the above-mentioned solution with the speed of 1ml/min, the reinforced continued that finishes stirred 30 minutes, with NaOH solution the pH value was regulated and control between 10-12, obtained divalent metal salt sol deposition slurries, added the morphine quinoline then;
(4) change step (3) synthetic colloidal sol shape suspension-s over to the high pressure water heating kettle, with 5 ℃/min of heat-up rate, 250 ℃ of hydro-thermal reactions 15 hours;
(5) with obtain black solid product washing after the hydro-thermal reaction, magnet separates and lyophilize after 24 hours, prepare the pattern homogeneous, particle diameter is controlled and is the hollow structure magnetic nano-particle of single dispersing characteristic.
The thick 50nm of shell of gained hollow structure magnetic nano-particle, particle diameter is 200nm, and magnetic saturation intensity is at 80emu/g, and the surface has amido or carboxyl functional group.
Claims (9)
1. the method for a hydrothermal preparation monodisperse hollow magnetic nano-particle is characterized in that, this method is that the divalent metal salts solution is mixed with urea soln; Add organic dispersing agent and divalent metal oxidation co-inhibitor then; The alkaline sedimentation agent solution is slowly added in the above-mentioned solution, then mixing solutions pH value is adjusted to 10-12, add the surface group modifier again; At 150-250 ℃ of hydro-thermal reaction 5-15 hour, prepare the hollow structure magnetic nano-particle then;
The mol ratio of described divalent metal salt and urea, organic dispersing agent, alkaline precipitating agent is (20-2): (1-7): (0.25-0.5): (3-9); TV in all raw materials; The add-on of described divalent metal oxidation co-inhibitor is (0.2-2) g/L, and the add-on of described surface group modifier is (0.001-0.01) mol/L.
2. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 is characterized in that, described method specifically may further comprise the steps:
(1) configuration concentration is the urea soln of (0.05-0.2) mol/L, (0.2-0.6) mol/L divalent metal salts solution, (0.2-0.5) the alkaline sedimentation agent solution of mol/L, (0.2-0.4) the NaOH solution of mol/L;
(2) at ambient temperature; The divalent metal salts solution is added in the urea soln with (2-3) ml/min speed; Stir after 10-15 minute, stirring velocity is controlled at (600-800) rev/min, adds organic dispersing agent in the mixing solutions that obtains; Continue to stir (20-40) min, add divalent metal oxidation co-inhibitor then;
(3) alkaline precipitating agent is added in the above-mentioned solution with the speed of (0.5-1) ml/min; The reinforced continued that finishes stirred 20-30 minute; With NaOH solution the pH value is regulated and control between 10-12, obtained divalent metal salt sol deposition slurries, add the surface group modifier then;
(4) change step (3) synthetic colloidal sol shape suspension-s over to the high pressure water heating kettle, with heat-up rate (2.5-5) ℃/min, in (150-250) ℃ hydro-thermal reaction (5-15) hour;
(5) with obtain black solid product washing after the hydro-thermal reaction, magnet separates and lyophilize after 24 hours, prepare the pattern homogeneous, particle diameter is controlled and is the hollow structure magnetic nano-particle of single dispersing characteristic.
3. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2; It is characterized in that described divalent metal salt is one or more in ferrous sulfate, iron protochloride, Iron nitrate, rose vitriol, single nickel salt, manganous sulfate and the zinc sulfate.
4. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2; It is characterized in that described dispersion agent is any in cetyl trimethylammonium bromide, X 2073, Vinylpyrrolidone polymer, the polyoxyethylene glycol.
5. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2 is characterized in that, described divalent metal oxidation co-inhibitor is any in glucose, xitix and the formaldehyde.
6. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2 is characterized in that, described alkaline precipitating agent is any in sodium hydrogencarbonate, yellow soda ash and the ammoniacal liquor.
7. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2 is characterized in that, described surface group modifier is any in morphine quinoline, sodium oleate, Trisodium Citrate, quadrol, the propylamine.
8. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2 is characterized in that, described hollow structure magnetic nano-particle is Fe
3O
4, Co
3O
4, NiO, γ-Fe
2O
3, CoFe
2O
4, MnFe
2O
4, ZnFe
2O
4In one or more.
9. the method for a kind of hydrothermal preparation monodisperse hollow magnetic nano-particle according to claim 1 and 2; It is characterized in that; The thick 10-50nm of the shell of described hollow structure magnetic nano-particle; Diameter is adjustable continuously between 80-200nm, and magnetic saturation intensity is at 20-80emu/g, and the surface has amido or carboxyl functional group.
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