CN101863517A - Preparation method of mesopore-controllable magnetic microsphere - Google Patents
Preparation method of mesopore-controllable magnetic microsphere Download PDFInfo
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- CN101863517A CN101863517A CN 201010186395 CN201010186395A CN101863517A CN 101863517 A CN101863517 A CN 101863517A CN 201010186395 CN201010186395 CN 201010186395 CN 201010186395 A CN201010186395 A CN 201010186395A CN 101863517 A CN101863517 A CN 101863517A
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Abstract
The invention belongs to the technical field of inorganic material preparation, relating to a preparation method of a mesopore-controllable magnetic microsphere. The preparation method comprises the following concrete steps: respectively adding soluble ferric ion salts, ammonium acetate and poly glutamic acid into ethylene glycol solution to obtain mixed solution; controlling clarification solution with the concentration of the ferric ion salts of 0.05-0.40mol/L, the concentration of the ammonium acetate of 0.50-4.00mol/L and the concentration of the poly (glutamic acid)of 2.50-50.00g/L in the mixed solution; placing the solution into a closed heating vessel, carrying out a solvent thermal reaction at 200-300DEG C and heating for 8-72 hours; and washing the obtained product with deionized water and drying at 40-80DEG C. The invention provides a novel simple and feasible preparation method capable of batch production. Meanwhile, the invention has the advantages of high magnetic response and specific area, easily-accessible raw materials, favorable repeatability in the preparation process and controllable grain size, specific surface area, pore volume and average pore size of the obtained microspheres.
Description
Technical field
The invention belongs to the inorganic material preparation process technical field, be specifically related to a kind of preparation method of mesoporous controllable magnetic microsphere.
Background technology
Magnetic Nano material is because its unique magnetic physicals, as can to externally-applied magnetic field have remote response special property, can under external magnetic field control, move and have the hot physical influence of mangneto under extraneous alternating magnetic field condition, obtained in daily life using widely, for example prepared highdensity magnetic storage apparatus, catalyzer, pigment, magnetic fluid and biological diagnosis related application etc.
The method for preparing at present magnetic nano-particle mainly is a coprecipitation method.Coprecipitation method is that room temperature or heating condition add alkali lye down and carry out co-precipitation with molysite and ferrous salt wiring solution-forming in certain proportion.The advantage of co-precipitation is to prepare magnetic nano-particle in a large number, but the nanoparticle that obtains is polydisperse often, and degree of crystallinity is not high, and particle diameter is less, has lower magnetic responsiveness, and this is disadvantageous to follow-up application.The synthetic method of bibliographical information submicron order magnetic particle is mainly solvent-thermal method at present, can obtain the magnetic microsphere of particle diameter at 200～800nm, compare with the magnetic nano-particle that coprecipitation method prepares, have very high magnetic responsiveness, but the increase of magnetic responsiveness is a cost to sacrifice specific surface area.
Therefore, develop a kind of have simultaneously high magnetic responsiveness and high-specific surface area, pattern homogeneous, good dispersity, the preparation method who is easy to the magnetic microsphere produced in batches simultaneously is the challenge that the chemical science and technology field faces.
Summary of the invention
The object of the invention is to provide a kind of preparation method of the simple mesoporous controllable magnetic microsphere that can manufacture.
Content of the present invention is a kind of preparation method of mesoporous controllable magnetic microsphere, and its concrete steps are as follows:
(1) join solubility ferric ion salt, ammonium acetate and polyglutamic acid in the ethylene glycol solution respectively, obtain mixing solutions, the ferric ion salt concn is 0.05～0.40mol/L in the control mixing solutions, ammonium acetate concentration is 0.50～4.00mol/L, and polyglutamic acid concentration is the settled solution of 2.50～50.00g/L;
(2) mixing solutions that step (1) is obtained is put into airtight heating container, carries out solvent thermal reaction under 200～300 ℃, and be 8～72 hours heat-up time;
(3) with step (2) products therefrom deionized water wash, oven dry promptly gets required product.
Among the present invention, employed solubility ferric ion salt is a kind of in iron(ic) chloride, iron nitrate, ferric sulfate or the iron acetate in the step (1).
Among the present invention, employed polyglutamic acid molecular weight is 100～1000kDa in the step (1).
Among the present invention, bake out temperature is 40～80 ℃ described in the step (3).
The present invention can control mesoporous magnetic microsphere particle diameter, specific surface area, pore volume and mean pore size by changing the input amount and the reaction times of solubility ferric ion salt, polyglutamic acid.
Above-mentioned reaction is expressed as follows with chemical equation:
Fe
3++HOCH
2-CH
2OH→Fe
3O
4
The mesoporous magnetic microsphere that utilizes the inventive method to obtain, microspherulite diameter is distributed in 50～500nm, and the controllable specific surface area of microballoon is built in 10～300m
2/ g, pore volume can be controlled in 0.05～1.50cm
3/ g, mean pore size can be controlled in 2.0～10.0nm.
Compared with prior art, beneficial effect of the present invention is: it is raw material that the present invention adopts solubility ferric ion salt, ammonium acetate, polyglutamic acid and ethylene glycol, adopts solvent thermal method, has prepared the mesoporous magnetic microsphere of a large amount of cheapnesss.Uniform product appearance and good dispersity, narrow diameter distribution.This method raw material is cheap and easy to get, and technology is quite simple, produces to be easy to amplify, and products obtained therefrom has bigger performance regulation and control space, makes particle diameter, specific surface area, pore volume and the mean pore size of product adjusted as the variation of condition by experiment.Because magnetic microsphere is modern industry, the good carrier of Industrial Catalysis especially, the product of the present invention's preparation has high magnetic responsiveness and high specific surface area simultaneously, steady quality, controllability is good, thereby has broad application prospects.
Description of drawings
Fig. 1 is the x-ray diffractogram of powder of the mesoporous magnetic microsphere in the embodiment of the invention 1;
Fig. 2 is the transmission electron microscope figure of the mesoporous magnetic microsphere in the embodiment of the invention 1;
Fig. 3 is the nitrogen adsorption desorption isothermal curve figure of the mesoporous magnetic microsphere in the embodiment of the invention 1.
Embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Fig. 1-the 3rd, the result who characterizes with powder x-ray diffraction, transmission electron microscope and nitrogen adsorption desorption isothermal curve.Microspherulite diameter is 436nm, and specific surface area is 182m
2/ g, pore volume are 0.65cm
3/ g, mean pore size can be controlled in 5.8nm.
Embodiment 2:
Get the iron(ic) chloride of 2mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 250 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 49nm, and specific surface area is 270m
2/ g, pore volume are 1.35cm
3/ g, mean pore size can be controlled in 2.5nm.
Embodiment 3:
Get the iron nitrate of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 300 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 407nm, and specific surface area is 210m
2/ g, pore volume are 0.75cm
3/ g, mean pore size can be controlled in 5.1nm.
Embodiment 4:
Get the ferric sulfate of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 413nm, and specific surface area is 197m
2/ g, pore volume are 0.70cm
3/ g, mean pore size can be controlled in 5.3nm.
Embodiment 5:
Get the iron acetate of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 450nm, and specific surface area is 176m
2/ g, pore volume are 0.59cm
3/ g, mean pore size can be controlled in 6.5nm.
Embodiment 6:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 20mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 483nm, and specific surface area is 52m
2/ g, pore volume are 0.15cm
3/ g, mean pore size can be controlled in 9.0nm.
Embodiment 7:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 160mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 79nm, and specific surface area is 281m
2/ g, pore volume are 1.38cm
3/ g, mean pore size can be controlled in 3.3nm.
Embodiment 8:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 50mmol, 0.1g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 498nm, and specific surface area is 12m
2/ g, pore volume are 0.06cm
3/ g, mean pore size can be controlled in 9.7nm.
Embodiment 9:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 50mmol, 2.0g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 52nm, and specific surface area is 296m
2/ g, pore volume are 1.51cm
3/ g, mean pore size can be controlled in 1.9nm.
Embodiment 10:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 24 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 451nm, and specific surface area is 152m
2/ g, pore volume are 0.58cm
3/ g, mean pore size can be controlled in 4.9nm.
Embodiment 11:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 1000kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 72 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 485nm, and specific surface area is 128m
2/ g, pore volume are 0.41cm
3/ g, mean pore size can be controlled in 4.3nm.
Embodiment 12:
Get the iron(ic) chloride of 16mmol, the ammonium acetate of 50mmol, 0.5g being the polyglutamic acid of 100kDa, molecular weight joins in 50 milliliters the water heating kettle, the ethylene glycol solution that in still, adds 40 milliliters, after the dissolving, 200 ℃ were heated 8 hours, and the gained black precipitate is through deionized water wash, dry between 40～80 ℃, make the mesoporous ferriferrous oxide magnetic microsphere.Microspherulite diameter is 348nm, and specific surface area is 145m
2/ g, pore volume are 0.49cm
3/ g, mean pore size can be controlled in 7.1nm.
Claims (3)
1. the preparation method of a mesoporous controllable magnetic microsphere is characterized in that concrete steps are as follows:
(1) solubility ferric ion salt, ammonium acetate and polyglutamic acid are joined respectively obtains mixing solutions in the ethylene glycol solution, the ferric ion salt concn is 0.05～0.40mol/L in the control mixing solutions, ammonium acetate concentration is 0.50～4.00mol/L, and polyglutamic acid concentration is the settled solution of 2.50～50.00g/L;
(2) solution of step (1) preparation is put into airtight heating container, carry out solvent thermal reaction under 200～300 ℃, be 8～72 hours heat-up time;
(3) with products therefrom deionized water wash in the step (2),, promptly get required product 40～80 ℃ of oven dry.
2. the preparation method of mesoporous controllable magnetic microsphere according to claim 1 is characterized in that: employed solubility ferric ion salt is a kind of in iron(ic) chloride, iron nitrate, ferric sulfate or the iron acetate in the step (1).
3. the preparation method of mesoporous controllable magnetic microsphere according to claim 1, it is characterized in that: employed polyglutamic acid molecular weight is 100～1000kDa in the step (1).
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153151A (en) * | 2011-04-29 | 2011-08-17 | 中国科学院合肥物质科学研究院 | Ferroferric oxide porous ball having micro-nano structure, and preparation method of ferroferric oxide porous ball |
| CN102381729A (en) * | 2011-07-27 | 2012-03-21 | 绍兴文理学院 | Preparation method of spherical ferroferric oxide |
| CN102417208A (en) * | 2011-08-08 | 2012-04-18 | 江苏大学 | Mesoporous magnetic ferriferrous oxide, its preparation method and application |
| CN102502877A (en) * | 2011-10-18 | 2012-06-20 | 南开大学 | Simple method for synthesizing porous magnetic ferroferric oxide (Fe3O4) microspheres |
| CN102637499A (en) * | 2012-04-13 | 2012-08-15 | 复旦大学 | Preparation method of magnetic mesoporous colloid nanocluster with stable natural polysaccharides |
| CN107601576A (en) * | 2017-10-23 | 2018-01-19 | 广东顺德工业设计研究院(广东顺德创新设计研究院) | Ferroso-ferric oxide hollow magnetic nano particle and preparation method thereof |
| CN113083217A (en) * | 2021-03-25 | 2021-07-09 | 苏州环亚欣智能科技有限公司 | Preparation method of magnetic silica gel microspheres with controllable high pore diameters |
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| WO2000071465A1 (en) * | 1999-05-22 | 2000-11-30 | Henkel Kommanditgesellschaft Auf Aktien | Redispersable metal oxides and hydroxides with particle sizes in the nanometric size range |
| CN101314483A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | Method for synthesizing alpha-Fe2O3 nano-particle with controllable shape size |
| CN101525159A (en) * | 2009-04-20 | 2009-09-09 | 中南大学 | Solvothermal preparation method of monodisperse Fe3O4 nano-particles |
| CN101559984A (en) * | 2009-05-27 | 2009-10-21 | 山东大学 | Preparation method of superparamagnetic Fe3O4 nano-particles |
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| WO2000071465A1 (en) * | 1999-05-22 | 2000-11-30 | Henkel Kommanditgesellschaft Auf Aktien | Redispersable metal oxides and hydroxides with particle sizes in the nanometric size range |
| CN101314483A (en) * | 2008-06-20 | 2008-12-03 | 大连理工大学 | Method for synthesizing alpha-Fe2O3 nano-particle with controllable shape size |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102153151A (en) * | 2011-04-29 | 2011-08-17 | 中国科学院合肥物质科学研究院 | Ferroferric oxide porous ball having micro-nano structure, and preparation method of ferroferric oxide porous ball |
| CN102153151B (en) * | 2011-04-29 | 2012-11-21 | 中国科学院合肥物质科学研究院 | Ferroferric oxide porous ball having micro-nano structure, and preparation method of ferroferric oxide porous ball |
| CN102381729A (en) * | 2011-07-27 | 2012-03-21 | 绍兴文理学院 | Preparation method of spherical ferroferric oxide |
| CN102381729B (en) * | 2011-07-27 | 2013-08-14 | 绍兴文理学院 | Preparation method of spherical ferroferric oxide |
| CN102417208A (en) * | 2011-08-08 | 2012-04-18 | 江苏大学 | Mesoporous magnetic ferriferrous oxide, its preparation method and application |
| CN102502877A (en) * | 2011-10-18 | 2012-06-20 | 南开大学 | Simple method for synthesizing porous magnetic ferroferric oxide (Fe3O4) microspheres |
| CN102502877B (en) * | 2011-10-18 | 2014-06-25 | 南开大学 | Simple method for synthesizing porous magnetic ferroferric oxide (Fe3O4) microspheres |
| CN102637499A (en) * | 2012-04-13 | 2012-08-15 | 复旦大学 | Preparation method of magnetic mesoporous colloid nanocluster with stable natural polysaccharides |
| CN107601576A (en) * | 2017-10-23 | 2018-01-19 | 广东顺德工业设计研究院(广东顺德创新设计研究院) | Ferroso-ferric oxide hollow magnetic nano particle and preparation method thereof |
| CN107601576B (en) * | 2017-10-23 | 2020-01-31 | 广东顺德工业设计研究院(广东顺德创新设计研究院) | Ferroferric oxide hollow magnetic nano-particles and preparation method thereof |
| CN113083217A (en) * | 2021-03-25 | 2021-07-09 | 苏州环亚欣智能科技有限公司 | Preparation method of magnetic silica gel microspheres with controllable high pore diameters |
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