CN102974285B - Producing method of magnetic microsphere with hierarchical-pore structure and adjustable uniform grain size - Google Patents
Producing method of magnetic microsphere with hierarchical-pore structure and adjustable uniform grain size Download PDFInfo
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- CN102974285B CN102974285B CN201210508992.XA CN201210508992A CN102974285B CN 102974285 B CN102974285 B CN 102974285B CN 201210508992 A CN201210508992 A CN 201210508992A CN 102974285 B CN102974285 B CN 102974285B
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- aqueous slkali
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Abstract
The invention discloses a producing method of a magnetic microsphere with a hierarchical-pore structure and an adjustable uniform grain size. The method comprises the steps of adopting an ionic liquid containing iron as a material; adding the material to an alkali source which generates gas when being heated; using ethylene glycol as a solvent; uniformly stirring the mixture, and then pouring the mixture into a sealed reaction container for reacting for 3 hours to 24 hours at 180 DEG C to 300 DEG C to obtain the magnetic microsphere with the hierarchical-pore structure and the adjustable uniform grain size, wherein the composition of the magnetic microsphere is MFe2O4 (M is Fe, Co, Ni, Mn and Zn). Reaction conditions are adjusted, so that the grain size of the magnetic nanometer microsphere can be adjusted with a range of 23 nanometers to 600 nanometers, the saturation magnetization rate is high (73-89emu/g), the specific surface area is 55-74m<2>/g, and the bore diameter distribution ranges of the three-stage bore are respectively 2-3 nm, 7-12nm and 7-70nm.
Description
technical field:
The invention belongs to nano material technology of preparing, be specifically related to a kind of preparation method with hierarchical porous structure, magnetic microsphere that uniform particle diameter is adjustable.
background technology:
Ionic liquid at room temperature be by certain cationic and anion, formed in room temperature or be bordering on the material being in a liquid state under room temperature, it has non-volatile, low melting point, wide liquid journey, strong electrostatic field, wide electrochemical window, good conduction and thermal conductivity, high heat capacity, high stability, selective dissolution power and designability.These features are impelled the research of ionic liquid and are used from initial chemical field, are extended to rapidly the various fields that comprises functional material, the energy, resource environment, life science.
In the synthetic field of nano material, ionic liquid can substitute conventional organic solvent, reaction can be carried out under normal pressure, and avoid environment; Ionic liquid has very strong self assembly ability, and it can form supramolecular structure by hydrogen bond, as template or auxiliary template, exists; In addition, because ionic liquid has lower surface energy, can play the effect that improves nucleation rate and stable nanoparticles.With respect to synthesis of nano particle in water, if take ionic liquid as template, can stop nanoparticle agglomerates, after reaction, can ionic liquid be removed by simple method again.
At present; people use and in ionic liquid, have synthesized many eurypalynous nano materials; comprise that metal (gold, silver, palladium etc.), nonmetal (selenium, tellurium etc.), silica, organic silicon oxide, metal oxide, metal chalcogenides, slaine etc. are [referring to Ma, Z.; Yu, J.; Dai, S.:Preparation of inorganic materials using ionic liquids.
advanced materials 2010,
22, 261-285.].Zhu Yingjie etc. [referring to: Cao, S.-W.; Zhu, Y.-J.:Iron oxide hollow spheres:Microwave-hydrothermal ionic liquid preparation, formation mechanism, crystal phase and morphology control and properties.
acta Materialia 2009,
57, 2154-2165.] and use Microwave-assisted ionic liquid method first to prepare alpha-feooh hollow ball, then take it as template, add ferrous sulfate coprecipitation to prepare Fe
3o
4hollow ball.Zhou etc. [referring to: Zhou, S.; Ma, Z.; Baker, G. A.; Rondinone, A. J.; Zhu, Q.; Luo, H.; Wu, Z.; Dai, S.:Self-Assembly of Metal Oxide Nanoparticles into Hierarchically Patterned Porous Architectures Using Ionic Liquid/Oil Emulsions.
langmuir 2009,
25, 7229-7233.] and in the emulsion of ionic liquid and olefin solvent composition, synthesized the Fe with approximately 300 nanometers or micron level aperture
3o
4foam.Hu etc. [referring to: Hu, H.; Yang, H.; Huang, P.; Cui, D.; Peng, Y.; Zhang, J.; Lu, F.; Lian, J.; Shi, D.:Unique role of ionic liquid in microwave-assisted synthesis of monodisperse magnetite nanoparticles.
chemical Communications 2010,
46, 3866-3868.] and in 1,2-, 16 glycol and diphenyl ether, add a small amount of oleic acid and [BMIM] [BF
4], with Fe (acac)
3as source of iron, synthesized the monodispersed Fe that particle diameter is 6nm
3o
4nano particle.Oliveira etc. [referring to: Oliveira, F. C. C.; Effenberger, F. B.; Sousa, M. H.; Jardim, R. F.; Kiyohara, P. K.; Dupont, J.; Rubim, J. C.; Rossi, L. M.:Ionic liquids as recycling solvents for the synthesis of magnetic nanoparticles.
physical Chemistry Chemical Physics 2011,
13, 13558-13564.] and with [BMIM] [PF
6] or [BMIM] [NTf
2] ionic liquid is as solvent, with Fe (acac)
3/ M (acac)
3(M=Co, Fe, Mn or Ni) as raw material, and adding oleyl amine to synthesize particle diameter as reducing agent and stabilizing agent is the MFe of 8 nanometer ~ 15 nanometers
2o
4(M=Co, Fe, Mn or Ni) nano particle.Zhang etc. [referring to: Zhang, Y.; Liu, D.; Wang, X.; Song, S.; Zhang, H.:Synthesis of Ferrite Nanocrystals Stabilized by Ionic-Liquid Molecules through a Thermal Decomposition Route.
chemistry--A European Journal 2011,
17, 920-924.] and using the PEG of end band carboxyl and ionic liquid group as structure guiding agent and stabilizing agent, with Fe (acac)
3/ M (acac)
2(M=Co, Fe, Zn or Ni) is the M of 8 ~ 11 nanometers for raw material has synthesized particle diameter
xfe
3-xo
4(M=Co, Fe, Zn or Ni, 0<x<1) is nanocrystalline.Yin etc. [referring to: Yin, S.; Luo, Z.; Xia, J.; Li, H.:Microwave-assisted synthesis of Fe
3o
4nanorods and nanowires in an ionic liquid.
journal of Physics and Chemistry of Solids 2010,
71, 1785-1788.] and at [BMIM] [BF
4] by the auxiliary coprecipitation of microwave, synthesized Fe in ionic liquid situation about existing
3o
4nanorod and nanowire.Li etc. [referring to: Li, X.; Liu, D.; Song, S.; Wang, X.; Ge, X.; Zhang, H.:Rhombic dodecahedral Fe
3o
4: ionic liquid-modulated and microwave-assisted synthesis and their magnetic properties.
crystEngComm 2011,
13, 6017-6020.] and at [C
12py] [ClO
4] take iron ammonium sulfate as raw material in ionic liquid situation about existing, add phenol and hexamethylenetetramine, Microwave-assisted firing has synthesized Fe
3o
412 nano particles.
About having the magnetic Nano microsphere of hierarchical porous structure, the synthetic method of existing report is very complicated at present.Kido etc. [referring to: Kido, Y.; Nakanishi, K.; Miyasaka, A.; Kanamori, K.:Synthesis of Monolithic Hierarchically Porous Iron-Based Xerogels from Iron (III) Salts via an Epoxide-Mediated Sol – Gel Process.
chemistry of Materials 2012,
24, 2071-2077.] and adopt sol-gal process to synthesize a kind of have micron order macropore and mesoporous Fe simultaneously
3o
4/ Fe/Fe
3c is composite porous.This method is first by FeCl
3be dissolved in the mixed solvent of water and glycerine with polyacrylamide, then add expoxy propane to form gel as crosslinking agent, be further processed into aerosol after high temperature cabonization obtain magnetic composite.But with ionic liquid, synthesize there is hierarchical porous structure, the method for magnetic Nano microsphere that uniform particle diameter is adjustable there is not yet bibliographical information.
summary of the invention:
The invention discloses and a kind ofly take iron content ionic liquid and as raw material is synthetic, there is the method for hierarchical porous structure, uniform particle diameter and adjustable magnetic Nano microsphere.This synthetic method preparation technology is simple, and productive rate is high.
Technical scheme of the present invention is as follows:
A method for making with hierarchical porous structure, magnetic microsphere that uniform particle diameter is adjustable, it comprises the following steps:
1. the preparation of iron content ionic liquid:
The cation of the ionic liquid of described iron content is one or more in the following stated cation, anion is one or more in the following stated anion, and add the mixture of soluble iron (III) salt or soluble iron (III) salt and solubility divalent salts, especially, the Fe that is iron content when anion (III) Cl
4 -time, can not add soluble iron (III) salt and solubility divalent salts, or only add solubility divalent salts;
Described cation is 1,3-dialkylimidazolium ion [R
1r
2iM]
+, 1,2,3-trialkyl imidazol ion [R
1r
2r
3iM]
+, N-alkyl pyridine ion [RPy]
+, N
1, N
2-dialkyl group pyrazoles ion [R
1r
2pz]
+, N-alkyl thiazole ion [RTz]
+, N
1, N
2-dialkyl piperidine ion [R
1r
2pp]
+, N
1, N
2-dialkyl group pyrrolidines ion [R
1r
2p]
+, tetraalkyl quaternary ammonium ion [NR
1r
2r
3r
4]
+, four Wan Ji quaternary phosphine ion [PR
1r
2r
3r
4]
+or trialkyl sulfonium cation [SR
1r
2r
3]
+;
Described anion is Fe (III) Cl
4 -, M (II) Cl
4 2-(M=Fe, Co, Ni, Mn, Zn), Cl
-, Br
-, BF
4 -, PF
6 -, CH
3cOO
-, CF
3cOO
-, C
3f
7cOO
-, CF
3sO
3 -, C
4f
9sO
3 -, (CF
3sO
2)
2n
-, (C
2f
5sO
2)
2n
-, (CF
3sO
2)
3c
-, SbF
6 -, AsF
6 -, CB
11h
12 -, [BR
1r
2r
3r
4]
-, [N (CN)
2]
-, NO
3 -, NO
2 -in a kind of;
Described soluble iron (III) salt comprises iron chloride, ferric bromide, ferric nitrate, ferric sulfate, ferric acetate etc.;
Described solubility divalent salts comprises the nitrate of ferrous iron, cobalt, nickel, manganese or zinc etc., sulfate, acetate, chloride or bromide etc.;
2. in the situation that stirring, the ion liquid dissolving of iron content is formed to 0.01mol/L ~ 0.2mol/L solution in ethylene glycol, then adding concentration is the aqueous slkali of 0.5mol/L ~ 2mol/L, the consumption of aqueous slkali is 2 ~ 50 times of molal quantity of iron (III) in the ionic liquid of iron content, continues to stir until evenly, and described aqueous slkali can produce gas aqueous slkali during for heating, comprise ammoniacal liquor, hydrazine hydrate, azanol, urea, the aqueous solution of hexamethylene tetramine etc.;
3. above-mentioned prepared solution is transferred to (as the steel autoclave of inner liner polytetrafluoroethylene) in closed container, then closed container is transferred to and in heater, be heated to a certain temperature within the scope of 180 ℃ ~ 300 ℃, keep thermotonus 3 hours ~ 24 hours, reaction finishes rear naturally cooling;
4. the solid product by means such as Magnetic Isolation, centrifugal or filtrations, above-mentioned reaction being obtained is separated, and water and ethanol cyclic washing repeatedly, and the vacuum drying chamber that is finally placed in 40 ℃ ~ 80 ℃ is dry, obtains target product magnetic microsphere.
The method for making of above-mentioned magnetic microsphere, step 2 can be by regulating the addition of described aqueous slkali to regulate the particle diameter of magnetic microsphere, the concentration of the aqueous slkali adding or volume, can reduce particle diameter, in the concentration of aqueous slkali, be that 0.5mol/L ~ 2mol/L, consumption are that under the condition of 2 ~ 50 times of molal quantity of iron (III), particle diameter adjustable extent is 600nm ~ 23nm.
Magnetic Nano microsphere prepared by the present invention consist of MFe
2o
4(M=Fe, Co, Ni, Mn and Zn), its particle diameter adjustable extent is 23～600 nanometers, and its saturated magnetization rate is 73 ~ 89emu/g, and specific area is 55 ~ 74m
2/ g.This magnetic Nano microsphere has the hole of three grades of different pore sizes simultaneously, and average pore size distribution is respectively 2 ~ 3nm, 7 ~ 12nm, 7 ~ 70nm.As shown in Fig. 2 and Fig. 3 a, first order pore size distribution is on the surface of Nano microsphere, and its average pore size is distributed as 7 ~ 70nm; As shown in Figure 3 b, second level pore size distribution is in the inside of Nano microsphere, and its average pore size is distributed as 7 ~ 12nm; As shown in Figure 3 c, third level pore size distribution is in the inside of Nano microsphere, and between nanocrystal, its average pore size is distributed as 2 ~ 3nm.Especially, when the particle diameter of Nano microsphere is less than 100nm, first order hole and hole, the second level have close pore-size distribution.
The magnetic material with hierarchical porous structure that the present invention is prepared, because of its unique pore structure and excellent magnetic property, is expected to be applied to biomedicine, sensor, lithium ion battery, medicine storage and slowly-releasing, catalysis, the dirty harmful Adsorption of environment and radar absorbing material etc.
Accompanying drawing explanation
Fig. 1. there is the x-ray diffractogram of powder of the magnetic Nano microsphere of hierarchical porous structure.
Fig. 2. there is the scanning electron microscope (SEM) photograph of the magnetic Nano microsphere of hierarchical porous structure.
Fig. 3. there is the transmission electron microscope picture of the magnetic Nano microsphere of hierarchical porous structure, wherein: Fig. 3 a, Fig. 3 b and Fig. 3 c are different amplification figure.
Fig. 4. there is the saturated magnetization rate of the magnetic Nano microsphere of hierarchical porous structure.
the specific embodiment:
Embodiment 1: by [the FeCl of 1-methyl-3-butyl imidazole ion of 1mmol
4]
-salt ([C
4c
1iM] [FeCl
4]) join in 35mL ethylene glycol, magnetic agitation obtains homogeneous solution, adds 1mL 25wt% ammoniacal liquor, continues to stir 30min, solution is proceeded in the autoclave of 50mL inner liner polytetrafluoroethylene.Then autoclave is put into baking oven, be heated to 200 ℃, reaction 12h.Take out after autoclave, treat that it naturally cools to room temperature, with the solids of sedimentation in the separating obtained solution of magnet, and wash 3 times with a small amount of water and a small amount of ethanol, dry in 40 ℃ ~ 80 ℃ vacuum drying ovens.Prepared magnetic microsphere average grain diameter is 300 nanometers, and its saturated magnetization rate is 89emu/g, and specific area is 70m
2/ g, the average pore size of multi-stage porous is respectively 2nm, 10nm, 60nm.Its pattern and test data are as shown in Fig. 1 ~ Fig. 4.
Embodiment 2: by the chlorination of 0.5mmol (1-Ethyl-2-Methyl-3-butyl imidazole) ([C
2c
1c
4iM] Cl), 0.4mmolFeCl
3and 0.1mmolFeCl
2join in 35mL ethylene glycol, magnetic agitation obtains homogeneous solution, adds 0.5mL 50wt% hydrazine hydrate solution, continues to stir 30min, solution is proceeded in the autoclave of 50mL inner liner polytetrafluoroethylene.Then autoclave is put into baking oven, be heated to 260 ℃, reaction 3h.Take out after autoclave, treat that it naturally cools to room temperature, with the solids of sedimentation in the separating obtained solution of magnet, and wash 3 times with a small amount of water and a small amount of ethanol, dry in 40 ℃ ~ 80 ℃ vacuum drying ovens.Prepared magnetic microsphere average grain diameter is 600 nanometers, and its saturated magnetization rate is 89emu/g, and specific area is 74m
2/ g, the average pore size of multi-stage porous is respectively 3nm, 12nm, 70nm.
Embodiment 3: by [the AsF of the N-butyl-pyridinium ion of 2.5mmol
6]
-salt ([C
4py] [AsF
6], the N of 2.5mmold
1-hexyl-N
2the borofluoride ([C of-methyl piperidine ion
6c
1pp] BF
4), the Fe (NO of 5mmol
3)
3ni (NO with 1mmol
3)
2join in 30mL ethylene glycol, magnetic agitation obtains homogeneous solution, adds 5mL 40wt% urea liquid, continues to stir 30min, solution is proceeded in the autoclave of 50mL inner liner polytetrafluoroethylene.Then autoclave is put into baking oven, be heated to 300 ℃, reaction 24h.Take out after autoclave, treat that it naturally cools to room temperature, with the solids of sedimentation in the separating obtained solution of magnet, and wash 3 times with a small amount of water and a small amount of ethanol, dry in 40 ℃ ~ 80 ℃ vacuum drying ovens.Prepared magnetic microsphere average grain diameter is 23 nanometers, and its saturated magnetization rate is 73emu/g, and specific area is 55m
2/ g, the average pore size of multi-stage porous is respectively 2nm, 7nm, 7nm.
Embodiment 4: by the N of 0.5mmol
1-hexyl-N
2hyptafluorobutyric acid the salt ([C of-crassitude ion
6c
1p] [C
3f
7cOO]), the N of 1mmol
1-butyl-N
2-methylpyrazole acetate ([C
4c
1pz] [CH
3cOO]), N-butyl the thiazole ([C of 1mmol
4tz] [CF
3sO
3]), the Fe (CH of 1.5mmol
3cOO)
3mn (CH with 0.5mol
3cOO)
2join in 35mL ethylene glycol, magnetic agitation obtains homogeneous solution, adds 1mL 50wt% hexamethylenetetramine solution, continues to stir 30min, solution is proceeded in the autoclave of 50mL inner liner polytetrafluoroethylene.Then autoclave is put into baking oven, be heated to 180 ℃, reaction 18h.Take out after autoclave, treat that it naturally cools to room temperature, with the solids of sedimentation in the separating obtained solution of magnet, and wash 3 times with a small amount of water and a small amount of ethanol, dry in 40 ℃ ~ 80 ℃ vacuum drying ovens.Prepared magnetic microsphere average grain diameter is 250 nanometers, and its saturated magnetization rate is 81emu/g, and specific area is 64m
2/ g, the average pore size of multi-stage porous is respectively 2nm, 10nm, 54nm.
Embodiment 5: by the ([NC of the tetrabutyl quaternary ammonium ion of 1mmol
4c
4c
4c
4] [N (CN)
2]), ([the P C of the tetrapropyl quaternary phosphine ion of 0.5mmol
3c
3c
3c
3] [(CF
3sO
2)
3c]), 0.5mmol [SC
3c
3c
3] [CB
11h
12], 0.5mmol Fe
2(SO
4)
3with 0.5mol CoCl
2join in 35mL ethylene glycol, magnetic agitation obtains homogeneous solution, adds 2mL 50wt% hydroxylamine solution, continues to stir 30min, solution is proceeded in the autoclave of 50mL inner liner polytetrafluoroethylene.Then autoclave is put into baking oven, be heated to 220 ℃, reaction 10h.Take out after autoclave, treat that it naturally cools to room temperature, with the solids of sedimentation in the separating obtained solution of magnet, and wash 3 times with a small amount of water and a small amount of ethanol, dry in 40 ℃ ~ 80 ℃ vacuum drying ovens.Prepared magnetic microsphere average grain diameter is 100 nanometers, and its saturated magnetization rate is 79emu/g, and specific area is 60m
2/ g, the average pore size of multi-stage porous is respectively 2nm, 8nm, 10nm.
Claims (2)
1. a method for making with hierarchical porous structure, magnetic microsphere that uniform particle diameter is adjustable, is characterized in that it comprises the following steps:
1) preparation of iron content ionic liquid:
The cation of the ionic liquid of described iron content is one or more in the following stated cation, anion is one or more in the following stated anion, and add the mixture of solubility trivalent iron salt or solubility trivalent iron salt and solubility divalent salts, especially, the FeCl that is iron content when anion
4 -time, can not add solubility trivalent iron salt and solubility divalent salts, or only add solubility divalent salts;
Described cation is 1,3-dialkylimidazolium ion [R
1r
2iM]
+, 1,2,3-trialkyl imidazol ion [R
1r
2r
3iM]
+, N-alkyl pyridine ion [RPy]
+, N
1, N
2-dialkyl group pyrazoles ion [R
1r
2pz]
+, N-alkyl thiazole ion [RTz]
+, N
1, N
2-dialkyl piperidine ion [R
1r
2pp]
+, N
1, N
2-dialkyl group pyrrolidines ion [R
1r
2p]
+, tetraalkyl quaternary ammonium ion [NR
1r
2r
3r
4]
+, four Wan Ji quaternary phosphine ion [PR
1r
2r
3r
4]
+or trialkyl sulfonium cation [SR
1r
2r
3]
+;
Described anion is FeCl
4 -, MCl
4 2-, Cl
-, Br
-, BF
4 -, PF
6 -, CH
3cOO
-, CF
3cOO
-, C
3f
7cOO
-, CF
3sO
3 -, C
4f
9sO
3 -, (CF
3sO
2)
2n
-, (C
2f
5sO
2)
2n
-, (CF
3sO
2)
3c
-, SbF
6 -, AsF
6 -, CB
11h
12 -, [BR
1r
2r
3r
4]
-, [N (CN)
2]
-, NO
3 -, NO
2 -in a kind of, M=Fe wherein, Co, Ni, Mn or Zn;
Described solubility trivalent iron salt comprises iron chloride, ferric bromide, ferric nitrate, ferric sulfate or ferric acetate;
Described solubility divalent salts comprises the nitrate of ferrous iron, cobalt, nickel, manganese or zinc, sulfate, acetate, chloride or bromide;
2) in the situation that stirring, the ion liquid dissolving of iron content is formed to 0.01mol/L～0.2mol/L solution in ethylene glycol, then adding concentration is the aqueous slkali of 0.5mol/L～2mol/L, the consumption of aqueous slkali is 2～50 times of ferric molal quantity in the ionic liquid of iron content, continues to stir until evenly, and described aqueous slkali can produce the aqueous slkali of gas during for heating, comprise ammoniacal liquor, hydrazine hydrate, azanol, urea, the aqueous solution of hexamethylene tetramine;
3) above-mentioned prepared solution is transferred in closed container, then closed container is transferred in heater and be heated to a certain temperature within the scope of 180 ℃～300 ℃, keep thermotonus 3 hours～24 hours, reaction finishes rear naturally cooling;
4) by Magnetic Isolation, centrifugal or to filter the solid product that above-mentioned reaction is obtained separated, and water and ethanol cyclic washing repeatedly, the vacuum drying chamber that is finally placed in 40 ℃～80 ℃ is dry, obtains target product magnetic microsphere.
2. the method for making of magnetic microsphere according to claim 1, it is characterized in that: in step 2, by regulating the addition of described aqueous slkali to regulate the particle diameter of magnetic microsphere, the concentration of the aqueous slkali adding or volume, particle diameter reduces, in the concentration of aqueous slkali, be that under 0.5mol/L～2mol/L, the consumption condition of 2～50 times that is ferric molal quantity, particle diameter adjustable extent is 600nm～23nm.
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