CN103551094A - Preparation method of core-shell structured Fe3O4@MCM-41 magnetic nano material - Google Patents
Preparation method of core-shell structured Fe3O4@MCM-41 magnetic nano material Download PDFInfo
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Abstract
The invention provides a preparation method of a core-shell structured Fe3O4@MCM-41 magnetic nano material, and relates to a method for synthesizing Fe3O4 magnetic nano material from a vesicle phase. The preparation method of the core-shell structured Fe3O4@MCM-41 magnetic nano material aims to solve the problems of uneven core-shell structure and small specific surface area of the magnetic nano material. The preparation method comprises the following steps of: 1, preparing a vesicle phase solution from hexadecyl trimethyl ammonium bromide and sodium dodecyl benzene sulfonate; 2, dissolving FeCl3 and FeSO4 in secondary distilled water, and then adding the vesicle phase solution to the obtained iron salt solution, adding quadrol to adjust the pH value of the system after ultrasonic treatment to obtain a black suspension; and 3, adding hexadecyl trimethyl ammonium bromide and TEOS (Tetra Ethyl Ortho Silicate) to the black suspension, carrying out a crystallization reaction after pH adjustment, washing and drying the solid-phase crystals and then roasting the solid-phase crystals to obtain the magnetic nano material. The preparation method of the core-shell structured Fe3O4@MCM-41 magnetic nano material is characterized in that the vesicles formed by compounding an anionic surfactant with a cationic surfactant are taken as micro-reactors, the thermodynamic performance of the system is stable, and in the meantime, the specific surface area of the magnetic nano material is large.
Description
Technical field
The present invention relates to a kind of vesica and be combined to Fe
3o
4the method of magnetic Nano material.
Background technology
Magnetic nano-particle has wide application space in research fields such as magnetic fluid, drug targeting release, catalysis, medical imaging, treatment of cancer, isolation technics, biochemical microreactor design and spectral detection.But pure magnetic nano-particle due to himself unstability, difficult modify, high chemism and the shortcoming such as oxidizable be difficult to realize industrial applications.In order to solve this difficult problem, researcher, by the different parcel shell of magnetic nano-particle surface construction, so as to reducing its agglomeration, has improved the stability of magnetic nano-particle to a great extent.Therefore the research of magnetic core-shell structure nano particle becomes a focus in materials chemistry field in recent years.
Common Shell Materials has metal material (gold, silver), Inorganic Non-metallic Materials (silicon, carbon) and organic material (surfactant, polymer) etc., and researcher can build according to different Research Requirements suitable magnetic core-shell nano particle.The magnetic silicon oxide of nucleocapsid structure, because of magnetic response ability, hypotoxicity and the surface chemical modification of the function uniqueness of its compound kernel and shell, gives it at the great application potential of every field.The bibliographical information of relevant magnetic core-shell structural silica dioxide microballoon was more in recent years, particle size generally between 200-500nm, favorable dispersibility in specific solvent.The preparation method of hud typed material is a lot, the main problem existing is that the target product free degree is large, the yardstick of wayward nano particle, pattern, the defect of the coated uneven first-class aspect of shell structurre, this just makes researcher in synthetic method, seek new breakthrough.
Negative ions surfactant compound system (C-A), because it is with the strong electrostatic interaction between the ion head base of opposite charges, there is strong cooperative effect and high surface, in the aqueous solution, can form abundant microstructure, show complicated phase behavior, at the aspects such as impact of adsorption, surface charging, temperature and ionic strength effects on surface character and Micelle formation, all have specific characteristics.The composite system of C-A can form in the aqueous solution spherical, bar-shaped, worm shape micella, stratiform, sheet, plate-like, band shape, six sides, cubic liquid crystal phase, vesica, precipitation etc.Wherein vesica is the interested especially a kind of microstructures of people, and reason is that it can be used as the model of cell membrane, pharmaceutical carrier and microreactor etc., has broad application prospects in fields such as biology, pharmacy, material, catalysis.The formed vesica of positive and negative surfactant compound is a kind of thermodynamic stable system, can be used as microreactor and is used for nano materials.
Though vesica phase is the metastable state system of the spontaneous formation of surfactant, but still belongs to thermodynamic unstable system, along with the minor variations of external condition, such as the interference of foreign ion, system pH change, the rising of temperature etc. all can be impelled vesica phase transformation.Research shows, heat cell foam system gradually, and there is the process changing from gel state to liquid crystal state in the hydrocarbon chain in vesica duplicature, now, system has produced larger enthalpy change.This transition temperature is called phase transition temperature (phase transition temperature), and also someone is called chain melting temperatur (chain melting tmperature).Therefore the formation of vesica is the product of external condition, and the change of external condition, is easy to mutual conversion between vesica and liquid crystalline phase, lamellar phase.
Summary of the invention
The present invention seeks to the Fe obtaining in order to solve existing method
3o
4magnetic Nano material nucleocapsid structure inequality and the little problem of specific area, and nucleocapsid structure Fe is provided
3o
4the preparation method of@MCM-41 magnetic Nano material.
Nucleocapsid structure Fe of the present invention
3o
4the preparation method of@MCM-41 magnetic Nano material follows these steps to realize:
One, 1.0:(1.5～3.0 in molar ratio) softex kw (CTAB) and neopelex (SDBS) are dissolved in redistilled water, make anion/cation surfactant mixed liquor, anion/cation surfactant mixed liquor standing 24～48h under 25～35 ℃ of conditions, obtain vesica phase solution;
Two, be that 2.0:1.0 is by FeCl in molar ratio
3and FeSO
4be dissolved in the redistilled water of processing through letting nitrogen in and deoxidizing, obtain iron salt solutions, the vesica phase solution to adding step 1 in iron salt solutions, to add pH value to 9～10 of ethylenediamine regulation system after 25～35 ℃ of ultrasonic 2～3h, obtains black suspension;
Three, in the black suspension of step 2, add softex kw (CTAB), in the situation that stirring, add again ethyl orthosilicate (TEOS), drip pH to 11～12 that ammoniacal liquor regulates black suspension, reaction 5～7h, with 48～52 ℃ of crystallization 24～36h, collect solid phase crystal, solid phase crystal filters washing to neutral with absolute ethyl alcohol and redistilled water, then through vacuum drying, obtain white solid powder, then white solid powder is put into muffle furnace with 548～552 ℃ of roasting 10～12h, obtained nucleocapsid structure Fe
3o
4@MCM-41 magnetic Nano material.
The nucleocapsid structure Fe that the present invention obtains
3o
4the kernel of@MCM-41 magnetic Nano material is ferroferric oxide magnetic nano crystal, and particle diameter is less than 100nm, and shell is the regular MCM-41 layer of texture structure, Fe
3o
4@MCM-41 magnetic Nano material particle diameter is less than 200nm, and average pore size is 6.28nm.
The vesica phase that the present invention forms by positive and negative surfactant, liquid crystalline phase are microreactor synthesis of nano oxide structure unit, and by regulation and control vesica phase morphology, form liquid crystal templated, the Thermodynamically stable of system, the orderly self assembly that realizes binary oxide nano super-lattice forms the Fe of shell structurre homogeneous
3o
4@MCM-41 magnetic Nano material, the specific area of magnetic Nano material can reach 513.9m simultaneously
2/ g.
Accompanying drawing explanation
Fig. 1 is the nucleocapsid structure Fe that embodiment mono-obtains
3o
4the transmission electron microscope picture of@MCM-41 magnetic Nano material;
Fig. 2 is the nucleocapsid structure Fe that embodiment bis-obtains
3o
4the transmission electron microscope picture of@MCM-41 magnetic Nano material;
Fig. 3 is nucleocapsid structure Fe
3o
4the XRD figure of@MCM-41 magnetic Nano material and contrast sample MCM-41, a-contrast sample MCM-41 curve wherein, b-nucleocapsid structure Fe
3o
4the curve of@MCM-41 magnetic Nano material;
Fig. 4 is the nucleocapsid structure Fe that embodiment mono-obtains
3o
4the projection Electronic Speculum figure of@MCM-41 magnetic Nano material;
Fig. 5 is the nucleocapsid structure Fe that embodiment bis-obtains
3o
4the high power projection Electronic Speculum figure of@MCM-41 magnetic Nano material part;
Fig. 6 is the nucleocapsid structure Fe that embodiment bis-obtains
3o
4the N of@MCM-41 magnetic Nano material
2adsorption-desorption figure, the curve of a-contrast sample MCM-41, b-nucleocapsid structure Fe
3o
4the curve of@MCM-41 magnetic Nano material;
Fig. 7 is the nucleocapsid structure Fe that embodiment bis-obtains
3o
4the graph of pore diameter distribution of@MCM-41 magnetic Nano material, the pore-size distribution of a-contrast sample MCM-41, b-nucleocapsid structure Fe
3o
4the pore-size distribution of@MCM-41 magnetic Nano material;
Fig. 8 is nucleocapsid structure Fe
3o
4the VSM figure of@MCM-41 magnetic Nano material, the nucleocapsid structure Fe that a-embodiment mono-obtains
3o
4the curve of@MCM-41 magnetic Nano material, the nucleocapsid structure Fe that b-embodiment bis-obtains
3o
4the curve of@MCM-41 magnetic Nano material.
The specific embodiment
The specific embodiment one: present embodiment nucleocapsid structure Fe
3o
4the preparation method of@MCM-41 magnetic Nano material follows these steps to implement:
One, 1.0:(1.5～3.0 in molar ratio) softex kw (CTAB) and neopelex (SDBS) are dissolved in redistilled water, make anion/cation surfactant mixed liquor, anion/cation surfactant mixed liquor standing 24～48h under 25～35 ℃ of conditions, obtain vesica phase solution;
Two, be that 2.0:1.0 is by FeCl in molar ratio
3and FeSO
4be dissolved in the redistilled water of processing through letting nitrogen in and deoxidizing, obtain iron salt solutions, the vesica phase solution to adding step 1 in iron salt solutions, to add pH value to 9～10 of ethylenediamine regulation system after 25～35 ℃ of ultrasonic 2～3h, obtains black suspension;
Three, in the black suspension of step 2, add softex kw (CTAB), in the situation that stirring, add again ethyl orthosilicate (TEOS), drip pH to 11～12 that ammoniacal liquor regulates black suspension, reaction 5～7h, with 48～52 ℃ of crystallization 24～36h, collect solid phase crystal, solid phase crystal filters washing to neutral with absolute ethyl alcohol and redistilled water, then through vacuum drying, obtain white solid powder, then white solid powder is put into muffle furnace with 548～552 ℃ of roasting 10～12h, obtained nucleocapsid structure Fe
3o
4@MCM-41 magnetic Nano material.
It is microreactor that present embodiment adopts the vesica of the spontaneous formation of anionic-cationic surfactant mixed system, obtains the magnetic Nano kernel of yardstick homogeneous, and adjustment solution morphology forms liquid crystal templated, one-step synthesis nucleocapsid structure Fe
3o
4@MCM-41 magnetic Nano material.
The specific embodiment two: present embodiment is different from the specific embodiment one is that in step 1 anion/cation surfactant mixed liquor, the total concentration of softex kw (CTAB) and neopelex (SDBS) is 0.028～0.032mol/L.Other step and parameter are identical with the specific embodiment one.
The specific embodiment three: present embodiment is different from the specific embodiment one or two is that the concentration of Fe ion in step 2 iron salt solutions is 0.25～0.32mol/L.Other step and parameter are identical with the specific embodiment one or two.
The specific embodiment four: present embodiment is different from one of specific embodiment one to three, and to be step 3 add softex kw (CTAB) in the black suspension in step 2, and making CTAB total concentration in black suspension is 0.05～0.06moL/L.Other step and parameter are identical with one of specific embodiment one to three.
The specific embodiment five: what present embodiment was different from one of specific embodiment one to four is that step 3 adds ethyl orthosilicate in the situation that stirring again, and the speed wherein stirring is 500～1000r/min.Other step and parameter are identical with one of specific embodiment one to four.
The specific embodiment six: what present embodiment was different from one of specific embodiment one to five is that step 3 adds ethyl orthosilicate (TEOS) in the situation that stirring again, and the addition of ethyl orthosilicate makes n(TEOS in black suspension): n(Fe)=(5.0～10.0): 1.0.Other step and parameter are identical with one of specific embodiment one to five.
The specific embodiment seven: present embodiment is different from one of specific embodiment one to six is that vacuum drying described in step 3 is to be dried at 200 ℃.Other step and parameter are identical with one of specific embodiment one to six.
Embodiment mono-: the present embodiment nucleocapsid structure Fe
3o
4the preparation method of@MCM-41 magnetic Nano material follows these steps to implement:
One, the neopelex (SDBS) of the softex kw of 0.36g (CTAB) and 0.697g is dissolved in 100mL redistilled water, make anion/cation surfactant mixed liquor, anion/cation surfactant mixed liquor standing 24h under 30 ℃ of conditions, obtain vesica phase solution;
Two, by 1.7g(0.01moL) FeCl
3and 0.76g(0.005moL) FeSO
4be dissolved in the redistilled water of processing through letting nitrogen in and deoxidizing, obtain iron salt solutions, the vesica phase solution to adding step 1 in iron salt solutions, to add the pH value to 10 of ethylenediamine regulation system after 30 ℃ of ultrasonic 3h, obtains black suspension;
Three, in the black suspension of step 2, add 6g softex kw (CTAB), in intensively stirred situation, add again 20mL(0.08moL) ethyl orthosilicate (TEOS), drip the pH to 11 that ammoniacal liquor regulates black suspension, reaction 7h, with 50 ℃ of crystallization 24h, collect solid phase crystal, solid phase crystal filters washing to neutral with absolute ethyl alcohol and redistilled water, then through vacuum drying, obtain white solid powder, then white solid powder is put into muffle furnace with 550 ℃ of roasting 10h, obtained nucleocapsid structure Fe
3o
4@MCM-41 magnetic Nano material.
Embodiment bis-: what the present embodiment was different from embodiment mono-is that step 3 adds 30mL(0.13moL in intensively stirred situation) ethyl orthosilicate.Other step and parameter are identical with embodiment mono-.
To the nucleocapsid structure Fe obtaining
3o
4the crystal formation of@MCM-41 magnetic nano-particle and surface nature thereof are characterized by X-ray diffractometer (RigakuD/max-II, Japan Ricoh) and Fourier infrared spectrograph (PE1600, U.S. Perkin Elmer company) respectively; Particle diameter distributes and adopts Ma Erwen nanometer particle size analyzer (ZEN3600, Britain Malvern Instrument Ltd.) to analyze; Pattern and microstructure are to adopt transmission electron microscope (H-7650 FDAC) to characterize; Chemical composition is analyzed by x-ray photoelectron power spectrum (250Xi, U.S. Thermo Fisher ESCALAB); The magnetic property of magnetic nano-particle is to adopt vibrating specimen magnetometer (HH-15, Nanjing Univ. Instrument Factory) to measure; And the aperture of magnetic nano particle sub-surface and hole area are to analyze with BEL-Cat specificity of catalyst analyzer (BELCAT-M, Dutch Ankersmid Co., Ltd).
The nucleocapsid structure Fe that embodiment mono-and embodiment bis-obtain
3o
4the transmission electron microscope picture of@MCM-41 magnetic Nano material is shown in respectively Fig. 1 and Fig. 2, the particle diameter of core-shell structure magnetic nano particle is generally within the scope of 80-200nm as we can see from the figure, and along with adding the increase outer casing thickness of TEOS amount to increase, it is large that particle radii become, shell structurre homogeneous.
Nucleocapsid structure Fe
3o
4as shown in Figure 3, the characteristic peak of contrast sample MCM-41 mesopore molecular sieve generally appears near 2 θ=2 ° the XRD figure of@MCM-41 magnetic Nano material.Known by comparative analysis, a occurs that in 2 θ=2.42 ° diffraction maximum is the hexagonal mesoporous structure diffraction maximum of MCM-41, and b occurs diffraction maximum in 2 θ=2.38 °, and peak position slightly to 0.4 ° of low-angle skew, illustrates magnetic core-shell Fe with respect to former powder
3o
4the shell of@MCM-41 nanoparticle is still keeping the hexagonal mesoporous structure of rule, and wherein MCM-41 mesopore molecular sieve modifies by < < applied chemistry > > the 4th phase < < aluminium lanthanum in 2005 the method preparation relating in synthesizing, characterizing of hexagonal mesoporous silica and the catalytic performance > > in ethoxylation.
High multiple projection Electronic Speculum figure by Fig. 4 and Fig. 5 can find out Fe
3o
4the surface of@MCM-41 magnetic nano-particle has mesoporous framework, and pore distribution is even, has Hexagonal array crystal structure, and as shown in Figure 5, magnetic nano-particle has clear striped, consistent with XRD result.
The means of testing that BET characterizes as mesoporous material, not only can adsorb N by sample
2content is how many and obtain the value of specific area, can also obtain the data of aperture, pore volume and pore passage structure type aspect, so the structure of mesoporous material and the relation between performance can obtain more deep analysis.This experiment has adopted the NOVA-2000e type physical adsorption appearance of U.S. Kang Ta company to carry out definite kernel shell structure Fe
3o
4the aperture of@MCM-41 magnetic nano particle subshell MCM-41, and with BET equation, calculate the specific area of shell.
Magnetic core-shell Fe
3o
4as shown in Figure 6, graph of pore diameter distribution as shown in Figure 7 for the isothermal nitrogen adsorption desorption curve of@MCM-41 nano particle.Known according to the classification of IUPAC, the adsorpting type of this nano particle belongs to IV type.A is contrast sample MCM-41 mesopore molecular sieve curve, and specific area is 966.9m
2/ g, pore volume is 0.5636mL/g, aperture is 2.998nm; B is magnetic core-shell Fe
3o
4the shell MCM-41 curve of@MCM-41 nano particle, specific area is 513.9m
2/ g, pore volume 0.307mL/g, aperture 6.281nm.Shell MCM-41 specific area from the known core-shell particles of above data, pore volume diminish, and aperture increases.
Fig. 8 is nucleocapsid structure Fe
3o
4the VSM figure of@MCM-41 magnetic Nano material, the increase of measuring along with TEOS as we know from the figure, Fe
3o
4the saturation magnetisation value of@MCM-41 magnetic nano-particle reduces, and along with the addition of TEOS is from 20ml to 30ml, saturation magnetisation value is reduced to 25emu/g from 33emu/g, not the Fe of coated MCM-41 shell
3o
4the saturation magnetisation value of nano particle is 54.19emu/g, the known Fe that is coated shell data
3o
4@MCM-41 nano particle saturation magnetisation value weakens, and along with the increase of thickness of the shell, the degree weakening strengthens, but still has certain magnetic response ability.
Claims (6)
1. nucleocapsid structure Fe
3o
4the preparation method of@MCM-41 magnetic Nano material, is characterized in that nucleocapsid structure Fe
3o
4the preparation method of@MCM-41 magnetic Nano material follows these steps to realize:
One, 1.0:(1.5～3.0 in molar ratio) softex kw and neopelex are dissolved in redistilled water, make anion/cation surfactant mixed liquor, anion/cation surfactant mixed liquor standing 24～48h under 25～35 ℃ of conditions, obtain vesica phase solution;
Two, be that 2.0:1.0 is by FeCl in molar ratio
3and FeSO
4be dissolved in the redistilled water of processing through letting nitrogen in and deoxidizing, obtain iron salt solutions, the vesica phase solution to adding step 1 in iron salt solutions, to add pH value to 9～10 of ethylenediamine regulation system after 25～35 ℃ of ultrasonic 2～3h, obtains black suspension;
Three, in the black suspension of step 2, add softex kw, in the situation that stirring, add again ethyl orthosilicate, drip pH to 11～12 that ammoniacal liquor regulates black suspension, reaction 5～7h, with 48～52 ℃ of crystallization 24～36h, collect solid phase crystal, solid phase crystal filters washing to neutral with absolute ethyl alcohol and redistilled water, then through vacuum drying, obtain white solid powder, then white solid powder is put into muffle furnace with 548～552 ℃ of roasting 10～12h, obtained nucleocapsid structure Fe
3o
4@MCM-41 magnetic Nano material.
2. nucleocapsid structure Fe according to claim 1
3o
4the preparation method of@MCM-41 magnetic Nano material, is characterized in that in step 1 anion/cation surfactant mixed liquor, the total concentration of softex kw and neopelex is 0.028～0.032mol/L.
3. nucleocapsid structure Fe according to claim 1
3o
4the preparation method of@MCM-41 magnetic Nano material, the concentration that it is characterized in that Fe ion in step 2 iron salt solutions is 0.25～0.32mol/L.
4. nucleocapsid structure Fe according to claim 1
3o
4the preparation method of@MCM-41 magnetic Nano material, is characterized in that in the black suspension of step 2, adding softex kw in step 3, and making softex kw total concentration in black suspension is 0.05～0.06moL/L.
5. nucleocapsid structure Fe according to claim 1
3o
4the preparation method of@MCM-41 magnetic Nano material, is characterized in that step 3 adds ethyl orthosilicate in the situation that stirring again, and the speed wherein stirring is 500～1000r/min.
6. nucleocapsid structure Fe according to claim 1
3o
4the preparation method of@MCM-41 magnetic Nano material, is characterized in that the vacuum drying described in step 3 is to be dried at 200 ℃.
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