CN101485969B - Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles - Google Patents
Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles Download PDFInfo
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- CN101485969B CN101485969B CN200810124076XA CN200810124076A CN101485969B CN 101485969 B CN101485969 B CN 101485969B CN 200810124076X A CN200810124076X A CN 200810124076XA CN 200810124076 A CN200810124076 A CN 200810124076A CN 101485969 B CN101485969 B CN 101485969B
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- 239000002245 particle Substances 0.000 title claims abstract description 43
- 239000004964 aerogel Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000013329 compounding Methods 0.000 title abstract 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title 2
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 69
- 239000002131 composite material Substances 0.000 claims abstract description 53
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000011240 wet gel Substances 0.000 claims abstract description 15
- 239000012670 alkaline solution Substances 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 164
- 239000000243 solution Substances 0.000 claims description 40
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000084 colloidal system Substances 0.000 claims description 18
- 150000001875 compounds Chemical class 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000002525 ultrasonication Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 5
- 238000006460 hydrolysis reaction Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000005291 magnetic effect Effects 0.000 abstract description 25
- 239000000463 material Substances 0.000 abstract description 10
- 238000009826 distribution Methods 0.000 abstract description 4
- 238000003980 solgel method Methods 0.000 abstract description 3
- 238000000352 supercritical drying Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract description 2
- 238000005054 agglomeration Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000000499 gel Substances 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- 239000011246 composite particle Substances 0.000 description 5
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- 238000012360 testing method Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
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- VFNGKCDDZUSWLR-UHFFFAOYSA-L disulfate(2-) Chemical compound [O-]S(=O)(=O)OS([O-])(=O)=O VFNGKCDDZUSWLR-UHFFFAOYSA-L 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
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- AHADSRNLHOHMQK-UHFFFAOYSA-N methylidenecopper Chemical compound [Cu].[C] AHADSRNLHOHMQK-UHFFFAOYSA-N 0.000 description 2
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- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
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Abstract
The invention relates to a supercritical method for preparing nano Fe3O 4/SiO 2A method of compounding aerogel particles, characterized by: firstly, the sol-gel method is utilized to prepare Fe3O 4Precursors of the crystals Fe (OH)2And Fe (OH)3Then adding it to SiO2Performing ultrasonic treatment on a precursor of the aerogel for several minutes, stirring at a high speed, adding a certain alkaline solution to make the precursor gel to obtain a composite wet gel system, and drying by using a supercritical drying method to prepare the nano magnetic Fe3O 4/SiO 2Compounding aerogel material to prepare nano magnetic Fe with stable dispersion, no obvious agglomeration and even distribution3O 4/SiO 2Compounding aerogel material, and finally performing ball milling on the composite aerogel material to obtain nano magnetic Fe3O 4/SiO 2Composite aerogel particles. The preparation method has simple and feasible process, easily controlled preparation process and prepared nano magnetic Fe3O 4/SiO 2The composite material has stable quality.
Description
Technical field
The present invention relates to prepare nanometer Fe
3O
4/ SiO
2The method of composite aerogel particle, especially a kind of supercritical methanol technology prepares nanometer Fe
3O
4/ SiO
2The method of composite aerogel particle.
Background technology
Nanometer Fe
3O
4Has excellent properties at aspects such as magnetic, catalysis, biologies.Nanometer Fe
3O
4Because particle diameter is little, specific area is big, magnetic is strong, have skin effect, magnetic effect etc., again because of its chemical stability is good, raw material is easy to get, cheap, so nanometer Fe
3O
4Obtained using widely in fields such as pigment, magnetic fluid, magnetic microsphere, magnetic recording, catalysis, electronics, finance, communication, coating, printing ink, medicine, developer, photosensitive material and microwave absorbing materials.
SiO
2Aeroge is a kind of novel controlled poroid material of structure, and it has very that bigger serface (is up to 1000g/m
2), high porosity (reaching as high as more than 90%), low-density (the minimum 0.02g/cm of reaching
3), the character of low refractive index, strong adsorptivity, the typical multiple uniqueness of fractal structure, a plurality of research fields have obtained using widely.
Nano-magnetic Fe
3O
4/ SiO
2The composite aerogel material combines the advantage of above-mentioned two kinds of materials, has that specific area is big, magnetic is strong, have surperficial adsorption effect and special optics, magnetics and electrical properties, so nanometer Fe
3O
4/ SiO
2The composite aerogel material all is with a wide range of applications in fields such as opto-electronic conversion, gas sensitive, transparent material and transparent magnet, pigment, magnetic fluid, magnetic microsphere, magnetic recording, environment absorption protection, electronics, communication, coating, neoplasm targeted therapy, photosensitive material and microwave absorbing materials.
Present nano-magnetic Fe
3O
4/ SiO
2The preparation thinking of composite aerogel material has two kinds, and the one, at Fe
3O
4Surface recombination one deck SiO
2Film makes complex microsphere; The 2nd, with nanometer Fe
3O
4Be distributed to SiO
2Make Fe in the system
3O
4/ SiO
2Compound system.But the Fe of preparation
3O
4/ SiO
2Compound system is because SiO
2The simple clad nano Fe of system
3O
4Particle, Fe
3O
4The hydroxyl and the SiO on surface
2Compound ability does not show fully, makes the particle covered effect not good, SiO
2Come off easily, make on using, to be very limited.
Summary of the invention
The objective of the invention is in the past the preparation nanometer Fe
3O
4/ SiO
2Composite aerogel particle SiO in application process
2Easily come off and Fe
3O
4The nano particle problem of uneven distribution, and provide a kind of supercritical methanol technology to prepare nanometer Fe
3O
4/ SiO
2The method of composite aerogel particle, the nano particle uniform particles that this method technology is simple, preparation process is easily controlled, prepare, magnetic is strong.
Technical scheme of the present invention is: a kind of supercritical methanol technology prepares nanometer Fe
3O
4/ SiO
2The method of composite aerogel particle, its concrete steps are as follows:
A, preparation Fe (OH)
2With Fe (OH)
3Colloid mixture
By total concentration of iron is 0.1～0.5mol/L preparation Fe
2+And Fe
3+Solution, wherein Fe
2+With Fe
3+Mol ratio be 1: 10～10: 1, stir and to make its dissolving, and in solution, add alkaline solution, stir fast, washing, ultrasonication obtains Fe (OH)
2With Fe (OH)
3Colloid mixture;
B, preparation SiO
2Aeroge precursor solution
In the ethanolic solution of positive tetraethyl orthosilicate or silicic acid soluble-salt, add acid solution and distilled water, regulate pH value to 6.0～8.0, add thermal agitation, make positive tetraethyl orthosilicate or silicic acid soluble-salt complete hydrolysis generate Si (OH)
4
The preparation of C, compound wet gel system
According to the iron silicon ratio of experimental design, the Fe (OH) that steps A is made
2With Fe (OH)
3Colloid mixture join the Si (OH) that step B makes
4In, constantly stir, adding alkaline solution adjusting pH value is 2.0～10.0, constant temperature 1～24h in 10～90 ℃ insulating box, mixed solution generates compound wet gel; .
D, nano-magnetic Fe
3O
4/ SiO
2The preparation of composite aerogel particle
Compound wet gel is placed in the high-temperature high-pressure reaction kettle, uses N
2Emptying, the adjusting nitrogen pressure is 2～20MPa, and the control temperature is 100～300 ℃, and supercritical reaction makes nanometer Fe
3O
4/ SiO
2Composite; At last to Fe
3O
4/ SiO
2Block composite ball milling obtains magnetic Fe
3O
4/ SiO
2The composite aerogel particle.
Wherein total concentration of iron is controlled to be 0.1～0.3mol/L, Fe in the steps A
2+With Fe
3+Mol ratio is 3: 2～10: 1; The Fe that is prepared in the steps A
2+And Fe
3+Solution is for containing Fe
2+And Fe
3+The ethanol solution of sulfate, disulfate, villaumite or nitrate, or contain Fe
2+And Fe
3+The aqueous solution of sulfate, disulfate, villaumite or nitrate.Alkaline solution described in the above-mentioned steps A is NaOH, KOH, ammoniacal liquor, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3Ethanolic solution, or NaOH, KOH, ammoniacal liquor, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3The aqueous solution, its concentration is 0.2～1.5mol/L.Wherein the alkaline solution addition generates Fe (OH) according to alkali and iron ion reaction
2And Fe (OH)
3Suitable reaction mole calculate, perhaps exceed 1～10% of this reaction mole.
Washing process described in the steps A is removed foreign ion washing colloid mixture for the washing colloid mixture and is removed foreign ion, and wash solution is ethanol or redistilled water, and preferred washing times is 2～10 times.Ultrasonication described in the steps A is that colloid is dispersed in the solution uniformly, and ultrasonic dispersion frequency is 10～100KHz, and ultrasonic time is 1～5min.
Acid solution described in the step B is HCl, H
2SO
4, HF or HNO
3Etc. the solubility acid solution, its concentration is 0.01～1mol/L.The addition of acid solution is 6.0～7.5 for the pH value scope of control solution; The control heating-up temperature is 10～95 ℃ among the step B, and control adds thermal agitation 0.5～10h.
Iron silicon mol ratio described in the step C is preferably 1: 1～and 1: 10.Alkaline solution described in the step C is NaOH, KOH, ammoniacal liquor, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3Ethanolic solution or NaOH, KOH, ammoniacal liquor, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3The aqueous solution, its concentration is 0.5～1mol/L.Calorstat temperature described in the step C is 30～90 ℃.
The control nitrogen pressure is 2.5～15MPa among the step D, and the control temperature is 90～270 ℃, and the supercritical reaction time is 1～6h; Ball milling time range described in the step D is 8～16h.
Beneficial effect:
1, the present invention successively makes nano-magnetic Fe with sol-gel process and supercritical methanol technology
3O
4/ SiO
2Compound system.At first go out compound wet gel system, utilize supercritical drying to make the nano-magnetic Fe of uniform and stable dispersion again by Prepared by Sol Gel Method
3O
4/ SiO
2Compound system.Because Fe
3O
4The formation of particle is to form in final overcritical process, and the Fe in the course of reaction (OH)
2With Fe (OH)
3The hydroxyl of particle surface can with Si (OH)
4The hydroxyl on surface reacts, thereby has well solved SiO
2Coat Fe
3O
4The problem of particle poor effect.
2, the present invention is at preparation Fe
3O
4/ SiO
2Do not need surfactant in the compound system and the magnetic-particle stabilized uniform is dispersed in the system, and ferrite and SiO
2Combination be with the form combination of chemical bond, make SiO
2Coat Fe
3O
4Ability had and significantly improved, be nano-magnetic Fe
3O
4/ SiO
2The broader applications of compound system are laid a good foundation.
3, the Fe of the present invention's preparation
3O
4/ SiO
2The composite particles system, its creative place is Fe
3O
4/ SiO
2Composite particles system preparation method's innovation.The present invention directly utilizes Fe
3O
4Precursor prepares compound wet gel, utilizes in the supercritical drying in later stage and forms nanometer Fe
3O
4Particle, rather than with Fe
3O
4Nano particle directly adding is dispersed in SiO
2Form SiO in the aeroge
2The simple Fe that coats
3O
4Nano particle utilizes Fe (OH) in this process
2With Fe (OH)
3Direct and the Si (OH) of the hydroxyl that the surface exists
4The reaction of shrinking takes place, and reaction obtains firm Fe-O-Si key, efficiently solves to prepare Fe in the past
3O
4/ SiO
2Fe in the composite particles system
3O
4Particle and SiO
2Aeroge is in conjunction with insecure, caducous shortcoming.
Description of drawings
Fig. 1 is the prepared nanometer Fe of embodiment 1
3O
4/ SiO
2The HRTEM spectrogram of composite aerogel particle; Wherein figure (b) is the partial enlarged drawing of figure (a).
Fig. 2 is the transmission electron microscope diffraction spectrogram of nucleus among (b) figure among Fig. 1.
Fig. 3 is the prepared nanometer Fe of embodiment 1
3O
4/ SiO
2The ESEM of composite aerogel particle can spectrogram (EDS).
Fig. 4 is the prepared nanometer Fe of embodiment 1
3O
4/ SiO
2The vibrating example magnetometer (VSM) of composite aerogel particle can spectrogram.
Fig. 5 is the prepared nanometer Fe of embodiment 2
3O
4/ SiO
2The XRD spectra of composite aerogel particle.
Fig. 6 is the prepared nanometer Fe of embodiment 2
3O
4/ SiO
2The SEM spectrogram of composite aerogel particle.
Fig. 7 is a nanometer Fe
3O
4/ SiO
2The FT-IR spectrogram of composite aerogel particle; Curve A is Fe
3O
4The infrared spectrum analysis of monomer, curve B and curve C are Fe
3O
4/ SiO
2The infrared spectrum analysis of composite, the wherein Fe that adds in the curve B
2+With Fe
3+Concentration ratio be 1: 1, the Fe that adds in the curve C
2+With Fe
3+Concentration ratio be 1: 4.
The specific embodiment
By total concentration of iron is the condition preparation FeCl of 0.5mol/L
24H
2O and FeCl
36H
2The mixed aqueous solution of O, wherein Fe
2+With Fe
3+Mol ratio is 8: 1, stirs and makes its dissolving, adds the 20mL1mol/LNaOH ethanolic solution then, stirs fast, with absolute ethanol washing colloid mixture 3 times, ultrasonication, supersonic frequency is 20KHz, ultrasonic time is 10min, colloid is dispersed in the ethanol uniformly, wherein Fe (OH)
2With Fe (OH)
3Be 8: 1 in molar ratio.Add HCl solution and the 5.4mL redistilled water of 50mL absolute ethyl alcohol, 2mL1mol/L in the positive tetraethyl orthosilicate of 11.2mL, add thermal agitation 6.5h, the control temperature makes positive tetraethyl orthosilicate complete hydrolysis generate Si (OH) at 85 ℃
4With Fe (OH)
2With Fe (OH)
3Colloid mixture join Si (OH) rapidly
4In, constantly stirring, the KOH ethanolic solution that added 1: 2 is regulated pH value 8.9, constant temperature 6h in 60 ℃ insulating box, mixed solution generates compound wet gel.Compound wet gel is placed in the high-temperature high-pressure reaction kettle, uses N
2N is regulated in emptying
2Pressure is at 6.5MPa, and the control temperature is at 290 ℃, and supercritical reaction 4.5h makes lumpy nanometer Fe
3O
4/ SiO
2Composite obtains magnetic Fe to block composite ball milling 12h at last
3O
4/ SiO
2The composite aerogel particle.
The lumpy nanometer Fe that the above-mentioned steps that takes a morsel makes
3O
4/ SiO
2Composite is bonded at and is coated with on the carbon copper mesh, utilizes transmission electron microscope observing granule-morphology and distribution situation.Shown in Fig. 1 (a) figure, can observe nanometer Fe
3O
4It is spherical that particle is, and particle diameter is evenly distributed between 2～7nm, do not have obviously and reunite, and stability is very good; (b) figure in the accompanying drawing 1 can see Fe clearly
3O
4The lattice fringe of particle has further confirmed Fe
3O
4The existence of nucleus; Accompanying drawing 2 figure are transmission electron microscope diffraction spectrograms of nucleus among (b) figure, typical as can clearly see from the figure face-centred cubic structure, the d that is calculated by the interplanar distance of this spectrogram diffraction spot
HklValue and Fe
3O
4Nucleus standard diffraction PDF card d
HklValue conforms to, and therefore can judge that this nucleus is Fe
3O
4Nucleus.
As shown in Figure 3, be the prepared nanometer Fe of present embodiment
3O
4/ SiO
2The ESEM energy spectrogram (EDS) of composite, EDS can carry out elementary analysis to sample, from spectrogram, can obtain the essential element that sample contains Si, Fe and O (wherein the Al in the spectrogram, Cu and C are for being coated with carbon copper mesh background element) are arranged, also contain a spot of Cl element, this is because added small amount of H Cl in the hydrolytic process of positive tetraethyl orthosilicate, final Cl
-Be adsorbed on the mesoporous material surface by electrostatic interaction.Can obtain testing the basic element that contains target material in the prepared composite by the EDS spectrum analysis.
As shown in Figure 4, be the prepared nanometer Fe of this example
3O
4/ SiO
2Vibrating example magnetometer (VSM) analytical spectra of composite aerogel particle.The saturation magnetization of the composite of Experiment Preparation is 36.7eum/g, than pure block Fe
3O
4(80.7eum/g) be much smaller, this is because SiO
2Coat Fe
3O
4Magnetic nanoparticle makes Fe
3O
4The content of magnetic nanoparticle reduces, and this is to cause nanometer Fe
3O
4/ SiO
2The saturated magnetic strength main reasons for decrease of composite aerogel particle.From reversible as can be seen coercivity of VSM spectrogram and remanent magnetism approaching zero, show as superparamagnetism, i.e. weakening along with externally-applied magnetic field, the intensity of magnetization of magnet is reduced to zero by stationary value, when H=0, coercivity and remanent magnetism are almost nil, the magnetic-particle dynamics of this explanation in composite particles near or less than the critical dimension of single domain particle.This performance is very important to this composite particles in bio-medical applications, can direct magnetic particles realize location, enrichment under the environment of externally-applied magnetic field, for its application at biomedical sector provides good possibility.When finding in the experiment, find that magnet can attract composite rapidly, shown good magnetic performance with the compound magnetic strength of this magnetic of attraction fritter shape composite material test.
By total concentration of iron is the condition preparation FeSO of 0.1mol/L
46H
2O and Fe (NO
3)
39H
2The mixed aqueous solution of O, wherein Fe
2+With Fe
3+Mol ratio is 1: 1, stirs fast and makes its dissolving, adds 60mL0.1mol/L ammoniacal liquor ethanolic solution then, stirs fast, with absolute ethanol washing colloid mixture 5 times, ultrasonication, ultrasonic dispersion frequency is 60KHz, ultrasonic time is 6min, colloid is dispersed in the ethanol uniformly, wherein Fe (OH)
2With Fe (OH)
3Be 1: 1 in molar ratio.At Na
2SiO
4Add HCl solution and the 7mL distilled water of 1mL1.5mol/L in the ethanolic solution, add thermal agitation 1h, the control temperature makes Na at 70 ℃
2SiO
4Complete hydrolysis generates Si (OH)
4With Fe (OH)
2With Fe (OH)
3Colloid mixture join Si (OH) rapidly
4In, constantly stirring, the NaOH ethanolic solution that added 1: 50 is regulated pH value 7.8, constant temperature 5h in 60 ℃ insulating box, mixed solution generates compound wet gel.Compound wet gel is placed in the high-temperature high-pressure reaction kettle, uses N
2N is regulated in emptying
2Pressure is at 11.0MPa, and the control temperature is at 200 ℃, and supercritical reaction 2h makes lumpy nanometer Fe
3O
4/ SiO
2Composite obtains magnetic Fe to block composite ball milling 8h at last
3O
4/ SiO
2The composite aerogel particle.
Be illustrated in figure 5 as the nanometer Fe of the prepared generation of this example
3O
4/ SiO
2The composite XRD spectra.Can get by the XRD figure analysis of spectrum, only occur a stronger diffraction maximum and some mixed and disorderly small peaks among the figure, and do not demonstrate magnetic Fe
3O
4The distinctive diffraction maximum of crystal, this is because because Fe
3O
4Nucleus is fully by unformed SiO
2Coat, thereby can not demonstrate Fe
3O
4The diffraction maximum of nucleus.This XRD structural analysis can prove SiO
2Coat Fe
3O
4The effect of nucleus is very good.
Be illustrated in figure 6 as the prepared nanometer Fe of this example
3O
4/ SiO
2The high resolution scanning Electronic Speculum figure of composite.Lumpy nanometer Fe takes a morsel
3O
4/ SiO
2Composite is bonded on the aluminium platform, observes granule-morphology and distribution situation.As we can see from the figure composite material surface have many marshallings, size evenly, have the mesoporous of network structure.
Embodiment 3
By total concentration of iron is the condition preparation FeCl of 0.1mol/L
24H
2O and FeCl
36H
2The mixed ethanol solution of O, wherein Fe
2+With Fe
3+Mol ratio is 1: 4, stirs fast and makes its dissolving, adds the 10mL1.2mol/LNaOH ethanolic solution then, stirs fast, with absolute ethanol washing colloid mixture 3 times, ultrasonication, ultrasonic dispersion frequency is 100KHz, ultrasonic time is 4min, colloid is dispersed in the ethanol uniformly, wherein Fe (OH)
2With Fe (OH)
3Be 1: 4 in molar ratio.Add HCl solution and the 5.4mL distilled water of 0.6mL1mol/L in the ethanolic solution of positive tetraethyl orthosilicate, add thermal agitation 1h, the control temperature makes positive tetraethyl orthosilicate complete hydrolysis generate Si (OH) at 60 ℃
4With Fe (OH)
2With Fe (OH)
3Colloid mixture join Si (OH) rapidly
4In, constantly stirring, the ammoniacal liquor ethanolic solution that added 1: 20 is regulated pH value 8.6, constant temperature 5h in 60 ℃ insulating box, mixed solution generates compound wet gel.Compound wet gel is placed in the high-temperature high-pressure reaction kettle, uses N
2N is regulated in emptying
2Pressure is at 13.0MPa, and the control temperature is at 120 ℃, and supercritical reaction 6h makes lumpy nanometer Fe
3O
4/ SiO
2Composite obtains magnetic Fe to block composite ball milling 12h at last
3O
4/ SiO
2The composite aerogel particle.
Fig. 7 is the nanometer Fe of example 2 and example 3 preparations
3O
4/ SiO
2The FT-IR spectrogram of composite aerogel particle.Adopt infrared-Raman spectrometer test Fe
3O
4The Fe of particle monomer and two kinds of method preparations
3O
4/ SiO
2The different situations of composite absworption peak.In accompanying drawing 7, curve A is Fe
3O
4The infrared spectrum analysis of monomer, curve B and curve C are Fe
3O
4/ SiO
2The infrared spectrum analysis of composite, the wherein Fe that adds in the curve B
2+With Fe
3+Concentration ratio be 1: 1, the Fe that adds in the curve C
2+With Fe
3+Concentration ratio be 1: 4.As can be seen from Figure 7,3400cm
-1Near the absworption peak correspondence be the hydroxyl of particle surface; 400cm
-1～500cm
-1, 1385cm
-1With 800cm
-1That the place is corresponding is Fe
3O
4The characteristic absorption peak of Fe-O in the particle; 1100cm
-1Near the absworption peak of big and broad is arranged, be the stretching vibration peak of Si-O; Curve B is relative with curve C can find 578cm with figure A
-1And 562.1cm
-1New peak having occurred, is Si element and Fe
3O
4The characteristic peak of particle surface hydroxyl reaction; 3386cm
-1Near corresponding be the characteristic peak of hydroxyl, and have significantly with respect to curve A and to weaken, Fe is described
3O
4The hydroxyl SiO that speaks more greatly on surface
2Chemical reaction has taken place in layer.
Claims (9)
1. a supercritical methanol technology prepares nanometer Fe
3O
4/ SiO
2The method of composite aerogel particle, its concrete steps are as follows:
A, preparation Fe (OH)
2With Fe (OH)
3Colloid mixture
By total concentration of iron is 0.1～0.5mol/L preparation Fe
2+And Fe
3+Solution, wherein Fe
2+With Fe
3+Mol ratio be 1: 10～10: 1, stir and to make its dissolving, and in solution, add alkaline solution, stir fast, washing, ultrasonication obtains Fe (OH)
2With Fe (OH)
3Colloid mixture;
B, preparation SiO
2Aeroge precursor solution
In the ethanolic solution of positive tetraethyl orthosilicate or silicic acid soluble-salt, add acid solution and distilled water, regulate pH value to 6.0～8.0, add thermal agitation, make positive tetraethyl orthosilicate or silicic acid soluble-salt complete hydrolysis generate Si (OH)
4
The preparation of C, compound wet gel system
According to the iron silicon mol ratio is 1: 1～1: 10, the Fe (OH) that steps A is made
2With Fe (OH)
3Colloid mixture join the Si (OH) that step B makes
4In, constantly stir, adding alkaline solution adjusting pH value is 2.0～10.0, constant temperature 1～24h in 10～90 ℃ insulating box, mixed solution generates compound wet gel;
D, nanometer Fe
3O
4/ SiO
2The preparation of composite aerogel particle
Compound wet gel is placed in the high-temperature high-pressure reaction kettle, uses N
2Emptying, the adjusting nitrogen pressure is 2～20MPa, and the control temperature is 100～300 ℃, and supercritical reaction makes nanometer Fe
3O
4/ SiO
2Composite; At last to Fe
3O
4/ SiO
2Block composite ball milling obtains nanometer Fe
3O
4/ SiO
2The composite aerogel particle.
2. method according to claim 1 is characterized in that total concentration of iron is 0.1～0.3mol/L in the steps A, Fe
2+With Fe
3+Mol ratio is 3: 2～10: 1; The Fe that is prepared in the steps A
2+And Fe
3+Solution is for containing Fe
2+And Fe
3+The ethanol solution of sulfate, villaumite or nitrate, or contain Fe
2+And Fe
3+The aqueous solution of sulfate, villaumite or nitrate.
3. method according to claim 1 is characterized in that the alkaline solution described in the steps A is NaOH, KOH, ammoniacal liquor, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3Ethanolic solution, or NaOH, KOH, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3The aqueous solution, or ammoniacal liquor, its concentration is 0.2～1.5mol/L.
4. method according to claim 1 is characterized in that wash solution used in the washing process described in the steps A is ethanol or redistilled water, and washing times is 2～10 times; Ultrasonic dispersion frequency is 10～100KHz in the ultrasonication process described in the steps A, and ultrasonic time is 1～10min.
5. method according to claim 1 is characterized in that the acid solution described in the step B is HCl, H
2SO
4, HF or HNO
3, its concentration is 0.01～1mol/L.
6. method according to claim 1 is characterized in that the pH value scope 6.0～7.5 of the dropping acid solution control solution described in the step B adding thermal agitation 0.5～10h, and controlling heating-up temperature is 10～95 ℃.
7. method according to claim 1 is characterized in that the alkaline solution described in the step C is NaOH, KOH, ammoniacal liquor, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3Ethanolic solution, or NaOH, KOH, NaHCO
3, KHCO
3, Na
2CO
3Or K
2CO
3The aqueous solution, or ammoniacal liquor, its concentration is 0.5～1mol/L.
8. method according to claim 1 is characterized in that the calorstat temperature described in the step C is 30～90 ℃.
9. method according to claim 1 is characterized in that the control nitrogen pressure is 2.5～15MPa among the step D, and the control temperature is 90～270 ℃, and the supercritical reaction time is 1～6h; Ball milling time range described in the step D is 8～16h.
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