CN101485969A - 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 PDF

Info

Publication number
CN101485969A
CN101485969A CNA200810124076XA CN200810124076A CN101485969A CN 101485969 A CN101485969 A CN 101485969A CN A200810124076X A CNA200810124076X A CN A200810124076XA CN 200810124076 A CN200810124076 A CN 200810124076A CN 101485969 A CN101485969 A CN 101485969A
Authority
CN
China
Prior art keywords
sio
solution
preparation
composite
steps
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA200810124076XA
Other languages
Chinese (zh)
Other versions
CN101485969B (en
Inventor
沈晓冬
伊希斌
崔升
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jiangsu Anjia New Material Technology Co ltd
Original Assignee
Nanjing Tech University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing Tech University filed Critical Nanjing Tech University
Priority to CN200810124076XA priority Critical patent/CN101485969B/en
Publication of CN101485969A publication Critical patent/CN101485969A/en
Application granted granted Critical
Publication of CN101485969B publication Critical patent/CN101485969B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Landscapes

  • Silicon Compounds (AREA)

Abstract

The invention relates to a supercritical method for preparing nano Fe3O4/SiO2A method of compounding aerogel particles, characterized by: firstly, the sol-gel method is utilized to prepare Fe3O4Precursors of 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 Fe3O4/SiO2Compounding aerogel material to prepare nano magnetic Fe with stable dispersion, no obvious agglomeration and even distribution3O4/SiO2Compounding aerogel material, and finally performing ball milling on the composite aerogel material to obtain nano magnetic Fe3O4/SiO2Composite aerogel particles. The preparation method has simple and feasible process, easily controlled preparation process and prepared nano magnetic Fe3O4/SiO2The composite material has stable quality.

Description

A kind of supercritical methanol technology prepares nanometer Fe 3O 4/ SiO 2The method of composite aerogel particle
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 1:1～1:10.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 processing 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
Embodiment 1
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 20mL 1mol/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 adds 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.
Embodiment 2
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 adds 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 adds 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 of composite aerogel particle-IR spectrogram.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 (10)

1, 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.
2, preparation 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, disulfate, villaumite or nitrate, or contain Fe 2+And Fe 3+The aqueous solution of sulfate, disulfate, villaumite or nitrate.
3, preparation 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, ammoniacal liquor, NaHCO 3, KHCO 3, Na 2CO 3Or K 2CO 3The aqueous solution, its concentration is 0.2～1.5mol/L.
4, preparation 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, preparation 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, preparation 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, preparation method according to claim 1 is characterized in that the iron silicon mol ratio described in the step C is 1:1～1:10.
8, preparation 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, ammoniacal liquor, NaHCO 3, KHCO 3, Na 2CO 3Or K 2CO 3The aqueous solution, its concentration is 0.5～1mol/L.
9, preparation method according to claim 1 is characterized in that the calorstat temperature described in the step C is 30～90 ℃.
10, preparation 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.
CN200810124076XA 2008-06-23 2008-06-23 Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles Active CN101485969B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN200810124076XA CN101485969B (en) 2008-06-23 2008-06-23 Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN200810124076XA CN101485969B (en) 2008-06-23 2008-06-23 Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles

Publications (2)

Publication Number Publication Date
CN101485969A true CN101485969A (en) 2009-07-22
CN101485969B CN101485969B (en) 2010-09-29

Family

ID=40889123

Family Applications (1)

Application Number Title Priority Date Filing Date
CN200810124076XA Active CN101485969B (en) 2008-06-23 2008-06-23 Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles

Country Status (1)

Country Link
CN (1) CN101485969B (en)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851009A (en) * 2010-06-10 2010-10-06 南京工业大学 Preparation method of lobate ferroferric oxide aerogel particles
CN102343285A (en) * 2011-07-18 2012-02-08 南京工业大学 Preparation method of massive silicon-carbon composite aerogel
CN102786810A (en) * 2011-05-18 2012-11-21 中国石油化工股份有限公司 Magnetic polymer particle, its preparation method and its application
CN102863201A (en) * 2012-08-31 2013-01-09 航天材料及工艺研究所 Preparation method of low-density high-temperature-resistant SiO2-MxOy compound aerogel heat insulating material
CN103301787A (en) * 2013-07-03 2013-09-18 陕西盟创纳米新型材料股份有限公司 Silicon dioxide aerogel composite material and molding method
CN103333523A (en) * 2013-06-08 2013-10-02 安徽天泰环保科技有限公司 Method for preparing black iron oxide wrapped with silicon dioxide
CN103357375A (en) * 2013-07-23 2013-10-23 武汉大学 Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof
CN104073788A (en) * 2014-07-21 2014-10-01 扬州大学 Modification method for surface hydrophilization of PVC plastic
CN104817117A (en) * 2015-04-30 2015-08-05 江苏大学 Preparation method of adjustable particle size aerogel-skeleton ferroferric oxide
CN105457590A (en) * 2015-11-27 2016-04-06 江苏华夏制漆科技有限公司 Preparation method of FexOy/SiO2 aerogel nano-composite
CN105854744A (en) * 2016-05-17 2016-08-17 浙江大学 Magnetic nanoparticle/SiO2 aerogel and preparation method thereof and method for treating high level liquid waste
CN106824025A (en) * 2017-03-05 2017-06-13 江苏华盛节能科技有限公司 Magnetic SiO2Aerogel powder preparation method
CN108358210A (en) * 2018-01-29 2018-08-03 郑州世科科技有限公司 A kind of composite material and preparation method and the application of intermetallic compound and aeroge
CN109369975A (en) * 2018-11-12 2019-02-22 南京工业大学 Preparation method of magnetic chitosan-silicon dioxide composite aerogel
CN113793924A (en) * 2021-08-25 2021-12-14 浙江工业大学 By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102923788B (en) * 2012-11-09 2014-07-02 北京理工大学 Preparation method of ferroferric oxide aerogel

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1546226A (en) * 2003-12-17 2004-11-17 同济大学 TiO2/SiO2 aerogel and method for making same
CN1966141A (en) * 2006-11-13 2007-05-23 同济大学 Preparation method of ferro-doped TiO2/SiO2 aerogel microball

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101851009B (en) * 2010-06-10 2012-03-07 南京工业大学 Preparation method of lobate ferroferric oxide aerogel particles
CN101851009A (en) * 2010-06-10 2010-10-06 南京工业大学 Preparation method of lobate ferroferric oxide aerogel particles
CN102786810B (en) * 2011-05-18 2014-12-31 中国石油化工股份有限公司 Magnetic polymer particle, its preparation method and its application
CN102786810A (en) * 2011-05-18 2012-11-21 中国石油化工股份有限公司 Magnetic polymer particle, its preparation method and its application
CN102343285A (en) * 2011-07-18 2012-02-08 南京工业大学 Preparation method of massive silicon-carbon composite aerogel
CN102343285B (en) * 2011-07-18 2013-04-10 南京工业大学 Preparation method of massive silicon-carbon composite aerogel
CN102863201A (en) * 2012-08-31 2013-01-09 航天材料及工艺研究所 Preparation method of low-density high-temperature-resistant SiO2-MxOy compound aerogel heat insulating material
CN102863201B (en) * 2012-08-31 2014-03-05 航天材料及工艺研究所 Preparation method of low-density high-temperature-resistant SiO2-MxOy compound aerogel heat insulating material
CN103333523A (en) * 2013-06-08 2013-10-02 安徽天泰环保科技有限公司 Method for preparing black iron oxide wrapped with silicon dioxide
CN103301787A (en) * 2013-07-03 2013-09-18 陕西盟创纳米新型材料股份有限公司 Silicon dioxide aerogel composite material and molding method
CN103301787B (en) * 2013-07-03 2015-09-09 陕西盟创纳米新型材料股份有限公司 A kind of silicon dioxide silica aerogel composite material and forming method
CN103357375B (en) * 2013-07-23 2015-07-15 武汉大学 Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof
CN103357375A (en) * 2013-07-23 2013-10-23 武汉大学 Magnetic mesoporous silica adsorbent for removing organic pollutants in water body and preparation method and application thereof
CN104073788A (en) * 2014-07-21 2014-10-01 扬州大学 Modification method for surface hydrophilization of PVC plastic
CN104817117A (en) * 2015-04-30 2015-08-05 江苏大学 Preparation method of adjustable particle size aerogel-skeleton ferroferric oxide
CN105457590A (en) * 2015-11-27 2016-04-06 江苏华夏制漆科技有限公司 Preparation method of FexOy/SiO2 aerogel nano-composite
CN105854744B (en) * 2016-05-17 2018-09-11 浙江大学 A kind of magnetic nanoparticle/SiO2Aeroge and preparation method thereof and the method for handling high activity liquid waste
CN105854744A (en) * 2016-05-17 2016-08-17 浙江大学 Magnetic nanoparticle/SiO2 aerogel and preparation method thereof and method for treating high level liquid waste
CN106824025B (en) * 2017-03-05 2019-03-26 新华盛节能科技股份有限公司 Magnetic SiO2Aerogel powder preparation method
CN106824025A (en) * 2017-03-05 2017-06-13 江苏华盛节能科技有限公司 Magnetic SiO2Aerogel powder preparation method
CN108358210A (en) * 2018-01-29 2018-08-03 郑州世科科技有限公司 A kind of composite material and preparation method and the application of intermetallic compound and aeroge
CN108358210B (en) * 2018-01-29 2020-12-25 河北大学 Intermetallic compound and aerogel composite material and preparation method and application thereof
CN109369975A (en) * 2018-11-12 2019-02-22 南京工业大学 Preparation method of magnetic chitosan-silicon dioxide composite aerogel
CN109369975B (en) * 2018-11-12 2021-04-20 南京工业大学 Preparation method of magnetic chitosan-silicon dioxide composite aerogel
CN113793924A (en) * 2021-08-25 2021-12-14 浙江工业大学 By using supercritical CO2Preparation of Si/Fe by fluid medium3O4Method for preparing/C composite material
CN113793924B (en) * 2021-08-25 2023-03-14 浙江工业大学 By using supercritical CO 2 Preparation of Si/Fe by fluid medium 3 O 4 Method for preparing/C composite material

Also Published As

Publication number Publication date
CN101485969B (en) 2010-09-29

Similar Documents

Publication Publication Date Title
CN101485969B (en) Supercritical method for preparing nano Fe3O4/SiO2Method of compounding aerogel particles
Wei et al. Light-weight gadolinium hydroxide@ polypyrrole rare-earth nanocomposites with tunable and broadband electromagnetic wave absorption
Wu et al. Peculiar porous α-Fe2O3, γ-Fe2O3 and Fe3O4 nanospheres: facile synthesis and electromagnetic properties
Zheng et al. Fabrication of porous graphene-Fe3O4 hybrid composites with outstanding microwave absorption performance
Xu et al. Facile synthesis of three-dimensional porous Co/MnO composites derived from bimetal oxides for highly efficient electromagnetic wave absorption
Fan et al. Dielectric control of ultralight hollow porous carbon spheres and excellent microwave absorbing properties
Vaidya et al. Nanospheres, nanocubes, and nanorods of nickel oxalate: control of shape and size by surfactant and solvent
Zhou et al. Size-controllable porous flower-like NiCo2O4 fabricated via sodium tartrate assisted hydrothermal synthesis for lightweight electromagnetic absorber
Qing et al. Facile synthesis of size-tunable, multilevel nanoporous Fe3O4 microspheres for application in electromagnetic wave absorption
Tong et al. Morphology dependence of static magnetic and microwave electromagnetic characteristics of polymorphic Fe 3 O 4 nanomaterials
Shen et al. Ni/NiO/SiO2/C nanofibers with strong wideband microwave absorption and robust hydrophobicity
Yang et al. Self-assembled three-dimensional graphene/Fe3O4 hydrogel for efficient pollutant adsorption and electromagnetic wave absorption
Liu et al. Building on size-controllable hollow nanospheres with superparamagnetism derived from solid Fe 3 O 4 nanospheres: preparation, characterization and application for lipase immobilization
Cannas et al. Hierarchical formation mechanism of CoFe2O4 mesoporous assemblies
Yao et al. Ultrathin self‐assembly MXene@ flake carbonyl iron composites with efficient microwave absorption at elevated temperatures
Li et al. MnFe2O4/rGO/Diatomite composites with excellent wideband electromagnetic microwave absorption
Cao et al. Green synthesis and surface properties of Fe3O4@ SA core–shell nanocomposites
Wang et al. Enhanced electrorheological performance and antisedimentation property of mesoporous anatase TiO2 shell prepared by hydrothermal process
Xu et al. Three-dimensional magnetic functionalized graphene composite aerogels for microwave absorption: a review
Guo et al. Comparative study of cobalt ferrite and polyacrylamide decorated cobalt ferrite microspheres in structural, optical, magnetic, photoluminescence, and photocatalytic properties
Wu et al. Porous Fe hollow structures with optimized impedance matching as highly efficient, ultrathin, and lightweight electromagnetic wave absorbers
Shi et al. Thermal physical and magnetic properties of water-based yolk-shell Fe3O4@ C nanofluids
CN105129765A (en) Highly-ordered mesoporous carbon spheres and preparation method thereof
Fan et al. GO@ Fe3O4@ CuSilicate composite with a hierarchical structure: fabrication, microstructure, and highly electromagnetic shielding performance
Maleki et al. Synthesis, characterization and morphology of new magnetic fluorochromate hybrid nanomaterials with triethylamine surface modified iron oxide nanoparticles

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
ASS Succession or assignment of patent right

Owner name: NANJING TIANYIN NEW MATERIAL TECHNOLOGY CO., LTD.

Free format text: FORMER OWNER: NANJING UNIVERSITY OF TECHNOLOGY

Effective date: 20120718

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: 210009 NANJING, JIANGSU PROVINCE TO: 211806 NANJING, JIANGSU PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20120718

Address after: 211806 Nanjing city Pukou District Qiaolin Shi Qi Road No. 1

Patentee after: NANJING TIANYIN ADVANCED MATERIAL TECHNOLOGY Co.,Ltd.

Address before: 210009 Zhongshan North Road, Jiangsu, No. 200,

Patentee before: Nanjing Tech University

ASS Succession or assignment of patent right

Owner name: NANJING TIANYIN TECHNOLOGY CO., LTD.

Free format text: FORMER OWNER: NANJING TIANYIN NEW MATERIAL TECHNOLOGY CO., LTD.

Effective date: 20130321

C41 Transfer of patent application or patent right or utility model
COR Change of bibliographic data

Free format text: CORRECT: ADDRESS; FROM: NANJING, JIANGSU PROVINCE TO: 211800 NANJING, JIANGSU PROVINCE

TR01 Transfer of patent right

Effective date of registration: 20130321

Address after: 211800 No. 8, Qiaolin industrial concentration zone, Pukou District, Jiangsu, Nanjing

Patentee after: NANJING TIANYIN SCIENCE & TECHNOLOGY Co.,Ltd.

Address before: Nanjing city Pukou District Qiaolin Shi Qi Road No. 1

Patentee before: NANJING TIANYIN ADVANCED MATERIAL TECHNOLOGY Co.,Ltd.

EE01 Entry into force of recordation of patent licensing contract

Application publication date: 20090722

Assignee: NANJING TIANYIN ADVANCED MATERIAL TECHNOLOGY Co.,Ltd.

Assignor: NANJING TIANYIN SCIENCE & TECHNOLOGY Co.,Ltd.

Contract record no.: 2014320000356

Denomination of invention: Method for preparing nano Fe3O4/SiO2 composite aerogel particles by supercritical method

Granted publication date: 20100929

License type: Exclusive License

Record date: 20140429

LICC Enforcement, change and cancellation of record of contracts on the licence for exploitation of a patent or utility model
C41 Transfer of patent application or patent right or utility model
TR01 Transfer of patent right

Effective date of registration: 20160905

Address after: Jiang Yuan Lu, Pukou Economic Development Zone, Nanjing City, Jiangsu Province, No. 8 211899

Patentee after: NANJING TIANYIN SPECIAL PURPOSE VEHICLE Co.,Ltd.

Address before: 211800 No. 8, Qiaolin industrial concentration zone, Pukou District, Jiangsu, Nanjing

Patentee before: NANJING TIANYIN SCIENCE & TECHNOLOGY Co.,Ltd.

TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20190404

Address after: 210000 875-4 Ying Tian street, Jianye District, Nanjing, Jiangsu.

Patentee after: Nanjing Tianyin New Energy Automobile Co.,Ltd.

Address before: 211899 No. 8 Jiangyuan Road, Pukou Economic Development Zone, Jiangsu Province, No. 8 Jiangyuan Road, Pukou Economic Development Zone

Patentee before: NANJING TIANYIN SPECIAL PURPOSE VEHICLE Co.,Ltd.

TR01 Transfer of patent right

Effective date of registration: 20200722

Address after: No.99 Fuchunjiang Road, Suqian high tech Industrial Development Zone, Suqian City, Jiangsu Province

Patentee after: Jiangsu Anjia New Material Technology Co.,Ltd.

Address before: 210000 875-4 Ying Tian street, Jianye District, Nanjing, Jiangsu.

Patentee before: Nanjing Tianyin New Energy Automobile Co.,Ltd.

TR01 Transfer of patent right