CN103803659B - A kind of preparation method of ferric oxide hollow ball - Google Patents
A kind of preparation method of ferric oxide hollow ball Download PDFInfo
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- CN103803659B CN103803659B CN201410055796.0A CN201410055796A CN103803659B CN 103803659 B CN103803659 B CN 103803659B CN 201410055796 A CN201410055796 A CN 201410055796A CN 103803659 B CN103803659 B CN 103803659B
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- ammoniacal liquor
- sio
- ferric oxide
- hollow ball
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 239000011521 glass Substances 0.000 claims abstract description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 60
- 239000000243 solution Substances 0.000 claims description 50
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 40
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- 239000002243 precursor Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000011790 ferrous sulphate Substances 0.000 claims description 10
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 10
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 10
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 206010013786 Dry skin Diseases 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229960004756 ethanol Drugs 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 4
- 230000005684 electric field Effects 0.000 abstract description 2
- 238000001354 calcination Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
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- Compounds Of Iron (AREA)
- Silicon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation method of ferric oxide hollow ball, prepared ferric oxide hollow ball particle diameter distribution uniform, better dispersed, introduce the KCl Syntheses in water silica colloidal spheres of surface charge, in ito glass substrate, prepare silica colloidal crystal with Rapid lifting process under the electric field, then filled calcining after iron oxide gel wherein, remove silica template and namely obtain ferric oxide hollow ball.
Description
Technical field
The present invention relates to a kind of preparation method of ferric oxide hollow ball.
Background technology
The features such as ferric oxide tool chemical stability is good, hardness is high, good weatherability, aboundresources, cheap, toxicological harmless, nano-sized iron oxide specific surface area is large, surface charge is high, to pollutent, there is stronger adsorptive power, have a wide range of applications and DEVELOPMENT PROSPECT in catalyzer, coating, magnetic recording material, fine ceramics and biomedical engineering etc., but just because of nano-sized iron oxide particle, there is high surface charge, therefore easily cause agglomeration.Ferric oxide hollow ball not only has larger specific surface area and lower density of material, and be conducive to the dispersiveness of particle, its current preparation method mainly comprises soft template method, hard template method, hydrothermal method, solvent-thermal method, microemulsion method etc., but how to prepare monodispersity is good, the ferric oxide hollow ball of even particle size distribution remains research at present one of focus and difficult point.
Summary of the invention
In order to overcome the shortcoming of above-mentioned prior art, the object of the present invention is to provide a kind of preparation method of ferric oxide hollow ball, processing unit is simple, can obtain the ferric oxide hollow ball of even particle size distribution.
To achieve these goals, the technical solution used in the present invention is:
A preparation method for ferric oxide hollow ball, comprises the steps:
(1) the KCl aqueous solution that mass concentration is 0.1% ~ 0.15% is prepared, configure the ethanolic soln A of tetraethoxy and the ethanolic soln B of ammoniacal liquor respectively, wherein solution A is equal with dehydrated alcohol amount in solution B, the volume ratio of dehydrated alcohol total amount and ammoniacal liquor is (5 ~ 16.7): 1, the consumption of ammoniacal liquor and the volume ratio of tetraethoxy are (1 ~ 4): 1, again the KCl aqueous solution of 1 ~ 3mL is added in solution B, the volume ratio of the KCl aqueous solution and ammoniacal liquor is 1:(1 ~ 10), then do not stopping under stirring, solution A to be added in solution B, after reaction 20 ~ 22h, precipitation separation, in 50 ~ 60 DEG C of dryings after centrifuge washing, obtain the SiO of surface modification
2nanometer ball or sub-micron ball powder,
(2) SiO is weighed
2powder, by its ultrasonic disperse in organic solution, ultrasonic time is 2 ~ 3h, obtains SiO
2the suspension of particle, the massfraction of its particle is 1.5% ~ 2%;
(3) two panels ITO slide be parallel to each other and vertically immerse SiO
2in particle suspension liquid, wherein, the spacing of two ito glasses is 0.4 ~ 0.6cm, logical 10 ~ 13V voltage on two ITO slides, with the speed of 0.5 ~ 0.6cm/min lift positive pole ITO slide after energising 20 ~ 30s, finally dries ITO slide in 60 DEG C and namely obtains SiO
2colloidal crystal template.
(4) taking a certain amount of citric acid is dissolved in 25 ~ 28% ammoniacal liquor, ammoniacal liquor is as the criterion can dissolve citric acid, add ferrous sulfate and water and stirring and dissolving, use ammoniacal liquor adjust ph to 7 ~ 9 again, wherein the mol ratio of citric acid and ferrous sulfate is 0.8 ~ 1, the consumption of water is 3 ~ 4 times of the ammoniacal liquor volume dissolving citric acid, at 60 ~ 75 DEG C after stirring reaction 2 ~ 3h as precursor solution, by SiO
2colloidal crystal template immerses 5 ~ 10min in precursor solution at a certain angle, slowly lift out rete, with the precursor solution that adsorption paper removing surface is excessive, the slide pressing a cleaning, drying at film surface forms double-basis sheet, dries after its horizontal positioned at 70 ~ 80 DEG C;
(5), after double-basis sheet being calcined 2 ~ 3h at 600 ~ 700 DEG C, rete is immersed 5 ~ 6h in the NaOH solution of mass concentration 15 ~ 20%, namely obtain ferric oxide hollow ball by washed with de-ionized water post-drying.
Preferably, the organic solution in described step (2) is ethanol or methyl alcohol.SiO in described step (4)
2the immersion angle of colloidal crystal is be 45 ~ 60 degree with horizontal direction.
Compared with prior art, in the preparation method of ferric oxide hollow ball provided by the invention, mainly make use of the silica colloidal crystal with periodically ordered arrangement is template, iron oxide gel is filled in the space of template equably, thus in limited space homoepitaxial, when removal silica template after can obtain ferric oxide hollow ball.This method mainly make use of 2 points, and on the one hand, silicon-dioxide itself has good size distribution and circularity, and in the colloidal crystal arranged, each pore size is more even; On the other hand, adopt the silica colloidal spheres of KCl modification, utilize the mode of lift fast in the electric field to carry out the preparation of colloidal crystal template, thus non-close heap-type structure can be obtained, and space is also adjustable greatlyr, this is all conducive to the uniform filling of gel in colloidal crystal template.
Embodiment
Embodiments of the present invention are described in detail below in conjunction with embodiment.
Embodiment 1
A preparation method for ferric oxide hollow ball, comprises the steps:
(1) the KCl aqueous solution that mass concentration is 0.1% is prepared, configure the ethanolic soln A of tetraethoxy and the ethanolic soln B of ammoniacal liquor respectively, wherein solution A is equal with dehydrated alcohol amount in solution B, the volume ratio of dehydrated alcohol total amount and ammoniacal liquor is 5:1, the consumption of ammoniacal liquor and the volume ratio of tetraethoxy are 1:1, again the KCl aqueous solution of 1mL is added in solution B, the volume ratio of the KCl aqueous solution and ammoniacal liquor is 1:1, then do not stopping under stirring, solution A to be added in solution B, after reaction 20h, precipitation separation, in 50 DEG C of dryings after centrifuge washing, obtain the SiO of surface modification
2nanometer ball or sub-micron ball powder,
(2) SiO is weighed
2powder, by its ultrasonic disperse in ethanol, ultrasonic time is 2h, obtains SiO
2the suspension of particle, the massfraction of its particle is 1.5%;
(3) two panels ITO slide be parallel to each other and vertically immerse SiO
2in particle suspension liquid, wherein, the spacing of two ito glasses is 0.4cm, logical 10V voltage on two ITO slides, with the speed of 0.5cm/min lift positive pole ITO slide after energising 20s, finally dries ITO slide in 60 DEG C and namely obtains SiO
2colloidal crystal template;
(4) taking a certain amount of citric acid is dissolved in 25% ammoniacal liquor, ammoniacal liquor is as the criterion can dissolve citric acid, add ferrous sulfate and water and stirring and dissolving, use ammoniacal liquor adjust ph to 7 again, wherein the mol ratio of citric acid and ferrous sulfate is 0.8, the consumption of water is 3 times of the ammoniacal liquor volume dissolving citric acid, at 60 DEG C after stirring reaction 2h as precursor solution, by SiO
2colloidal crystal template immerses 10min in precursor solution at a certain angle, slowly lift out rete, with the precursor solution that adsorption paper removing surface is excessive, the slide pressing a cleaning, drying at film surface forms double-basis sheet, dries after its horizontal positioned at 80 DEG C;
(5) after double-basis sheet being calcined 2h at 700 DEG C, rete is immersed 6h in the NaOH solution of mass concentration 15%, namely obtain ferric oxide hollow ball by washed with de-ionized water post-drying.
Embodiment 2
A preparation method for ferric oxide hollow ball, comprises the steps:
(1) the KCl aqueous solution that mass concentration is 0.15% is prepared, configure the ethanolic soln A of tetraethoxy and the ethanolic soln B of ammoniacal liquor respectively, wherein solution A is equal with dehydrated alcohol amount in solution B, the volume ratio of dehydrated alcohol total amount and ammoniacal liquor is 16.7:1, the consumption of ammoniacal liquor and the volume ratio of tetraethoxy are 4:1, again the KCl aqueous solution of 3mL is added in solution B, the volume ratio of the KCl aqueous solution and ammoniacal liquor is 1:10, then do not stopping under stirring, solution A to be added in solution B, after reaction 22h, precipitation separation, in 60 DEG C of dryings after centrifuge washing, obtain the SiO of surface modification
2nanometer ball or sub-micron ball powder,
(2) SiO is weighed
2powder, by its ultrasonic disperse in methyl alcohol, ultrasonic time is 3h, obtains SiO
2the suspension of particle, the massfraction of its particle is 2%;
(3) two panels ITO slide be parallel to each other and vertically immerse SiO
2in particle suspension liquid, wherein, the spacing of two ito glasses is 0.6cm, logical 13V voltage on two ITO slides, with the speed of 0.6cm/min lift positive pole ITO slide after energising 30s, finally dries ITO slide in 60 DEG C and namely obtains SiO
2colloidal crystal template;
(4) taking a certain amount of citric acid is dissolved in 28% ammoniacal liquor, ammoniacal liquor is as the criterion can dissolve citric acid, add ferrous sulfate and water and stirring and dissolving, use ammoniacal liquor adjust ph to 9 again, wherein the mol ratio of citric acid and ferrous sulfate is 1:1, the consumption of water is 4 times of the ammoniacal liquor volume dissolving citric acid, at 75 DEG C after stirring reaction 3h as precursor solution, by SiO
2colloidal crystal template immerses 10min in precursor solution at a certain angle, slowly lift out rete, with the precursor solution that adsorption paper removing surface is excessive, the slide pressing a cleaning, drying at film surface forms double-basis sheet, dries after its horizontal positioned at 80 DEG C;
(5) after double-basis sheet being calcined 3h at 600 DEG C, rete is immersed 5h in the NaOH solution of mass concentration 20%, namely obtain ferric oxide hollow ball by washed with de-ionized water post-drying.
Embodiment 3
A preparation method for ferric oxide hollow ball, comprises the steps:
(1) the KCl aqueous solution that mass concentration is 0.125% is prepared, configure the ethanolic soln A of tetraethoxy and the ethanolic soln B of ammoniacal liquor respectively, wherein solution A is equal with dehydrated alcohol amount in solution B, the volume ratio of dehydrated alcohol total amount and ammoniacal liquor is 12.5:1, the consumption of ammoniacal liquor and the volume ratio of tetraethoxy are 2.5:1, again the KCl aqueous solution of 2mL is added in solution B, the volume ratio of the KCl aqueous solution and ammoniacal liquor is 1:6.5, then do not stopping under stirring, solution A to be added in solution B, after reaction 21h, precipitation separation, in 55 DEG C of dryings after centrifuge washing, obtain the SiO of surface modification
2nanometer ball or sub-micron ball powder,
(2) SiO is weighed
2powder, by its ultrasonic disperse in methyl alcohol, ultrasonic time is 2.5h, obtains SiO
2the suspension of particle, the massfraction of its particle is 1.75%;
(3) two panels ITO slide be parallel to each other and vertically immerse SiO
2in particle suspension liquid, wherein, the spacing of two ito glasses is 0.5cm, logical 12V voltage on two ITO slides, with the speed of 0.55cm/min lift positive pole ITO slide after energising 25s, finally dries ITO slide in 60 DEG C and namely obtains SiO
2colloidal crystal template;
(4) taking a certain amount of citric acid is dissolved in 26% ammoniacal liquor, ammoniacal liquor is as the criterion can dissolve citric acid, add ferrous sulfate and water and stirring and dissolving, use ammoniacal liquor adjust ph to 8 again, wherein the mol ratio of citric acid and ferrous sulfate is 0.9, the consumption of water is 3.5 times of the ammoniacal liquor volume dissolving citric acid, at 70 DEG C after stirring reaction 2.5h as precursor solution, by SiO
2colloidal crystal template immerses 6min in precursor solution at a certain angle, slowly lift out rete, with the precursor solution that adsorption paper removing surface is excessive, the slide pressing a cleaning, drying at film surface forms double-basis sheet, dries after its horizontal positioned at 75 DEG C;
(5) after double-basis sheet being calcined 2.5h at 650 DEG C, rete is immersed 5.5h in the NaOH solution of mass concentration 18%, namely obtain ferric oxide hollow ball by washed with de-ionized water post-drying.
In the present invention, when the immersion angle of silica colloidal crystal is for being 45 ~ 60 degree with horizontal direction, effect is better.
Claims (1)
1. a preparation method for ferric oxide hollow ball, is characterized in that, comprises the steps:
(1) the KCl aqueous solution that mass concentration is 0.1% ~ 0.15% is prepared, configure the ethanolic soln A of tetraethoxy and the ethanolic soln B of ammoniacal liquor respectively, wherein solution A is equal with dehydrated alcohol amount in solution B, the volume ratio of dehydrated alcohol total amount and ammoniacal liquor is (5 ~ 16.7): 1, the consumption of ammoniacal liquor and the volume ratio of tetraethoxy are (1 ~ 4): 1, again the KCl aqueous solution of 1 ~ 3mL is added in solution B, the volume ratio of the KCl aqueous solution and ammoniacal liquor is 1:(1 ~ 10), then do not stopping under stirring, solution A to be added in solution B, after reaction 20 ~ 22h, precipitation separation, in 50 ~ 60 DEG C of dryings after centrifuge washing, obtain the SiO of surface modification
2nanometer ball or sub-micron ball powder,
(2) SiO is weighed
2powder, by its ultrasonic disperse in organic solution, ultrasonic time is 2 ~ 3h, obtains SiO
2the suspension of particle, the massfraction of its particle is 1.5% ~ 2%;
(3) two panels ITO slide be parallel to each other and vertically immerse SiO
2in particle suspension liquid, wherein, the spacing of two ito glasses is 0.4 ~ 0.6cm, logical 10 ~ 13V voltage on two ITO slides, with the speed of 0.5 ~ 0.6cm/min lift positive pole ITO slide after energising 20 ~ 30s, finally dries ITO slide in 60 DEG C and namely obtains SiO
2colloidal crystal template;
(4) taking a certain amount of citric acid is dissolved in 25 ~ 28% ammoniacal liquor, ammoniacal liquor is as the criterion can dissolve citric acid, add ferrous sulfate and water and stirring and dissolving, use ammoniacal liquor adjust ph to 7 ~ 9 again, wherein the mol ratio of citric acid and ferrous sulfate is 0.8 ~ 1, the consumption of water is 3 ~ 4 times of the ammoniacal liquor volume dissolving citric acid, at 60 ~ 75 DEG C after stirring reaction 2 ~ 3h as precursor solution, by SiO
2colloidal crystal template immerses 5 ~ 10min in precursor solution at a certain angle, slowly lift out rete, with the precursor solution that adsorption paper removing surface is excessive, the slide pressing a cleaning, drying at film surface forms double-basis sheet, dries after its horizontal positioned at 70 ~ 80 DEG C;
(5), after double-basis sheet being calcined 2 ~ 3h at 600 ~ 700 DEG C, rete is immersed 5 ~ 6h in the NaOH solution of mass concentration 15 ~ 20%, namely obtain ferric oxide hollow ball by washed with de-ionized water post-drying;
Organic solution in described step (2) is ethanol or methyl alcohol;
In described step (4), the immersion angle of silica colloidal crystal is be 45 ~ 60 degree with horizontal direction.
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| CN104174415B (en) * | 2014-07-21 | 2016-05-04 | 浙江大学 | A kind of Bi2O3/ BiOX nano-heterogeneous structure hollow ball and preparation method thereof |
| CN107467672B (en) * | 2017-06-27 | 2020-11-13 | 福格森（武汉）生物科技股份有限公司 | Preparation method of ferrous composite gel microspheres |
| CN110624548B (en) * | 2019-09-26 | 2020-09-08 | 中国矿业大学(北京) | Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil |
| CN113529125B (en) * | 2021-06-16 | 2023-03-28 | 佛山市格瑞芬新能源有限公司 | Iron phosphide composite material and preparation method and application thereof |
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| 双尺寸超材料结构的设计及自组装;伍媛婷;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20130515;B020-50（第31页最后1段-第32页第1段，表3-1，第33页第1段，第43页第2段，第73页第2段，第73页最后1段-第74页第1段，第92页第2段，第98页第3、5段） * |
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