CN101468817A - Mesoporous nanocrystalline assembled porous bengala microsphere and preparation thereof - Google Patents
Mesoporous nanocrystalline assembled porous bengala microsphere and preparation thereof Download PDFInfo
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- CN101468817A CN101468817A CNA2007103041395A CN200710304139A CN101468817A CN 101468817 A CN101468817 A CN 101468817A CN A2007103041395 A CNA2007103041395 A CN A2007103041395A CN 200710304139 A CN200710304139 A CN 200710304139A CN 101468817 A CN101468817 A CN 101468817A
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Abstract
The invention provides a method for preparing porous ferric oxide microspheres by assembling mesoporous nanocrystals. The method comprises: preparing ferric hydroxide-polymer composite microspheres by combining a microemulsion method and a light-induced polymerization method; and removing an organic template through heat treatment and obtaining the crystallized ferric oxide microspheres with multistage pores. The crystallized porous ferric oxide microspheres prepared by the method is stacked with ferric oxide nano monocrystals which are uniform in particle size, a large amount of pores exist between particles and the ferric oxide nanocrystals have a mesoporous structure. The product is used in fields of absorption, crystallization, separation and so on. The method overcomes the drawbacks of a soft template method that the product is low in crystallinity and poor in thermostability and a hard template method of complex process and single template structure, can effectively adjust primary nanoparticles and mesoporous structure and is simple in technical process, strong in controllability and high in product repeatability.
Description
Technical field
The invention belongs to technical field of function materials.Specifically, the present invention relates to a kind of porous ferric oxide microballoon that assembles by mesoporous nanocrystalline and preparation method thereof.
Background technology
Ferric oxide is a kind of important ceramic, and its nontoxic, pollution-free, uvioresistant has obtained using widely in fields such as pigment, catalyzer, magnetic recording materials.The conduct of porous ferric oxide is a very important class wherein, because of having tangible surface effects, has the potential using value in fields such as catalysis, absorption, separation, photoelectric device, biological medicines.
At present, the preparation method of porous iron oxide material mainly contains two kinds, and the one, be the soft template method of guiding with the tensio-active agent, the 2nd, be the hard template method of rigid template with prefabricated porous material.The porous material of soft template method preparation, its hole wall is normally unformed or degree of crystallinity is not high, compare with silica-based porous material in addition, the thermostability of transition metal oxide is relatively poor, and easy structure is caved in (as Sumit Banerjee in the process of removing tensio-active agent, AshwinSanthanam, Aruna Dhathathreyan, and P.Madhusudhan Rao.Synthesis of Ordered Hexagonal Mesostructured Nickel Oxide.Langmuir, 2003,19:5522-5525), thus this method have certain limitation.Hard template method is to utilize prefabricated porous material as rigid template, with the pre-reaction material wiring solution-forming, is encased in the duct of template, obtains the thing phase that needs by thermal treatment, duplicates the vesicular structure that obtains template thereby rigid template is removed again; As Feng Jiao, Andrew Harrison, Jean-Claude Jumas, Alan V.Chadwick Winfried Kockelmann, andPeterG.Bruce.Ordered Mesoporous Fe
2O
3With Crystalline Walls.Journal of the American Chemical Society, 2006, utilize mesopore silicon oxide KIT-6 to be template among the 128:5468-5474, iron nitrate is dissolved in the ethanol as precursor liquid, the two at room temperature mixes to solution and evaporates fully, the dried powder that obtains at 500 ℃ of calcining 3h, is removed the silicon oxide template with the sodium hydroxide solution of heat at last and has been obtained mesoporous iron oxide again at 300 ℃ of calcining 3h; Can see preparation technology's more complicated of hard template method, and alternative vesicular structure is more single.
Summary of the invention
The objective of the invention is to overcome all deficiencies of prior art for preparing porous iron oxide material, a kind of easy and simple to handle, method for preparing high crystalline porous iron oxide material that repeatability is high is provided.
The objective of the invention is to realize by the following technical solutions:
The invention provides a kind of preparation method of the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline, at first utilize the water-in-oil microemulsion legal system to be equipped with the nanometer ironic hydroxide, be easy to photopolymerisable high polymer monomer to wherein adding then, this mixed solution is placed on carries out ultraviolet lighting under the high voltage mercury lamp with the trigger monomer polymerization, thereby form ironic hydroxide/polymer composite microsphere, remove organic formwork by thermal treatment at last and just obtained the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline.The preparation method of the porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline of the present invention comprises the following steps:
1) tensio-active agent and cosurfactant are stirred with certain mass ratio, molysite aqueous solution with certain mass concentration joins in the surfactant soln then, a certain amount of oil phase of adding makes the formation water in oil microemulsion after mixing, and precipitation agent is joined to stir to make in the above-mentioned microemulsion system again to react completely;
Wherein the mass ratio of tensio-active agent and cosurfactant is 1.4～2:1, and the mol ratio of water and tensio-active agent is 10～24:1, and the concentration of molysite aqueous solution is that the massfraction of 0.08～1mol/L and oil phase is 40～80%;
2) high polymer monomer and radical initiator are joined in the microemulsion of step 1) gained and mix;
3) with step 2) mixed solution that obtains is placed under the UV-light and shines 8～20min;
4) turbid solution that step 3) is obtained is put into the baking oven drying with washing with alcohol, separation, gained solid product; With
5) dried powder that step 4) is obtained is at 100～300 ℃ of thermal treatment 1～5h, be warming up to 500～800 ℃ of thermal treatment 2～6h again, 1～10 ℃/min of temperature rise rate removing the organic formwork in the complex microsphere, thereby obtains the porous ferric oxide microballoon that assembled by mesoporous nanocrystalline.
In the preparation method of the porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline of the present invention, described tensio-active agent is preferably octyl phenyl Soxylat A 25-7 (triton x-100), cetyl trimethylammonium bromide (CTAB), two (2-ethylhexyl) sulfonic acid Soduxins (AOT), polyoxyethylene nonylphenol ether (Igepal-CO520) or its mixture; Described cosurfactant is preferably n-hexyl alcohol, propyl carbinol or its mixture; Described molysite is preferably iron nitrate, iron(ic) chloride or its mixture; Described oil phase is preferably hexanaphthene, octane-iso, normal heptane or its mixture; Be preferably ammoniacal liquor, sodium hydroxide or its mixture with described precipitation agent.
Preferably, in the preparation method of the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline of the present invention, the mol ratio of described high polymer monomer and iron be 1.5～55 and the consumption of initiator be 0～15% of monomer mass.
Preferably, described high polymer monomer is acrylamide, vinylbenzene, methyl methacrylate, propylated (3) glycerol tri-acrylate or its mixture.Preferably, described initiator is azo-bis-isobutyl cyanide, st-yrax dme or Potassium Persulphate.When described high polymer monomer and initiator are when solid-state, preferably in advance they are dissolved in the solvent, used solvent is preferably n-hexyl alcohol, propyl carbinol or its mixture.
In the preparation method's of the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline of the present invention step 3), preferably use predominant wavelength to bring out monomer polymerization in the system as the high voltage mercury lamp of 365nm.
Preferably, in the preparation method's of the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline of the present invention described step 1), utilize the water-in-oil microemulsion method to prepare the nanometer ironic hydroxide.
Preferably, in the preparation method of the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline of the present invention, utilize formed polymkeric substance of high polymer monomer in-situ polymerization and the formed micella of tensio-active agent as template.
Preferably, in the preparation method of the porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline of the present invention, utilizing light source used in ultraviolet excitation monomer polymerization and the described step 3) is high voltage mercury lamp.
Another object of the present invention has provided a kind of porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline.Assembled by the crystallinity porous ferric oxide microballoon of the inventive method preparation nanometer ferro oxide monocrystalline by uniform particle diameter, there is a large amount of holes in intergranular, and nano oxidized iron monocrystal also has meso-hole structure.Preferably, the particle size range of crystallinity porous ferric oxide microballoon of the present invention is 120～3000nm, and the particle size range of ferric oxide nano crystalline substance is 20～100nm, and the specific surface area of porous ferric oxide microballoon is 50～102m
2g
-1More preferably, crystallinity porous ferric oxide microballoon of the present invention has the aperture of two kinds of different gradess respectively at 2～8nm in 15～30nm scope, belongs to the intergranular pore between mesoporous and nanocrystalline on the ferric oxide nano crystalline substance respectively.It is that the submicron that assembles of primitive is to micron-sized spherical products with the nano crystal that the present invention has constructed out a kind of, not only make the small size surface effects of nano crystal obtain keeping largely, and make material be easy to fixing in actual applications more and reclaim than the spherical characteristic of big scale, this microballoon not only has higher degree of crystallinity and bigger specific surface area, and has a multi-stage artery structure, wherein the aperture on the nano crystal can be used as the microreactor that holds guest molecule, the intergranular pore of large-size then helps flowing of guest molecule and transmission, and the combination of these several specific characters will make this material in absorption, catalysis, fields such as separation have application potential widely.
The microemulsion that the present invention will generate ironic hydroxide be easy to photopolymerisable high polymer monomer and mix mutually, because monomer trends towards being distributed on the water-oil interface and (promptly is positioned on tensio-active agent and the formed interfacial layer of cosurfactant molecule), make that the magnetism between little pond strengthens in the microemulsion, form the one-level packaging assembly that constitutes by a plurality of little ponds thereby assemble mutually; By mixed solution being carried out the polymerization of ultraviolet lighting trigger monomer, under the effect of UV-light, monomeric pair of key opened the formation long-chain, meanwhile above-mentioned one-level packaging assembly is twined and be bundled together, form the complex microsphere of ironic hydroxide/polymkeric substance, micella in the time of monomer polymerization in the one-level packaging assembly is arranged destroyed, and ironic hydroxide and surfactant molecule are chaotic distribution in the zone of polymkeric substance parcel; In the exsiccant process, along with evaporation of water in the one-level packaging assembly, the tensio-active agent assembling forms micellar while ironic hydroxide and solidifies; Remove organic formwork by thermal treatment at last, ironic hydroxide decomposes generation ferric oxide and crystallization simultaneously, duct on the porous ferric oxide microballoon that formation is assembled by mesoporous nanocrystalline, nanocrystalline and microballoon be respectively the decomposes by surfactant micelle and polymkeric substance discharge and.
With respect to the present method for preparing the porous iron oxide material, the present invention has overcome the soft template method preparation difficulty of using tensio-active agent, products therefrom degree of crystallinity is low, the shortcoming of thermally-stabilised difference, and the single shortcoming of hard template method complex process, formwork structure of using the rigidity porous material.In addition, the present invention can also be by changing the effective regulation and control of microemulsion system reaction conditions realization to the nano crystal shape and size, by changing the kind and the consumption of monomer and initiator, intensity of illumination, time, heat-treat conditions etc. realize the effective regulation and control to vesicular structure.Present method technical process is simple, controllability strong, product repeatability height.
Description of drawings
Below, describe embodiment of the present invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 is the distribution of sizes of the water in oil microemulsion that generates ironic hydroxide that recorded by the dynamic light scattering particle size analysis, and mean sizes is 4.6nm;
Fig. 2 carries out the high multiple electron scanning micrograph of ironic hydroxide/polymer composite microsphere of forming after the photopolymerization for adding monomer, and microsphere surface is fine and close substantially;
Fig. 3 is the electron scanning micrograph of the porous ferric oxide microballoon that obtains after the product among Fig. 2 heat-treated, and the sphericity of product is very good, and particle diameter is that 220～2500nm does not wait;
Fig. 4 is the high multiple electron scanning micrograph of porous ferric oxide microballoon, and this porous microsphere is to be that the spheroidal particle of the size homogeneous about 45nm is piled up and to be formed by median size, and intergranular has tangible hole to exist;
Fig. 5 is the transmission electron microscope photo of the nano particle of formation porous ferric oxide microballoon, and this nano particle is a monocrystalline, and has vesicular structure, and the aperture is 2～4nm;
Fig. 6 is the X-ray diffraction spectrogram of porous ferric oxide microballoon, and product is α-Fe
2O
3, have higher degree of crystallinity.
Embodiment
Below in conjunction with specific embodiment the present invention is described in more detail and illustrates, but those skilled in the art will recognize that these embodiment only are used to illustrate the present invention, it does not constitute any restriction to scope of the present invention.
Embodiment 1
With 10.6g triton x-100 and 8.6mL n-hexyl alcohol mixing and stirring, iron nitrate aqueous solution with 0.8mol/L joins in the above-mentioned surfactant soln then, in system, add 30mL hexanaphthene stirring 16h again after mixing, to dropwise be joined in the above-mentioned microemulsion system by the saturated 20mL cyclohexane solution of ammoniacal liquor, react 10min after dropwising again; Wherein the mol ratio of water and tensio-active agent is 10:1.2g acrylamide and 0.05g Diisopropyl azodicarboxylate are dissolved in the 25mL n-hexyl alcohol, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 10min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 2h at 200 ℃, be warming up to 500 ℃ of calcining 2h again, 5 ℃/min of temperature rise rate.
Embodiment 2
With 10.6g triton x-100 and 8.6mL n-hexyl alcohol mixing and stirring, iron nitrate aqueous solution with 0.8mol/L joins in the above-mentioned surfactant soln then, in system, add 30mL hexanaphthene stirring 16h again after mixing, to dropwise be joined in the above-mentioned microemulsion system by the saturated 20mL cyclohexane solution of ammoniacal liquor, react 30min after dropwising again; Wherein the mol ratio of water and tensio-active agent is 24:1.2g acrylamide and 0.3g Diisopropyl azodicarboxylate are dissolved in the 25mL n-hexyl alcohol, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 10min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 1h at 100 ℃, be warming up to 600 ℃ of calcining 6h again, 5 ℃/min of temperature rise rate.
Embodiment 3
With 7.2g Igepal-CO520 and 5.8mL n-hexyl alcohol mixing and stirring, iron nitrate aqueous solution with 1mol/L joins in the above-mentioned surfactant soln then, in system, add 30mL hexanaphthene stirring 12h again after mixing, to dropwise be joined in the above-mentioned microemulsion system by the saturated 20mL cyclohexane solution of ammoniacal liquor, react 5h after dropwising again; Wherein the mol ratio of water and tensio-active agent is 10:1.The 2g acrylamide is dissolved in the 25mL n-hexyl alcohol, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 12min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 5h at 200 ℃, be warming up to 500 ℃ of calcining 2h again, 1 ℃/min of temperature rise rate.
Embodiment 4
With 10.5g CTAB and 9.2mL propyl carbinol mixing and stirring, iron nitrate aqueous solution with 0.08mol/L joins in the above-mentioned surfactant soln then, add the 60mL octane-iso after mixing again in the system and be made into microemulsion one, wherein the mol ratio of water and tensio-active agent is 20:1; Same proportioning is made into microemulsion two with the NaOH aqueous solution that iron nitrate solution changes 1.0mol/L into; Then microemulsion two is joined and make the generation precipitin reaction in the microemulsion one.2g acrylamide and 0.05g Diisopropyl azodicarboxylate are dissolved in the 25mL propyl carbinol, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 8min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 5h at 300 ℃, be warming up to 500 ℃ of calcining 2h again, 10 ℃/min of temperature rise rate.
With 10.6g triton x-100 and 8.6mL n-hexyl alcohol mixing and stirring, iron nitrate aqueous solution with 0.8mol/L joins in the above-mentioned surfactant soln then, in system, add 30mL hexanaphthene stirring 16h again after mixing, to dropwise be joined in the above-mentioned microemulsion system by the saturated 20mL cyclohexane solution of ammoniacal liquor, react 5min after dropwising again; Wherein the mol ratio of water and tensio-active agent is 20:1.The 0.01g Potassium Persulphate is dissolved in the 0.7g vinylbenzene, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 10min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 5h at 300 ℃, be warming up to 800 ℃ of calcining 5h again, 5 ℃/min of temperature rise rate.
Embodiment 6
With 10.6g triton x-100 and 8.6mL n-hexyl alcohol mixing and stirring, iron nitrate aqueous solution with 0.2mol/L joins in the above-mentioned surfactant soln then, in system, add 30mL hexanaphthene stirring 24h again after mixing, to dropwise be joined in the above-mentioned microemulsion system by the saturated 20mL cyclohexane solution of ammoniacal liquor, react 10min after dropwising again; Wherein the mol ratio of water and tensio-active agent is 24:1.The 0.06g Potassium Persulphate is dissolved in the 5.6g methyl methacrylate, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 20min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 2h at 200 ℃, be warming up to 500 ℃ of calcining 2h again, 5 ℃/min of temperature rise rate.
Embodiment 7
With 7.3g AOT and 4.5mL propyl carbinol mixing and stirring, ferric chloride in aqueous solution with 0.5mol/L joins in the above-mentioned surfactant soln then, add the 35mL normal heptane after mixing again in the system and be made into microemulsion one, wherein the mol ratio of water and tensio-active agent is 15:1; Same proportioning is made into microemulsion two with the NaOH aqueous solution that ferric chloride Solution changes 1.0mol/L into; Then microemulsion two is joined and make the generation precipitin reaction in the microemulsion one.2g acrylamide and 0.05g Diisopropyl azodicarboxylate are dissolved in the 25mL propyl carbinol, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 15min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 5h at 300 ℃, be warming up to 500 ℃ of calcining 2h again, 5 ℃/min of temperature rise rate.
Embodiment 8
With 10.6g triton x-100 and 8.6mL n-hexyl alcohol mixing and stirring, iron nitrate aqueous solution with 0.4mol/L joins in the above-mentioned surfactant soln then, in system, add 30mL hexanaphthene stirring 12h again after mixing, to dropwise be joined in the above-mentioned microemulsion system by the saturated 20mL cyclohexane solution of ammoniacal liquor, react 5min after dropwising again; Wherein the mol ratio of water and tensio-active agent is 20:1.0.12g st-yrax dme is dissolved in 12g propylated (3) glycerol tri-acrylate, and with the above-mentioned microemulsion mixing and stirring that has generated ironic hydroxide after be placed on irradiation 20min under the high voltage mercury lamp.With gained turbid solution washing with alcohol, separation, it is dry that solid product is put into baking oven.At last product is calcined 5h at 300 ℃, be warming up to 500 ℃ of calcining 2h again, 5 ℃/min of temperature rise rate.
Claims (10)
1. the preparation method of a porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline comprises following step:
1) tensio-active agent and cosurfactant are stirred with certain mass ratio, molysite aqueous solution with certain mass concentration joins in the surfactant soln then, a certain amount of oil phase of adding makes the formation water in oil microemulsion after mixing, and precipitation agent is joined to stir to make in the above-mentioned microemulsion system again to react completely;
Wherein the mass ratio of tensio-active agent and cosurfactant is 1.4～2:1, and the mol ratio of water and tensio-active agent is 10～24:1, and the concentration of molysite aqueous solution is that the massfraction of 0.08～1mol/L and oil phase is 40～80%;
2) high polymer monomer and radical initiator are joined in the microemulsion of step 1) gained and mix;
3) with step 2) mixed solution that obtains is placed under the UV-light and shines 8～20min;
4) turbid solution that step 3) is obtained is put into the baking oven drying with washing with alcohol, separation, gained solid product; With
5) dried powder that step 4) is obtained is warming up to 500～800 ℃ of thermal treatment 2～6h again at 100～300 ℃ of thermal treatment 1～5h, and 1～10 ℃/min of temperature rise rate removing the organic formwork in the complex microsphere, thereby obtains crystallinity porous ferric oxide microballoon.
2. the preparation method of the porous ferric oxide microballoon that assembles by mesoporous nanocrystalline as claimed in claim 1, it is characterized in that described tensio-active agent is octyl phenyl Soxylat A 25-7, cetyl trimethylammonium bromide, two (2-ethylhexyl) sulfonic acid Soduxin, polyoxyethylene nonylphenol ether or its mixture; Described cosurfactant is n-hexyl alcohol, propyl carbinol or its mixture; Described molysite is iron nitrate, iron(ic) chloride or its mixture; Described oil phase is hexanaphthene, octane-iso, normal heptane or its mixture; With described precipitation agent be ammoniacal liquor, sodium hydroxide or its mixture.
3. the preparation method of the porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline as claimed in claim 1 or 2 is characterized in that, the mol ratio of described high polymer monomer and iron be 1.5～55 and the consumption of described initiator be 0～15% of monomer mass.
4. as the preparation method of each described porous ferric oxide microballoon that assembles by mesoporous nanocrystalline among the claim 1-3, it is characterized in that, described high polymer monomer is that acrylamide, vinylbenzene, methyl methacrylate, propylated (3) glycerol tri-acrylate or its mixture and described initiator are azo-bis-isobutyl cyanide, st-yrax dme or Potassium Persulphate.
5. the preparation method of the porous ferric oxide microballoon that is assembled by mesoporous nanocrystalline as claimed in claim 4 is characterized in that, when described high polymer monomer and initiator are when solid-state, in advance they is dissolved in the solvent; Preferably, described solvent is n-hexyl alcohol, propyl carbinol or its mixture.
6. as the preparation method of each described porous ferric oxide microballoon that assembles by mesoporous nanocrystalline among the claim 1-5, it is characterized in that, in step 3), use predominant wavelength to bring out monomer polymerization in the system as the high voltage mercury lamp of 365nm.
7. as the preparation method of each described porous ferric oxide microballoon that assembles by mesoporous nanocrystalline among the claim 1-6, it is characterized in that, in described step 1), utilize the water-in-oil microemulsion method to prepare the nanometer ironic hydroxide; Preferably, utilize formed polymkeric substance of high polymer monomer in-situ polymerization and the formed micella of tensio-active agent as template.
8. as the preparation method of each described porous ferric oxide microballoon that assembles by mesoporous nanocrystalline among the claim 1-7, it is characterized in that utilizing light source used in ultraviolet excitation monomer polymerization and the described step 3) is high voltage mercury lamp.
9. crystallinity porous ferric oxide microballoon, its ferric oxide nano monocrystalline by uniform particle diameter is piled up and is formed, and there is a large amount of holes in intergranular, and the ferric oxide nano crystalline substance has meso-hole structure.
10. crystallinity porous ferric oxide microballoon according to claim 9 is characterized in that the particle size range of described microballoon is 120～3000nm, and the particle size range of ferric oxide nano crystalline substance is 20～100nm, and the specific surface area of porous ferric oxide microballoon is 50～102m
2g
-1Preferably, described microballoon has the aperture of two kinds of different gradess in 2～8nm, 15～30nm scope, belongs to the intergranular pore between mesoporous and nanocrystalline on the ferric oxide nano crystalline substance respectively.
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| CN102190428A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Ordered mesoporous microsphere medicine carrier and preparation method thereof |
| CN102275997A (en) * | 2011-07-14 | 2011-12-14 | 浙江大学 | Porous ferric oxide constructed by nanocrystalline and preparation method thereof |
| CN102951687A (en) * | 2012-03-01 | 2013-03-06 | 纳米籽有限公司 | Ferric oxide mesoporous microsphere and preparation method thereof |
| CN103579581A (en) * | 2013-07-23 | 2014-02-12 | 湖南大学 | Monocrystalline porous iron oxide powder material and preparation method thereof |
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| CN102190428A (en) * | 2010-03-10 | 2011-09-21 | 中国科学院上海硅酸盐研究所 | Ordered mesoporous microsphere medicine carrier and preparation method thereof |
| CN102275997A (en) * | 2011-07-14 | 2011-12-14 | 浙江大学 | Porous ferric oxide constructed by nanocrystalline and preparation method thereof |
| CN102951687A (en) * | 2012-03-01 | 2013-03-06 | 纳米籽有限公司 | Ferric oxide mesoporous microsphere and preparation method thereof |
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| CN105174316A (en) * | 2015-08-28 | 2015-12-23 | 河南大学 | Cake-shaped iron oxide nanoparticles with hierarchical structures and preparation method therefor |
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| CN111235625A (en) * | 2020-01-21 | 2020-06-05 | 江苏理工学院 | Iron oxide single crystal nano spherical particle and molten salt method synthesis method thereof |
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| CN111604037B (en) * | 2020-05-12 | 2023-08-25 | 中国人民解放军陆军军医大学 | Polyphenol microsphere for treating heavy metal ions and radionuclides in industrial wastewater and preparation method and application thereof |
| CN115386955A (en) * | 2022-08-31 | 2022-11-25 | 上海旦元新材料科技有限公司 | Mesoporous ferric oxide single crystal and hydrothermal preparation method thereof |
| CN115386955B (en) * | 2022-08-31 | 2023-09-05 | 上海旦元新材料科技有限公司 | Mesoporous ferric oxide monocrystal and hydrothermal preparation method thereof |
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