WO2015196864A1 - Method for preparing ferroferric oxide hollow spheres - Google Patents
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- WO2015196864A1 WO2015196864A1 PCT/CN2015/077819 CN2015077819W WO2015196864A1 WO 2015196864 A1 WO2015196864 A1 WO 2015196864A1 CN 2015077819 W CN2015077819 W CN 2015077819W WO 2015196864 A1 WO2015196864 A1 WO 2015196864A1
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- ferroferric oxide
- oxide hollow
- hollow sphere
- mixed solution
- organic solvent
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- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 28
- 239000011259 mixed solution Substances 0.000 claims abstract description 26
- 239000003960 organic solvent Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012429 reaction media Substances 0.000 claims abstract description 21
- 150000001720 carbohydrates Chemical class 0.000 claims abstract description 16
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 14
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 9
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-XLOQQCSPSA-N Alpha-Lactose Chemical compound O[C@@H]1[C@@H](O)[C@@H](O)[C@@H](CO)O[C@H]1O[C@@H]1[C@@H](CO)O[C@H](O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-XLOQQCSPSA-N 0.000 claims description 2
- 229930091371 Fructose Natural products 0.000 claims description 2
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 2
- 239000005715 Fructose Substances 0.000 claims description 2
- GUBGYTABKSRVRQ-QKKXKWKRSA-N Lactose Natural products OC[C@H]1O[C@@H](O[C@H]2[C@H](O)[C@@H](O)C(O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@H]1O GUBGYTABKSRVRQ-QKKXKWKRSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-PHYPRBDBSA-N alpha-D-galactose Chemical compound OC[C@H]1O[C@H](O)[C@H](O)[C@@H](O)[C@H]1O WQZGKKKJIJFFOK-PHYPRBDBSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- GUBGYTABKSRVRQ-QUYVBRFLSA-N beta-maltose Chemical compound OC[C@H]1O[C@H](O[C@H]2[C@H](O)[C@@H](O)[C@H](O)O[C@@H]2CO)[C@H](O)[C@@H](O)[C@@H]1O GUBGYTABKSRVRQ-QUYVBRFLSA-N 0.000 claims description 2
- 229930182830 galactose Natural products 0.000 claims description 2
- 239000008101 lactose Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 description 9
- 239000000203 mixture Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 230000001603 reducing effect Effects 0.000 description 3
- 239000004094 surface-active agent Substances 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004277 Ferrous carbonate Substances 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 2
- 229960004652 ferrous carbonate Drugs 0.000 description 2
- 235000019268 ferrous carbonate Nutrition 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical group 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- CDRCPXYWYPYVPY-UHFFFAOYSA-N iron(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+2].[Fe+2].[Fe+2] CDRCPXYWYPYVPY-UHFFFAOYSA-N 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
Definitions
- the invention relates to a preparation method of a ferroferric oxide material, in particular to a preparation method of a triiron tetroxide hollow sphere.
- nano hollow sphere As a new nanostructure, nano hollow sphere has broad prospects in the fields of chemistry, materials science, biology and pharmacology due to its light weight, high strength, large specific surface area and surface penetrating ability.
- Ferric oxide (Fe 3 O 4 ) is a very important spinel ferrite and one of the most widely used soft magnetic materials. It is often used as a magnetic recording material, a basic material for magnetic fluids, a magnetic pigment, Drugs, catalysts and electronic materials have broad application prospects in many fields.
- the research of nano-Fe 3 O 4 mainly focuses on: (1) improving traditional synthesis methods and exploring new synthetic methods; (2) synthesizing nano-Fe 3 O 4 with special morphology; (3) modifying the surface of materials (4) Application research of nano Fe 3 O 4 in new fields.
- Fe 3 O 4 nanospheres having a porous structure are prepared by adding a surfactant polyvinylpyrrolidone and urea to a solution of a ferric salt solution in a high pressure reactor, but the surface needs to be added during the preparation process.
- the active agent controls the morphology and size of the crystal, the crystallization process is complicated, difficult to control, and the washing and separation processes are difficult.
- ferric chloride, ascorbic acid and urea are mixed in an organic solvent to prepare a micro-nano structure ferrous carbonate porous sphere, and then calcined in an inert atmosphere to obtain a micro-nano structure Fe 3 O 4 porous sphere
- the preparation method has It does not add dispersant, surfactant and templating agent, and has the advantages of green environmental protection and simple purification process.
- the preparation process requires synthesis of a ferrous carbonate precursor, and the precursor is calcined to obtain a Fe 3 O 4 porous sphere.
- the high-temperature calcination process has high energy consumption, increases production costs, and is difficult to industrialize.
- a method for preparing a ferroferric oxide hollow sphere comprising the steps of: mixing and dissolving a source of ferric iron in a solvothermal reaction medium to form a first mixed solution, the solvothermal reaction medium comprising water and an organic solvent;
- the saccharide reducing agent is added to the first mixed mixed solution to be mixed and dissolved to form a second mixed solution, and the second mixed solution is subjected to solvothermal reaction to obtain a reaction product of ferroferric oxide hollow spheres.
- the embodiment of the present invention uses a mixture of water and an organic solvent as a solvothermal reaction medium, and uses a saccharide as a reducing agent to prepare a triiron tetroxide hollow having a monodisperse, uniform phase and high purity.
- the spherical structure, the ferroferric oxide hollow sphere is assembled from one-dimensional nanoparticles.
- the preparation process is simple, the raw materials are widely used, and the prepared structure of the ferroferric oxide hollow spheres is controllable and easy to industrialize.
- Example 1 is a scanning electron micrograph of a ferroferric oxide hollow sphere synthesized in Example 1 of the present invention.
- Embodiments of the present invention provide a method for preparing a ferroferric oxide hollow sphere, comprising the following steps:
- the second mixed solution is subjected to a solvothermal reaction to obtain a reaction product of ferroferric oxide hollow spheres.
- the ferric iron source is soluble in the solvothermal reaction medium.
- This may be a source of ferric iron chloride (FeCl 3), ferric nitrate (Fe (NO 3) 3) .
- the molar amount of the ferric iron source may be from 0.2 mmol to 20 mmol.
- the solvothermal reaction medium is a mixture of the water and an organic solvent.
- the water and the organic solvent are uniformly mixed with each other.
- the water may be distilled water.
- the organic solvent is a polyol having a reducing property.
- the organic solvent is preferably a polyol.
- the organic solvent is sparingly soluble or insoluble with water, i.e., the organic solvent has a lower solubility in water.
- a uniform mixture of an organic solvent having a low solubility in water and water is used to form a hollow sphere structure of ferroferric oxide.
- the organic solvent having low solubility in water may preferably be at least one of n-butanol, isobutanol, n-pentanol, n-hexanol and n-heptanol, and the organic solvent is simultaneously reducing and capable of ferric iron Part of the reduction to ferrous iron, the formation of a controlled shape of the hollow sphere structure of triiron tetroxide.
- the organic solvent is isobutanol.
- the volume ratio of the water to the organic solvent may be from 15:1 to 1:10.
- the use of the solvothermal reaction medium in the volume ratio range can effectively control the subsequent formation of the hollow sphere structure of the ferroferric oxide.
- the volume ratio of the water to the organic solvent may be from 10:1 to 1:8. More preferably, the volume ratio of the water to the organic solvent is 2.5:1.
- step S1 the step of forming the first mixed solution further comprises:
- the organic solvent can be brought to the maximum solubility in water by stirring.
- step S12 stirring is continued during the addition of the ferric iron source to the solvothermal reaction medium to sufficiently dissolve the ferric source and uniformly mix with the solvothermal reaction medium.
- the stirring rate may be from 100 r/min to 3000 r/min, and the stirring may be from 0.5 hour to 2 hours.
- the first mixed solution is a clear transparent solution.
- the saccharide reducing agent can be used to obtain the ferroferric oxide by using the reducing property, and at the same time, to assist in the growth of the hollow sphere structure of the ferroferric oxide.
- the saccharide reducing agent may be at least one of glucose, lactose, galactose, maltose, and fructose.
- the saccharide reducing agent is glucose.
- the saccharide reducing agent has a relatively low content relative to the ferric iron source to better form a hollow structure having a pure phase and a spherical shape.
- the molar ratio of the saccharide reducing agent to the ferric iron source may be 1:2 to 1:200. More preferably, the molar ratio of the saccharide reducing agent to the ferric iron source is 1:5 to 1:50. More preferably, the molar ratio of the saccharide reducing agent to the ferric source is 1:10.
- the above step S2 may further include a stirring step to sufficiently dissolve the saccharide reducing agent in the first mixed solution and uniformly mix with the first mixed solution.
- the stirring rate may be 100 r/min to 3000 r/min, and the stirring time may be 0.5 hour to 2 hours.
- the second mixed solution is still a clear solution.
- the solvothermal reaction is carried out in a high pressure reactor at a temperature of from 120 ° C to 240 ° C.
- the solvothermal reaction vessel may be a sealed autoclave, and the internal pressure of the reactor is raised under the high temperature and high pressure condition by pressurizing the sealed autoclave or using the autogenous pressure of the steam inside the reactor to raise the internal pressure of the reactor. Carry out the reaction.
- the internal pressure of the reaction vessel may be 0.2 MPa to 30 MPa, and the reaction time is 2 hours to 48 hours, thereby obtaining a hollow iron tetraoxide hollow sphere. After the reaction is completed, the reaction vessel can be naturally cooled to room temperature.
- the reaction product can be further separated and purified.
- the manner of separation can be filtration or centrifugation.
- the reaction product is separated by centrifugal separation, and the rotational speed of the centrifugal separation may be 3000r/min to 8000r/min.
- the separated reaction product can be further washed.
- the reaction product is washed several times with water and absolute ethanol, respectively.
- the separated and purified reaction product may be further dried to remove the solvent.
- the drying can be vacuum filtration or heat drying.
- the heating and drying temperature may be 60 ° C to 80 ° C, and the heating time may be 12 hours to 24 hours.
- the obtained reaction product is in the form of a powder, and the reaction product is a triiron tetroxide hollow sphere assembled from one-dimensional nano-iron tetraoxide particles, wherein the hollow sphere has a diameter of 3 micrometers to 4 micrometers, and the hollow sphere The hollow portion has a diameter of about 1.5 microns.
- the ferroferric oxide hollow sphere has a rough surface and a large number of voids, and has the advantages of light weight, high specific surface area, high strength, heat resistance and corrosion resistance.
- a mixture of water and an organic solvent is used as a solvothermal reaction medium, and a saccharide is used as a reducing agent to prepare a triiron tetroxide hollow sphere structure having a monodisperse, a uniform phase and a high purity.
- Iron hollow spheres are assembled from one-dimensional nanoparticles.
- the preparation process is simple, the raw materials are widely used, and no dispersant and surfactant are added, and the prepared ferroferric oxide hollow sphere has a controllable structure and is easy to be industrialized.
- the reaction product was centrifuged under conditions of 5000 r/min, and then washed 5 times with distilled water and absolute ethanol, placed in a dry box, and dried at 80 ° C for 20 hours to obtain a ferroferric oxide nanomaterial.
- FIG. 1 it can be seen from the scanning electron micrograph of the ferroferric oxide nano material that the ferroferric oxide is a hollow sphere structure having a diameter of 3 micrometers to 4 micrometers and a hollow portion of about 1.5 micrometers. .
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
Abstract
The present invention relates to a method for preparing ferroferric oxide hollow spheres. The method comprises the following steps: mixing and dissolving a trivalent iron source in a solvothermal reaction medium to form a first mixed solution, wherein the solvothermal reaction medium comprises water and an organic solvent; adding a carbohydrate reducer into the first mixed solution for mixing and dissolving, so as to form a second mixed solution, and performing a solvothermal reaction for the second mixed solution so as to obtain the reaction product of ferroferric oxide hollow spheres.
Description
本发明涉及一种四氧化三铁材料的制备方法，尤其涉及一种四氧化三铁空心球的制备方法。The invention relates to a preparation method of a ferroferric oxide material, in particular to a preparation method of a triiron tetroxide hollow sphere.
纳米空心球作为一种新的纳米结构，由于其具有轻质、强度高、比表面积大、表面渗透能力等特点，在化学、材料科学、生物学、药物学等领域有着广阔的前景。As a new nanostructure, nano hollow sphere has broad prospects in the fields of chemistry, materials science, biology and pharmacology due to its light weight, high strength, large specific surface area and surface penetrating ability.
四氧化三铁（Fe3O4）是一种非常重要的尖晶石型铁氧体，也是应用最广泛的软磁性材料之一，常用作磁记录材料、磁流体的基本材料、磁性颜料、药物、催化剂和电子材料等，在诸多领域具有广阔的应用前景。目前纳米Fe3O4的研究主要集中在：(1) 改进传统的合成方法和探索新的合成方法；(2) 合成具有特殊形貌的纳米Fe3O4；(3) 对材料表面进行改性；(4) 纳米Fe3O4在新领域的应用研究。Ferric oxide (Fe 3 O 4 ) is a very important spinel ferrite and one of the most widely used soft magnetic materials. It is often used as a magnetic recording material, a basic material for magnetic fluids, a magnetic pigment, Drugs, catalysts and electronic materials have broad application prospects in many fields. At present, the research of nano-Fe 3 O 4 mainly focuses on: (1) improving traditional synthesis methods and exploring new synthetic methods; (2) synthesizing nano-Fe 3 O 4 with special morphology; (3) modifying the surface of materials (4) Application research of nano Fe 3 O 4 in new fields.
现有技术中有利用在三价铁盐的溶液中加入表面活性剂聚乙烯吡咯烷酮和尿素来高压反应釜中密闭反应制备具有多孔结构的Fe3O4纳米球，但是该制备过程中需要加入表面活性剂来控制晶体的形貌和尺寸，结晶过程较为复杂，难以控制，而且洗涤、分离过程困难。此外，也有将三氯化铁、抗坏血酸、尿素在有机溶剂中混合后制备得到微纳结构碳酸亚铁多孔球，然后在惰性气氛下煅烧得到微纳结构Fe3O4多孔球，该制备方法具有不添加分散剂、表面活性剂和模板剂，绿色环保、后期提纯工艺简单等优点，但是该制备过程需要先合成出碳酸亚铁前驱体，前驱体经过煅烧后才能得到Fe3O4多孔球，而高温煅烧工序能耗高，加大了生产成本，工业化过程困难。In the prior art, Fe 3 O 4 nanospheres having a porous structure are prepared by adding a surfactant polyvinylpyrrolidone and urea to a solution of a ferric salt solution in a high pressure reactor, but the surface needs to be added during the preparation process. The active agent controls the morphology and size of the crystal, the crystallization process is complicated, difficult to control, and the washing and separation processes are difficult. In addition, ferric chloride, ascorbic acid and urea are mixed in an organic solvent to prepare a micro-nano structure ferrous carbonate porous sphere, and then calcined in an inert atmosphere to obtain a micro-nano structure Fe 3 O 4 porous sphere, the preparation method has It does not add dispersant, surfactant and templating agent, and has the advantages of green environmental protection and simple purification process. However, the preparation process requires synthesis of a ferrous carbonate precursor, and the precursor is calcined to obtain a Fe 3 O 4 porous sphere. The high-temperature calcination process has high energy consumption, increases production costs, and is difficult to industrialize.
有鉴于此，确有必要提供一种生产工艺简单、环保、成本低且易于实现产业化生产的四氧化三铁空心球的制备方法。In view of this, it is indeed necessary to provide a method for preparing a ferroferric oxide hollow sphere which is simple in production process, environmentally friendly, low in cost, and easy to realize industrial production.
一种四氧化三铁空心球的制备方法，包括以下步骤：将三价铁源在一溶剂热反应介质中混合并溶解形成一第一混合溶液，该溶剂热反应介质包括水和有机溶剂；将糖类还原剂加入到该第一混合混合溶液中混合并溶解形成一第二混合溶液，以及将该第二混合溶液进行溶剂热反应，得到反应产物四氧化三铁空心球。A method for preparing a ferroferric oxide hollow sphere, comprising the steps of: mixing and dissolving a source of ferric iron in a solvothermal reaction medium to form a first mixed solution, the solvothermal reaction medium comprising water and an organic solvent; The saccharide reducing agent is added to the first mixed mixed solution to be mixed and dissolved to form a second mixed solution, and the second mixed solution is subjected to solvothermal reaction to obtain a reaction product of ferroferric oxide hollow spheres.
与现有技术相比较，本发明实施例利用水和有机溶剂的混合作为溶剂热反应介质，并采用糖类作为还原剂，可制备出单分散、物相均匀、纯度高的四氧化三铁空心球结构，该四氧化三铁空心球由一维纳米颗粒组装而成。此外，该制备工艺简单，原料来源广泛，制备获得的四氧化三铁空心球结构形貌可控、易于产业化生产。Compared with the prior art, the embodiment of the present invention uses a mixture of water and an organic solvent as a solvothermal reaction medium, and uses a saccharide as a reducing agent to prepare a triiron tetroxide hollow having a monodisperse, uniform phase and high purity. The spherical structure, the ferroferric oxide hollow sphere is assembled from one-dimensional nanoparticles. In addition, the preparation process is simple, the raw materials are widely used, and the prepared structure of the ferroferric oxide hollow spheres is controllable and easy to industrialize.
图1为本发明实施例1合成的四氧化三铁空心球的扫描电镜照片。1 is a scanning electron micrograph of a ferroferric oxide hollow sphere synthesized in Example 1 of the present invention.
如下具体实施方式将结合上述附图进一步说明本发明。The invention will be further illustrated by the following detailed description in conjunction with the accompanying drawings.
下面将结合附图及具体实施例对本发明提供的四氧化三铁空心球的制备方法作进一步的详细说明。The preparation method of the ferroferric oxide hollow sphere provided by the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.
本发明实施方式提供一种四氧化三铁空心球的制备方法，包括以下步骤：Embodiments of the present invention provide a method for preparing a ferroferric oxide hollow sphere, comprising the following steps:
S1，将三价铁（Fe3+）源在一溶剂热反应介质中混合并溶解形成一第一混合溶液，该溶剂热反应介质包括水和有机溶剂；S1, mixing and dissolving a source of ferric iron (Fe 3+ ) in a solvothermal reaction medium to form a first mixed solution, the solvothermal reaction medium comprising water and an organic solvent;
S2，将糖类还原剂加入到该第一混合混合溶液中混合并溶解形成一第二混合溶液，以及S2, adding a saccharide reducing agent to the first mixed mixed solution, mixing and dissolving to form a second mixed solution, and
S3，将该第二混合溶液进行溶剂热反应，得到反应产物四氧化三铁空心球。S3, the second mixed solution is subjected to a solvothermal reaction to obtain a reaction product of ferroferric oxide hollow spheres.
在上述步骤S1中，所述三价铁源可溶于所述溶剂热反应介质。该三价铁源可以为氯化铁（FeCl3）、硝酸铁（Fe(NO3)3）。所述三价铁源的摩尔量可以为0.2mmol至20mmol。In the above step S1, the ferric iron source is soluble in the solvothermal reaction medium. This may be a source of ferric iron chloride (FeCl 3), ferric nitrate (Fe (NO 3) 3) . The molar amount of the ferric iron source may be from 0.2 mmol to 20 mmol.
所述溶剂热反应介质为所述水和有机溶剂的混合液。所述水和有机溶剂之间相互混合均匀。所述水可以为蒸馏水。所述有机溶剂为具有还原性质的多元醇。所述有机溶剂优选为多元醇。优选地，所述有机溶剂与水相互微溶或不溶，即所述有机溶剂在水中具有较低的溶解度。采用该在水中溶解度较低的有机溶剂与水形成的均匀混合液作为所述溶剂热反应介质利于形成空心球结构的四氧化三铁。该在水中溶解度较低的有机溶剂优选可以为正丁醇、异丁醇、正戊醇、正己醇以及正庚醇中的至少一种，该类有机溶剂同时具有还原性，能够将三价铁部分的还原成二价铁，形成形貌可控的空心球结构的四氧化三铁。优选地，所述有机溶剂为异丁醇。The solvothermal reaction medium is a mixture of the water and an organic solvent. The water and the organic solvent are uniformly mixed with each other. The water may be distilled water. The organic solvent is a polyol having a reducing property. The organic solvent is preferably a polyol. Preferably, the organic solvent is sparingly soluble or insoluble with water, i.e., the organic solvent has a lower solubility in water. As the solvothermal reaction medium, a uniform mixture of an organic solvent having a low solubility in water and water is used to form a hollow sphere structure of ferroferric oxide. The organic solvent having low solubility in water may preferably be at least one of n-butanol, isobutanol, n-pentanol, n-hexanol and n-heptanol, and the organic solvent is simultaneously reducing and capable of ferric iron Part of the reduction to ferrous iron, the formation of a controlled shape of the hollow sphere structure of triiron tetroxide. Preferably, the organic solvent is isobutanol.
所述水和有机溶剂的体积比可以为15:1~1:10。采用该体积比范围内的溶剂热反应介质可有效地控制后续形成空心球结构的四氧化三铁。优选地，所述水和有机溶剂的体积比可以为10:1~1:8。更为优选地，所述水和有机溶剂的体积比为2.5：1。The volume ratio of the water to the organic solvent may be from 15:1 to 1:10. The use of the solvothermal reaction medium in the volume ratio range can effectively control the subsequent formation of the hollow sphere structure of the ferroferric oxide. Preferably, the volume ratio of the water to the organic solvent may be from 10:1 to 1:8. More preferably, the volume ratio of the water to the organic solvent is 2.5:1.
在上述步骤S1中，形成所述第一混合溶液的步骤进一步包括：In the above step S1, the step of forming the first mixed solution further comprises:
S11，均匀混合所述水和有机溶剂形成所述溶剂热反应介质，以及S11, uniformly mixing the water and an organic solvent to form the solvothermal reaction medium, and
S12，将所述三价铁源加入到该溶剂热反应介质中混合并溶解形成所述第一混合溶液。S12, adding the ferric iron source to the solvothermal reaction medium to mix and dissolve to form the first mixed solution.
在上述步骤S11中可通过搅拌的方式使有机溶剂在水中达到最大的溶解度。In the above step S11, the organic solvent can be brought to the maximum solubility in water by stirring.
在上述步骤S12中，在将所述三价铁源加入到该溶剂热反应介质的过程中持续搅拌以使所述三价铁源充分溶解并与所述溶剂热反应介质均匀混合。在该步骤S12中，所述搅拌的速率可以为100r/min至3000r/min，所述搅拌的时间可以为0.5小时至2小时。该第一混合溶液为一澄清透明溶液。In the above step S12, stirring is continued during the addition of the ferric iron source to the solvothermal reaction medium to sufficiently dissolve the ferric source and uniformly mix with the solvothermal reaction medium. In this step S12, the stirring rate may be from 100 r/min to 3000 r/min, and the stirring may be from 0.5 hour to 2 hours. The first mixed solution is a clear transparent solution.
在上述步骤S2中，采用所述糖类还原剂既可利用其还原性能制备获得四氧化三铁，同时可辅助生长出空心球结构的四氧化三铁。所述糖类还原剂可以为葡萄糖、乳糖、半乳糖、麦芽糖以及果糖中的至少一种。优选地，所述糖类还原剂为葡萄糖。In the above step S2, the saccharide reducing agent can be used to obtain the ferroferric oxide by using the reducing property, and at the same time, to assist in the growth of the hollow sphere structure of the ferroferric oxide. The saccharide reducing agent may be at least one of glucose, lactose, galactose, maltose, and fructose. Preferably, the saccharide reducing agent is glucose.
优选地，所述糖类还原剂相对于所述三价铁源具有较少的含量以更好地形成纯相且形貌为球形的空心结构。优选地，所述糖类还原剂与所述三价铁源的含量摩尔比可以为1：2~1：200。更为优选地，所述糖类还原剂与所述三价铁源的含量摩尔比为1：5~1：50。更为优选地，所述糖类还原剂与所述三价铁源的含量摩尔比为1：10。Preferably, the saccharide reducing agent has a relatively low content relative to the ferric iron source to better form a hollow structure having a pure phase and a spherical shape. Preferably, the molar ratio of the saccharide reducing agent to the ferric iron source may be 1:2 to 1:200. More preferably, the molar ratio of the saccharide reducing agent to the ferric iron source is 1:5 to 1:50. More preferably, the molar ratio of the saccharide reducing agent to the ferric source is 1:10.
上述步骤S2可进一步包括一搅拌的步骤以使所述糖类还原剂在所述第一混合溶液中充分溶解且与所述第一混合溶液均匀混合。该步骤中，搅拌速率可以为100r/min~3000r/min，搅拌的时间可以为0.5小时~2小时。该第二混合溶液仍为一澄清的溶液。The above step S2 may further include a stirring step to sufficiently dissolve the saccharide reducing agent in the first mixed solution and uniformly mix with the first mixed solution. In this step, the stirring rate may be 100 r/min to 3000 r/min, and the stirring time may be 0.5 hour to 2 hours. The second mixed solution is still a clear solution.
在上述步骤S3中，该溶剂热反应在一高压反应釜中进行，反应的温度为120℃~240℃。所述溶剂热反应釜可为一密封高压釜，通过对该密封高压釜加压或利用反应釜内部蒸汽的自生压力使反应釜内部压力上升，从而使反应釜内部的反应原料在高温高压条件下进行反应。该反应釜内部压力可以为0.2MPa~30MPa，反应时间为2小时至48小时，即可得到四氧化三铁空心球。在反应完毕后，所述反应釜可自然冷却至室温。In the above step S3, the solvothermal reaction is carried out in a high pressure reactor at a temperature of from 120 ° C to 240 ° C. The solvothermal reaction vessel may be a sealed autoclave, and the internal pressure of the reactor is raised under the high temperature and high pressure condition by pressurizing the sealed autoclave or using the autogenous pressure of the steam inside the reactor to raise the internal pressure of the reactor. Carry out the reaction. The internal pressure of the reaction vessel may be 0.2 MPa to 30 MPa, and the reaction time is 2 hours to 48 hours, thereby obtaining a hollow iron tetraoxide hollow sphere. After the reaction is completed, the reaction vessel can be naturally cooled to room temperature.
进一步地，在通过所述步骤S3得到反应产物后，可进一步分离提纯该反应产物。所述分离的方式可以为过滤或离心分离。本发明实施例中采用离心分离的方式分离所述反应产物，所述离心分离的转速可为3000r/min~8000r/min。所述分离后的反应产物可进一步进行洗涤。本发明实施例中采用水和无水乙醇分别多次洗涤该反应产物。Further, after the reaction product is obtained by the step S3, the reaction product can be further separated and purified. The manner of separation can be filtration or centrifugation. In the embodiment of the present invention, the reaction product is separated by centrifugal separation, and the rotational speed of the centrifugal separation may be 3000r/min to 8000r/min. The separated reaction product can be further washed. In the examples of the present invention, the reaction product is washed several times with water and absolute ethanol, respectively.
所述分离提纯后的反应产物可进一步进行干燥以去除溶剂。该干燥可以是真空抽滤或加热干燥。所述加热干燥的温度可以为60℃~80℃，加热的时间可以为12小时~24小时。The separated and purified reaction product may be further dried to remove the solvent. The drying can be vacuum filtration or heat drying. The heating and drying temperature may be 60 ° C to 80 ° C, and the heating time may be 12 hours to 24 hours.
所述获得的反应产物为粉末状，该反应产物为由一维纳米四氧化三铁颗粒组装而成的四氧化三铁空心球，其中该空心球的直径为3微米至4微米，该空心球空心部分的直径为1.5微米左右。该四氧化三铁空心球表面粗糙且分布着大量的空隙，具有轻质、高比表面积、高强度和耐热耐腐蚀等优点。The obtained reaction product is in the form of a powder, and the reaction product is a triiron tetroxide hollow sphere assembled from one-dimensional nano-iron tetraoxide particles, wherein the hollow sphere has a diameter of 3 micrometers to 4 micrometers, and the hollow sphere The hollow portion has a diameter of about 1.5 microns. The ferroferric oxide hollow sphere has a rough surface and a large number of voids, and has the advantages of light weight, high specific surface area, high strength, heat resistance and corrosion resistance.
本发明实施例利用水和有机溶剂的混合作为溶剂热反应介质，并采用糖类作为还原剂，可制备出单分散、物相均匀、纯度高的四氧化三铁空心球结构，该四氧化三铁空心球由一维纳米颗粒组装而成。此外，该制备工艺简单，原料来源广泛，无需添加任何分散剂和表面活性剂，制备获得的四氧化三铁空心球结构形貌可控、易于产业化生产。In the embodiment of the present invention, a mixture of water and an organic solvent is used as a solvothermal reaction medium, and a saccharide is used as a reducing agent to prepare a triiron tetroxide hollow sphere structure having a monodisperse, a uniform phase and a high purity. Iron hollow spheres are assembled from one-dimensional nanoparticles. In addition, the preparation process is simple, the raw materials are widely used, and no dispersant and surfactant are added, and the prepared ferroferric oxide hollow sphere has a controllable structure and is easy to be industrialized.
实施例1Example 1
量取25ml的蒸馏水和10ml的异丁醇混合均匀，然后加入5mmol的三氯化铁，在400r/min的搅拌速度下，机械搅拌1小时，得到均匀的三氯化铁溶液。称取0.5mmol的葡萄糖，溶解到所述三氯化铁溶液中，以400r/min的搅拌速度，搅拌1小时，得到所述第二混合溶液。将该第二混合溶液转移到具有聚四氟乙烯内衬的高压反应釜中，恒温190℃，反应20小时，然后自然冷却到室温得到所述反应产物。将该反应产物在5000r/min中的条件下离心分离，然后用蒸馏水和无水乙醇各洗涤5次，置于干燥箱中，80℃条件下干燥20小时得到四氧化三铁纳米材料。请参阅图1，从所述四氧化三铁纳米材料的扫描电镜照片中可以看出，四氧化三铁为空心球结构，该空心球的直径为3微米至4微米，空心部分为1.5微米左右。25 ml of distilled water and 10 ml of isobutanol were uniformly mixed, and then 5 mmol of ferric chloride was added, and mechanical stirring was carried out for 1 hour at a stirring speed of 400 r/min to obtain a uniform ferric chloride solution. 0.5 mmol of glucose was weighed, dissolved in the ferric chloride solution, and stirred at a stirring speed of 400 r/min for 1 hour to obtain the second mixed solution. The second mixed solution was transferred to an autoclave having a polytetrafluoroethylene liner, and the reaction product was obtained by keeping the temperature at 190 ° C for 20 hours and then naturally cooling to room temperature. The reaction product was centrifuged under conditions of 5000 r/min, and then washed 5 times with distilled water and absolute ethanol, placed in a dry box, and dried at 80 ° C for 20 hours to obtain a ferroferric oxide nanomaterial. Referring to FIG. 1 , it can be seen from the scanning electron micrograph of the ferroferric oxide nano material that the ferroferric oxide is a hollow sphere structure having a diameter of 3 micrometers to 4 micrometers and a hollow portion of about 1.5 micrometers. .
另外，本领域技术人员还可在本发明精神内做其他变化，当然，这些依据本发明精神所做的变化，都应包含在本发明所要求保护的范围之内。In addition, those skilled in the art can make other changes in the spirit of the present invention. Of course, the changes made in accordance with the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
- 一种四氧化三铁空心球的制备方法，包括以下步骤：A preparation method of a ferroferric oxide hollow sphere, comprising the following steps:将三价铁源在一溶剂热反应介质中混合并溶解形成一第一混合溶液，该溶剂热反应介质包括水和有机溶剂；Mixing and dissolving the ferric iron source in a solvothermal reaction medium to form a first mixed solution, the solvothermal reaction medium comprising water and an organic solvent;将糖类还原剂加入到该第一混合溶液中混合并溶解形成一第二混合溶液，以及Adding a saccharide reducing agent to the first mixed solution, mixing and dissolving to form a second mixed solution, and将该第二混合溶液进行溶剂热反应，得到反应产物四氧化三铁空心球。The second mixed solution is subjected to a solvothermal reaction to obtain a reaction product of ferroferric oxide hollow spheres.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述三价铁源为氯化铁或硝酸铁。 The method for preparing a ferroferric oxide hollow sphere according to claim 1, wherein the ferric iron source is ferric chloride or ferric nitrate.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述溶剂热反应介质中水和所述有机溶剂的体积比为15:1至1:10。 The method for preparing a ferroferric oxide hollow sphere according to claim 1, wherein a volume ratio of water to the organic solvent in the solvothermal reaction medium is from 15:1 to 1:10.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述有机溶剂与水均匀混合且相互微溶或不溶。 The method for producing a ferroferric oxide hollow sphere according to claim 1, wherein the organic solvent is uniformly mixed with water and slightly soluble or insoluble with each other.
- 如权利要求4所述的四氧化三铁空心球的制备方法，其特征在于，所述有机溶剂为正丁醇、异丁醇、正戊醇、正己醇以及正庚醇中的至少一种。 The method for producing a ferroferric oxide hollow sphere according to claim 4, wherein the organic solvent is at least one of n-butanol, isobutanol, n-pentanol, n-hexanol, and n-heptanol.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，形成所述第一混合溶液的步骤进一步包括： The method for preparing a ferroferric oxide hollow sphere according to claim 1, wherein the step of forming the first mixed solution further comprises:均匀混合所述水和有机溶剂形成所述溶剂热反应介质，以及Uniformly mixing the water and an organic solvent to form the solvothermal reaction medium, and将所述三价铁源加入到该溶剂热反应介质中混合并溶解形成所述第一混合溶液。The ferric iron source is added to the solvothermal reaction medium to be mixed and dissolved to form the first mixed solution.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述糖类还原剂为葡萄糖、乳糖、半乳糖、麦芽糖以及果糖中的至少一种。 The method for producing a ferroferric oxide hollow sphere according to claim 1, wherein the saccharide reducing agent is at least one of glucose, lactose, galactose, maltose, and fructose.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述糖类还原剂与所述三价铁源的摩尔比为1：2~1：200。 The method according to claim 1, wherein the molar ratio of the saccharide reducing agent to the ferric source is 1:2 to 1:200.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述溶剂热反应的温度为120℃至240℃。 The method for producing a ferroferric oxide hollow sphere according to claim 1, wherein the solvothermal reaction temperature is from 120 ° C to 240 ° C.
- 如权利要求1所述的四氧化三铁空心球的制备方法，其特征在于，所述四氧化三铁空心球由一维纳米四氧化三铁颗粒组装而成。 The method for preparing a ferroferric oxide hollow sphere according to claim 1, wherein the ferroferric oxide hollow sphere is assembled from one-dimensional nano-iron tetraoxide particles.
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| CN104876280A (en) * | 2015-04-17 | 2015-09-02 | 济南大学 | Method for preparing ferroferric oxide microspheres by two-phase solvothermal method |
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| CN101698516A (en) * | 2009-11-06 | 2010-04-28 | 南京大学 | Method for preparing hollow spherical ferroferric oxide nano material |
| CN102531070A (en) * | 2011-12-30 | 2012-07-04 | 郑州轻工业学院 | Co3O4 nanometer material for supercapacitor and preparation method thereof |
| CN103035907A (en) * | 2012-12-08 | 2013-04-10 | 浙江工业大学 | Carbon-coated hollow ferriferrous oxide and application thereof |
| CN104098144A (en) * | 2014-06-27 | 2014-10-15 | 江苏华东锂电技术研究院有限公司 | Preparation method for ferroferric oxide hollow balls |
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| CN101698516A (en) * | 2009-11-06 | 2010-04-28 | 南京大学 | Method for preparing hollow spherical ferroferric oxide nano material |
| CN102531070A (en) * | 2011-12-30 | 2012-07-04 | 郑州轻工业学院 | Co3O4 nanometer material for supercapacitor and preparation method thereof |
| CN103035907A (en) * | 2012-12-08 | 2013-04-10 | 浙江工业大学 | Carbon-coated hollow ferriferrous oxide and application thereof |
| CN104098144A (en) * | 2014-06-27 | 2014-10-15 | 江苏华东锂电技术研究院有限公司 | Preparation method for ferroferric oxide hollow balls |
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