CN106629863B - A kind of porous iron oxide micro-nano ball and preparation method thereof - Google Patents
A kind of porous iron oxide micro-nano ball and preparation method thereof Download PDFInfo
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- CN106629863B CN106629863B CN201611262554.4A CN201611262554A CN106629863B CN 106629863 B CN106629863 B CN 106629863B CN 201611262554 A CN201611262554 A CN 201611262554A CN 106629863 B CN106629863 B CN 106629863B
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 239000011807 nanoball Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000002105 nanoparticle Substances 0.000 claims abstract description 31
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 24
- 229910052742 iron Inorganic materials 0.000 claims abstract description 22
- 239000000084 colloidal system Substances 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 9
- 238000002425 crystallisation Methods 0.000 claims abstract description 8
- 230000008025 crystallization Effects 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 18
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 17
- 238000005119 centrifugation Methods 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 15
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 235000013339 cereals Nutrition 0.000 claims description 13
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 12
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 12
- 229940040526 anhydrous sodium acetate Drugs 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims description 7
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 7
- 229940059939 kayexalate Drugs 0.000 claims description 7
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 5
- 229910052709 silver Inorganic materials 0.000 claims description 5
- 239000004332 silver Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical class CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkyl tributyl ammonium bromides Chemical class 0.000 claims description 4
- RLGQACBPNDBWTB-UHFFFAOYSA-N cetyltrimethylammonium ion Chemical compound CCCCCCCCCCCCCCCC[N+](C)(C)C RLGQACBPNDBWTB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- FIUXEBBRCRBWTE-UHFFFAOYSA-M hexadecyl(tripropyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CCC)(CCC)CCC FIUXEBBRCRBWTE-UHFFFAOYSA-M 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002077 nanosphere Substances 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- 239000010695 polyglycol Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- HNJXPTMEWIVQQM-UHFFFAOYSA-M triethyl(hexadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](CC)(CC)CC HNJXPTMEWIVQQM-UHFFFAOYSA-M 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000011805 ball Substances 0.000 claims description 2
- 239000003093 cationic surfactant Substances 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 1
- 239000006193 liquid solution Substances 0.000 claims 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N propane-1,3-diol Chemical class OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims 1
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 21
- 239000000463 material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000003519 biomedical and dental material Substances 0.000 abstract description 2
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 35
- 238000010792 warming Methods 0.000 description 14
- 239000012298 atmosphere Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 235000011091 sodium acetates Nutrition 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- FMBHCBGNBUNBCM-UHFFFAOYSA-N CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC.N Chemical compound CCCCCCCCCCCCCCCC[P+](CCCC)(CCCC)CCCC.N FMBHCBGNBUNBCM-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229940068984 polyvinyl alcohol Drugs 0.000 description 2
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- AJXBTRZGLDTSST-UHFFFAOYSA-N amino 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)ON AJXBTRZGLDTSST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229910003145 α-Fe2O3 Inorganic materials 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
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]
-
- 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
- C01G49/06—Ferric oxide [Fe2O3]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of porous iron oxide micro-nano ball of the present invention and preparation method thereof, the special template agent obtained is difficult to independent of expensive, the complexity proportioning independent of expensive solvent；Therefore template agent removing need not be removed, and porous iron oxide micro-nano ball of the diameter between 20 to 800 nanometers is directly obtained by one-step method, it is not only simple and efficient to handle, prepared suitable for large-scale production, obtained porous iron oxide micro-nano ball is adapted as catalysis material, Industrial Catalysis material, biomedical material, lithium ion battery material.By the way that the raw material including source of iron, sacrifice agent, reducing agent and solvent are configured into precursor liquid by a certain percentage during one-step method；Precursor liquid is granulated by solvent thermal reaction, obtains different crystallization degrees, out of phase iron oxide micro-nano ball.By adjusting the addition of sacrifice agent nanoparticle colloid solution, the porous iron oxide micro-nano ball of different surface morphology can be obtained.
Description
Technical field
The present invention relates to technical field of function materials, specially a kind of porous iron oxide micro-nano ball and its preparation side
Method.
Background technology
Abundance of the ferro element in the earth's crust comes first five position in all elements, thus iron oxide is cheap.
Meanwhile the species of iron oxide is enriched, wherein common iron oxide includes Fe3O4、γ-Fe2O3With α-Fe2O3, and have
The features such as having stability high and be environment-friendly.Therefore, iron oxide is shown in catalysis, lithium ion battery and biologic applications
Huge application prospect.Porous iron oxide can have magnetic and high specific surface area simultaneously, and both properties are dirty
The degraded of dye thing, adsorbing separation, catalysis, biology carry two kinds of properties that the application such as medicine is strongly pursued.Therefore, develop easy, quick, honest and clean
Valency, the method for extensive synthesis iron oxide are always an important goal of domestic and international researcher.
At present, the method for preparing porous iron oxide mainly has two classes, soft template method and hard template method.In soft template method
In, using polymer molecule or surfactant small molecule as template, it can surround template molecule nucleation using source of iron and grow up, from
And template molecule can be included in the iron oxide micro nano structure formed, further remove template molecule and obtain porous iron oxidation
Compound.Removing the method for template molecule typically has organic solvent to clean and calcines two methods, for polymer molecular template one
As be difficult that the method cleaned by organic matter solvent removes, then must pass through the method removing of calcining.As LongKuai et al. is adopted
Porous iron oxide (Aerosol- is prepared for using the method for ullrasonic spraying by the use of triblock polymer as template
spraydiversemesoporousmetaloxidesfrommetalnitrates,Sci.Rep.2015,5:9923.), the party
Micro nano structure prepared by method needs subsequent high temperature calcining to remove polymer molecule and form porous iron oxide, is forging
Area carbon is may result in during burning, it is unfavorable to follow-up application.In hard template method, template is generally porous material,
Need first to put into source of iron in the hole of template, then reaction forms iron oxide, finally optionally removes template.Obtain
Porous iron oxide is, it is necessary to which the hole in hard template is cross-linked with each other, and otherwise after template is removed, iron oxide will be discrete,
And porous material can not be formed.In addition, hard template method is difficult to prepare aperture in mesoporous following porous iron oxide.Can be with
Find out, either soft template or hard template method, be required for follow-up processing to remove template, can just access porous iron oxidation and close
Thing.
The content of the invention
For problems of the prior art, the present invention provides a kind of porous iron oxide micro-nano ball and its preparation
Method, independent of special template agent, it is not necessary to remove template agent removing, one-step method obtains porous iron oxide micro-nano ball, behaviour
Make it is simple and efficient, suitable for large-scale production prepare porous iron oxide micro-nano ball.
The present invention is to be achieved through the following technical solutions：
A kind of preparation method of porous iron oxide micro-nano ball, comprises the following steps：
Step 1, the sacrifice agent nanoparticle colloid solution that can disperse in alcohol is prepared；At ambient temperature, to concentration
For 0.01~100nM using cetyltrimethyl ammonium quasi-molecule as the sacrifice agent nanoparticle colloid solution of surfactant in add etc.
The polymer solution that volume and concentration are 1~10mM, resulting solution is stirred at room temperature 5~14 hours, and supernatant is removed in centrifugation,
Obtain the sacrifice agent nanoparticle colloid solution that can disperse in alcohol；
Step 2, iron oxide precursor solution is prepared；By source of iron, polyalcohol, anhydrous sodium acetate and sacrifice agent nanometer
Grain colloidal solution is configured to precursor liquid, and configuration proportion is source of iron：Anhydrous sodium acetate：Polyalcohol：Sacrifice agent nano-particle colloid is molten
Liquid=(1~10mmol)：(7~50mmol)：(700~750mmol)：(1~100 × 10-6Mmol), persistently stir at normal temperatures
Obtain iron oxide precursor solution within 5~15 minutes；
Step 3, porous ferroferric oxide micro-nano ball is prepared；Above-mentioned iron oxide precursor solution is subjected to solvent heat
Reaction, heating rate be 0.1~5 DEG C/min, and solvent thermal reaction temperature is 180~200 DEG C, the solvent thermal reaction time for 4~
24h, reaction mixture is then naturally cooled into room temperature；Black precipitate is collected, and is repeatedly washed with detergent, by black precipitate
1~24h is dried in vacuo at 25~80 DEG C, to obtain the porous ferroferric oxide micro-nano ball of different crystallization degrees.
Preferably, in addition to step 4, porous di-iron trioxide micro-nano ball is prepared：Porous four oxidation that step 3 is obtained
Three-iron micro-nano ball is calcined, and heating rate is 0.1~5 DEG C/min, and calcining heat is 200~900 DEG C, calcination time 1
~9 hours, to obtain the porous di-iron trioxide micro-nano ball of different crystallization degrees.
Preferably, in the step 1, the nano particle in sacrifice agent nanoparticle colloid solution is gold nano grain, silver
At least one of nano particle, copper nano particles and palladium nano-particles.
Preferably, the cetyltrimethyl ammonium quasi-molecule as cationic surfactant includes cetyl trimethyl bromination
Ammonium, cetyltriethylammonium bromide, cetyl tripropyl ammonium bromide or hexadecyl tributyl phosphonium ammonium, cetyl three
Ammonio methacrylate.
Preferably, in the step 1, polymer is in mercapto-polyglycol, kayexalate and polyvinyl alcohol
Any one.
Preferably, in the step 2, source of iron is ferric chloride (FeCl36H2O) or nine water ferric nitrates or mol ratio 1:3 iron oxide
With the mixture of concentrated nitric acid.
Preferably, in the step 2,
After first source of iron is dissolved completely in polyalcohol, anhydrous sodium acetate is added；
Or after anhydrous sodium acetate is dissolved completely in polyalcohol, add source of iron；
After source of iron, polyalcohol and anhydrous sodium acetate are sufficiently mixed uniformly, it is molten to be eventually adding sacrifice agent nano-particle colloid
Liquid is sufficiently mixed uniformly.
Preferably, in the step 2, polyalcohol is appointing in ethylene glycol, glycerine, 1,3-PD and 1,2-PD
Meaning is a kind of.
Preferably, in the step 3, detergent includes at least one of deionized water, absolute ethyl alcohol and 95% ethanol.
A kind of porous iron oxide micro-nano ball obtained by preparation method of the present invention of the present invention.
Compared with prior art, the present invention has technique effect beneficial below：
The present invention is difficult to the special template agent obtained independent of expensive, and the complexity independent of expensive solvent is matched somebody with somebody
Than；Therefore template agent removing need not be removed, and porous iron of the diameter between 20 to 800 nanometers is directly obtained by one-step method and aoxidized
Compound micro-nano ball, it is not only simple and efficient to handle, prepared suitable for large-scale production, obtained porous iron oxide micro-nano ball
It is adapted as catalysis material, Industrial Catalysis material, biomedical material, lithium ion battery material.Pass through during one-step method
Raw material including source of iron, sacrifice agent, reducing agent and solvent are configured to precursor liquid by a certain percentage；Precursor liquid is passed through into solvent
Thermal response is granulated, and obtains different crystallization degrees, out of phase iron oxide micro-nano ball.By adjusting sacrifice agent nano particle
The addition of colloidal solution, the porous iron oxide micro-nano ball of different surface morphology can be obtained.
Further, by adjusting calcination condition, by different crystallization degrees, out of phase iron oxide micro-nano ball powder
End is calcined at high temperature, to obtain the iron oxide micro-nano ball of different crystallization degrees, different phases and different valence state.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of porous iron oxide micro-nano ball prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of porous iron oxide micro-nano ball prepared by the embodiment of the present invention 1.
Fig. 3 is the scanning electron microscope (SEM) photograph of porous iron oxide micro-nano ball prepared by the embodiment of the present invention 2.
Fig. 4 is the transmission electron microscope picture of porous iron oxide micro-nano ball prepared by the embodiment of the present invention 2.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, it is described be explanation of the invention and
It is not to limit.Purpose be in order to which the public is better understood from described technology, with identical or approximate principle to the porous iron
The improvement that oxygen compound micro-nano ball and preparation method thereof is carried out, include the replacement of effect identical reagent, and to preparing work
The improvement that skill is carried out, all within the present patent application technical scheme claimed.
Embodiment 1
1) gold nano using cetyl trimethylammonium bromide molecule as surfactant for being 10nM to 100mL concentration
The kayexalate solution that isometric and concentration is 2mM is added in grain colloidal solution, it is small that resulting solution is stirred at room temperature 8
When, supernatant is removed in centrifugation, obtains the gold nano-particle colloid solution disperseed in alcohol；
2) 5mmol ferric chloride (FeCl36H2O)s, 35mmol anhydrous sodium acetates and 720mmol ethylene glycol are well mixed, thereto
Add above-mentioned gold nano grain 10 × 10-6Mmol is sufficiently mixed uniformly.Then the solution of acquisition is transferred to 50mL polytetrafluoroethyl-nes
The stainless steel cauldron of alkene liner, 200 DEG C are warming up to the 3 DEG C/min rate of heat addition, heat 6 hours, then by reactor from
So it is cooled to room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully eluted with absolute ethyl alcohol, it is true at subsequent 60 DEG C
Sky is dried 24 hours, and to obtain the porous ferroferric oxide micro-nano ball that rough surface is fine and close and surface texture is regular, it is swept
Electron microscope is retouched as shown in figure 1, transmission electron microscope picture is as shown in Figure 2.
Embodiment 2
Except the gold nano grain for adding the addition in step 2 is 40 × 10 in the present embodiment-6Outside mmol, remaining step and reality
Apply that example 1 is identical, obtain that surface is smooth and the porous ferroferric oxide micro-nano ball to cave in, its ESEM occurs in surface texture
Figure is as shown in figure 3, transmission electron microscope picture is as shown in Figure 4.
Embodiment 3
1) gold nano using cetyltriethylammonium bromide molecule as surfactant for being 100nM to 50mL concentration
The mercapto-polyglycol solution that isometric and concentration is 10mM is added in grain colloidal solution, it is small that resulting solution is stirred at room temperature 10
When, supernatant is removed in centrifugation, obtains the gold nano-particle colloid solution disperseed in alcohol；
2) the water ferric nitrates of 2mmol nine, 45mmol anhydrous sodium acetates and 750mmol ethylene glycol are well mixed, added thereto
Enter above-mentioned gold nano grain 20 × 10-6Mmol is sufficiently mixed uniformly.Then the solution of acquisition is transferred to 50mL polytetrafluoroethylene (PTFE)
The stainless steel cauldron of liner, 180 DEG C are warming up to the 3 DEG C/min rate of heat addition, heated 15 hours, it is then that reactor is natural
It is cooled to room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully cleaned with deionized water, then at 80 DEG C
Vacuum drying 10 hours；
4) by the product after vacuum drying, 900 DEG C is warming up to 5 DEG C/min heating rate, calcines 6 in air atmosphere
Hour, then it is naturally cooling to room temperature and obtains porous α-di-iron trioxide micro-nano that rough surface is fine and close and surface texture is regular
Rice ball.
Embodiment 4
First three steps and embodiment 3 are identical in the present embodiment, by obtained product with 5 DEG C/min heating in the 3rd step
Speed is warming up to 200 DEG C, calcines 3 hours in air atmosphere, is then naturally cooling to room temperature, obtains the oxidation of porous gamma-three two
Iron micro-nano ball.
Embodiment 5
1) the palladium nanometer using hexadecyltrimethylammonium chloride molecule as surfactant for being 30nM to 30mL concentration
The kayexalate solution that isometric and concentration is 2mM is added in grain colloidal solution, it is small that resulting solution is stirred at room temperature 5
When, supernatant is removed in centrifugation, obtains the palladium nano-particles colloidal solution disperseed in alcohol；
2) 8mmol ferric chloride (FeCl36H2O)s, 10mmol anhydrous sodium acetates and 700mmol glycerine are well mixed, thereto
Add above-mentioned palladium nano-particles 60 × 10-6Mmol is sufficiently mixed uniformly.Then the solution of acquisition is transferred to 50mL polytetrafluoroethyl-nes
The stainless steel cauldron of alkene liner, 190 DEG C are warming up to the 1 DEG C/min rate of heat addition, heat 15 hours, then by reactor from
So it is cooled to room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully eluted with absolute ethyl alcohol, it is true at subsequent 60 DEG C
Sky is dried 4 hours；
4) by the product after vacuum drying, 300 DEG C is warming up to 5 DEG C/min heating rate, calcines 3 in air atmosphere
Hour, obtain porous gamma-di-iron trioxide micro-nano ball.
Embodiment 6
1) the copper nanometer using cetyl trimethylammonium bromide molecule as surfactant for being 40nM to 70mL concentration
The kayexalate solution that isometric and concentration is 8mM is added in grain colloidal solution, it is small that resulting solution is stirred at room temperature 5
When, supernatant is removed in centrifugation, obtains the copper nano particles colloidal solution disperseed in alcohol；
2) 10mmol ferric chloride (FeCl36H2O)s, 40mmol anhydrous sodium acetates and 730mmol 1,3-PDs are well mixed,
Above-mentioned palladium nano-particles 50 × 10 are added thereto-6Mmol is sufficiently mixed uniformly.Then the solution of acquisition is transferred into 50mL to gather
The stainless steel cauldron of tetrafluoroethene liner, 200 DEG C are warming up to the 5 DEG C/min rate of heat addition, is heated 15 hours, then will be anti-
Kettle is answered to naturally cool to room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully eluted with deionized water, it is true at subsequent 60 DEG C
Sky is dried 4 hours；
4) by the product after vacuum drying, 850 DEG C is warming up to 5 DEG C/min heating rate, calcines 8 in air atmosphere
Hour, to obtain porous α-di-iron trioxide micro-nano ball.
Embodiment 7
1) silver nanoparticle using cetyl trimethylammonium bromide molecule as surfactant for being 0.01nM to 100mL concentration
The kayexalate solution that isometric and concentration is 1mM is added in particle colloid solution, resulting solution is stirred at room temperature 5
Hour, supernatant is removed in centrifugation, obtains the silver nano-grain colloidal solution disperseed in alcohol；
2) 1mmol ferric chloride (FeCl36H2O)s, 7mmol anhydrous sodium acetates and 710mmol ethylene glycol are well mixed, added thereto
Enter above-mentioned silver nano-grain 1 × 10-6Mmol is sufficiently mixed uniformly.Then the solution of acquisition is transferred in 50mL polytetrafluoroethylene (PTFE)
The stainless steel cauldron of lining, 185 DEG C are warming up to the 0.1 DEG C/min rate of heat addition, heated 4 hours, it is then that reactor is natural
It is cooled to room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully eluted with absolute ethyl alcohol, it is true at subsequent 50 DEG C
Sky is dried 12 hours, to obtain the porous ferroferric oxide micro-nano ball that rough surface is fine and close and surface texture is regular.
Embodiment 8
First three steps and embodiment 7 are identical in the present embodiment, by obtained product with 0.1 DEG C/min liter in the 3rd step
Warm speed is warming up to 400 DEG C, calcines 1 hour in air atmosphere, is then naturally cooling to room temperature, obtains porous di-iron trioxide
Micro-nano ball.
Embodiment 9
1) gold nano using cetyl tripropyl ammonium bromide molecule as surfactant for being 50nM to 100mL concentration
The poly-vinyl alcohol solution that isometric and concentration is 5mM is added in grain colloidal solution, resulting solution is stirred at room temperature 10 hours, from
The heart removes supernatant, obtains the gold nano-particle colloid solution disperseed in alcohol；
2) it is the 1,2- mixed with propylene glycol of 3mmol ferric chloride (FeCl36H2O), 50mmol anhydrous sodium acetate and 730mmol is equal
It is even, above-mentioned gold nano grain 40 × 10 is added thereto-6Mmol is sufficiently mixed uniformly.Then the solution of acquisition is transferred to 50mL
The stainless steel cauldron of polytetrafluoroethyllining lining, 200 DEG C are warming up to the 2 DEG C/min rate of heat addition, is heated 24 hours, then will
Reactor naturally cools to room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully eluted with 95% ethanol, it is true at subsequent 80 DEG C
Sky is dried 1 hour, to obtain the porous ferroferric oxide micro-nano ball that rough surface is fine and close and surface texture is regular.
Embodiment 10
First three steps and embodiment 9 are identical in the present embodiment, by obtained product with 2 DEG C/min heating in the 3rd step
Speed is warming up to 500 DEG C, calcines 9 hours in air atmosphere, is then naturally cooling to room temperature, it is micro- to obtain porous di-iron trioxide
Nanosphere.
Embodiment 11
1) gold nano using hexadecyl tributyl phosphonium ammonium molecule as surfactant for being 100nM to 100mL concentration
The kayexalate solution that isometric and concentration is 10mM is added in particle colloid solution, resulting solution is stirred at room temperature
14 hours, supernatant was removed in centrifugation, obtained the gold nano-particle colloid solution disperseed in alcohol；
2) by 6mmol mol ratios 1:The 3 iron oxide and mixture of concentrated nitric acid, 15mmol anhydrous sodium acetates and 740mmol
Ethylene glycol is well mixed, and adds above-mentioned gold nano grain 80 × 10 thereto-6Mmol is sufficiently mixed uniformly.Then by the molten of acquisition
Liquid is transferred to the stainless steel cauldron of 50mL polytetrafluoroethyllining linings, is warming up to 195 DEG C with the 4 DEG C/min rate of heat addition, heating
12 hours, reactor is then naturally cooled into room temperature；
3) black precipitate in above-mentioned reaction product is collected by centrifugation, and is fully eluted with absolute ethyl alcohol, it is true at subsequent 25 DEG C
Sky is dried 24 hours, to obtain the porous ferroferric oxide micro-nano ball that rough surface is fine and close and surface texture is regular.
Embodiment 12
First three steps and embodiment 12 are identical in the present embodiment, by obtained product with 4 DEG C/min heating in the 3rd step
Speed is warming up to 600 DEG C, calcines 5 hours in air atmosphere, is then naturally cooling to room temperature, it is micro- to obtain porous di-iron trioxide
Nanosphere.
Claims (7)
1. a kind of preparation method of porous iron oxide micro-nano ball, it is characterised in that comprise the following steps：
Step 1, the sacrifice agent nanoparticle colloid solution that can disperse in alcohol is prepared；At ambient temperature, it is to concentration
0.01~100nM using cetyltrimethyl ammonium quasi-molecule as the sacrifice agent nanoparticle colloid solution of surfactant in add etc. body
The polymer solution that product and concentration are 1~10mM, resulting solution is stirred at room temperature 5~14 hours, and supernatant is removed in centrifugation, obtains
To the sacrifice agent nanoparticle colloid solution that can disperse in alcohol；
Nano particle in sacrifice agent nanoparticle colloid solution is gold nano grain, silver nano-grain, copper nano particles and palladium
At least one of nano particle；
Polymer is any one in mercapto-polyglycol, kayexalate and polyvinyl alcohol；
Step 2, iron oxide precursor solution is prepared；By source of iron, polyalcohol, anhydrous sodium acetate and sacrifice agent nano particle glue
Liquid solution is configured to precursor liquid, and configuration proportion is source of iron：Anhydrous sodium acetate：Polyalcohol：Sacrifice agent nanoparticle colloid solution=
(1~10mmol)：(7~50mmol)：(700~750mmol)：(1~100 × 10-6Mmol), at normal temperatures persistently stirring 5~
Obtain iron oxide precursor solution within 15 minutes；
Step 3, porous ferroferric oxide micro-nano ball is prepared；It is anti-that above-mentioned iron oxide precursor solution is subjected to solvent heat
Should, heating rate is 0.1~5 DEG C/min, and solvent thermal reaction temperature is 180~200 DEG C, and the solvent thermal reaction time is 4~24h,
Reaction mixture is then naturally cooled into room temperature；Black precipitate is collected, and is repeatedly washed with detergent, by black precipitate 25
1~24h is dried in vacuo at~80 DEG C, to obtain the porous ferroferric oxide micro-nano ball of different crystallization degrees.
2. preparation method according to claim 1, it is characterised in that：Also include step 4, it is micro- to prepare porous di-iron trioxide
Nanosphere：The porous ferroferric oxide micro-nano ball that step 3 obtains is calcined, heating rate is 0.1~5 DEG C/min, is forged
It is 200~900 DEG C to burn temperature, and calcination time is 1~9 hour, to obtain the porous di-iron trioxide micro-nano of different crystallization degrees
Rice ball.
3. preparation method according to claim 1, it is characterised in that：Cetyltrimethyl ammonium as cationic surfactant
Quasi-molecule includes cetyl trimethylammonium bromide, cetyltriethylammonium bromide, cetyl tripropyl ammonium bromide or ten
Six alkyl tributyl ammonium bromides, hexadecyltrimethylammonium chloride.
4. preparation method according to claim 1, it is characterised in that：In the step 2, source of iron be ferric chloride (FeCl36H2O) or
Nine water ferric nitrates or mol ratio 1:3 iron oxide and the mixture of concentrated nitric acid.
5. preparation method according to claim 1, it is characterised in that：In the step 2,
After first source of iron is dissolved completely in polyalcohol, anhydrous sodium acetate is added；
Or after anhydrous sodium acetate is dissolved completely in polyalcohol, add source of iron；
After source of iron, polyalcohol and anhydrous sodium acetate are sufficiently mixed uniformly, it is eventually adding sacrifice agent nanoparticle colloid solution and fills
Divide well mixed.
6. preparation method according to claim 1, it is characterised in that：In the step 2, polyalcohol is ethylene glycol, the third three
Any one in alcohol, 1,3- propane diols and 1,2- propane diols.
7. preparation method according to claim 1, it is characterised in that：In the step 3, detergent include deionized water,
At least one of absolute ethyl alcohol and 95% ethanol.
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| CN109368706B (en) * | 2018-08-29 | 2021-04-02 | 中国科学院合肥物质科学研究院 | Pd-modified three-dimensional hierarchical porous alpha-Fe2O3Material, preparation method and application thereof |
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