CN105664950B - A kind of porous nano ZnFe2O4Preparation method - Google Patents
A kind of porous nano ZnFe2O4Preparation method Download PDFInfo
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- CN105664950B CN105664950B CN201610008270.6A CN201610008270A CN105664950B CN 105664950 B CN105664950 B CN 105664950B CN 201610008270 A CN201610008270 A CN 201610008270A CN 105664950 B CN105664950 B CN 105664950B
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims abstract description 18
- 238000000227 grinding Methods 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 10
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- -1 isopropyl ester Chemical class 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 5
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 5
- WHRBSMVATPCWLU-UHFFFAOYSA-K iron(3+);triformate Chemical compound [Fe+3].[O-]C=O.[O-]C=O.[O-]C=O WHRBSMVATPCWLU-UHFFFAOYSA-K 0.000 claims description 5
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 5
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 241000723346 Cinnamomum camphora Species 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 4
- 150000004056 anthraquinones Chemical class 0.000 claims description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 4
- 229960000846 camphor Drugs 0.000 claims description 4
- 229930008380 camphor Natural products 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229940102001 zinc bromide Drugs 0.000 claims description 4
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 0.000 claims description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- KBPZVLXARDTGGD-UHFFFAOYSA-N 2,3-dihydroxybutanedioic acid;iron Chemical compound [Fe].OC(=O)C(O)C(O)C(O)=O KBPZVLXARDTGGD-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical group CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000877 Melamine resin Polymers 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- 239000000908 ammonium hydroxide Substances 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 claims description 2
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 239000012266 salt solution Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 6
- 229960001763 zinc sulfate Drugs 0.000 description 6
- 229910000368 zinc sulfate Inorganic materials 0.000 description 6
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001172 regenerating effect Effects 0.000 description 3
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000002563 ionic surfactant Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000004530 micro-emulsion Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Inorganic materials [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 1
- 239000012761 high-performance material Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 229940011051 isopropyl acetate Drugs 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B01J35/39—
-
- B01J35/60—
Abstract
The invention discloses a kind of porous nano ZnFe2O4Preparation method, this method mixes molysite, zinc salt with deionized water, stirring and dissolving obtains the mixed solution of molysite and zinc salt, alkali is mixed with deionized water, stirring and dissolving obtains aqueous slkali, the mixed solution of molysite and zinc salt is added dropwise in aqueous slkali under stirring, to the reaction was complete, product is washed and is centrifugally separating to obtain ZnFe for stirring after dripping2O4Colloidal sol；By ZnFe2O4Colloidal sol is mixed with deionized water, after being disperseed with ultrasonic wave, add organic solvent and sublimable compound template, by the hot method of aqueous organic solvent mixed solvent after the reaction was complete, product is through being distilled off mixed solvent, fired again, cooling, grinding, washing, filtering, dry and grinding technics process, that is, obtain porous nano ZnFe2O4Powder.This method is simple for process, and investment is small, is conducive to promote and apply.
Description
Technical field
The present invention relates to a kind of porous nano ZnFe2O4Preparation method, belong to field of photocatalytic material.
Background technology
With the quickening of process of industrialization, energy crisis and environmental crisis getting worse, the exploitation of renewable new energy is standby
It is concerned.Solar energy is inexhaustible, nexhaustible, pollution-free, cheap, world community can as a kind of clean energy resource
The energy freely utilized peacefully, and various regenerative resources for example biomass energy, wind energy, ocean energy, water can etc. other energy it
This.National governments all attach great importance to the exploitation of regenerative resource, and regenerative resource is the hot research field that various countries invest energetically.
Photochemical catalyst is the semi-conducting material of a kind of utilization solar energy indispensability.At present, by scientists study
Semiconductor light-catalyst species is various, such as TiO2、CdS、SrTiO3、RuO2, ZnO and Fe2O3Deng.ZnFe2O4Partly led as one kind
Body photochemical catalyst, has the characteristics that good stability, indissoluble, environmental-friendly, band gap is narrow, aboundresources and application cost are low, especially
When being with other semiconductors couplings, photocatalytic activity can be effectively improved, is one of the photochemical catalyst that application prospect is had an optimistic view of.
The structure of material and performance are closely related, structures shape performance, and the controllable preparation of material structure is material science neck
The hot research direction in domain, is the important means for preparing high performance material.Grinding on nano material controllable method for preparing at present
It is many to study carefully report.Since Penner in 1987 et al. proposes the template synthesis method of nano material, template is because having work
Skill is simple and convenient to operate, low power consumption and other advantages, is had received widespread attention.Using template, by varying template diameter and
Other technological parameters can obtain the controllable nano material of shapes and sizes.Nanocrystalline, nano thin-film is had been used at present, is partly led
The preparation of the materials such as body, nanotube and nano wire, has consequence in field of nano material preparation, becomes preparation high-performance
The important means of nano material.
ZnFe2O4Nanosizing and porous are to improve ZnFe2O4One of effective ways of photocatalysis efficiency.Prepare porous receive
Rice ZnFe2O4Can use template, template mainly have microemulsion template, emulsion template, ionic surfactant template, it is non-from
Subtype surfactant templates, block copolymer template, composition template (such as polyoxyethylene lauryl ether and polyethylene glycol)
With monodisperse polymer particles template etc..Pass through solgel reaction, ZnFe2O4Colloidal sol forms bone with secondary bond and template action
Frame structure, then takes solvent extraction or high-temperature roasting method to remove template, so as to obtain the hole suitable with template size.But
It is to prepare porous nano ZnFe using above-mentioned traditional template2O4When, template is either removed using roasting method or extraction
All there are major defect.When roasting method removes template, since the temperature of template to be eliminated is high, caving in for duct can be caused, makes system
Into porous nano ZnFe2O4Semiconductor light-catalyst surface defect is too many, becomes the complex centre of electron-hole, reduces light and urges
Change efficiency.Extraction rule is difficult to thoroughly eliminate template so that porous nano ZnFe2O4The purity of semiconductor light-catalyst reduces, and leads
Photocatalysis performance is caused to decline.Therefore, how to prepare duct without cave in, surface zero defect, template noresidue and high-specific surface area
Porous nano ZnFe2O4Semiconductor light-catalyst is an important topic.
Easily removed since sublimate easily distils, the present invention is by using the appropriate compound of sublimation temperature
Template prepares ZnFe2O4Colloidal sol, reheating make template distillation removing can be prepared by porous nano ZnFe2O4.With traditional template
Compare, the present invention use sublimate for template can preparation structure is controllable, duct without cave in, surface zero defect, template noresidue and
The big porous nano ZnFe of specific surface area2O4Semiconductor light-catalyst.At present, on being prepared by template of sublimable compound
Porous nano ZnFe2O4The method of semiconductor light-catalyst is there is not yet document report, is porous nano ZnFe2O4Preparation open up
One new way, has an important practical significance.
The content of the invention
A kind of porous nano ZnFe of the present invention2O4Preparation method, there is provided it is a kind of with molysite, zinc salt, alkali, go from
Sub- water is raw material, and ZnFe is prepared by stirring reaction2O4Colloidal sol；ZnFe2O4Colloidal sol is after ultrasonic disperse, by certain ratio
Example adds organic solvent and sublimable compound template, and after the hot method reaction of water-organic solvent mixed solvent, product is through steaming
Distillation removes mixed solvent, heats removing sublimable compound template, cooling, washing, drying and grinding technics process, i.e.,
Obtain porous nano ZnFe2O4。
A kind of porous nano ZnFe of the present invention2O4Preparation method, obtained porous nano ZnFe2O4, can
Light and sunlight are seen under conditions of light source, to can be directly used for photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition,
Also the photochemical catalyst of active higher by the method with other semiconductors couplings, can further be made, in visible ray and sunlight
Under conditions of light source, for photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition；
A kind of porous nano ZnFe of the present invention2O4Preparation method, adopt the following technical scheme that：
1st, it is by the mass percent of molysite, zinc salt, alkali, deionized water, organic solvent and sublimable compound template
(0.001%~70%): (0.00001%~70%): (0.001%~75%): (0.001%~90%): (0.001%~
90%): the ratio of (0.001%~90%), by a meromict of molysite, zinc salt and the total dosage of deionized water, stirring and dissolving obtains
To molysite and the mixed solution of zinc salt, by another meromict of alkali and the total dosage of deionized water, stirring and dissolving obtains aqueous slkali, stirs
The lower mixed solution by molysite and zinc salt is mixed to be added dropwise in aqueous slkali, continue after dripping stirring reaction 1~24h, product pass through from
The heart separates and washing operation and in triplicate, then is centrifugally separating to obtain ZnFe2O4Colloidal sol；By ZnFe2O4Colloidal sol and deionized water
After the ratio mixing that mass ratio is 1: 2~20, disperseed with the ultrasonic wave that frequency is 20KHz~1MHz, power is 30W~15KW
0.1h~24h, adds organic solvent and sublimable compound template, by water-hot method of organic solvent mixed solvent 100
0.5~24h is reacted at~250 DEG C, product heats up after mixed solvent is distilled off by 0.5~3 DEG C per minute of programming rate
To 400~650 DEG C, heat 0.5~24h and remove sublimable compound template, then through cooling down, grinding, washing, filtering,
Dry and grinding technics process, that is, obtain porous nano ZnFe2O4Powder.
2nd, a kind of porous nano ZnFe of the present invention2O4Preparation method, its outstanding feature is：Using traditional
Microemulsion template, emulsion template, ionic surfactant template, nonionic surface active agent template, block copolymer mould
Plate, composition template (such as polyoxyethylene lauryl ether and polyethylene glycol) and monodisperse polymer particles template template, lead to
Crossing solgel reaction makes ZnFe2O4Colloidal sol forms skeleton structure with secondary bond and template action, then take solvent extraction or
When high-temperature roasting method removes template, all there are major defect, duct is such as caused to cave in, surface defect, specific surface area are low and template
The problems such as residual, reduce photocatalysis efficiency；Compared with traditional template, during using sublimate as template, sublimate easily distils and holds
Easily eliminate, therefore, ZnFe is prepared for template by using the appropriate compound of sublimation temperature2O4Colloidal sol, reheats processing and removes liter
Magnificent thing template can be prepared by structure-controllable, duct without cave in, surface zero defect, template noresidue and specific surface area are big porous receives
Rice ZnFe2O4, be conducive to improve photocatalysis efficiency.
3rd, a kind of porous nano ZnFe of the present invention2O4Preparation method, the molysite for reacting used be ferric trichloride,
Any of ferric bromide, ferric sulfate, ferric nitrate, ferric formate, ferric acetate, ironic citrate and tartaric acid iron are a variety of.
4th, a kind of porous nano ZnFe of the present invention2O4Preparation method, the zinc salt for reacting used is zinc chloride, bromine
Change any of zinc, zinc sulfate, zinc nitrate, zinc formate and zinc acetate or a variety of.
5th, a kind of porous nano ZnFe of the present invention2O4Preparation method, the alkali for reacting used is lithium hydroxide, hydrogen
Any of sodium oxide molybdena, potassium hydroxide, ammonium hydroxide and barium hydroxide are a variety of.
6th, a kind of porous nano ZnFe of the present invention2O4Preparation method, react sublimable compound mould used
Plate is in 1,4-benzoquinone, melamine, iodine, hexa, camphor, anthraquinone, naphthalene, anthracene, metaformaldehyde and triethylamine hydrochloride
It is any one or more.
7th, a kind of porous nano ZnFe of the present invention2O4Preparation method, the organic solvent for reacting used be methanol,
Ethanol, isopropanol, ether, isopropyl ether, formic acid, acetic acid, dichloromethane, chloroform, carbon tetrachloride, acetone, cyclohexanone, Methylethyl
Any of ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate are a variety of.
8th, a kind of porous nano ZnFe of the present invention2O4Preparation method, porous nano ZnFe2O4Preparation process
In used ultrasonic disperser frequency be 20KHz~1MHz, power be 30W~15KW.
Embodiment
Here is a kind of porous nano ZnFe of the present invention2O4Preparation method non-limiting example.These examples
Be only given for illustrative purposes, limitation of the invention can not be interpreted as.Because the essence of the present invention is not being departed from
God can carry out many conversion with the basis of scope to the present invention.In these embodiments, unless stated otherwise, it is all
Percentage is all referring to mass percent.
Embodiment 1
Porous nano ZnFe2O4Preparation：
According to above-mentioned mass percent, by ferric trichloride, ferric bromide, zinc sulfate, zinc bromide and the total dosage of deionized water
One meromict, stirring and dissolving obtains the mixed solution of ferric trichloride, ferric bromide, zinc sulfate and zinc bromide, by potassium hydroxide with going
Another meromict of the total dosage of ionized water, stirring and dissolving obtain potassium hydroxide solution, by ferric trichloride, ferric bromide, sulphur under stirring
The mixed solution of sour zinc and zinc bromide is added dropwise in potassium hydroxide solution, continues stirring reaction 1h after dripping, product is through centrifugation
Separation and washing operation and in triplicate, then it is centrifugally separating to obtain ZnFe2O4Colloidal sol；By ZnFe2O4The matter of colloidal sol and deionized water
After amount is than the ratio mixing for 1: 10, disperse 1.5h with the ultrasonic wave that frequency is 28KHz, power is 2KW, add isopropanol, benzene,
After anthraquinone and hexa, 12h is reacted at 150 DEG C by water-hot method of organic solvent mixed solvent, product is removed through distillation
After removing solvent, 500 DEG C are warming up to by 1 DEG C per minute of programming rate, heats 8h at 500 DEG C, removes anthraquinone and six methylenes
After the sublimable compound template of urotropine, then through cooling down, grinding, washing, filtering, dry and grinding technics process, that is, obtain
Porous nano ZnFe2O4Powder.
Embodiment 2
Porous nano ZnFe2O4Preparation：
According to above-mentioned mass percent, by the one of ferric nitrate, ferric formate, zinc chloride and zinc nitrate and the total dosage of deionized water
Meromict, stirring and dissolving obtain the mixed solution of ferric nitrate, ferric formate, zinc chloride and zinc nitrate, by sodium hydroxide and deionization
Another meromict of the total dosage of water, stirring and dissolving obtain sodium hydroxide solution, under stirring by ferric nitrate, ferric formate, zinc chloride and
The mixed solution of zinc nitrate is added dropwise in sodium hydroxide solution, continues stirring reaction 2.5h after dripping, and product is centrifuged
With washing operation and in triplicate, then it is centrifugally separating to obtain ZnFe2O4Colloidal sol；By ZnFe2O4The mass ratio of colloidal sol and deionized water
After 1: 8 ratio mixing, disperse 1.5h with the ultrasonic wave that frequency is 68KHz, power is 3KW, add ethanol, toluene, to benzene
After quinone and camphor, 10h is reacted at 160 DEG C by water-hot method of organic solvent mixed solvent, product after solvent is distilled off,
550 DEG C are warming up to by 0.5 DEG C per minute of programming rate, heats 6h at 550 DEG C, 1,4-benzoquinone is removed and camphor is sublimable
After compound template, then through cooling down, grinding, washing, filtering, dry and grinding technics process, that is, obtain porous nano ZnFe2O4
Powder.
Embodiment 3
Porous nano ZnFe2O4Preparation：
According to above-mentioned mass percent, by ferric sulfate, ironic citrate, zinc chloride and zinc acetate and the total dosage of deionized water
One meromict, stirring and dissolving obtain the mixed solution of ferric sulfate, ironic citrate, zinc chloride and zinc acetate, by lithium hydroxide and hydrogen
Barium monoxide and another meromict of the total dosage of deionized water, stirring and dissolving obtain lithium hydroxide and barium hydroxide mixed solution, stir
Mix the lower mixed solution by ferric sulfate, ironic citrate, zinc chloride and zinc acetate be added dropwise to lithium hydroxide and barium hydroxide mixing it is molten
In liquid, continue stirring reaction 3h after dripping, product is centrifuged with washing operation and in triplicate, then is centrifugally separating to obtain
ZnFe2O4Colloidal sol；By ZnFe2O4With frequency it is 40KHz, work(after the ratio mixing that colloidal sol and the mass ratio of deionized water are 1: 7
The ultrasonic wave that rate is 1.5KW disperses 1.5h, after adding ethyl acetate, methyl ethyl ketone, acetone, naphthalene, metaformaldehyde and anthracene, passes through
Water-hot method of organic solvent mixed solvent reacts 5h at 170 DEG C, and product is after being distilled off solvent, by 1.5 DEG C per minute of liter
Warm speed is warming up to 520 DEG C, heats 7h at 520 DEG C, after removing naphthalene, metaformaldehyde and the sublimable compound template of anthracene,
Again through cooling down, grinding, washing, filtering, dry and grinding technics process, that is, obtain porous nano ZnFe2O4Powder.
Embodiment 4
Porous nano ZnFe2O4Preparation：
According to above-mentioned mass percent, by ferric acetate, ferric trichloride, zinc formate and zinc sulfate and the total dosage of deionized water
One meromict, stirring and dissolving obtains the mixed solution of ferric acetate, ferric trichloride, zinc formate and zinc sulfate, by sodium hydroxide with going
Another meromict of the total dosage of ionized water, stirring and dissolving obtain sodium hydroxide solution, by ferric acetate, ferric trichloride, first under stirring
The mixed solution of sour zinc and zinc sulfate is added dropwise in sodium hydroxide solution, continue after dripping stirring reaction 1.5h, product pass through from
The heart separates and washing operation and in triplicate, then is centrifugally separating to obtain ZnFe2O4Colloidal sol；By ZnFe2O4Colloidal sol and deionized water
After the mixing of ratio that mass ratio is 1: 12, disperse 1.0h with the ultrasonic wave that frequency is 50KHz, power is 2.5KW, add ethanol,
After methyl acetate and anthracene, 5.5h is reacted at 180 DEG C by water-hot method of organic solvent mixed solvent, product is molten through being distilled off
After agent, 560 DEG C are warming up to by 2 DEG C per minute of programming rate, heats 6h at 560 DEG C, removes the sublimable compound of anthracene
After template, then through cooling down, grinding, washing, filtering, dry and grinding technics process, that is, obtain porous nano ZnFe2O4Powder.
Claims (4)
- A kind of 1. porous nano ZnFe2O4Preparation method, it is characterised in that：By trivalent iron salt, divalent zinc salt, alkali, deionization The mass percent of water, organic solvent and sublimable compound template is (13.0%~17.8%): (4.6%~7.7%): (8.9%~18.0%): (37.7%~50.4%): (15.0%~20.0%): the ratio of (2.0%~4.0%), by trivalent One meromict of molysite, divalent zinc salt and the total dosage of deionized water, stirring and dissolving obtain the mixing of trivalent iron salt and divalent zinc salt Solution, by another meromict of alkali and the total dosage of deionized water, stirring and dissolving obtains aqueous slkali, by trivalent iron salt and two under stirring The mixed solution of valency zinc salt is added dropwise in aqueous slkali, continues stirring 1~24h of reaction after dripping, and product is centrifuged and washes Operation and in triplicate is washed, then is centrifugally separating to obtain ZnFe2O4Colloidal sol；By ZnFe2O4Colloidal sol and the mass ratio of deionized water are 1: 2~20 ratio is by the deionized water separately taken and ZnFe2O4After colloidal sol mixing, with frequency be 20KHz~1MHz, power be 30W~ The ultrasonic wave of 15KW disperses 0.1h~24h, adds organic solvent and sublimable compound template, is mixed by water-organic solvent The hot method of bonding solvent reacts 0.5~24h at 100~250 DEG C, and product is after being distilled off mixed solvent, by per minute 0.5~3 DEG C programming rate be warming up to 400~650 DEG C, heat 0.5~24h and remove sublimable compound template, then through cooling, Grinding, washing, filtering, dry and grinding technics process, that is, obtain porous nano ZnFe2O4Powder；Wherein, the sublimable compound template for reacting used be 1,4-benzoquinone, melamine, iodine, hexa, camphor, Any of anthraquinone, naphthalene, anthracene, metaformaldehyde and triethylamine hydrochloride are a variety of；Wherein, the organic solvent for reacting used be methanol, ethanol, isopropanol, ether, isopropyl ether, formic acid, acetic acid, dichloromethane, Chloroform, carbon tetrachloride, acetone, cyclohexanone, methyl ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and acetic acid Any of isopropyl ester is a variety of.
- 2. the preparation method described in claim 1, it is characterised in that the trivalent iron salt for reacting used be ferric trichloride, ferric bromide, Any of ferric sulfate, ferric nitrate, ferric formate, ferric acetate, ironic citrate and tartaric acid iron are a variety of.
- 3. the preparation method described in claim 1, it is characterised in that the divalent zinc salt for reacting used is zinc chloride, zinc bromide, sulphur Any of sour zinc, zinc nitrate, zinc formate and zinc acetate are a variety of.
- 4. the preparation method described in claim 1, it is characterised in that the alkali for reacting used is lithium hydroxide, sodium hydroxide, hydrogen-oxygen Change any of potassium, ammonium hydroxide and barium hydroxide or a variety of.
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| CN107486163A (en) * | 2017-08-23 | 2017-12-19 | 苏州安特实业有限公司 | A kind of composite type foreign smell adsorbent and preparation method thereof |
| KR102223471B1 (en) * | 2017-12-26 | 2021-03-04 | 주식회사 엘지화학 | Method for preparing zinc ferrite catalysts and zinc ferrite catalysts prepared thereof |
| CN108855202A (en) * | 2018-06-05 | 2018-11-23 | 上海交通大学 | For photocatalytic water and the composite photo-catalyst of contaminant degradation and preparation method thereof |
| CN108940291A (en) * | 2018-07-06 | 2018-12-07 | 武汉霖泉环保科技有限公司 | A kind of preparation method and applications of zinc ferrite magnetic photocatalyst |
| CN109292829B (en) * | 2018-10-22 | 2021-06-29 | 安庆泽远化工有限公司 | Porous nano CoFe2O4Process for preparing nanoparticles |
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| JPH04321522A (en) * | 1991-04-18 | 1992-11-11 | Fuji Elelctrochem Co Ltd | Production of manganese-zinc-based ferrite |
| JP2001270701A (en) * | 2000-03-28 | 2001-10-02 | Yutaka Tamaura | Decomposition method of water |
| CN1673098A (en) * | 2005-03-24 | 2005-09-28 | 上海大学 | Prepn process of nanometer spinel type ZnFe2O4 |
| CN105126855A (en) * | 2015-07-15 | 2015-12-09 | 浙江大学 | ZnO/ZnFe2O4/C nano-structure hollow spheres and preparation method of same |
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| JPH04321522A (en) * | 1991-04-18 | 1992-11-11 | Fuji Elelctrochem Co Ltd | Production of manganese-zinc-based ferrite |
| JP2001270701A (en) * | 2000-03-28 | 2001-10-02 | Yutaka Tamaura | Decomposition method of water |
| CN1673098A (en) * | 2005-03-24 | 2005-09-28 | 上海大学 | Prepn process of nanometer spinel type ZnFe2O4 |
| CN105126855A (en) * | 2015-07-15 | 2015-12-09 | 浙江大学 | ZnO/ZnFe2O4/C nano-structure hollow spheres and preparation method of same |
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