CN105664950A - Preparation method of nano porous ZnFe2O4 - Google Patents
Preparation method of nano porous ZnFe2O4 Download PDFInfo
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- CN105664950A CN105664950A CN201610008270.6A CN201610008270A CN105664950A CN 105664950 A CN105664950 A CN 105664950A CN 201610008270 A CN201610008270 A CN 201610008270A CN 105664950 A CN105664950 A CN 105664950A
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- 229910001308 Zinc ferrite Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- NNGHIEIYUJKFQS-UHFFFAOYSA-L hydroxy(oxo)iron;zinc Chemical compound [Zn].O[Fe]=O.O[Fe]=O NNGHIEIYUJKFQS-UHFFFAOYSA-L 0.000 title abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 239000008367 deionised water Substances 0.000 claims abstract description 24
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 24
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000011259 mixed solution Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 15
- 150000002505 iron Chemical class 0.000 claims abstract description 14
- 150000003751 zinc Chemical class 0.000 claims abstract description 14
- 239000012046 mixed solvent Substances 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000000926 separation method Methods 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 16
- 230000001699 photocatalysis Effects 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 11
- 230000007547 defect Effects 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
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 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
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-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
- 238000007146 photocatalysis Methods 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
- 229910021578 Iron(III) chloride Inorganic materials 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
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 8
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000011592 zinc chloride Substances 0.000 claims description 8
- 235000005074 zinc chloride Nutrition 0.000 claims description 8
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- 239000006185 dispersion Substances 0.000 claims description 6
- -1 polyoxyethylene lauryl ether Polymers 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 5
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 5
- 229960002413 ferric citrate Drugs 0.000 claims description 5
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 5
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 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
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 5
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium;hydroxide;hydrate Chemical compound [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 5
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 229940102001 zinc bromide Drugs 0.000 claims description 5
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 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
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-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
- 229940025250 camphora Drugs 0.000 claims description 4
- 239000010238 camphora Substances 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 4
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 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
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 238000009432 framing Methods 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- 239000004530 micro-emulsion Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002736 nonionic surfactant Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000000859 sublimation Methods 0.000 claims description 3
- 230000008022 sublimation Effects 0.000 claims description 3
- 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
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 229940093499 ethyl acetate Drugs 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
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 claims description 2
- 229940011051 isopropyl acetate Drugs 0.000 claims description 2
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-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
- 238000003303 reheating Methods 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 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
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 6
- 238000001914 filtration Methods 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract 3
- 238000001035 drying Methods 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 239000004065 semiconductor Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- 239000011941 photocatalyst Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000001172 regenerating effect Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 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
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 238000000605 extraction Methods 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
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000003786 synthesis reaction 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 preparation method of nano porous ZnFe2O4; the method comprises the steps: mixing an iron salt, a zinc salt and deionized water, and stirring to dissolve, to obtain a mixed solution of the iron salt and the zinc salt; mixing an alkali with deionized water, and stirring to dissolve, to obtain an alkali solution; dropping the mixed solution of the iron salt and the zinc salt into the alkali solution while stirring; after completion of dropping, stirring until a reaction is completed; carrying out washing and centrifugal separation of the product to obtain a ZnFe2O4 sol; mixing the ZnFe2O4 sol with deionized water, carrying out ultrasonic dispersion, then adding an organic solvent and a sublimable compound template, after a water-organic solvent mixed solvent thermal reaction is completed, distilling the product to remove the mixed solvent, then carrying out roasting, cooling, grinding, washing, filtering, drying and grinding processes, and thus obtaining a porous nano ZnFe2O4 powder. The method is simple and easy to operate, small in investment, and favorable for popularization and application.
Description
Technical field
The present invention relates to a kind of porous nano ZnFe2O4Preparation method, belong to field of photocatalytic material.
Background technology
Along with the quickening of process of industrialization, energy crisis and environmental crisis are day by day serious, the exploitation of renewable new forms of energy receives much concern. Solar energy as a kind of clean energy resource, is the energy that all can freely utilize peacefully of inexhaustible, nexhaustible, pollution-free, cheap, world community, be also other energy such as various regenerative resource such as biomass energy, wind energy, ocean energy, water energy. 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.
Photocatalyst is the semi-conducting material that a class develops that solar energy is indispensable. At present, of a great variety by the semiconductor light-catalyst of scientists study, such as TiO2、CdS、SrTiO3、RuO2, ZnO and Fe2O3Deng. ZnFe2O4As a based semiconductor photocatalyst, have that good stability, indissoluble, environmental friendliness, band gap be narrow, aboundresources and the feature such as application cost is low, especially time with other semiconductors coupling, photocatalytic activity can be effectively improved, be one of good photocatalyst of application prospect.
The structure of material is closely related with performance, and structures shape performance, the controlled synthesis of material structure is the hot research direction of material science, is the important means preparing high performance material. Report a lot at present about the research of nano material controllable method for preparing. Since Penner in 1987 et al. proposes the template synthesis method of nano material, technique is simple, easy to operate, low power consumption and other advantages because having for template, of great interest. Utilize template, by changing the diameter of template and other technological parameter can obtain shape and the controlled nano material of size. Have been used for the preparation of the materials such as nanocrystalline, nano thin-film, quasiconductor, nanotube and nano wire at present, in field of nano material preparation, there is consequence, become the important means preparing high-performance nano material.
ZnFe2O4Nanorize and porous are to improve ZnFe2O4One of effective ways of photocatalysis efficiency. Prepare porous nano ZnFe2O4Can adopting template, template mainly has microemulsion template, emulsion template, ionic surfactant template, nonionic surfactant template, block copolymer template, compositions template (such as polyoxyethylene lauryl ether and Polyethylene Glycol) and monodisperse polymer particles template etc.By solgel reaction, ZnFe2O4Colloidal sol forms framing structure with secondary bond with template action, then takes solvent extraction or high-temperature roasting method to remove template, thus obtaining the hole suitable with template size. But, use above-mentioned traditional template to prepare porous nano ZnFe2O4Time, it is adopt roasting method or extraction to remove template all to there is major defect. When roasting method removes template, the temperature owing to eliminate template is high, can cause caving in of duct, make the porous nano ZnFe made2O4Semiconductor light-catalyst surface defect is too many, becomes the complex centre of electron-hole, reduces photocatalysis efficiency. Extract rule and be difficult to thoroughly eliminate template so that porous nano ZnFe2O4The purity of semiconductor light-catalyst reduces, and causes that photocatalysis performance declines. Therefore, how to prepare duct without caving in, surface zero defect, template noresidue and high-specific surface area porous nano ZnFe2O4Semiconductor light-catalyst is an important topic.
Easily removing owing to sublimate easily distils, therefore, by adopting sublimation temperature, suitable compound is that template prepares ZnFe to the present invention2O4Colloidal sol, reheats and makes template distillation removing can be prepared by porous nano ZnFe2O4. Compared with traditional template, the present invention adopt sublimate be template can prepare structure-controllable, duct without caving in, surface zero defect, template noresidue and the big porous nano ZnFe of specific surface area2O4Semiconductor light-catalyst. Porous nano ZnFe is prepared for template currently, with respect to sublimable compound2O4The method of semiconductor light-catalyst there is not yet bibliographical information, for porous nano ZnFe2O4Preparation open a new way, there is important practical significance.
Summary of the invention
A kind of porous nano ZnFe of the present invention2O4Preparation method, it is provided that a kind of with iron salt, zinc salt, alkali, deionized water for raw material, prepare ZnFe by stirring reaction2O4Colloidal sol; ZnFe2O4Colloidal sol is after ultrasonic disperse, add organic solvent and sublimable compound template according to a certain percentage, after water-organic solvent mixed solvent full-boiled process reaction, product, through mixed solvent, heat treated removing sublimable compound template, cooling, washing, dry and grinding technics process are distilled off, namely obtains porous nano ZnFe2O4。
A kind of porous nano ZnFe of the present invention2O4Preparation method, obtained porous nano ZnFe2O4When visible ray and sunlight are light source, can be directly used for photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition, also by the method with other semiconductors coupling, prepare the photocatalyst that activity is higher further, when visible ray and sunlight are 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
1, by iron salt, zinc salt, alkali, deionized water, the mass percent of organic solvent and sublimable compound template is (0.001%～70%): (0.00001%～70%): (0.001%～75%): (0.001%～90%): (0.001%～90%): the ratio of (0.001%～90%), by iron salt, one meromict of zinc salt and the total consumption of deionized water, stirring and dissolving obtains the mixed solution of iron salt and zinc salt, second half of total to alkali and deionized water consumption is mixed, stirring and dissolving obtains aqueous slkali, under stirring, the mixed solution of iron salt and zinc salt is added dropwise in aqueous slkali, stirring reaction 1～24h is continued after dripping, product is performing centrifugal separation on and washing operation in triplicate, it is centrifugally separating to obtain ZnFe again2O4Colloidal sol;By ZnFe2O4After colloidal sol mixes with the ratio that mass ratio is 1: 2～20 of deionized water, it is 20KHz～1MHz by frequency, power is the ultrasound wave dispersion 0.1h～24h of 30W～15KW, add organic solvent and sublimable compound template, at 100～250 DEG C, 0.5～24h is reacted by water-organic solvent mixed solvent full-boiled process, product is after being distilled off mixed solvent, it is warmed up to 400～650 DEG C by the programming rate of 0.5～3 DEG C per minute, heat treated 0.5～24h removes sublimable compound template, then through cooling, grind, washing, filter, dry and grinding technics process, namely porous nano ZnFe is obtained2O4Powder.
2, a kind of porous nano ZnFe of the present invention2O4Preparation method, its outstanding feature is: adopts the templates such as traditional microemulsion template, emulsion template, ionic surfactant template, nonionic surfactant template, block copolymer template, compositions template (such as polyoxyethylene lauryl ether and Polyethylene Glycol) and monodisperse polymer particles template, makes ZnFe by solgel reaction2O4Colloidal sol forms framing structure with secondary bond with template action, when then taking solvent extraction or high-temperature roasting method to remove template, all there is major defect, as caused duct to cave in, surface defect, specific surface area be low and the problem such as template residual, reduces photocatalysis efficiency; Compared with traditional template, during with sublimate for template, sublimate easily distils and easily eliminates, and therefore, by adopting sublimation temperature, suitable compound is that template prepares ZnFe2O4Colloidal sol, reheating process remove sublimate template can be prepared by structure-controllable, duct without caving in, surface zero defect, template noresidue and the big porous nano ZnFe of specific surface area2O4, be conducive to improving photocatalysis efficiency.
3, a kind of porous nano ZnFe of the present invention2O4Preparation method, the used iron salt of reaction is any one or more in ferric chloride, ferric bromide, iron sulfate, ferric nitrate, ferric formate, ferric acetate, ferric citrate and tartaric acid ferrum.
4, a kind of porous nano ZnFe of the present invention2O4Preparation method, the used zinc salt of reaction is any one or more in zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, zinc formate and zinc acetate.
5, a kind of porous nano ZnFe of the present invention2O4Preparation method, the used alkali of reaction is any one or more in Lithium hydrate, sodium hydroxide, potassium hydroxide, ammonia and barium hydroxide.
6, a kind of porous nano ZnFe of the present invention2O4Preparation method, the used sublimable compound template of reaction is any one or more in 1,4-benzoquinone, tripolycyanamide, iodine, hexamethylenetetramine, Camphora, anthraquinone, naphthalene, anthracene, metaformaldehyde and triethylamine hydrochloride.
7, a kind of porous nano ZnFe of the present invention2O4Preparation method, the used organic solvent of reaction is any one or more in methanol, ethanol, isopropanol, ether, diisopropyl ether, formic acid, acetic acid, dichloromethane, chloroform, carbon tetrachloride, acetone, Ketohexamethylene, methyl ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate.
8, a kind of porous nano ZnFe of the present invention2O4Preparation method, porous nano ZnFe2O4Preparation process in the frequency of used ultrasonic disperser be 20KHz～1MHz, power be 30W～15KW.
Detailed description of the invention
Of the present invention a kind of porous nano ZnFe is presented herein below2O4The non-limiting example of preparation method.These examples be only given for illustrative purposes, limitation of the invention can not be interpreted as. Because without departing from the spirit and scope of the present invention, it is possible to the present invention is carried out many conversion. In these embodiments, unless stated otherwise, all of percentage ratio is all referring to mass percent.
Embodiment 1
Porous nano ZnFe2O4Preparation:
According to above-mentioned mass percent, by ferric chloride, ferric bromide, zinc sulfate, one meromict of zinc bromide and the total consumption of deionized water, stirring and dissolving obtains ferric chloride, ferric bromide, the mixed solution of zinc sulfate and zinc bromide, second half of total to potassium hydroxide and deionized water consumption is mixed, stirring and dissolving obtains potassium hydroxide solution, by ferric chloride under stirring, ferric bromide, the mixed solution of zinc sulfate and zinc bromide is added dropwise in potassium hydroxide solution, stirring reaction 1h is continued after dripping, product is performing centrifugal separation on and washing operation in triplicate, it is centrifugally separating to obtain ZnFe again2O4Colloidal sol; By ZnFe2O4After colloidal sol mixes with the ratio that mass ratio is 1: 10 of deionized water, it is 28KHz by frequency, power is the ultrasound wave dispersion 1.5h of 2KW, add isopropanol, benzene, after anthraquinone and hexamethylenetetramine, at 150 DEG C, 12h is reacted by water-organic solvent mixed solvent full-boiled process, product is after being distilled off solvent, it is warmed up to 500 DEG C by the programming rate of 1 DEG C per minute, heat treated 8h at 500 DEG C, after removing anthraquinone and the sublimable compound template of hexamethylenetetramine, then through cooling, grind, washing, filter, dry and grinding technics process, namely porous nano ZnFe is obtained2O4Powder.
Embodiment 2
Porous nano ZnFe2O4Preparation:
According to above-mentioned mass percent, by ferric nitrate, ferric formate, one meromict of zinc chloride and zinc nitrate and the total consumption of deionized water, stirring and dissolving obtains ferric nitrate, ferric formate, the mixed solution of zinc chloride and zinc nitrate, second half of total to sodium hydroxide and deionized water consumption is mixed, stirring and dissolving obtains sodium hydroxide solution, by ferric nitrate under stirring, ferric formate, the mixed solution of zinc chloride and zinc nitrate is added dropwise in sodium hydroxide solution, stirring reaction 2.5h is continued after dripping, product is performing centrifugal separation on and washing operation in triplicate, it is centrifugally separating to obtain ZnFe again2O4Colloidal sol; By ZnFe2O4After colloidal sol mixes with the ratio that mass ratio is 1: 8 of deionized water, ultrasound wave dispersion 1.5h with frequency to be 68KHz, power be 3KW, after adding ethanol, toluene, 1,4-benzoquinone and Camphora, at 160 DEG C, 10h is reacted by water-organic solvent mixed solvent full-boiled process, product is after being distilled off solvent, it is warmed up to 550 DEG C by the programming rate of 0.5 DEG C per minute, heat treated 6h at 550 DEG C, after removing 1,4-benzoquinone and the sublimable compound template of Camphora, then through cooling, grinding, washing, filtration, dry and grinding technics process, namely obtain porous nano ZnFe2O4Powder.
Embodiment 3
Porous nano ZnFe2O4Preparation:
According to above-mentioned mass percent, by iron sulfate, ferric citrate, one meromict of zinc chloride and zinc acetate and the total consumption of deionized water, stirring and dissolving obtains iron sulfate, ferric citrate, the mixed solution of zinc chloride and zinc acetate, second half of Lithium hydrate and barium hydroxide and the total consumption of deionized water is mixed, stirring and dissolving obtains Lithium hydrate and barium hydroxide mixed solution, by iron sulfate under stirring, ferric citrate, the mixed solution of zinc chloride and zinc acetate is added dropwise in Lithium hydrate and barium hydroxide mixed solution, stirring reaction 3h is continued after dripping, product is performing centrifugal separation on and washing operation in triplicate, it is centrifugally separating to obtain ZnFe again2O4Colloidal sol;By ZnFe2O4After colloidal sol mixes with the ratio that mass ratio is 1: 7 of deionized water, it is 40KHz by frequency, power is the ultrasound wave dispersion 1.5h of 1.5KW, add ethyl acetate, methyl ethyl ketone, acetone, naphthalene, after metaformaldehyde and anthracene, at 170 DEG C, 5h is reacted by water-organic solvent mixed solvent full-boiled process, product is after being distilled off solvent, it is warmed up to 520 DEG C by the programming rate of 1.5 DEG C per minute, heat treated 7h at 520 DEG C, remove naphthalene, after metaformaldehyde and the sublimable compound template of anthracene, then through cooling, grind, washing, filter, dry and grinding technics process, namely porous nano ZnFe is obtained2O4Powder.
Embodiment 4
Porous nano ZnFe2O4Preparation:
According to above-mentioned mass percent, by ferric acetate, ferric chloride, one meromict of zinc formate and zinc sulfate and the total consumption of deionized water, stirring and dissolving obtains ferric acetate, ferric chloride, the mixed solution of zinc formate and zinc sulfate, second half of total to sodium hydroxide and deionized water consumption is mixed, stirring and dissolving obtains sodium hydroxide solution, by ferric acetate under stirring, ferric chloride, the mixed solution of zinc formate and zinc sulfate is added dropwise in sodium hydroxide solution, stirring reaction 1.5h is continued after dripping, product is performing centrifugal separation on and washing operation in triplicate, it is centrifugally separating to obtain ZnFe again2O4Colloidal sol; By ZnFe2O4After colloidal sol mixes with the ratio that mass ratio is 1: 12 of deionized water, ultrasound wave dispersion 1.0h with frequency to be 50KHz, power be 2.5KW, after adding ethanol, methyl acetate and anthracene, at 180 DEG C, 5.5h is reacted by water-organic solvent mixed solvent full-boiled process, product is after being distilled off solvent, it is warmed up to 560 DEG C by the programming rate of 2 DEG C per minute, heat treated 6h at 560 DEG C, after removing the sublimable compound template of anthracene, then through cooling, grinding, washing, filtration, dry and grinding technics process, namely obtain porous nano ZnFe2O4Powder.
Claims (8)
1. a porous nano ZnFe2O4Preparation method, it is characterized in that: by iron salt, zinc salt, alkali, deionized water, the mass percent of organic solvent and sublimable compound template is (0.001%～70%): (0.00001%～70%): (0.001%～75%): (0.001%～90%): (0.001%～90%): the ratio of (0.001%～90%), by iron salt, one meromict of zinc salt and the total consumption of deionized water, stirring and dissolving obtains the mixed solution of iron salt and zinc salt, second half of total to alkali and deionized water consumption is mixed, stirring and dissolving obtains aqueous slkali, under stirring, the mixed solution of iron salt and zinc salt is added dropwise in aqueous slkali, stirring reaction 1～24h is continued after dripping, product is performing centrifugal separation on and washing operation in triplicate, it is centrifugally separating to obtain ZnFe again2O4Colloidal sol; By ZnFe2O4After colloidal sol mixes with the ratio that mass ratio is 1: 2～20 of deionized water, it is 20KHz～1MHz by frequency, power is the ultrasound wave dispersion 0.1h～24h of 30W～15KW, add organic solvent and sublimable compound template, at 100～250 DEG C, 0.5～24h is reacted by water-organic solvent mixed solvent full-boiled process, product is after being distilled off mixed solvent, it is warmed up to 400～650 DEG C by the programming rate of 0.5～3 DEG C per minute, heat treated 0.5～24h removes sublimable compound template, then through cooling, grind, washing, filter, dry and grinding technics process, namely porous nano ZnFe is obtained2O4Powder.
2. the preparation method described in claim 1, it is characterized in that: adopt the templates such as traditional microemulsion template, emulsion template, ionic surfactant template, nonionic surfactant template, block copolymer template, compositions template (such as polyoxyethylene lauryl ether and Polyethylene Glycol) and monodisperse polymer particles template, make ZnFe by solgel reaction2O4Colloidal sol forms framing structure with secondary bond with template action, when then taking solvent extraction or high-temperature roasting method to remove template, all there is major defect, as caused duct to cave in, surface defect, specific surface area be low and the problem such as template residual, reduces photocatalysis efficiency;Compared with traditional template, during with sublimate for template, sublimate easily distils and easily eliminates, and therefore, by adopting sublimation temperature, suitable compound is that template prepares ZnFe2O4Colloidal sol, reheating process remove sublimate template can be prepared by structure-controllable, duct without caving in, surface zero defect, template noresidue and the big porous nano ZnFe of specific surface area2O4, be conducive to improving photocatalysis efficiency.
3. the preparation method described in claim 1, it is characterised in that the iron salt used by reaction is any one or more in ferric chloride, ferric bromide, iron sulfate, ferric nitrate, ferric formate, ferric acetate, ferric citrate and tartaric acid ferrum.
4. the preparation method described in claim 1, it is characterised in that the zinc salt used by reaction is any one or more in zinc chloride, zinc bromide, zinc sulfate, zinc nitrate, zinc formate and zinc acetate.
5. the preparation method described in claim 1, it is characterised in that the alkali used by reaction is any one or more in Lithium hydrate, sodium hydroxide, potassium hydroxide, ammonia and barium hydroxide.
6. the preparation method described in claim 1, it is characterised in that the sublimable compound template used by reaction is any one or more in 1,4-benzoquinone, tripolycyanamide, iodine, hexamethylenetetramine, Camphora, anthraquinone, naphthalene, anthracene, metaformaldehyde and triethylamine hydrochloride.
7. the preparation method described in claim 1, it is characterised in that the organic solvent used by reaction is any one or more in methanol, ethanol, isopropanol, ether, diisopropyl ether, formic acid, acetic acid, dichloromethane, chloroform, carbon tetrachloride, acetone, Ketohexamethylene, methyl ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate.
8. the preparation method described in claim 1, it is characterised in that the frequency of ultrasonic disperser used in course of reaction is 20KHz～1MHz, power is 30W～15KW.
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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 |
| CN108314779A (en) * | 2017-01-18 | 2018-07-24 | 美桦兴业股份有限公司 | Three-dimensional porous structure of parylene and method for forming the same |
| 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 |
| CN109292829A (en) * | 2018-10-22 | 2019-02-01 | 安徽理工大学 | A kind of porous nano CoFe2O4The preparation method of nanoparticle |
| CN109589984A (en) * | 2018-12-12 | 2019-04-09 | 江苏大学 | A kind of preparation method and applications of double reaction channel photochemical catalysts |
| CN110198783A (en) * | 2017-12-26 | 2019-09-03 | 株式会社Lg化学 | The preparation method of iron acid zinc catalyst and iron acid zinc catalyst prepared therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109292829A (en) * | 2018-10-22 | 2019-02-01 | 安徽理工大学 | A kind of porous nano CoFe2O4The preparation method of nanoparticle |
| CN109589984A (en) * | 2018-12-12 | 2019-04-09 | 江苏大学 | A kind of preparation method and applications of double reaction channel photochemical catalysts |
| CN109589984B (en) * | 2018-12-12 | 2021-11-23 | 江苏大学 | Preparation method and application of double-reaction-channel photocatalyst |
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