CN105600828A - Preparation method of porous nano CuFe2O4 - Google Patents
Preparation method of porous nano CuFe2O4 Download PDFInfo
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- CN105600828A CN105600828A CN201610008269.3A CN201610008269A CN105600828A CN 105600828 A CN105600828 A CN 105600828A CN 201610008269 A CN201610008269 A CN 201610008269A CN 105600828 A CN105600828 A CN 105600828A
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- 229910016516 CuFe2O4 Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- DXKGMXNZSJMWAF-UHFFFAOYSA-N copper;oxido(oxo)iron Chemical compound [Cu+2].[O-][Fe]=O.[O-][Fe]=O DXKGMXNZSJMWAF-UHFFFAOYSA-N 0.000 title abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 29
- 238000003756 stirring Methods 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 239000011259 mixed solution Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 15
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 11
- 238000005119 centrifugation Methods 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
- 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 230000007547 defect Effects 0.000 claims description 6
- -1 polyoxy Polymers 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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 5
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 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
- 239000000203 mixture 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
- 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 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
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 4
- 229960000846 camphor Drugs 0.000 claims description 4
- 229930008380 camphor Natural products 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 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
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims description 4
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 claims description 3
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 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 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 229920001400 block copolymer Polymers 0.000 claims description 3
- 239000000839 emulsion Substances 0.000 claims description 3
- 239000002563 ionic surfactant Substances 0.000 claims description 3
- 239000004530 micro-emulsion 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
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 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
- 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
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 2
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 235000019994 cava Nutrition 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-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
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 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 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
- 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
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims 2
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims 1
- 229910001950 potassium oxide Inorganic materials 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract description 2
- 150000001879 copper Chemical class 0.000 abstract 3
- 150000002505 iron Chemical class 0.000 abstract 3
- 230000009286 beneficial effect Effects 0.000 abstract 1
- 238000001354 calcination Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000004729 solvothermal method Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 8
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 6
- 239000000463 material Substances 0.000 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 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 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
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000010438 heat treatment Methods 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
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002370 SrTiO3 Inorganic materials 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 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
- 239000002070 nanowire Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000005287 template synthesis Methods 0.000 description 1
- DGQOCLATAPFASR-UHFFFAOYSA-N tetrahydroxy-1,4-benzoquinone Chemical compound OC1=C(O)C(=O)C(O)=C(O)C1=O DGQOCLATAPFASR-UHFFFAOYSA-N 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/39—
-
- B01J35/60—
Abstract
The invention discloses a preparation method of porous nano CuFe2O4. The preparation method includes the steps that iron salt, copper salt and deionized water are mixed, stirring and dissolving are conducted, and a mixed solution of the iron salt and the copper salt is obtained, alkali and deionized water are mixed, stirring and dissolving are conducted, and aqueous alkali is obtained; under stirring, the mixed solution of the iron salt and the copper salt is dropwise added to the aqueous alkali, a stirring reaction continues after the mixed solution is dropwise added till the reaction is complete, a product is washed and eccentrically washed, and CuFe2O4 sol is obtained; after the CuFe2O4 sol is mixed with deionized water, ultrasonic dispersion is conducted, an organic solvent and a sublimable compound template are added, a reaction is conducted through a water-organic solvent mixed solvothermal method, and after the mixed solvent of the product is removed through distillation, the porous nano CuFe2O4 powder is obtained through the technological processes of calcining, cooling, grinding, washing, filtering, drying and grinding. The method is simple and feasible in process, low in investment and beneficial for application and popularization.
Description
Technical field
The present invention relates to a kind of porous nano CuFe2O4Preparation 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, and the exploitation of renewable new forms of energy receives much concern.Solar energy is as a kind of clean energy resource, be inexhaustible, nexhaustible, pollution-free, cheap, global various countries all can be freely andThe energy that flat interest is used is also that various regenerative resources are as basis of other energy such as biomass energy, wind energy, ocean energy, water energy. RespectivelyGovernment of state all attaches 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 that a class develops solar energy indispensability. At present, by the semiconductor of scientists studyPhotochemical catalyst is of a great variety, as TiO2、CdS、SrTiO3、RuO2, ZnO and Fe2O3Deng. CuFe2O4As a based semiconductorPhotochemical catalyst, has that good stability, indissoluble, environmental friendliness, band gap are narrow, aboundresources and a feature such as application cost is low, especiallyBeing and other semiconductor compound tense, can effectively improving photocatalytic activity, is one of good photochemical catalyst of application prospect.
Structure and the performance of material are closely related, structures shape performance, and the controlled preparation of material structure is the heat of material sciencePoint research direction is the important means of preparing high performance material. Report very about the research of nano material controllable method for preparing at presentMany. Since the people such as Penner in 1987 have proposed the template synthesis method of nano material, technique is simple, behaviour because having for templateMake convenient, low power consumption and other advantages, be subject to paying close attention to widely. Utilize template, by changing diameter and other technique of templateParameter can obtain shape and the controlled nano material of size. At present for nanocrystalline, nano thin-film, semiconductor, nanometerThe preparation of the materials such as pipe and nano wire, has consequence in field of nano material preparation, becomes and prepares high-performance nano materialImportant means.
CuFe2O4Nanometer and porous are to improve CuFe2O4One of effective ways of photocatalysis efficiency. Prepare porous nanoCuFe2O4Can adopt template, template mainly contains microemulsion template, emulsion template, ionic surfactant template, nonionicType surfactant templates, block copolymer template, composition template (as polyoxyethylene lauryl ether and polyethylene glycol) and singleDispersed polymeres particle template etc. By solgel reaction, CuFe2O4Colloidal sol forms skeleton structure with secondary bond and template action,Then take solvent extraction or high-temperature roasting method to remove template, thereby obtain the hole suitable with template size. But, useAbove-mentioned traditional template is prepared porous nano CuFe2O4Time, be to adopt roasting method or extraction to remove template all to exist seriouslyDefect. When roasting method is removed template, owing to eliminating, the temperature of template is high, can cause caving in of duct, and the porous of making is receivedRice CuFe2O4Semiconductor light-catalyst blemish is too many, becomes the complex centre of electron-hole, reduces photocatalysis efficiency. ExtractionFollow the example of and be difficult to thoroughly eliminate template, make porous nano CuFe2O4The purity of semiconductor light-catalyst reduces, and causes photocatalyticCan decline. Therefore, how to prepare duct without caving in, the porous nano of surperficial zero defect, template noresidue and high-specific surface areaCuFe2O4Semiconductor light-catalyst is an important topic.
Easily remove because sublimate easily distils, therefore, the present invention is template system by adopting the suitable compound of sublimation temperatureStandby CuFe2O4Colloidal sol, then heating removes template distillation can to make porous nano CuFe2O4. Compared with traditional template,The present invention adopts that sublimate is that template can prepare that structure is controlled, duct without caving in, surperficial zero defect, template noresidue and specific surfaceLong-pending large porous nano CuFe2O4Semiconductor light-catalyst. At present, about preparing porous nano taking sublimable compound as templateCuFe2O4The method of semiconductor light-catalyst there is not yet bibliographical information, is porous nano CuFe2O4Preparation opened up a new wayFootpath, has important practical significance.
Summary of the invention
A kind of porous nano CuFe of the present invention2O4Preparation method, provide a kind of with molysite, mantoquita, alkali, go fromSub-water is raw material, prepares CuFe by stirring reaction2O4Colloidal sol; CuFe2O4Colloidal sol is after ultrasonic dispersion, by certainRatio adds organic solvent and sublimable compound template, and after the hot method reaction of water-organic solvent mixed solvent, product is through steamingHeat up in a steamer and remove mixed solvent, heat treated and remove sublimable compound template, cooling, washing, dry and grinding technics process,Obtain porous nano CuFe2O4。
A kind of porous nano CuFe of the present invention2O4Preparation method, prepared porous nano CuFe2O4, visibleLight and sunshine are under the condition of light source, can be directly used in photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition, also canBy the method compound with other semiconductor, further make active higher photochemical catalyst, be light source at visible ray and sunshineCondition under, for photocatalysis degradation organic contaminant and photocatalytic hydrogen production by water decomposition;
A kind of porous nano CuFe of the present invention2O4Preparation method, adopt following technical scheme:
1, by the mass percent of molysite, mantoquita, alkali, deionized water, organic solvent and sublimable compound template be(0.001％～70％)∶(0.00001％～70％)∶(0.001％～65％)∶(0.001％～90％)∶(0.001％～90％)∶The ratio of (0.001%～90%), by a meromict of molysite, mantoquita and the total consumption of deionized water, stirring and dissolving obtain molysite andThe mixed solution of mantoquita, mixes second half of alkali and the total consumption of deionized water, and stirring and dissolving obtains aqueous slkali, under stirring by ironThe mixed solution of salt and mantoquita is added dropwise in aqueous slkali, drips rear continuation stirring reaction 1～24h, and product is through centrifugation and washWash operation also in triplicate, then centrifugation obtains CuFe2O4Colloidal sol; Press CuFe2O4The mass ratio of colloidal sol and deionized waterBe after 1: 2～15 ratio is mixed, with frequency be the ultrasonic wave dispersion that 20KHz～1MHz, power are 30W～15KW0.1h～24h, adds organic solvent and sublimable compound template, exists by the hot method of water-organic solvent mixed solventAt 100～250 DEG C, react 0.5～24h, product is removed after mixed solvent through distillation, by the programming rate liter of 0.5～3 DEG C per minuteTemperature to 300～600 DEG C, heat treated 0.5～24h removes sublimable compound template, then through cooling, grind, washing, filter,Be dried and grinding technics process, obtain porous nano CuFe2O4Powder.
2, a kind of porous nano CuFe of the present invention2O4Preparation method, its outstanding feature is: adopt traditional micro-Emulsion template, emulsion template, ionic surfactant template, nonionic surface active agent template, block copolymer template,The templates such as composition template (as polyoxyethylene lauryl ether and polyethylene glycol) and monodisperse polymer particles template, pass through colloidal solGel reaction makes CuFe2O4Colloidal sol forms skeleton structure with secondary bond and template action, then takes solvent extraction or high temperature roastingWhen burning method is removed template, all have major defect, as caused, duct caves in, blemish, specific area are low and template is residual etc.Problem, reduces photocatalysis efficiency; Compared with traditional template, during taking sublimate as template, sublimate easily distils and easily eliminates,Therefore be, that template is prepared CuFe by adopting the suitable compound of sublimation temperature2O4Colloidal sol, then heat treated removes sublimate,Go that template can make that structure is controlled, duct without caving in, surperficial zero defect, template noresidue and the large porous nano of specific areaCuFe2O4, be conducive to improve photocatalysis efficiency.
3, a kind of porous nano CuFe of the present invention2O4Preparation method, the molysite that reacts used is ferric trichloride, bromineAny one or more in change iron, ferric sulfate, ferric nitrate, ferric formate, ferric acetate, ironic citrate and tartaric acid iron.
4, a kind of porous nano CuFe of the present invention2O4Preparation method, the mantoquita that reacts used is copper chloride, brominationAny one or more in copper, copper sulphate, copper nitrate, copper formate and copper acetate.
5, a kind of porous nano CuFe of the present invention2O4Preparation method, the alkali that reacts used is lithium hydroxide, hydrogen-oxygenAny one or more in change sodium, potassium hydroxide, ammoniacal liquor and barium hydroxide.
6, a kind of porous nano CuFe of the present invention2O4Preparation method, react sublimable compound template used1,4-benzoquinone, melamine, iodine, hexa, camphor, anthraquinone, naphthalene, anthracene, metaformaldehyde and triethylamine saltAny one or more in hydrochlorate.
7, a kind of porous nano CuFe of the present invention2O4Preparation method, the organic solvent that reacts used is methyl alcohol, secondAlcohol, isopropyl alcohol, ether, isopropyl ether, formic acid, acetic acid, carrene, chloroform, carbon tetrachloride, acetone, cyclohexanone,Any in methyl ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate or manyKind.
8, a kind of porous nano CuFe of the present invention2O4Preparation method, porous nano CuFe2O4Preparation process inThe frequency of ultrasonic disperser used is that 20KHz～1MHz, power are 30W～15KW.
Detailed description of the invention
A kind of porous nano CuFe of the present invention below2O4Preparation method's non-limiting example. Giving of these examplesThe object that goes out to be only used to explanation, can not be interpreted as limitation of the invention. Because do not departing from spirit of the present invention and modelOn the basis of enclosing, can carry out many conversion to the present invention. In these embodiments, unless stated otherwise, all percentageAll refer to mass percent.
Embodiment 1
Porous nano CuFe2O4Preparation:
According to above-mentioned mass percent, by the half of ferric trichloride, ferric bromide, copper sulphate, copper bromide and the total consumption of deionized waterMix, stirring and dissolving obtains the mixed solution of ferric trichloride, ferric bromide, copper sulphate and copper bromide, by potassium hydroxide and deionizationThe total consumption of water second half mix, stirring and dissolving obtains potassium hydroxide solution, under stirring by ferric trichloride, ferric bromide, copper sulphateBe added dropwise in potassium hydroxide solution with the mixed solution of copper bromide, drip rear continuation stirring reaction 3h, product is through centrifugationWith washing operation in triplicate, then centrifugation obtains CuFe2O4Colloidal sol; Press CuFe2O4The matter of colloidal sol and deionized waterAfter amount is mixed than the ratio that is 1: 5, be that the ultrasonic wave that 28KHz, power are 2KW disperses 2h by frequency, add isopropylAfter alcohol, benzene, anthraquinone and hexa, at 150 DEG C, react 10h by the hot method of water-organic solvent mixed solvent, produceThing except after desolventizing, is warmed up to 450 DEG C by the programming rate of 1 DEG C per minute through distillation, and heat treated 9h at 450 DEG C, removes anthraceneAfter the sublimable compound template of quinone and hexa, then through cooling, grinding, washing, filtration, dry and grinding technicsProcess, obtains porous nano CuFe2O4Powder.
Embodiment 2
Porous nano CuFe2O4Preparation:
According to above-mentioned mass percent, the half of ferric nitrate, ferric formate, copper formate and copper nitrate and the total consumption of deionized water is mixedClose, stirring and dissolving obtains the mixed solution of ferric nitrate, ferric formate, copper formate and copper nitrate, by total to NaOH and deionized waterConsumption second half mix, stirring and dissolving obtains sodium hydroxide solution, under stirring by ferric nitrate, ferric formate, copper formate and nitric acidThe mixed solution of copper is added dropwise in sodium hydroxide solution, drips rear continuation stirring reaction 2.5h, and product is through centrifugation and washWash operation also in triplicate, then centrifugation obtains CuFe2O4Colloidal sol; Press CuFe2O4The mass ratio of colloidal sol and deionized waterBe after the ratio of 1: 8 is mixed, with frequency be 68KHz, the power ultrasonic wave dispersion 2.5h that is 3KW, add ethanol,After toluene, 1,4-benzoquinone and camphor, react 7h by the hot method of water-organic solvent mixed solvent at 160 DEG C, product removes through distillationAfter desolventizing, be warmed up to 480 DEG C by the programming rate of 0.5 DEG C per minute, heat treated 10h at 480 DEG C, remove 1,4-benzoquinone andAfter the sublimable compound template of camphor, then through cooling, grinding, washing, filtration, dry and grinding technics process, obtainPorous nano CuFe2O4Powder.
Embodiment 3
Porous nano CuFe2O4Preparation:
According to above-mentioned mass percent, by the half of ferric sulfate, ironic citrate, copper chloride and copper acetate and the total consumption of deionized waterMix, stirring and dissolving obtains the mixed solution of ferric sulfate, ironic citrate, copper chloride and copper acetate, by lithium hydroxide and hydroxideSecond half of barium and the total consumption of deionized water mixes, and stirring and dissolving obtains lithium hydroxide and barium hydroxide mixed solution, stir lower willThe mixed solution of ferric sulfate, ironic citrate, copper chloride and copper acetate is added dropwise in lithium hydroxide and barium hydroxide mixed solution, dripsAdd rear continuation stirring reaction 1.5h, through centrifugation and washing operation and in triplicate, then centrifugation obtains productCuFe2O4Colloidal sol; Press CuFe2O4After the ratio that colloidal sol is 1: 5 with the mass ratio of deionized water is mixed, with frequency be 40KHz,Power is that the ultrasonic wave of 1.5KW disperses 1.5h, adds ethyl acetate, methyl ethyl ketone, acetone, naphthalene, metaformaldehydeAfter anthracene, at 170 DEG C, react 12h by the hot method of water-organic solvent mixed solvent, product except after desolventizing, is pressed every through distillationThe programming rate of minutes 1.5 DEG C is warmed up to 420 DEG C, heat treated 12h at 420 DEG C, and removing naphthalene, metaformaldehyde and anthracene can distilCompound template after, then through cooling, grind, washing, filter, dry and grinding technics process, obtain porous nano CuFe2O4Powder.
Embodiment 4
Porous nano CuFe2O4Preparation:
According to above-mentioned mass percent, by a meromict of ferric trichloride and copper sulphate and the total consumption of deionized water, stirring and dissolving obtainsTo the mixed solution of ferric trichloride and copper sulphate, second half of NaOH and the total consumption of deionized water to be mixed, stirring and dissolving obtainsTo sodium hydroxide solution, under stirring, the mixed solution of ferric trichloride and copper sulphate is added dropwise in sodium hydroxide solution, after drippingContinue stirring reaction 3.0h, through centrifugation and washing operation and in triplicate, then centrifugation obtains CuFe to product2O4Colloidal sol; Press CuFe2O4After the ratio that colloidal sol is 1: 10 with the mass ratio of deionized water is mixed, with frequency be 50KHz, meritRate be 2.5KW ultrasonic wave disperse 1.0h, add after ethanol and anthracene, by the hot method of water-organic solvent mixed solvent at 180 DEG CLower reaction 4h, product except after desolventizing, is warmed up to 500 DEG C by the programming rate of 2 DEG C per minute through distillation, heating place at 500 DEG CReason 5h, removes after the sublimable compound template of anthracene, then through cooling, grinding, washing, filtration, dry and grinding technics process,Obtain porous nano CuFe2O4Powder.
Claims (8)
1. a porous nano CuFe2O4Preparation method, it is characterized in that: by molysite, mantoquita, alkali, deionized water, haveThe mass percent of machine solvent and sublimable compound template is (0.001%～70%): (0.00001%～70%):(0.001%～65%): (0.001%～90%): (0.001%～90%): the ratio of (0.001%～90%), by molysite,One meromict of mantoquita and the total consumption of deionized water, stirring and dissolving obtains the mixed solution of molysite and mantoquita, by alkali and deionized waterSecond half of total consumption mixes, and stirring and dissolving obtains aqueous slkali, under stirring, the mixed solution of molysite and mantoquita is added dropwise to aqueous slkaliIn, drip rear continuation stirring reaction 1～24h, product through centrifugation and washing operation and in triplicate, then centrifugationObtain CuFe2O4Colloidal sol; Press CuFe2O4The ratio that colloidal sol is 1: 2～15 with the mass ratio of deionized water is used frequency after mixingThe ultrasonic wave that is 30W～15KW for 20KHz～1MHz, power disperses 0.1h～24h, adds organic solvent and can distilCompound template, at 100～250 DEG C, react 0.5～24h by the hot method of water-organic solvent mixed solvent, product through distillation removeGo after mixed solvent, be warmed up to 300～600 DEG C by the programming rate of 0.5～3 DEG C per minute, heat treated 0.5～24h removes canThe compound template of distillation, then through cooling, grinding, washing, filtration, dry and grinding technics process, obtain porous nanoCuFe2O4Powder.
2. preparation method claimed in claim 1, its outstanding feature is: adopt traditional microemulsion template, emulsion template,Ionic surfactant template, nonionic surface active agent template, block copolymer template, composition template are (as polyoxy secondAlkene lauryl ether and polyethylene glycol) and the template such as monodisperse polymer particles template, make CuFe by solgel reaction2O4MoltenGlue forms skeleton structure with secondary bond and template action, while then taking solvent extraction or high-temperature roasting method to remove template, all depositsIn major defect, the problem such as duct caves in as caused, blemish, specific area are low and template is residual, reduces photocatalysis efficiency;Compared with traditional template, during taking sublimate as template, sublimate easily distils and easily eliminates, therefore, and by the employing temperature that distilsSpending suitable compound is that template is prepared CuFe2O4Colloidal sol, then heat treated removes sublimate, going template can make structure canControl, duct without caving in, surperficial zero defect, template noresidue and the large porous nano CuFe of specific area2O4, be conducive to improvePhotocatalysis efficiency.
3. preparation method claimed in claim 1, is characterized in that the molysite that reacts used is ferric trichloride, ferric bromide, sulphurAny one or more in acid iron, ferric nitrate, ferric formate, ferric acetate, ironic citrate and tartaric acid iron.
4. preparation method claimed in claim 1, is characterized in that the mantoquita that reacts used is copper chloride, copper bromide, sulfuric acidAny one or more in copper, copper nitrate, copper formate and copper acetate.
5. preparation method claimed in claim 1, is characterized in that the alkali that reacts used is lithium hydroxide, NaOH, hydrogenAny one or more in potassium oxide, ammoniacal liquor and barium hydroxide.
6. preparation method claimed in claim 1, it is characterized in that the sublimable compound template of reacting used be 1,4-benzoquinone,Appointing in melamine, iodine, hexa, camphor, anthraquinone, naphthalene, anthracene, metaformaldehyde and triethylamine hydrochlorideOne or more.
7. preparation method claimed in claim 1, is characterized in that the organic solvent that reacts used is methyl alcohol, ethanol, differentPropyl alcohol, ether, isopropyl ether, formic acid, acetic acid, carrene, chloroform, carbon tetrachloride, acetone, cyclohexanone, methylAny one or more in ethyl ketone, benzene, toluene, methyl acetate, ethyl acetate, propyl acetate and isopropyl acetate.
8. preparation method claimed in claim 1, is characterized in that the frequency of ultrasonic disperser used in course of reactionFor 20KHz～1MHz, power are 30W～15KW.
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