CN104327574B - Micro/nano Cu2O/ZnO composite material, preparation method and application thereof - Google Patents
Micro/nano Cu2O/ZnO composite material, preparation method and application thereof Download PDFInfo
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- CN104327574B CN104327574B CN201410515220.8A CN201410515220A CN104327574B CN 104327574 B CN104327574 B CN 104327574B CN 201410515220 A CN201410515220 A CN 201410515220A CN 104327574 B CN104327574 B CN 104327574B
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title abstract description 31
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 162
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 46
- 239000008103 glucose Substances 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 78
- 239000011259 mixed solution Substances 0.000 claims description 59
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 58
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 57
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 56
- 239000011248 coating agent Substances 0.000 claims description 46
- 238000000576 coating method Methods 0.000 claims description 46
- 230000003373 anti-fouling effect Effects 0.000 claims description 45
- 238000003756 stirring Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 35
- 239000004925 Acrylic resin Substances 0.000 claims description 29
- 235000005074 zinc chloride Nutrition 0.000 claims description 29
- 239000011592 zinc chloride Substances 0.000 claims description 29
- 238000000034 method Methods 0.000 claims description 23
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000012752 auxiliary agent Substances 0.000 claims description 12
- 229910052802 copper Inorganic materials 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000945 filler Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- XKMZOFXGLBYJLS-UHFFFAOYSA-L zinc;prop-2-enoate Chemical compound [Zn+2].[O-]C(=O)C=C.[O-]C(=O)C=C XKMZOFXGLBYJLS-UHFFFAOYSA-L 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000015556 catabolic process Effects 0.000 claims description 10
- 238000006731 degradation reaction Methods 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 10
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000049 pigment Substances 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 7
- IIZPXYDJLKNOIY-JXPKJXOSSA-N 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine Chemical group CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCC\C=C/C\C=C/C\C=C/C\C=C/CCCCC IIZPXYDJLKNOIY-JXPKJXOSSA-N 0.000 claims description 6
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 6
- 239000000787 lecithin Substances 0.000 claims description 6
- 229940067606 lecithin Drugs 0.000 claims description 6
- 235000010445 lecithin Nutrition 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 239000000178 monomer Substances 0.000 claims description 6
- 229920000058 polyacrylate Polymers 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 5
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 5
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 4
- 239000000440 bentonite Substances 0.000 claims description 4
- 229910000278 bentonite Inorganic materials 0.000 claims description 4
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 230000007717 exclusion Effects 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000000853 adhesive Substances 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 239000002957 persistent organic pollutant Substances 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 12
- 238000004458 analytical method Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 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 10
- 238000001782 photodegradation Methods 0.000 description 10
- 229910052708 sodium Inorganic materials 0.000 description 10
- 239000011734 sodium Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 8
- 229940012189 methyl orange Drugs 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 238000010183 spectrum analysis Methods 0.000 description 8
- 241000196324 Embryophyta Species 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000001699 photocatalysis Effects 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004070 electrodeposition Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 ZnO composites compound Chemical class 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229960004643 cupric oxide Drugs 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 235000001727 glucose Nutrition 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000002061 nanopillar Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 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
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
- C09D131/04—Homopolymers or copolymers of vinyl acetate
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2248—Oxides; Hydroxides of metals of copper
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- Chemical Kinetics & Catalysis (AREA)
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- Life Sciences & Earth Sciences (AREA)
- Nanotechnology (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to a micro/nano Cu2O/ZnO composite material, a preparation method and an application thereof. The preparation method comprises following steps: preparing a mixture solution, adding sodium hydroxide, adding glucose and the like. The micro/nano Cu2O/ZnO composite material, as a catalyst, has a strong visible light catalytic activity on organic pollutants. When being used as an anti-pollution agent for preparing a high-performance environmental-friendly marine anti-pollution paint, the micro/nano Cu2O/ZnO composite material has an actual-sea plate-adhesive period of 360 days and has a more excellent anti-pollution performance when being compared with a conventional pure Cu2O material.
Description
【Technical field】
The invention belongs to inorganic functional material preparing technical field.More particularly it relates to a kind of micro-/ nano
Cu2O/ZnO composites, further relate to the micro-/ nano Cu2The preparation method of O/ZnO composites, further relates to the micro-/ nano
Cu2The purposes of O/ZnO composites.
【Background technology】
Cu2O is a kind of inorganic oxide, and it is the p-type semiconductor material of band gap about 2.17eV, to visible ray have compared with
Absorption coefficient high.In technical fields such as photocatalysis, novel solar battery, magnetic storage device, biology sensor and coating all
Have a wide range of applications.It is similar with other semiconductor light-catalysts, Cu2O there is also and easily be combined institute by light induced electron and hole
The poor problem of caused catalytic effect.Research finds that it is a kind of important side for improving photocatalysis efficiency to prepare composite semiconductor
Method.
In recent years, Cu2The main preparation method of O composites has photochemical precipitation method, electrochemical deposition method, physical mixed
The methods such as method.Mittiga research groups (A.Mittiga, E.Salza, F.Sarto, et a1.Heterojunction solar
Cell with 2%efficiency based on a Cu2O substrate.Appl.Phys.Lett., 2006,88
(16), 163-502.) two-step method is utilized, thermal oxide Cu pieces prepare crystallite dimension up to 1mm2, mobility be up to 100cm2Vs-1's
Cu2O films, one layer of ito thin film of substrate deposition is made with this, so as to prepare pn heterojunction solar batteries, obtains about 2%
Sun light conversion efficiency；Cui et al. (J.Cui, U.J.Glbson.A simple two-step electrodeposition
ofCu2O/ZnO nanopillar solar cells.J.Phys.Chem.C., 2010,114 (14), 6408-6412.) use
Two-step electrochemical deposition process prepares a nanometer Cu2O/ZnO composite wood stock columns.However, these existing methods were generally prepared
Journey is complicated, and condition requirement is harsh, significantly limit Cu2The large-scale production of O composites and commercial Application.
The present inventor, by lot of experiments, completes the present invention on the basis of prior art is summarized.The present invention is adopted
Simple liquid phase reduction is used, in the case of without any complementary organic additive or surfactant, with copper sulphate, hydrogen
Sodium oxide molybdena and glucose prepare micro-/ nano Cu for raw material2O/ZnO composites.The synthetic method is simple, it is easy to operate,
The micro-/ nano Cu of synthesis2O/ZnO composites can be as catalyst degradation organic pollution, again can be multiple as anti-fouling agent
With high-performance environment-friendly type marine antifouling coating.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of micro-/ nano Cu2O/ZnO composites.
It is a further object to provide the micro-/ nano Cu2The preparation method of O/ZnO composites.
It is a further object to provide the micro-/ nano Cu2The purposes of O/ZnO composites.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of micro-/ nano Cu2The preparation method of O/ZnO composites.
The step of preparation method, is as follows：
A, prepare mixed solution
Copper sulphate is with zinc chloride according to mol ratio 1:0.025~2.000 is added in deionized water, and stirring and dissolving obtains one
Plant the copper zinc mixed solution of 0.5~2.0mol/L of copper concentration；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:2~5, add in the mixed solution obtained toward step A
Enter the sodium hydrate aqueous solution that concentration is 0.1~3.0mol/L, be then heated to 30~90 DEG C of temperature, then continue to stirring 5~
60min, obtains a kind of mixed solution containing NaOH；
C, addition glucose
According to copper sulphate and the mol ratio 1 of glucose:0.1~5.0, toward the mixing containing NaOH that step B is obtained
Reducing agent glucose is added in solution, then, the reaction system 40~100 DEG C of temperature is heated to, and protect at this temperature
Temperature 5~60min, isolated micro-/ nano Cu2O/ZnO composites.
The invention further relates to the micro-/ nano Cu prepared using the preparation method2O/ZnO composites.Described
Micro-/ nano Cu2O/ZnO composites, its scantling is 0.1~5.0 μm.
The invention further relates to described micro-/ nano Cu2Purposes of the O/ZnO composites in light degradation organic pollution.
The invention further relates to described micro-/ nano Cu2O/ZnO composites prepare high-performance environment-friendly type ocean prevent
Purposes in dirty coating.
According to the present invention, described high-performance environment-friendly type marine antifouling coating is by 20~60 parts by weight resin solution, 1
~20 weight portion auxiliary agents, 1~30 weight portion pigment or filler and 1~50 weight portion micro-/ nano Cu2O/ZnO composites are constituted.
A preferred embodiment of the invention, described resin solution is by selected from acrylic resin, acrylic acid
The resin of zinc resin or acrylate resin is constituted with the solvent selected from ethyl acetate, butyl acetate, dimethylbenzene, toluene or butanol
's.
Another preferred embodiment of the invention, the concentration of the resin solution is by weight 20~60%.
Another preferred embodiment of the invention, described zinc acrylate resin or acrylate resin is to use
What following method synthesis were obtained：
The preparation of I, prepolymer
1000~1400 weight portions are compared 4 by toluene and n-butanol according to weight:The mixed solvent of 1 composition is heated to backflow
Temperature, is then added dropwise 18~22 weight portion azodiisobutyronitriles molten in 700~900 parts by weight of acrylic acid monomer mixtures
Liquid, the acrylic monomers mixture is by 104 parts by weight of acrylic acid, 161 parts by weight of methylmethacrylate, 320 weight portion vinegar
Sour ethene and 216 weight parts of methacrylic acid butyl esters are constituted, and keep being heated to reflux during dropwise addition；Continue to react after dripping
3.5~4.5 hours, obtain the acrylic polymer of slightly yellow clear；
The preparation of II, zinc acrylate resin or acrylate resin
Acrylic polymer, 11.5 weight portion zinc hydroxides or the 11.3 weight portion hydrogen that 150 weight portions are prepared in step I
Cupric oxide, 13.2 parts by weight, 27 weight portion butyl acetates mix with 10 weight portions in the mixed solvent that step I is used
It is even, then reacted 5.5~6.5 hours under conditions of 70~80 DEG C of temperature, temperature is then risen to 125 DEG C and is dehydrated, treat
Terminate reaction when reactant mixture is transparent and exclusion is distillated, obtain transparent zinc acrylate resin or acrylate resin.
Another preferred embodiment of the invention, described pigment is iron oxide red, iron oxide yellow or titanium dioxide；
Described filler is aerosil or talcum powder.
Another preferred embodiment of the invention, described auxiliary agent is lecithin or bentonite.
The present invention is described in more detail below.
The present invention relates to a kind of micro-/ nano Cu2The preparation method of O/ZnO composites.
The step of preparation method, is as follows：
A, prepare mixed solution
Copper sulphate is with zinc chloride according to mol ratio 1:0.025~2.000 is added in deionized water, and stirring and dissolving obtains one
Plant the copper zinc mixed solution of 0.5~2.0mol/L of copper concentration.
In the present invention, the mol ratio 1 of described copper sulphate and zinc chloride:0.025~2.000.If zinc chloride rubs
You obtain minimal amount of ZnO than being less than 0.025 in solution2 2-With substantial amounts of Cu (OH)4 2-, now ZnO2 2-To Cu2O crystal into
Core influence is little；If the mol ratio of zinc chloride is higher than 2.000, excessive Zn in solution2+With OH-Reaction, it is suppressed that Cu
(OH)4 2-Generation；Therefore, copper sulphate and the mol ratio of zinc chloride are 1:0.025~2.000 is appropriate；Preferably 1:
0.05~1.50；More preferably 1:0.30~1.00.
, it is necessary to fully, persistently stir during mixed solution is prepared, so that copper sulphate has fully dissolved with zinc chloride
Entirely.
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:2~5, add in the mixed solution obtained toward step A
Enter the sodium hydrate aqueous solution that concentration is 0.1~3.0mol/L, be then heated to 30~90 DEG C of temperature, then continue to stirring 5~
60min, obtains a kind of mixed solution containing NaOH.
In this step, the effect of addition NaOH is to provide alkalescence condition, makes the Cu in solution2+With OH-Reaction
Form Cu (OH)4 2-Solution, is further reduced by glucose.
In the present invention, described copper sulphate and the mol ratio of NaOH are 1:2~5.If NaOH mole
Than less than 2, then cannot get Cu (OH)4 2-Solution, finally inhibits Cu2The nucleation of O crystal；If the mol ratio of NaOH is high
In 5, then remaining excessive OH in solution-, consume substantial amounts of raw material；Therefore, copper sulphate and the mol ratio of NaOH are 1:2
~5 is appropriate；Preferably 1:3.4~4.5；More preferably 1:3.8~4.2.
C, addition glucose
According to copper sulphate and the mol ratio 1 of glucose:0.1~5.0, toward the mixing containing NaOH that step B is obtained
Reducing agent glucose is added in solution, then, the reaction system 40~100 DEG C of temperature is heated to, and protect at this temperature
Temperature 5~60min, isolated micro-/ nano Cu2O/ZnO composites.
In this step, the effect of addition reducing agent glucose is lentamente by the Cu in solution2+It is reduced into Cu+。
In the present invention, described copper sulphate and the mol ratio of glucose are 1:0.1~5.0.If glucose mole
Than less than 0.1, then Cu2+Reduction is insufficient；If the mol ratio of glucose is higher than 5.0, remaining substantial amounts of glucose in solution；
Therefore, copper sulphate and the mol ratio of glucose are 1:0.1~5.0 is appropriate；Preferably 1:0.8~4.0；More preferably
1:1.6~0.30.
The micro-/ nano Cu prepared using the inventive method2O/ZnO composites have carried out the X-ray diffraction analysis of routine
With conventional scanning electron microscope analysis and energy spectrum analysis.
Described X-ray diffraction analysis condition is as follows：
Instrument：German Bruker companies D8Advance type x-ray diffractometers.
Condition determination：CuKα(), 15 ° -85 ° of sweep limits, 4 ° of min of sweep speed-1, graphite flake filter
Ripple, pipe pressure 40kV, electric current 40mA.
Measurement result shows to have obtained Cu referring to accompanying drawing 1, the result of the figure2O/ZnO composite constructions.
Described scanning electron microscope analysis condition is as follows：
Instrument：Hitachi companies S-4800 type field emission scanning electron microscopes.
Condition determination：8~10kV of accelerating potential.
Measurement result shows referring to accompanying drawing 2 to 10, the result of these accompanying drawings：With Zn2+The change of consumption, product Cu2O/ZnO
Composite pattern changes.
Described energy spectrum analysis condition is as follows：
Instrument：Hitachi companies S-4800 type field emission scanning electron microscopes EDS is analyzed.
Condition determination：8~10kV of accelerating potential.
Referring to accompanying drawing 5,7 and 8, these results show to have obtained Cu measurement result2O/ZnO composite constructions.
The invention further relates to the micro-/ nano Cu prepared using the preparation method2O/ZnO composites.By accompanying drawing 2
Result to 10 knows, described micro-/ nano Cu2The size of O/ZnO composites is 0.1~5.0 μm.
The invention further relates to described micro-/ nano Cu2Purposes of the O/ZnO composites in light degradation organic pollution.
According to the mode that this specification Application Example 1 is described, micro-/ nano Cu of the present invention is have studied2O/ZnO composites
As catalyst, it is seen that photodegradation of the light to organic dyestuff methyl orange, its result is shown in accompanying drawing 11.Can be seen by accompanying drawing 11
Go out, micro-/ nano Cu of the invention2Under the irradiation of visible ray, photocatalytic activity prolongs O/ZnO composites with light application time
Grow and strengthen.Methyl orange degradation kinetics follows first order reaction kinetics model.It is 1 in copper zinc mol ratio:When 0.5, produce
Thing Cu2O/ZnO composites can reach 77.45% to the degradation rate of methyl orange under visible light.
In order to further illustrate micro-/ nano Cu of the present invention2The photocatalysis performance of O/ZnO composites, uses polyvinylidene fluoride
Alkene is by micro-/ nano Cu of the present invention2O/ZnO composites are tuned into slurry, are coated in electro-conductive glass FTO and prepare film forming as light anode,
Ag/AgCl is assembled into virtual battery as reference electrode, Pt electrodes as to electrode, using CHI660E type three-electrode electro Chemicals
Work station tests micro-/ nano Cu of the present invention2The bode impedance diagrams of O/ZnO composite catalysts, calculate the electronics longevity of catalyst
Life, its result is listed in Figure 12, and the figure clearly demonstrates the virtual battery of assembling by Cu2O/ZnO as light anode, in copper sulphate
It is 1 with zinc chloride mol ratio:When 0.5, the photoelectron life-span, (τ) was most long, and the Photocatalytic Degradation Property to methyl orange is best.
The invention further relates to described micro-/ nano Cu2O/ZnO composites prepare high-performance environment-friendly type ocean prevent
Purposes in dirty coating.
According to the present invention, described high-performance environment-friendly type marine antifouling coating is by 20~60 parts by weight resin solution, 1
~20 weight portion auxiliary agents, 1~30 weight portion pigment or filler and 1~50 weight portion micro-/ nano Cu2O/ZnO composites are constituted.
The concentration of the resin solution is by weight 20~60%.The concentration of the resin solution exceedes this concentration
During scope, the anti-fouling effect of antifouling paint can be all significantly affected.Preferably, the concentration of the resin solution be by weight 30~
50%, it is highly preferred that the concentration of the resin solution is by weight 36~45%.
Described resin solution is by the resin selected from acrylic resin, zinc acrylate resin or acrylate resin and choosing
Constituted from the solvent of ethyl acetate, butyl acetate, dimethylbenzene, toluene or butanol.
Described acrylic resin is the product sold in the market, such as by Changxing Chemical Industry Co Ltd
The acrylic resin of sale.
Described zinc acrylate resin or acrylate resin is obtained using the synthesis of following methods：
The preparation of I, prepolymer
1000~1400 weight portions are compared 4 by toluene and n-butanol according to weight:The mixed solvent of 1 composition is heated to backflow
Temperature, is then added dropwise 18~22 weight portion azodiisobutyronitriles molten in 700~900 parts by weight of acrylic acid monomer mixtures
Liquid, the acrylic monomers mixture is by 104 parts by weight of acrylic acid, 161 parts by weight of methylmethacrylate, 320 weight portion vinegar
Sour ethene and 216 weight parts of methacrylic acid butyl esters are constituted, and keep being heated to reflux during dropwise addition；Continue to react after dripping
3.5~4.5 hours, obtain the acrylic polymer of slightly yellow clear.
The equipment that this prepolymer preparation process is used is to install three mouthfuls of appearances of agitating device, condenser and thermometer
Device, this equipment is product usually used in chemical technology field, in extensive sale in the market.
The preparation of II, zinc acrylate resin or acrylate resin
Acrylic polymer, 11.5 weight portion zinc hydroxides or the 11.3 weight portion hydrogen that 150 weight portions are prepared in step I
Cupric oxide, 13.2 parts by weight, 27 weight portion butyl acetates mix with 10 weight portions in the mixed solvent that step I is used
It is even, then reacted 5.5~6.5 hours under conditions of 70~80 DEG C of temperature, temperature is then risen to 125 DEG C and is dehydrated, treat
Terminate reaction when reactant mixture is transparent and exclusion is distillated, obtain transparent zinc acrylate resin or acrylate resin.
The equipment that this preparation process is used is identical with the equipment that step I is used.
Described ethyl acetate, butyl acetate, dimethylbenzene, toluene or butanol are all usually used in chemical technology field
, in the market extensively sale product.
In high-performance environment-friendly type marine antifouling coating of the invention, described auxiliary agent has dispersion, anti-settling
Effect.Described auxiliary agent is lecithin or bentonite.
Described lecithin or bentonite is usually used in chemical technology field, is sold extensively in the market
Product, such as by the lecithin of Zhengzhou Nai Ruite Companies, the swelling sold by Zhejiang Fenghong New Material Co., Ltd.
Soil.
In high-performance environment-friendly type marine antifouling coating of the present invention, the effect of the pigment is coloring.Described face
Material is iron oxide red, iron oxide yellow or titanium dioxide.
Described iron oxide red, iron oxide yellow or titanium dioxide be usually used in chemical technology field, in existing market
The product of upper sale extensively, iron oxide red, the iron oxide yellow for example sold by Shanghai Yipin Pigments Co., Ltd., by Dupont
The titanium dioxide of the R-902 sale of company.
In high-performance environment-friendly type marine antifouling coating of the present invention, described filler has the effect of filling.It is described
Filler be aerosil or talcum powder.
Described aerosil or talcum powder is usually used in chemical technology field, extensive in the market
The product of sale, for example by the aerosil of Yantai Jia Hong Chemical Co., Ltd.s sale, by Penglai City Yongfeng reaches ultra-fine cunning
The superfine talcum powder of stone flour Company.
According to the present invention, micro-/ nano Cu2The amount of O/ZnO composites is 1~50 weight portion, and the amount of other components is in institute
In the range of stating, and the amount of the resin solution be less than 20 weight portion when, then the filming performance of antifouling paint can be made to be deteriorated, if institute
When the amount for stating resin solution is higher than 60 weight portion, then the antifouling property of antifouling paint can be reduced, therefore, the amount of resin solution is 20
~60 weight portions are suitable.
Similarly, micro-/ nano Cu2The amount of O/ZnO composites is 1~50 weight portion, and the amount of other components is described
In the range of, and the amount of auxiliary agent be less than 1 weight portion when, then dispersiveness, the anti-settling performance of antifouling paint can be reduced, if the amount of auxiliary agent
During higher than 20 weight portion, then the filming performance of antifouling paint can be influenceed, therefore, the amount of auxiliary agent is suitable for 1~20 weight portion.
Micro-/ nano Cu2The amount of O/ZnO composites be 1~50 weight portion, the amount of other components in described scope,
And the amount of filler be less than 1 weight portion when, then can reduce the anti-fouling effect of antifouling paint, if the amount of filler be higher than 30 weight portion,
The film forming of antifouling paint can be then reduced, therefore, the amount of filler is that 1~30 weight portion is appropriate.
Preferably, described high-performance environment-friendly type marine antifouling coating be by 30~48 parts by weight resin solution, 5~
14 weight portion auxiliary agents, 8~22 weight portion pigment or filler and 12~36 weight portion micro-/ nano Cu2O/ZnO composites are constituted.
It is highly preferred that described high-performance environment-friendly type marine antifouling coating is by 35~42 parts by weight resin solution, 8
~10 weight portion auxiliary agents, 12~18 weight portion pigment or filler and 18~30 weight portion micro-/ nano Cu2O/ZnO composite groups
Into.
Marine biofouling is to be engaged in the biological phenomena gradually recognized after Activities of Ocean, and the mankind adhere to ocean
Existing more than the 4000 years history of biological fight.Marine fouling organism brings numerous harm to shipping industry and ocean industry, and ocean is dirty
It has been insoluble significant problem always since being engaged in Activities of Ocean from the mankind to damage biological preventing and kill off, in order to reduce sea to greatest extent
The harm that foreign fouling organism is caused, brushing nonpolluting coating is method that is most economical, effectively and generally using.
The performance of high-performance environment-friendly type marine antifouling coating of the present invention is detected using following standard methods：
Dope viscosity determination method：GB/T 1723-1993
Coating fineness determination method：GB/T 1724-1979
Paint film adhesion determination method：GB/T1720-1979
By micro-/ nano Cu of the invention2O/ZnO composites compound self polishing copolymer antifouling paint as anti-fouling agent, according to state
Family's standard has carried out the performance evaluation of the coating, wherein viscosity (applying -4) cup, reach 85-92 (s), fineness for 50-55 (μm) and
Adhesive force is 1 (level), and this shows micro-/ nano Cu of the invention2O/ZnO composites are compounded from polishing antifouling as anti-fouling agent
Coating, viscosity, three performance indications of fineness and adhesive force meet the basic demand of marine antifouling coating.
[beneficial effect]
The beneficial effects of the invention are as follows：The present invention uses simple liquid phase reduction, complementary organic adds without any
Plus in the case of agent or surfactant, with copper sulphate, zinc chloride, NaOH and glucose it is micro- as raw material is prepared/receive
Rice Cu2O/ZnO composites, the preparation method is simple, it is easy to operate, and yield is up to more than 96%, and it can overcome the disadvantages that other are prepared
Preparation process in procedure is numerous and diverse, the limitation such as condition requirement harshness, while also can overcome the disadvantages that Cu2O photocatalysis efficiencies are low not
Foot.Micro-/ nano Cu of the invention2O/ZnO composites are prevented as photochemical catalyst and high-performance environment-friendly type ocean is prepared
There is very good application prospect in dirty coating.
【Brief description of the drawings】
Fig. 1 is the micro-/ nano Cu of different copper sulphate and zinc chloride mol ratio2O/ZnO composite x-ray diffraction patterns.
Fig. 2 is that embodiment 1 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.0252O/
The electron scanning micrograph of ZnO composites.
Fig. 3 is that embodiment 2 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.052O/ZnO
The electron scanning micrograph of composite.
Fig. 4 is that embodiment 3 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.152O/ZnO
The electron scanning micrograph of composite.
Fig. 5 is that embodiment 4 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.182O/ZnO
The SEM of composite, energy spectrum analysis photo and x-ray photoelectron spectroscopy.
Fig. 6 is that embodiment 5 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.252O/ZnO
The electron scanning micrograph of composite.
Fig. 7 is that embodiment 6 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.52O/ZnO
The SEM and energy spectrum analysis photo of composite.
Fig. 8 is that embodiment 7 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 0.82O/ZnO
The SEM and energy spectrum analysis photo of composite.
Fig. 9 is that embodiment 8 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 1.22O/ZnO
The electron scanning micrograph of composite.
Figure 10 is that embodiment 9 is 1 in copper sulphate and zinc chloride mol ratio:The micro-/ nano Cu prepared when 22O/ZnO is answered
The electron scanning micrograph of condensation material.
Figure 11 is micro-/ nano Cu of the present invention2O/ZnO composites as catalyst, in 5.5 hours radiation of visible light to having
Degradation rate curve (a) and pseudo-first-order kinetic model (b) figure of machine methyl orange.
Figure 12 is that design virtual battery calculates micro-/ nano Cu of the present invention2O/ZnO composites urging in organic pollution
Change life-span bode impedance diagram.
【Specific embodiment】
The present invention is will be better understood that by following embodiments.
Embodiment 1：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.025 is added in deionized water, stirs molten
Solution, obtains a kind of copper zinc mixed solution of copper concentration 1.0mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:4, added in the mixed solution obtained toward step A
Concentration is the sodium hydrate aqueous solution of 1.0mol/L, is then heated to 30 DEG C of temperature, then continues to stir 5min, obtains one kind and contains
There is the mixed solution of NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:0.4, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 40 DEG C of temperature, and in this temperature
Lower insulation 13min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 96.5%.
According to the scanning electron microscope analysis method described in this specification, to micro-/ nano manufactured in the present embodiment
Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 2.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 2：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.05 is added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 0.5mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:3, added in the mixed solution obtained toward step A
Concentration is the sodium hydrate aqueous solution of 0.6mol/L, is then heated to 55 DEG C of temperature, then continues to stir 18min, obtains one kind
Mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:0.1, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to temperature 70 C, and in this temperature
Lower insulation 44min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 97.5%.
According to the scanning electron microscope analysis method described in this specification, to micro-/ nano manufactured in the present embodiment
Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 3.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 3：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.15 is added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 1.2mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:5, added in the mixed solution obtained toward step A
Concentration is the sodium hydrate aqueous solution of 3.0mol/L, is then heated to 75 DEG C of temperature, then continues to stir 43min, obtains one kind
Mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:4.3, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 95 DEG C of temperature, and in this temperature
Lower insulation 52min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 96.2%.
According to the scanning electron microscope analysis method described in this specification, to micro-/ nano manufactured in the present embodiment
Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 4.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 4：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.18 is added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 1.4mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:3.8, add in the mixed solution obtained toward step A
Enter the sodium hydrate aqueous solution that concentration is 0.1mol/L, be then heated to temperature 50 C, then continue to stir 60min, obtain one
Plant the mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:2.8, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 55 DEG C of temperature, and in this temperature
Lower insulation 29min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 98.2%.
According to the scanning electron microscope analysis described in this specification and energy spectrum analysis method, to manufactured in the present embodiment
Micro-/ nano Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 5.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 5：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.25 is added in deionized water, stirring and dissolving,
Obtain a kind of copper concentration 1.6mol/L and copper zinc mixed solution；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:4.5, add in the mixed solution obtained toward step A
Enter the sodium hydrate aqueous solution that concentration is 2.1mol/L, be then heated to 85 DEG C of temperature, then continue to stir 30min, obtain one
Plant the mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:2, contain hydroxide toward what step B was obtained
Reducing agent glucose is added in the mixed solution of sodium, then, the reaction system 100 DEG C of temperature is heated to, and in this temperature
Lower insulation 5min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 96.6%.
According to the scanning electron microscope analysis method described in this specification, to micro-/ nano manufactured in the present embodiment
Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 6.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 6：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.5 is added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 1.0mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:4.2, add in the mixed solution obtained toward step A
Enter the sodium hydrate aqueous solution that concentration is 1.5mol/L, be then heated to 90 DEG C of temperature, then continue to stir 25min, obtain one
Plant the mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:1.8, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 100 DEG C of temperature, and in this temperature
The lower insulation 21min, isolated micro-/ nano Cu of degree2O/ZnO composites, its yield reaches 97.4%.
According to the scanning electron microscope analysis described in this specification and energy spectrum analysis method, to manufactured in the present embodiment
Micro-/ nano Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 7.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 7：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:0.8 is added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 0.8mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:2.5, add in the mixed solution obtained toward step A
Enter the sodium hydrate aqueous solution that concentration is 2.5mol/L, be then heated to 60 DEG C of temperature, then continue to stir 10min, obtain one
Plant the mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:3.6, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 85 DEG C of temperature, and in this temperature
Lower insulation 35min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 98.0%.
According to the scanning electron microscope analysis described in this specification and energy spectrum analysis method, to manufactured in the present embodiment
Micro-/ nano Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 8.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 8：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:1.2 are added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 1.8mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:5, added in the mixed solution obtained toward step A
Concentration is the sodium hydrate aqueous solution of 1.2mol/L, is then heated to temperature 45 C, then continues to stir 56min, obtains one kind
Mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:5.0, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 73 DEG C of temperature, and in this temperature
Lower insulation 56min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 96.9%.
According to the scanning electron microscope analysis method described in this specification, to micro-/ nano manufactured in the present embodiment
Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 9.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, the results are shown in Table 1 to prepare the coating property of marine antifouling coating using it.
Embodiment 9：Prepare micro-/ nano Cu2O/ZnO composites
The implementation steps of the embodiment are as follows：
A, prepare mixed solution
Under continuous stirring, by copper sulphate and zinc chloride according to mol ratio 1:2.0 are added in deionized water, stirring and dissolving,
Obtain a kind of copper zinc mixed solution of copper concentration 2.0mol/L；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:2, added in the mixed solution obtained toward step A
Concentration is the sodium hydrate aqueous solution of 1.8mol/L, is then heated to 65 DEG C of temperature, then continues to stir 28min, obtains one kind
Mixed solution containing NaOH；
C, addition glucose
Under conditions of stirring, according to copper sulphate and the mol ratio 1 of glucose:1.0, contain hydrogen-oxygen toward what step B was obtained
Change addition reducing agent glucose in the mixed solution of sodium, then, the reaction system is heated to 95 DEG C of temperature, and in this temperature
Lower insulation 60min, isolated micro-/ nano Cu2O/ZnO composites, its yield reaches 97.2%.
According to the scanning electron microscope analysis method described in this specification, to micro-/ nano manufactured in the present embodiment
Cu2O/ZnO composites are analyzed, and its result is listed in accompanying drawing 10.
Micro-/ nano Cu manufactured in the present embodiment2Result of the test of the O/ZnO composites to the photodegradation of organic dyestuff
It is listed in accompanying drawing 11, uses it as anti-fouling agent compounding antifouling paint, is hung through real sea after a while in the numbering head of Qingdao eight
Plate, investigates the antifouling property of coating.The results are shown in Table 1 for specific hanging plate.
Application Example 1：Micro-/ nano Cu of the present invention2O/ZnO composite light degradation organic dyestuff is tested
The implementation steps of the embodiment are as follows：
Pipette 300mL, 20mg L-1Methyl orange (MO) dye solution, the micro-/ nano for respectively preparing 0.06g embodiments 1-9
Cu2O/ZnO composites are dispersed in the solution as photochemical catalyst.Magnetic agitation 1 hour under the conditions of lucifuge, makes MO dyestuffs
Molecule reaches adsorption-desorption balance in the catalyst surface.Light-catalyzed reaction is integrally fixed in SGY-IB photochemical reactors
500mL cylindrical glass container in carry out.The reactor configurations magnetic stirring apparatus, quartzy cold well and condenser pipe.Its
The effect of middle magnetic stirring apparatus is to allow reaction system to be in uniform state, and quartzy cold well and condenser pipe are to maintain the reaction system
Temperature stabilization and prevent solution from evaporating.High-pressure sodium lamp (500W) takes 5mL illumination and hangs as light-catalysed light source, every 30min
Turbid solution.Through being centrifuged at a high speed, the supernatant for obtaining is the solution containing methyl orange to the suspension solution, using by Hatachi
Company determines the absorbance of the supernatant with trade name UV-4100 visible spectrophotometers at wavelength 464nm, then by first
The standard curve that base orange standard liquid is drawn is calculated its methyl orange concentration.
Its experimental result is listed in Figure 11, and the ordinate of Figure 11 (a) is the absorbance of methyl orange solution, and abscissa is light
According to the time, it represents the relation of MO degradation rates and time, illustrates the photocatalytic activity of every kind of sample with the extension of light application time
Enhancing.
The ordinate of Figure 11 (b) is the negative logarithm for terminating concentration ratio initial concentration, and abscissa is light application time, Figure 11 (b)
Curve represents the kinetics of methyl orange degradation, it then follows pseudo-first order reaction kinetics model.
Application Example 2：High-performance environment-friendly type marine antifouling coating panel experiment of the invention
By butyl acetate solution, 2.5g lecithin, 10g iron oxide reds, the 2.5g of the weight % acrylic resins of 45g concentration 40
Aerosil, 40g micro-/ nano Cu of the present invention2O/ZnO composites are mixed, and the mixture is given birth to by Nai Chi companies
Produce with being sanded, dispersion, grind in the basket type sand mill of agitating function 20 minutes, then cross 100 eye mesh screens, obtain this hair
Bright high-performance environment-friendly type marine antifouling coating.
The antifouling property of the marine antifouling coating described in test, with reference to standard GB/T/T5370-2007《Anti-fouling paint sample
Plate shallow sea soak test method》, above-mentioned antifouling paint brushing is tested in plate 250mm long, width 150mm with the mild steel of thickness 2mm
On model, this experiment model two is fixed with iron bolt using the square wood strip long of trough of belt.The experiment model is hung over into Qingdao
Eight numbering head plant Experimental Base leaching sea experiment of city 1 year, obtains the experimental result listed such as table 1 below.
Table 1：High-performance environment-friendly type marine antifouling coating experimental result of the present invention
Commercially available Cu2O*：Chemical Reagent Co., Ltd., Sinopharm Group.
Blank plate *：There is no any nonpolluting coating.
Claims (8)
1. a kind of micro-/ nano Cu2The preparation method of O/ZnO composites, it is characterised in that as follows the step of the preparation method：
A, prepare mixed solution
Copper sulphate is with zinc chloride according to mol ratio 1:0.025~2.000 is added in deionized water, stirring and dissolving, obtains a kind of copper
The copper zinc mixed solution of 0.5~2.0mol/L of concentration；
B, addition NaOH
At normal temperatures, according to copper sulphate and the mol ratio 1 of NaOH:2~5, added in the mixed solution obtained toward step A dense
Spend the sodium hydrate aqueous solution for 0.1~3.0mol/L, be then heated to 30~90 DEG C of temperature, then continue to stirring 5~
60min, obtains a kind of mixed solution containing NaOH；
C, addition glucose
According to copper sulphate and the mol ratio 1 of glucose:0.1~5.0, toward the mixed solution containing NaOH that step B is obtained
Middle addition reducing agent glucose, then, 40~100 DEG C of temperature is heated to by the reaction system, and at this temperature insulation 5~
60min, isolated micro-/ nano Cu2O/ZnO composites.
2. the preparation-obtained micro-/ nano Cu of preparation method according to claim 12O/ZnO composites, it is characterised in that
The micro-/ nano Cu2The size of O/ZnO composites is 0.1~5.0 μm.
3. method is obtaining according to claim 1 or micro-/ nano Cu according to claim 22O/ZnO composites
Purposes in light degradation organic pollution.
4. method is obtaining according to claim 1 or micro-/ nano Cu according to claim 22O/ZnO composites
Purposes in high-performance environment-friendly type marine antifouling coating is prepared.
5. a kind of high-performance environment-friendly type marine antifouling coating, it is characterised in that described marine antifouling coating is by 20~60 weights
Amount part concentration is 20~60% resin solution, 1~20 weight portion auxiliary agent, 1~30 weight portion pigment or filler and 1 by weight
Method is obtaining according to claim 1 or micro-/ nano Cu according to claim 2 for~50 weight portions2O/ZnO is combined
Material is constituted；Described resin solution be by the resin selected from acrylic resin, zinc acrylate resin or acrylate resin with
Constituted selected from the solvent of ethyl acetate, butyl acetate, dimethylbenzene, toluene or butanol.
6. high-performance environment-friendly type marine antifouling coating according to claim 5, it is characterised in that zinc acrylate resin
Or acrylate resin is obtained using the synthesis of following methods：
The preparation of I, prepolymer
1000~1400 weight portions are compared 4 by toluene and n-butanol according to weight:The mixed solvent of 1 composition is heated to backflow temperature
Degree, is then added dropwise solution of 18~22 weight portion azodiisobutyronitriles in 700~900 parts by weight of acrylic acid monomer mixtures,
The acrylic monomers mixture is by parts by weight 104:161:320:216 acrylic acid, methyl methacrylate, acetic acid second
Alkene is constituted with butyl methacrylate, keeps being heated to reflux during dropwise addition；Continue to react 3.5~4.5 hours after dripping,
Obtain the acrylic polymer of slightly yellow clear；
The preparation of II, zinc acrylate resin or acrylate resin
Acrylic polymer, 11.5 weight portion zinc hydroxides or the 11.3 weight portion hydroxides that 150 weight portions are prepared in step I
Copper, 13.2 parts by weight, 27 weight portion butyl acetates are well mixed with 10 weight portions in the mixed solvent that step I is used,
Then reacted 5.5~6.5 hours under conditions of 70~80 DEG C of temperature, temperature is then risen to 125 DEG C and is dehydrated, question response
Terminate reaction when mixture is transparent and exclusion is distillated, obtain transparent zinc acrylate resin or acrylate resin.
7. high-performance environment-friendly type marine antifouling coating according to claim 5, it is characterised in that described pigment is
Iron oxide red, iron oxide yellow or titanium dioxide；Described filler is aerosil or talcum powder.
8. high-performance environment-friendly type marine antifouling coating according to claim 5, it is characterised in that described auxiliary agent is
Lecithin or bentonite.
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| CN105660696A (en) * | 2016-01-08 | 2016-06-15 | 南昌大学 | Preparation method of visible light excitation antibacterial coating layer containing nano cuprous oxide |
| CN106268831B (en) * | 2016-08-16 | 2019-04-23 | 浙江理工大学 | A kind of Template synthesis Cu2O@Zn(OH)2The method of heterojunction structure |
| CN106323940A (en) * | 2016-08-24 | 2017-01-11 | 合肥学院 | Method for in situ monitoring visible photocatalysis and organic dye degradation based on superficially reinforced Raman spectra technology |
| CN109126800B (en) * | 2018-07-20 | 2020-11-06 | 西安交通大学 | Preparation method of cuprous oxide-copper-zinc oxide composite photocatalyst |
| CN110327932B (en) * | 2019-07-03 | 2021-07-23 | 昆明理工大学 | Cu2Preparation method of O/ZnO composite photocatalyst |
| CN110270330A (en) * | 2019-07-10 | 2019-09-24 | 成都理工大学 | A kind of preparation method of low temperature liquid phase precipitation method cuprous oxide/reduced graphene visible-light photocatalyst |
| CN110467215B (en) * | 2019-08-06 | 2021-02-26 | 西安交通大学 | Preparation method of shape-controllable iron and zinc ion co-doped cuprous oxide crystal |
| CN110508248B (en) * | 2019-08-30 | 2022-07-15 | 四川神州奥特农业科技有限公司 | Iodine adsorption material and preparation method thereof |
| CN111066816B (en) * | 2019-11-21 | 2021-05-07 | 浙江大学 | Preparation for treating fouling of coastal mussels, and use method and application thereof |
| CN112499664B (en) * | 2020-12-07 | 2023-08-01 | 江苏汇诚医疗科技有限公司 | Cuprous oxide-doped nano zinc oxide composite material and preparation method thereof |
| CN112619655A (en) * | 2021-01-18 | 2021-04-09 | 武汉梓强生态科技有限公司 | SiO (silicon dioxide)2Loaded Cu2O-ZnO heterojunction photocatalytic degradation material and preparation method thereof |
| CN114752269B (en) * | 2022-05-17 | 2022-12-09 | 福建福松新材料科技有限公司 | Low-copper environment-friendly efficient self-polishing antifouling paint and preparation method thereof |
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