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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- 238000002360 preparation method Methods 0.000 title claims abstract description 38
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 title abstract description 99
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 203
- 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 18
- 239000000463 material Substances 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 131
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 67
- 239000011259 mixed solution Substances 0.000 claims description 61
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 58
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 56
- 230000003373 anti-fouling effect Effects 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 43
- 238000000576 coating method Methods 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 29
- 239000011592 zinc chloride Substances 0.000 claims description 29
- 235000005074 zinc chloride Nutrition 0.000 claims description 29
- 239000004925 Acrylic resin Substances 0.000 claims description 26
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical group [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 21
- 239000011248 coating agent Substances 0.000 claims description 20
- 239000011347 resin Substances 0.000 claims description 20
- 229920005989 resin Polymers 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 16
- 229910052802 copper Inorganic materials 0.000 claims description 16
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-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
- 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
- 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 12
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-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
- 239000000049 pigment Substances 0.000 claims description 9
- 229920000178 Acrylic resin Polymers 0.000 claims description 8
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 7
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-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
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 6
- 230000015556 catabolic process Effects 0.000 claims description 6
- 238000006731 degradation reaction Methods 0.000 claims description 6
- 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 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
- 239000000178 monomer Substances 0.000 claims description 6
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 239000000440 bentonite Substances 0.000 claims description 5
- 229910000278 bentonite Inorganic materials 0.000 claims description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 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
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical class [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 3
- 229920000058 polyacrylate Polymers 0.000 claims 2
- 229910002012 Aerosil® Inorganic materials 0.000 claims 1
- 150000001336 alkenes Chemical class 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 claims 1
- 230000007717 exclusion Effects 0.000 claims 1
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 238000009413 insulation Methods 0.000 claims 1
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical class CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 7
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 53
- 239000000975 dye Substances 0.000 description 14
- 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 13
- 229940012189 methyl orange Drugs 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 12
- 238000001782 photodegradation Methods 0.000 description 11
- 238000012360 testing method Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 238000010183 spectrum analysis Methods 0.000 description 8
- 239000000654 additive Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- XPLSDXJBKRIVFZ-UHFFFAOYSA-L copper;prop-2-enoate Chemical compound [Cu+2].[O-]C(=O)C=C.[O-]C(=O)C=C XPLSDXJBKRIVFZ-UHFFFAOYSA-L 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000002519 antifouling agent Substances 0.000 description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229910021485 fumed silica Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 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 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- 239000005711 Benzoic acid Substances 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- 239000005750 Copper hydroxide Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 235000010233 benzoic acid Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 229910001956 copper hydroxide Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000004062 sedimentation 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
- 239000000725 suspension Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 2
- 229940007718 zinc hydroxide Drugs 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
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000000703 high-speed centrifugation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 239000008204 material by function Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000000377 silicon dioxide 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
- 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
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000012086 standard solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000010998 test method Methods 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
-
- 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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- 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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- 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
-
- 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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- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
Description
【技术领域】【Technical field】
本发明属于无机功能材料制备技术领域。更具体地，本发明涉及一种微/纳米Cu2O/ZnO复合材料，还涉及所述微/纳米Cu2O/ZnO复合材料的制备方法，还涉及所述微/纳米Cu2O/ZnO复合材料的用途。The invention belongs to the technical field of preparation of inorganic functional materials. More specifically, the present invention relates to a micro/nano Cu 2 O/ZnO composite material, a method for preparing the micro/nano Cu 2 O/ZnO composite material, and a micro/nano Cu 2 O/ZnO The use of composite materials.
【背景技术】【Background technique】
Cu2O是一种无机氧化物，它是能带隙约2.17eV的p型半导体材料，对可见光具有较高的吸收系数。在光催化、新型太阳能电池、磁储存装置、生物传感器及涂料等技术领域都有着广泛的应用。与其他半导体光催化剂类似，Cu2O也存在着由光生电子和空穴易复合所导致的催化效果较差的问题。研究发现，制备复合半导体是提高光催化效率的一种重要方法。Cu 2 O is an inorganic oxide, which is a p-type semiconductor material with an energy band gap of about 2.17eV, and has a relatively high absorption coefficient for visible light. It has a wide range of applications in photocatalysis, new solar cells, magnetic storage devices, biosensors and coatings. Similar to other semiconductor photocatalysts, Cu 2 O also has the problem of poor catalytic effect caused by the easy recombination of photogenerated electrons and holes. Studies have found that preparing compound semiconductors is an important method to improve photocatalytic efficiency.
近年来，Cu2O复合材料主要的制备方法有光化学沉积法、电化学沉积法、物理混合法等方法。Mittiga研究小组(A.Mittiga,E.Salza,F.Sarto,et a1.Heterojunction solarcell with 2％efficiency based on a Cu2O substrate.Appl.Phys.Lett.,2006,88(16),163-502.)利用两步法，热氧化Cu片制备出晶粒尺寸达1mm2、迁移率高达100cm2Vs-1的Cu2O薄膜，以此作基底沉积一层ITO薄膜，从而制备出pn异质结太阳能电池，获得了约2％的太阳光转换效率；Cui等人(J.Cui,U.J.Glbson.A simple two-step electrodepositionofCu2O/ZnO nanopillar solar cells.J.Phys.Chem.C.,2010,114(14),6408-6412.)采用两步电化学沉积方法制备得到纳米Cu2O/ZnO复合材料柱。然而，这些现有方法通常制备过程复杂，条件要求苛刻，极大地限制了Cu2O复合材料的规模化生产和工业应用。In recent years, the main preparation methods of Cu 2 O composite materials include photochemical deposition method, electrochemical deposition method, physical mixing method and other methods. Mittiga Research Group (A.Mittiga, E.Salza, F.Sarto, et a1.Heterojunction solarcell with 2%efficiency based on a Cu2O substrate.Appl.Phys.Lett.,2006,88(16),163-502.) A Cu 2 O film with a grain size of 1 mm 2 and a mobility of 100 cm 2 Vs -1 was prepared by thermally oxidizing Cu sheets by a two-step method, and a layer of ITO film was deposited on this as a substrate to prepare a pn heterojunction solar energy cell, obtained about 2 % solar light conversion efficiency; Cui et al. 14), 6408-6412.) Prepare nano-Cu 2 O/ZnO composite column by two-step electrochemical deposition method. However, these existing methods usually have complex preparation processes and harsh conditions, which greatly limit the large-scale production and industrial application of Cu 2 O composites.
本发明人在总结现有技术的基础上，通过大量实验研究，完成了本发明。本发明采用简单的液相还原法，在无任何辅助性的有机添加剂或表面活性剂的情况下，以硫酸铜、氢氧化钠和葡萄糖为原料制备得到微/纳米 Cu2O/ZnO复合材料。该合成方法简单，易于操作，合成的微/纳米Cu2O/ZnO复合材料可以作为催化剂降解有机污染物，又可以作为防污剂复配高性能环境友好型海洋防污涂料。The present inventor has completed the present invention through a large number of experimental studies on the basis of summarizing the prior art. The invention adopts a simple liquid phase reduction method to prepare micro/nano Cu 2 O/ZnO composite materials by using copper sulfate, sodium hydroxide and glucose as raw materials without any auxiliary organic additives or surfactants. The synthesis method is simple and easy to operate, and the synthesized micro/nano Cu 2 O/ZnO composite material can be used as a catalyst to degrade organic pollutants, and can also be used as an antifouling agent to compound high-performance environment-friendly marine antifouling coatings.
【发明内容】【Content of invention】
[要解决的技术问题][Technical problem to be solved]
本发明的目的是提供一种微/纳米Cu2O/ZnO复合材料。The purpose of the present invention is to provide a micro/nano Cu 2 O/ZnO composite material.
本发明的另一个目的是提供所述微/纳米Cu2O/ZnO复合材料的制备方法。Another object of the present invention is to provide a method for preparing the micro/nano Cu 2 O/ZnO composite material.
本发明的另一个目的是提供所述微/纳米Cu2O/ZnO复合材料的用途。Another object of the present invention is to provide the use of the micro/nano Cu 2 O/ZnO composite material.
[技术方案][Technical solutions]
本发明是通过下述技术方案实现的。The present invention is achieved through the following technical solutions.
本发明涉及一种微/纳米Cu2O/ZnO复合材料的制备方法。The invention relates to a preparation method of a micro/nano Cu 2 O/ZnO composite material.
该制备方法的步骤如下：The steps of the preparation method are as follows:
A、制备混合溶液A. Prepare mixed solution
硫酸铜与氯化锌按照摩尔比1:0.025～2.000加到去离子水中，搅拌溶解，得到一种铜浓度0.5～2.0mol/L的铜锌混合溶液；Copper sulfate and zinc chloride are added to deionized water according to the molar ratio of 1:0.025-2.000, stirred and dissolved to obtain a copper-zinc mixed solution with a copper concentration of 0.5-2.0mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:2～5，往步骤A得到的混合溶液中加入浓度为0.1～3.0mol/L的氢氧化钠水溶液，然后加热到温度30～90℃，接着继续搅拌5～60min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:2~5, add an aqueous sodium hydroxide solution with a concentration of 0.1~3.0mol/L to the mixed solution obtained in step A, and then heat it to a temperature of 30~90 ℃, then continue to stir for 5-60min to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
按照硫酸铜与葡萄糖的摩尔比1:0.1～5.0，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度40～100℃，并在这个温度下保温5～60min，分离得到微/纳米Cu2O/ZnO复合材料。According to the molar ratio of copper sulfate to glucose 1:0.1～5.0, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then, heat the reaction system to a temperature of 40～100°C, and at this temperature Keeping it warm for 5 to 60 minutes, and separating and obtaining the micro/nano Cu 2 O/ZnO composite material.
本发明还涉及采用所述制备方法制备得到的微/纳米Cu2O/ZnO复合材料。所述的微/纳米Cu2O/ZnO复合材料，其材料尺寸是0.1～5.0μm。The invention also relates to the micro/nano Cu 2 O/ZnO composite material prepared by the preparation method. The material size of the micro/nano Cu 2 O/ZnO composite material is 0.1-5.0 μm.
本发明还涉及所述的微/纳米Cu2O/ZnO复合材料在光降解有机污染物中的用途。The invention also relates to the use of the micro/nano Cu 2 O/ZnO composite material in photodegrading organic pollutants.
本发明还涉及所述的微/纳米Cu2O/ZnO复合材料在制备高性能环境友好型海洋防污涂料中的用途。The present invention also relates to the use of the micro/nano Cu 2 O/ZnO composite material in the preparation of high-performance environment-friendly marine antifouling coatings.
根据本发明，所述的高性能环境友好型海洋防污涂料由20～60重量份树脂溶液、1～20重量份助剂、1～30重量份颜料或填料与1～50重量份微/纳米Cu2O/ZnO复合材料组成。According to the present invention, the high-performance environment-friendly marine antifouling paint consists of 20-60 parts by weight of resin solution, 1-20 parts by weight of additives, 1-30 parts by weight of pigments or fillers and 1-50 parts by weight of micro/nano Composition of Cu 2 O/ZnO composite material.
根据本发明的一种优选实施方式，所述的树脂溶液是由选自丙烯酸树脂、丙烯酸锌树脂或丙烯酸铜树脂的树脂与选自乙酸乙酯、乙酸丁酯、二甲苯、甲苯或丁醇的溶剂组成的。According to a preferred embodiment of the present invention, the resin solution is composed of a resin selected from acrylic resin, zinc acrylate resin or copper acrylate resin and a resin selected from ethyl acetate, butyl acetate, xylene, toluene or butanol composed of solvents.
根据本发明的另一种优选实施方式，所述树脂溶液的浓度是以重量计20～60％。According to another preferred embodiment of the present invention, the concentration of the resin solution is 20-60% by weight.
根据本发明的另一种优选实施方式，所述的丙烯酸锌树脂或丙烯酸铜树脂是采用下述方法合成得到的：According to another preferred embodiment of the present invention, the zinc acrylate resin or copper acrylate resin is synthesized by the following method:
I、预聚物的制备I, the preparation of prepolymer
将1000～1400重量份由甲苯与正丁醇按照重量比4:1组成的混合溶剂加热至回流温度，接着滴加18～22重量份偶氮二异丁腈在700～900重量份丙烯酸单体混合物中的溶液，所述丙烯酸单体混合物由104重量份丙烯酸、161重量份甲基丙烯酸甲酯、320重量份醋酸乙烯与216重量份甲基丙烯酸丁酯组成，在滴加过程中保持加热回流；滴加完后继续反应3.5～4.5小时，得到微黄色澄清透明的丙烯酸预聚物；Heat 1000-1400 parts by weight of a mixed solvent composed of toluene and n-butanol at a weight ratio of 4:1 to reflux temperature, and then dropwise add 18-22 parts by weight of azobisisobutyronitrile in 700-900 parts by weight of acrylic acid monomer The solution in the mixture, the acrylic acid monomer mixture is composed of 104 parts by weight of acrylic acid, 161 parts by weight of methyl methacrylate, 320 parts by weight of vinyl acetate and 216 parts by weight of butyl methacrylate, kept under reflux during the dropping process ; Continue to react for 3.5 to 4.5 hours after the dropwise addition to obtain a light yellow, clear and transparent acrylic acid prepolymer;
II、丙烯酸锌或丙烯酸铜树脂的制备II, the preparation of zinc acrylate or copper acrylate resin
将150重量份在步骤I制备的丙烯酸预聚物、11.5重量份氢氧化锌或11.3重量份氢氧化铜、13.2重量份苯甲酸、27重量份乙酸丁酯与10重量份在步骤I使用的混合溶剂混合均匀，然后在温度70～80℃的条件下反应5.5～6.5小时，接着将温度升至125℃进行脱水，待反应混合物透明并且无水份馏出时结束反应，得到透明的丙烯酸锌或丙烯酸铜树脂。Mix 150 parts by weight of acrylic acid prepolymer prepared in step I, 11.5 parts by weight of zinc hydroxide or 11.3 parts by weight of copper hydroxide, 13.2 parts by weight of benzoic acid, 27 parts by weight of butyl acetate with 10 parts by weight of Mix the solvent evenly, then react at a temperature of 70-80°C for 5.5-6.5 hours, then raise the temperature to 125°C for dehydration, and stop the reaction when the reaction mixture is transparent and no water is distilled out to obtain transparent zinc acrylate or Copper acrylic resin.
根据本发明的另一种优选实施方式，所述的颜料是氧化铁红、氧化铁黄或钛白粉；所述的填料是气相二氧化硅或滑石粉。According to another preferred embodiment of the present invention, the pigment is iron oxide red, iron oxide yellow or titanium dioxide; the filler is fumed silica or talcum powder.
根据本发明的另一种优选实施方式，所述的助剂是卵磷脂或膨润土。According to another preferred embodiment of the present invention, the auxiliary agent is lecithin or bentonite.
下面将更详细地描述本发明。The present invention will be described in more detail below.
本发明涉及一种微/纳米Cu2O/ZnO复合材料的制备方法。The invention relates to a preparation method of a micro/nano Cu 2 O/ZnO composite material.
该制备方法的步骤如下：The steps of the preparation method are as follows:
A、制备混合溶液A. Prepare mixed solution
硫酸铜与氯化锌按照摩尔比1:0.025～2.000加到去离子水中，搅拌溶解，得到一种铜浓度0.5～2.0mol/L的铜锌混合溶液。Copper sulfate and zinc chloride are added to deionized water at a molar ratio of 1:0.025-2.000, stirred and dissolved to obtain a copper-zinc mixed solution with a copper concentration of 0.5-2.0 mol/L.
在本发明中，所述的硫酸铜与氯化锌的摩尔比1:0.025～2.000。如果氯化锌的摩尔比小于0.025，溶液中得到极少量的ZnO2 2-和大量的Cu(OH)4 2-，此时ZnO2 2-对Cu2O晶体的成核影响不大；如果氯化锌的摩尔比高于2.000，则溶液中过量的Zn2+与OH-反应，抑制了Cu(OH)4 2-的生成；因此，硫酸铜与氯化锌的摩尔比为1:0.025～2.000是恰当的；优选地是1:0.05～1.50；更优选地是1:0.30～1.00。In the present invention, the molar ratio of copper sulfate to zinc chloride is 1:0.025-2.000. If the molar ratio of zinc chloride is less than 0.025, a very small amount of ZnO 2 2- and a large amount of Cu(OH) 4 2- are obtained in the solution, and ZnO 2 2- has little effect on the nucleation of Cu 2 O crystals; if When the molar ratio of zinc chloride is higher than 2.000, the excess Zn 2+ in the solution reacts with OH- , which inhibits the formation of Cu(OH) 4 2- ; therefore, the molar ratio of copper sulfate to zinc chloride is 1:0.025 ~2.000 is suitable; preferably 1:0.05-1.50; more preferably 1:0.30-1.00.
在制备混合溶液过程中，需要充分、持续搅拌，以便硫酸铜与氯化锌充分溶解完全。In the process of preparing the mixed solution, sufficient and continuous stirring is required so that the copper sulfate and zinc chloride can be fully dissolved.
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:2～5，往步骤A得到的混合溶液中加入浓度为0.1～3.0mol/L的氢氧化钠水溶液，然后加热到温度30～90℃，接着继续搅拌5～60min，得到一种含有氢氧化钠的混合溶液。At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:2~5, add an aqueous sodium hydroxide solution with a concentration of 0.1~3.0mol/L to the mixed solution obtained in step A, and then heat it to a temperature of 30~90 °C, and then continue stirring for 5-60 min to obtain a mixed solution containing sodium hydroxide.
在这个步骤中，添加氢氧化钠的作用是提供碱性条件，使溶液中的Cu2+与OH-反应形成Cu(OH)4 2-溶液，进一步通过葡萄糖还原。In this step, the role of adding sodium hydroxide is to provide alkaline conditions, so that Cu 2+ in the solution reacts with OH- to form a Cu(OH) 4 2- solution, which is further reduced by glucose.
在本发明中，所述的硫酸铜与氢氧化钠的摩尔比为1:2～5。如果氢氧化钠的摩尔比小于2，则得不到Cu(OH)4 2-溶液，最终抑制了Cu2O晶体的成核；如果氢氧化钠的摩尔比高于5，则溶液中剩余过量的OH-，消耗了大量的原料；因此，硫酸铜与氢氧化钠的摩尔比为1:2～5是恰当的；优选 地是1:3.4～4.5；更优选地是1:3.8～4.2。In the present invention, the molar ratio of copper sulfate to sodium hydroxide is 1:2-5. If the molar ratio of NaOH is less than 2 , no Cu(OH) 4 2- solution can be obtained, eventually inhibiting the nucleation of Cu2O crystals; if the molar ratio of NaOH is higher than 5, excess OH - , consumes a lot of raw materials; therefore, the molar ratio of copper sulfate to sodium hydroxide is 1:2-5 is appropriate; preferably 1:3.4-4.5; more preferably 1:3.8-4.2.
C、加入葡萄糖C. Add glucose
按照硫酸铜与葡萄糖的摩尔比1:0.1～5.0，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度40～100℃，并在这个温度下保温5～60min，分离得到微/纳米Cu2O/ZnO复合材料。According to the molar ratio of copper sulfate to glucose 1:0.1～5.0, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then, heat the reaction system to a temperature of 40～100°C, and at this temperature Keeping it warm for 5 to 60 minutes, and separating and obtaining the micro/nano Cu 2 O/ZnO composite material.
在这个步骤中，添加还原剂葡萄糖的作用是缓慢地将溶液中的Cu2+还原成Cu+。In this step, the effect of adding reducing agent glucose is to slowly reduce Cu 2+ in solution to Cu + .
在本发明中，所述的硫酸铜与葡萄糖的摩尔比为1:0.1～5.0。如果葡萄糖的摩尔比小于0.1，则Cu2+还原不充分；如果葡萄糖的摩尔比高于5.0，则溶液中剩余大量的葡萄糖；因此，硫酸铜与葡萄糖的摩尔比为1:0.1～5.0是恰当的；优选地是1:0.8～4.0；更优选地是1:1.6～0.30。In the present invention, the molar ratio of copper sulfate to glucose is 1:0.1-5.0. If the molar ratio of glucose is less than 0.1, the reduction of Cu 2+ is insufficient; if the molar ratio of glucose is higher than 5.0, a large amount of glucose remains in the solution; therefore, the molar ratio of copper sulfate to glucose is 1:0.1～5.0 is appropriate ; preferably 1:0.8-4.0; more preferably 1:1.6-0.30.
采用本发明方法制备的微/纳米Cu2O/ZnO复合材料进行了常规的X-射线衍射分析与常规的扫描电子显微镜分析与能谱分析。The micro/nano Cu 2 O/ZnO composite material prepared by the method of the present invention is subjected to conventional X-ray diffraction analysis, conventional scanning electron microscope analysis and energy spectrum analysis.
所述的X-射线衍射分析条件如下：Described X-ray diffraction analysis condition is as follows:
仪器：德国Bruker公司D8Advance型X-射线衍射仪。Instrument: D8Advance X-ray diffractometer from Bruker Company, Germany.
测定条件：CuKα()，扫描范围15°-85°，扫描速率4°min-1，石墨片滤波，管压40kV，电流40mA。Determination conditions: CuKα ( ), scanning range 15°-85°, scanning rate 4°min -1 , graphite filter, tube voltage 40kV, current 40mA.
测定结果参见附图1，该图的结果表明得到了Cu2O/ZnO复合结构。Refer to the accompanying drawing 1 for the measurement results, the results in this figure show that a Cu 2 O/ZnO composite structure was obtained.
所述的扫描电子显微镜分析条件如下：The scanning electron microscope analysis conditions are as follows:
仪器：Hitachi公司S-4800型场发射扫描电子显微镜。Instrument: Hitachi S-4800 field emission scanning electron microscope.
测定条件：加速电压8～10kV。Measuring conditions: accelerating voltage 8 ~ 10kV.
测定结果参见附图2至10，这些附图的结果表明：随Zn2+用量的改变，产物Cu2O/ZnO复合材料形貌发生变化。See Figures 2 to 10 for the measurement results. The results of these figures show that the morphology of the Cu 2 O/ZnO composite material changes with the change of the amount of Zn 2+ .
所述的能谱分析条件如下：Described energy spectrum analysis condition is as follows:
仪器：Hitachi公司S-4800型场发射扫描电子显微镜EDS分析。Instrument: Hitachi S-4800 Field Emission Scanning Electron Microscope for EDS analysis.
测定条件：加速电压8～10kV。Measuring conditions: accelerating voltage 8 ~ 10kV.
测定结果参见附图5、7与8，这些结果表明得到了Cu2O/ZnO复合结构。Refer to Figures 5, 7 and 8 for the measurement results, these results indicate that a Cu 2 O/ZnO composite structure was obtained.
本发明还涉及采用所述制备方法制备得到的微/纳米Cu2O/ZnO复合材料。由附图2至10的结果知道，所述的微/纳米Cu2O/ZnO复合材料的尺寸是0.1～5.0μm。The invention also relates to the micro/nano Cu 2 O/ZnO composite material prepared by the preparation method. It is known from the results of Figs. 2 to 10 that the size of the micro/nano Cu 2 O/ZnO composite material is 0.1-5.0 μm.
本发明还涉及所述的微/纳米Cu2O/ZnO复合材料在光降解有机污染物中的用途。The invention also relates to the use of the micro/nano Cu 2 O/ZnO composite material in photodegrading organic pollutants.
按照本说明书应用实施例1描述的方式，研究了本发明微/纳米Cu2O/ZnO复合材料作为催化剂，可见光对有机染料甲基橙的光降解作用，其结果见附图11。由附图11可以看出，本发明的微/纳米Cu2O/ZnO复合材料在可见光的照射下，光催化活性随着光照时间的延长而增强。甲基橙降解反应动力学遵循一级反应动力学模型。在铜锌摩尔比为1:0.5时，产物Cu2O/ZnO复合材料在可见光下对甲基橙的降解率可以达到77.45％。According to the method described in Application Example 1 of this specification, the micro/nano Cu 2 O/ZnO composite material of the present invention was used as a catalyst to study the photodegradation effect of visible light on the organic dye methyl orange, and the results are shown in Figure 11. It can be seen from FIG. 11 that the photocatalytic activity of the micro/nano Cu 2 O/ZnO composite material of the present invention increases with the extension of the irradiation time under the irradiation of visible light. The kinetics of methyl orange degradation followed the first-order kinetic model. When the molar ratio of copper to zinc is 1:0.5, the degradation rate of Cu 2 O/ZnO composite material to methyl orange under visible light can reach 77.45%.
为了进一步说明本发明微/纳米Cu2O/ZnO复合材料的光催化性能，使用聚偏氟乙烯将本发明微/纳米Cu2O/ZnO复合材料调成浆料，涂在导电玻璃FTO制备成膜作为光阳极，Ag/AgCl作为参比电极，Pt电极作为对电极，组装成虚拟电池，采用CHI660E型三电极电化学工作站测试本发明微/纳米Cu2O/ZnO复合材料催化剂的bode阻抗图，计算催化剂的电子寿命，其结果列于图12中，该图清楚地说明组装的虚拟电池将Cu2O/ZnO作为光阳极，在硫酸铜与氯化锌摩尔比为1:0.5时，光电子寿命(τ)最长，对甲基橙的光催化降解性能最好。In order to further illustrate the photocatalytic performance of the micro/nano Cu 2 O/ZnO composite material of the present invention, the micro/nano Cu 2 O/ZnO composite material of the present invention was adjusted into a slurry using polyvinylidene fluoride, and coated on conductive glass FTO to prepare The film is used as the photoanode, the Ag/AgCl is used as the reference electrode, and the Pt electrode is used as the counter electrode to assemble a virtual battery. The bode impedance diagram of the micro/nano Cu 2 O/ZnO composite catalyst of the present invention is tested by a CHI660E three-electrode electrochemical workstation. , to calculate the electron lifetime of the catalyst, and the results are listed in Fig. 12, which clearly shows that the assembled virtual cell uses Cu 2 O/ZnO as the photoanode, and when the molar ratio of copper sulfate to zinc chloride is 1:0.5, the photoelectrons The lifetime (τ) is the longest, and the photocatalytic degradation performance of methyl orange is the best.
本发明还涉及所述的微/纳米Cu2O/ZnO复合材料在制备高性能环境友好型海洋防污涂料中的用途。The present invention also relates to the use of the micro/nano Cu 2 O/ZnO composite material in the preparation of high-performance environment-friendly marine antifouling coatings.
根据本发明，所述的高性能环境友好型海洋防污涂料由20～60重量份树脂溶液、1～20重量份助剂、1～30重量份颜料或填料与1～50重量份微/纳米Cu2O/ZnO复合材料组成。According to the present invention, the high-performance environment-friendly marine antifouling paint consists of 20-60 parts by weight of resin solution, 1-20 parts by weight of additives, 1-30 parts by weight of pigments or fillers and 1-50 parts by weight of micro/nano Composition of Cu 2 O/ZnO composite material.
所述树脂溶液的浓度是以重量计20～60％。所述树脂溶液的浓度超过 这个浓度范围时，都会明显影响防污涂料的防污效果。优选地，所述树脂溶液的浓度是以重量计30～50％，更优选地，所述树脂溶液的浓度是以重量计36～45％。The concentration of the resin solution is 20-60% by weight. When the concentration of the resin solution exceeds this concentration range, the antifouling effect of the antifouling coating will be significantly affected. Preferably, the concentration of the resin solution is 30-50% by weight, more preferably, the concentration of the resin solution is 36-45% by weight.
所述的树脂溶液是由选自丙烯酸树脂、丙烯酸锌树脂或丙烯酸铜树脂的树脂与选自乙酸乙酯、乙酸丁酯、二甲苯、甲苯或丁醇的溶剂组成的。The resin solution is composed of a resin selected from acrylic resin, zinc acrylate resin or copper acrylate resin and a solvent selected from ethyl acetate, butyl acetate, xylene, toluene or butanol.
所述的丙烯酸树脂是目前市场上销售的产品，例如由长兴化学工业股份有限公司销售的丙烯酸树脂。Described acrylic resin is the product sold in the market at present, for example the acrylic resin sold by Changxing Chemical Industry Co., Ltd.
所述的丙烯酸锌树脂或丙烯酸铜树脂是采用下述方法合成得到的：Described zinc acrylate resin or copper acrylate resin is synthesized by the following method:
I、预聚物的制备I, the preparation of prepolymer
将1000～1400重量份由甲苯与正丁醇按照重量比4:1组成的混合溶剂加热至回流温度，接着滴加18～22重量份偶氮二异丁腈在700～900重量份丙烯酸单体混合物中的溶液，所述丙烯酸单体混合物由104重量份丙烯酸、161重量份甲基丙烯酸甲酯、320重量份醋酸乙烯与216重量份甲基丙烯酸丁酯组成，在滴加过程中保持加热回流；滴加完后继续反应3.5～4.5小时，得到微黄色澄清透明的丙烯酸预聚物。Heat 1000-1400 parts by weight of a mixed solvent composed of toluene and n-butanol at a weight ratio of 4:1 to reflux temperature, and then dropwise add 18-22 parts by weight of azobisisobutyronitrile in 700-900 parts by weight of acrylic acid monomer The solution in the mixture, the acrylic acid monomer mixture is composed of 104 parts by weight of acrylic acid, 161 parts by weight of methyl methacrylate, 320 parts by weight of vinyl acetate and 216 parts by weight of butyl methacrylate, kept under reflux during the dropping process ; Continue to react for 3.5 to 4.5 hours after the dropwise addition, and obtain a light yellow, clear and transparent acrylic acid prepolymer.
这个预聚物制备步骤所使用的设备是安装搅拌装置、冷凝器与温度计的三口容器，这种设备是化工技术领域里通常使用的、在目前市场上广泛销售的产品。The used equipment of this prepolymer preparation step is the three-necked container that agitator, condenser and thermometer are installed, and this equipment is the product that usually uses in the chemical technology field, widely sold in the present market.
II、丙烯酸锌或丙烯酸铜树脂的制备II, the preparation of zinc acrylate or copper acrylate resin
将150重量份在步骤I制备的丙烯酸预聚物、11.5重量份氢氧化锌或11.3重量份氢氧化铜、13.2重量份苯甲酸、27重量份乙酸丁酯与10重量份在步骤I使用的混合溶剂混合均匀，然后在温度70～80℃的条件下反应5.5～6.5小时，接着将温度升至125℃进行脱水，待反应混合物透明并且无水份馏出时结束反应，得到透明的丙烯酸锌或丙烯酸铜树脂。Mix 150 parts by weight of acrylic acid prepolymer prepared in step I, 11.5 parts by weight of zinc hydroxide or 11.3 parts by weight of copper hydroxide, 13.2 parts by weight of benzoic acid, 27 parts by weight of butyl acetate with 10 parts by weight of Mix the solvent evenly, then react at a temperature of 70-80°C for 5.5-6.5 hours, then raise the temperature to 125°C for dehydration, and stop the reaction when the reaction mixture is transparent and no water is distilled out to obtain transparent zinc acrylate or Copper acrylic resin.
这个制备步骤所使用的设备与步骤I所使用的设备相同。The equipment used in this preparation step is the same as that used in step I.
所述的乙酸乙酯、乙酸丁酯、二甲苯、甲苯或丁醇都是化工技术领域里通常使用的、在目前市场上广泛销售的产品。Described ethyl acetate, butyl acetate, xylene, toluene or butanol all are generally used in the chemical technology field, the product widely sold in the market at present.
在本发明的高性能环境友好型海洋防污涂料中，所述的助剂具有分散、防沉降的作用。所述的助剂是卵磷脂或膨润土。In the high-performance environment-friendly marine antifouling paint of the present invention, the additive has the functions of dispersing and anti-sedimentation. The auxiliary agent is lecithin or bentonite.
所述的卵磷脂或膨润土是化工技术领域里通常使用的、在目前市场上广泛销售的产品，例如由郑州耐瑞特公司销售的卵磷脂，由浙江丰虹新材料股份有限公司销售的膨润土。Described lecithin or bentonite are products commonly used in the chemical technology field and widely sold in the market, such as lecithin sold by Zhengzhou Neruite Company, and bentonite sold by Zhejiang Fenghong New Material Co., Ltd.
在本发明高性能环境友好型海洋防污涂料中，所述颜料的作用是着色。所述的颜料是氧化铁红、氧化铁黄或钛白粉。In the high-performance environment-friendly marine antifouling paint of the present invention, the function of the pigment is coloring. The pigment is iron oxide red, iron oxide yellow or titanium dioxide.
所述的氧化铁红、氧化铁黄或钛白粉是化工技术领域里通常使用的、在目前市场上广泛销售的产品，例如由上海一品颜料有限公司销售的氧化铁红、氧化铁黄，由美国杜邦公司的R-902销售的钛白粉。Described iron oxide red, iron oxide yellow or titanium dioxide are products commonly used in the chemical technology field and widely sold in the market, such as iron oxide red and iron oxide yellow sold by Shanghai Yipin Pigment Co., Ltd. Titanium dioxide is sold as R-902 by DuPont.
在本发明高性能环境友好型海洋防污涂料中，所述的填料具有填充的作用。所述的填料是气相二氧化硅或滑石粉。In the high-performance environment-friendly marine antifouling paint of the present invention, the filler has the function of filling. The filler is fumed silica or talcum powder.
所述的气相二氧化硅或滑石粉是化工技术领域里通常使用的、在目前市场上广泛销售的产品，例如由烟台佳宏化工有限公司销售的气相二氧化硅、由蓬莱市永丰达超细滑石粉公司销售的超细滑石粉。Described fumed silica or talcum powder are products commonly used in the chemical technology field and widely sold in the market, such as fumed silica sold by Yantai Jiahong Chemical Co., Ltd. Superfine talcum powder sold by Talc Powder Company.
根据本发明，微/纳米Cu2O/ZnO复合材料的量为1～50重量份，其它组分的量在所述的范围内，而所述树脂溶液的量低于20重量份时，则会使防污涂料的成膜性能变差，若所述树脂溶液的量高于60重量份时，则会降低防污涂料的防污性能，因此，树脂溶液的量为20～60重量份是合适的。According to the present invention, the amount of the micro/nano Cu 2 O/ZnO composite material is 1-50 parts by weight, the amount of other components is within the stated range, and when the amount of the resin solution is less than 20 parts by weight, then Can make the film-forming performance of antifouling paint worse, if the amount of described resin solution is higher than 60 weight parts, then can reduce the antifouling performance of antifouling paint, therefore, the amount of resin solution is 20～60 weight parts suitable.
同样地，微/纳米Cu2O/ZnO复合材料的量为1～50重量份，其它组分的量在所述的范围内，而助剂的量低于1重量份时，则会降低防污涂料的分散性、防沉降性能，若助剂的量高于20重量份时，则会影响防污涂料的成膜性能，因此，助剂的量为1～20重量份是合适的。Similarly, the amount of the micro/nano Cu 2 O/ZnO composite material is 1 to 50 parts by weight, the amount of other components is within the stated range, and when the amount of the auxiliary agent is less than 1 part by weight, the anti-corrosion effect will be reduced. For the dispersibility and anti-sedimentation performance of the fouling paint, if the amount of the additive is higher than 20 parts by weight, it will affect the film-forming performance of the antifouling paint. Therefore, the amount of the additive is 1-20 parts by weight.
微/纳米Cu2O/ZnO复合材料的量为1～50重量份，其它组分的量在所述的范围内，而填料的量低于1重量份时，则会降低防污涂料的防污效果，若填料的量高于30重量份时，则会降低防污涂料的成膜性，因此，填料 的量为1～30重量份是恰当的。The amount of the micro/nano Cu 2 O/ZnO composite material is 1 to 50 parts by weight, and the amount of other components is within the stated range, and when the amount of the filler is less than 1 part by weight, the antifouling coating will be reduced. For the fouling effect, if the amount of the filler is higher than 30 parts by weight, the film-forming property of the antifouling paint will be reduced. Therefore, the amount of the filler is 1-30 parts by weight.
优选地，所述的高性能环境友好型海洋防污涂料是由30～48重量份树脂溶液、5～14重量份助剂、8～22重量份颜料或填料与12～36重量份微/纳米Cu2O/ZnO复合材料组成。Preferably, the high-performance environment-friendly marine antifouling coating is composed of 30-48 parts by weight of resin solution, 5-14 parts by weight of additives, 8-22 parts by weight of pigments or fillers and 12-36 parts by weight of micro/nano Composition of Cu 2 O/ZnO composite material.
更优选地，所述的高性能环境友好型海洋防污涂料是由35～42重量份树脂溶液、8～10重量份助剂、12～18重量份颜料或填料与18～30重量份微/纳米Cu2O/ZnO复合材料组成。More preferably, the high-performance environment-friendly marine antifouling coating is composed of 35-42 parts by weight of resin solution, 8-10 parts by weight of additives, 12-18 parts by weight of pigments or fillers and 18-30 parts by weight of micro/ Composition of nano Cu 2 O/ZnO composite material.
海洋生物污损是从事海洋活动后逐渐认识到的生物学现象，并且人类与海洋附着生物的战斗已有四千多年的历史。海洋污损生物给海运业及海洋业带来众多危害，海洋污损生物的防除是自人类从事海洋活动以来一直难以解决的重大问题，为了最大限度减少海洋污损生物造成的危害，涂刷防污涂层是最经济、有效和普遍采用的方法。Marine biofouling is a biological phenomenon gradually recognized after engaging in marine activities, and the battle between human beings and marine growths has a history of more than 4,000 years. Marine fouling organisms have brought many hazards to the shipping industry and the marine industry. The prevention and control of marine fouling organisms has been a major problem that has been difficult to solve since human beings have engaged in marine activities. In order to minimize the harm caused by marine fouling organisms, paint anti Dirt coating is the most economical, effective and commonly used method.
采用下述标准方法对本发明高性能环境友好型海洋防污涂料的性能进行了检测：Adopt following standard method to detect the performance of high-performance environment-friendly marine antifouling paint of the present invention:
涂料粘度测定法：GB/T 1723-1993Coating Viscosity Determination Method: GB/T 1723-1993
涂料细度测定法：GB/T 1724-1979Coating fineness determination method: GB/T 1724-1979
漆膜附着力测定法：GB/T1720-1979Determination of paint film adhesion: GB/T1720-1979
将本发明的微/纳米Cu2O/ZnO复合材料作为防污剂复配自抛光防污涂料，按照国家标准进行了该涂料的性能分析，其中粘度(涂-4)杯，达到85-92(s)、细度为50-55(μm)和附着力均为1(级)，这表明本发明的微/纳米Cu2O/ZnO复合材料作为防污剂复配自抛光防污涂料，粘度、细度与附着力三项性能指标均符合海洋防污涂料的基本要求。The micro/nano Cu 2 O/ZnO composite material of the present invention is used as an antifouling agent to compound a self-polishing antifouling coating, and the performance analysis of the coating is carried out according to the national standard, wherein the viscosity (coating-4) cup reaches 85-92 (s), the fineness is 50-55 (μm) and the adhesion is 1 (level), which shows that the micro/nano Cu 2 O/ZnO composite material of the present invention is compounded as an antifouling agent from polishing antifouling paint, The three performance indicators of viscosity, fineness and adhesion all meet the basic requirements of marine antifouling coatings.
[有益效果][beneficial effect]
本发明的有益效果是：本发明采用简单的液相还原法，在无任何辅助性的有机添加剂或表面活性剂的情况下，以硫酸铜、氯化锌、氢氧化钠和葡萄糖为原料制备得到微/纳米Cu2O/ZnO复合材料，该制备方法简单，易于操作，产率高达96％以上，它能弥补其他制备方法过程中的制备过 程繁杂，条件要求苛刻等限制，同时也能弥补Cu2O光催化效率低的不足。本发明的微/纳米Cu2O/ZnO复合材料作为光催化剂和在制备高性能环境友好型海洋防污涂料中具有非常良好的应用前景。The beneficial effects of the present invention are: the present invention adopts a simple liquid-phase reduction method, without any auxiliary organic additives or surfactants, to prepare copper sulfate, zinc chloride, sodium hydroxide and glucose as raw materials Micro/nano Cu 2 O/ZnO composite material, the preparation method is simple, easy to operate, and the yield is as high as 96%, which can make up for the complicated preparation process and harsh conditions of other preparation methods, and can also make up for the 2 O photocatalytic efficiency is low. The micro/nano Cu 2 O/ZnO composite material of the present invention has very good application prospects as a photocatalyst and in the preparation of high-performance environment-friendly marine antifouling coatings.
【附图说明】【Description of drawings】
图1是不同硫酸铜与氯化锌摩尔比的微/纳米Cu2O/ZnO复合材料X-射线衍射图。Fig. 1 is an X-ray diffraction pattern of micro/nano Cu 2 O/ZnO composite materials with different molar ratios of copper sulfate and zinc chloride.
图2是实施例1在硫酸铜与氯化锌摩尔比为1:0.025时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜照片。Fig. 2 is a scanning electron micrograph of the micro/nano Cu 2 O/ZnO composite material prepared in Example 1 when the molar ratio of copper sulfate to zinc chloride is 1:0.025.
图3是实施例2在硫酸铜与氯化锌摩尔比为1:0.05时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜照片。Fig. 3 is a scanning electron micrograph of the micro/nano Cu 2 O/ZnO composite material prepared in Example 2 when the molar ratio of copper sulfate to zinc chloride is 1:0.05.
图4是实施例3在硫酸铜与氯化锌摩尔比为1:0.15时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜照片。Fig. 4 is a scanning electron micrograph of the micro/nano Cu 2 O/ZnO composite material prepared in Example 3 when the molar ratio of copper sulfate to zinc chloride is 1:0.15.
图5是实施例4在硫酸铜与氯化锌摩尔比为1:0.18时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜、能谱分析照片和X-射线光电子能谱。Fig. 5 is a scanning electron microscope, an energy spectrum analysis photo and an X-ray photoelectron spectrum of the micro/nano Cu 2 O/ZnO composite material prepared in Example 4 when the molar ratio of copper sulfate to zinc chloride is 1:0.18.
图6是实施例5在硫酸铜与氯化锌摩尔比为1:0.25时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜照片。Fig. 6 is a scanning electron micrograph of the micro/nano Cu 2 O/ZnO composite material prepared in Example 5 when the molar ratio of copper sulfate to zinc chloride is 1:0.25.
图7是实施例6在硫酸铜与氯化锌摩尔比为1:0.5时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜和能谱分析照片。Fig. 7 is a scanning electron microscope and an energy spectrum analysis photo of the micro/nano Cu 2 O/ZnO composite material prepared in Example 6 when the molar ratio of copper sulfate to zinc chloride is 1:0.5.
图8是实施例7在硫酸铜与氯化锌摩尔比为1:0.8时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜和能谱分析照片。Fig. 8 is a scanning electron microscope and an energy spectrum analysis photo of the micro/nano Cu 2 O/ZnO composite material prepared in Example 7 when the molar ratio of copper sulfate to zinc chloride is 1:0.8.
图9是实施例8在硫酸铜与氯化锌摩尔比为1:1.2时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜照片。Fig. 9 is a scanning electron micrograph of the micro/nano Cu 2 O/ZnO composite material prepared in Example 8 when the molar ratio of copper sulfate to zinc chloride is 1:1.2.
图10是实施例9在硫酸铜与氯化锌摩尔比为1:2时制备得到的微/纳米Cu2O/ZnO复合材料的扫描电子显微镜照片。Fig. 10 is a scanning electron micrograph of the micro/nano Cu 2 O/ZnO composite material prepared in Example 9 when the molar ratio of copper sulfate to zinc chloride is 1:2.
图11是本发明微/纳米Cu2O/ZnO复合材料作为催化剂，在5.5小时可见光照射对有机染料甲基橙的降解率曲线(a)和准一级动力学模型(b) 图。Fig. 11 shows the degradation rate curve (a) and the pseudo-first-order kinetic model (b) of the organic dye methyl orange irradiated by visible light for 5.5 hours with the micro/nano Cu 2 O/ZnO composite material of the present invention as a catalyst.
图12是设计虚拟电池计算本发明微/纳米Cu2O/ZnO复合材料在有机污染物中的催化寿命bode阻抗图。Fig. 12 is a bode impedance diagram for calculating the catalytic lifetime of the micro/nano Cu 2 O/ZnO composite material in organic pollutants by designing a virtual battery.
【具体实施方式】【detailed description】
通过下述实施例将能够更好地理解本发明。The present invention will be better understood by the following examples.
实施例1：制备微/纳米Cu2O/ZnO复合材料Example 1: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.025加到去离子水中，搅拌溶解，得到一种铜浓度1.0mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.025, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 1.0mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:4，往步骤A得到的混合溶液中加入浓度为1.0mol/L的氢氧化钠水溶液，然后加热到温度30℃，接着继续搅拌5min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:4, add an aqueous sodium hydroxide solution with a concentration of 1.0 mol/L to the mixed solution obtained in step A, then heat to a temperature of 30°C, and then continue to stir for 5 minutes , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:0.4，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度40℃，并在这个温度下保温13min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到96.5％。Under stirring conditions, according to the molar ratio of copper sulfate and glucose 1:0.4, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 40 ° C, and The temperature was kept at this temperature for 13 minutes, and the micro/nano Cu 2 O/ZnO composite material was separated, and the yield reached 96.5%.
按照本说明书中描述的扫描电子显微镜分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图2中。According to the scanning electron microscope analysis method described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 2 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例2：制备微/纳米Cu2O/ZnO复合材料Example 2: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.05加到去离子水中，搅拌溶解，得到一种铜浓度0.5mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.05, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 0.5mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:3，往步骤A得到的混合溶液中加入浓度为0.6mol/L的氢氧化钠水溶液，然后加热到温度55℃，接着继续搅拌18min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:3, add an aqueous sodium hydroxide solution with a concentration of 0.6 mol/L to the mixed solution obtained in step A, then heat to a temperature of 55°C, and continue stirring for 18 minutes , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:0.1，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度70℃，并在这个温度下保温44min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到97.5％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:0.1, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 70 ° C, and The temperature was kept at this temperature for 44 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 97.5%.
按照本说明书中描述的扫描电子显微镜分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图3中。According to the scanning electron microscope analysis method described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 3 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例3：制备微/纳米Cu2O/ZnO复合材料Example 3: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.15加到去离子水中，搅拌溶解，得到一种铜浓度1.2mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.15, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 1.2mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:5，往步骤A得到的混合溶液中加入浓度为3.0mol/L的氢氧化钠水溶液，然后加热到温度75℃，接着继续搅拌43min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:5, add an aqueous sodium hydroxide solution with a concentration of 3.0 mol/L to the mixed solution obtained in step A, then heat to a temperature of 75°C, and continue stirring for 43 minutes , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:4.3，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度95℃，并在这个温度下保温52min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到96.2％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:4.3, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 95 ° C, and The temperature was kept at this temperature for 52 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 96.2%.
按照本说明书中描述的扫描电子显微镜分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图4中。According to the scanning electron microscope analysis method described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 4 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例4：制备微/纳米Cu2O/ZnO复合材料Example 4: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.18加到去离子水中，搅拌溶解，得到一种铜浓度1.4mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.18, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 1.4mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:3.8，往步骤A得到的混合溶液中加入浓度为0.1mol/L的氢氧化钠水溶液，然后加热到温度50℃，接着继续搅拌60min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate to sodium hydroxide 1:3.8, add an aqueous sodium hydroxide solution with a concentration of 0.1mol/L to the mixed solution obtained in step A, then heat to a temperature of 50°C, and continue stirring for 60 minutes , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:2.8，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度55℃，并在这个温度下保温29min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到98.2％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:2.8, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 55 ° C, and The temperature was kept at this temperature for 29 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 98.2%.
按照本说明书中描述的扫描电子显微镜分析与能谱分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图5 中。According to the scanning electron microscope analysis and energy spectrum analysis methods described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 5 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例5：制备微/纳米Cu2O/ZnO复合材料Example 5: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.25加到去离子水中，搅拌溶解，得到一种铜浓度1.6mol/L与的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.25, stir and dissolve to obtain a mixed solution of copper and zinc with a copper concentration of 1.6 mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:4.5，往步骤A得到的混合溶液中加入浓度为2.1mol/L的氢氧化钠水溶液，然后加热到温度85℃，接着继续搅拌30min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate to sodium hydroxide 1:4.5, add an aqueous sodium hydroxide solution with a concentration of 2.1mol/L to the mixed solution obtained in step A, then heat to a temperature of 85°C, and continue stirring for 30min , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:2，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度100℃，并在这个温度下保温5min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到96.6％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:2, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 100 ° C, and The temperature was kept at this temperature for 5 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 96.6%.
按照本说明书中描述的扫描电子显微镜分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图6中。According to the scanning electron microscopy analysis method described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 6 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例6：制备微/纳米Cu2O/ZnO复合材料Example 6: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.5加到去离子水中，搅拌溶解，得到一种铜浓度1.0mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.5, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 1.0mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:4.2，往步骤A得到的混合溶液中加入浓度为1.5mol/L的氢氧化钠水溶液，然后加热到温度90℃，接着继续搅拌25min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:4.2, add an aqueous sodium hydroxide solution with a concentration of 1.5 mol/L to the mixed solution obtained in step A, then heat to a temperature of 90°C, and continue stirring for 25 minutes , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:1.8，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度100℃，并在这个温度下保温21min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到97.4％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:1.8, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 100 ° C, and The temperature was kept at this temperature for 21 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 97.4%.
按照本说明书中描述的扫描电子显微镜分析与能谱分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图7中。According to the scanning electron microscope analysis and energy spectrum analysis methods described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 7 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例7：制备微/纳米Cu2O/ZnO复合材料Example 7: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:0.8加到去离子水中，搅拌溶解，得到一种铜浓度0.8mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:0.8, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 0.8mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:2.5，往步骤A得到的混合溶液中加入浓度为2.5mol/L的氢氧化钠水溶液，然后加热到温度60 ℃，接着继续搅拌10min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:2.5, add an aqueous sodium hydroxide solution with a concentration of 2.5 mol/L to the mixed solution obtained in step A, then heat to a temperature of 60 ° C, and then continue to stir for 10 min , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:3.6，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度85℃，并在这个温度下保温35min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到98.0％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:3.6, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 85 ° C, and The temperature was kept at this temperature for 35 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 98.0%.
按照本说明书中描述的扫描电子显微镜分析与能谱分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图8中。According to the scanning electron microscope analysis and energy spectrum analysis methods described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 8 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例8：制备微/纳米Cu2O/ZnO复合材料Example 8: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:1.2加到去离子水中，搅拌溶解，得到一种铜浓度1.8mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:1.2, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 1.8mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:5，往步骤A得到的混合溶液中加入浓度为1.2mol/L的氢氧化钠水溶液，然后加热到温度45℃，接着继续搅拌56min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:5, add an aqueous sodium hydroxide solution with a concentration of 1.2mol/L to the mixed solution obtained in step A, then heat to a temperature of 45°C, and then continue to stir for 56min , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:5.0，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度73℃，并在这个温度下保温56min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到96.9％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:5.0, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 73 ° C, and The temperature was kept at this temperature for 56 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 96.9%.
按照本说明书中描述的扫描电子显微镜分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图9中。According to the scanning electron microscopy analysis method described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 9 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它制备海洋防污涂料的涂料性能结果列于表1中。The test results of photodegradation of organic dyes by the micro/nano Cu 2 O/ZnO composite prepared in this example are shown in Figure 11, and the performance results of marine antifouling coatings prepared using it are listed in Table 1.
实施例9：制备微/纳米Cu2O/ZnO复合材料Example 9: Preparation of micro/nano Cu 2 O/ZnO composite material
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
A、制备混合溶液A. Prepare mixed solution
在持续搅拌下，将硫酸铜与氯化锌按照摩尔比1:2.0加到去离子水中，搅拌溶解，得到一种铜浓度2.0mol/L的铜锌混合溶液；Under continuous stirring, add copper sulfate and zinc chloride to deionized water in a molar ratio of 1:2.0, stir and dissolve to obtain a copper-zinc mixed solution with a copper concentration of 2.0mol/L;
B、加入氢氧化钠B. Add sodium hydroxide
在常温下，按照硫酸铜与氢氧化钠的摩尔比1:2，往步骤A得到的混合溶液中加入浓度为1.8mol/L的氢氧化钠水溶液，然后加热到温度65℃，接着继续搅拌28min，得到一种含有氢氧化钠的混合溶液；At room temperature, according to the molar ratio of copper sulfate and sodium hydroxide 1:2, add an aqueous sodium hydroxide solution with a concentration of 1.8 mol/L to the mixed solution obtained in step A, then heat to a temperature of 65°C, and continue stirring for 28 minutes , to obtain a mixed solution containing sodium hydroxide;
C、加入葡萄糖C. Add glucose
在搅拌的条件下，按照硫酸铜与葡萄糖的摩尔比1:1.0，往步骤B得到的含有氢氧化钠的混合溶液中加入还原剂葡萄糖，然后，将该反应体系加热至温度95℃，并在这个温度下保温60min，分离得到微/纳米Cu2O/ZnO复合材料，其产率达到97.2％。Under stirring conditions, according to the molar ratio of copper sulfate to glucose 1:1.0, add reducing agent glucose to the mixed solution containing sodium hydroxide obtained in step B, then heat the reaction system to a temperature of 95 ° C, and The temperature was kept at this temperature for 60 minutes, and the micro/nano Cu 2 O/ZnO composite material was isolated, and the yield reached 97.2%.
按照本说明书中描述的扫描电子显微镜分析方法，对本实施例制备的微/纳米Cu2O/ZnO复合材料进行了分析，其结果列于附图10中。According to the scanning electron microscope analysis method described in this specification, the micro/nano Cu 2 O/ZnO composite material prepared in this example was analyzed, and the results are listed in Fig. 10 .
本实施例制备的微/纳米Cu2O/ZnO复合材料对有机染料的光降解作用的试验结果列于附图11中，使用它作为防污剂复配防污涂料，在青岛八号码头经过一段时间的实海挂板，考察涂料的防污性能。具体挂板结果列于表1中。The test results of the photodegradation effect of the micro/nano Cu2O/ZnO composite material prepared in this example on organic dyes are listed in the accompanying drawing 11. It is used as an antifouling agent to compound antifouling coatings, and passed through at Qingdao No. 8 Pier For a period of time, the real sea hangs the board to investigate the antifouling performance of the coating. The specific hanging board results are listed in Table 1.
应用实施例1：本发明微/纳米Cu2O/ZnO复合材料光降解有机染料实验Application Example 1: Photodegradation of organic dyes by micro/nano Cu 2 O/ZnO composite materials of the present invention
该实施例的实施步骤如下：The implementation steps of this embodiment are as follows:
移取300mL、20mg L-1甲基橙(MO)染料溶液，分别将0.06g实施例1-9制备的微/纳米Cu2O/ZnO复合材料作为光催化剂分散在该溶液中。在避光条件下磁力搅拌1小时，使MO染料分子在所述催化剂表面达到吸附-脱附平衡。光催化反应是固定在SGY-IB光化学反应器中的一个500mL圆柱形玻璃容器中进行的。该反应器配置磁力搅拌器、石英冷井和冷凝管。其中磁力搅拌器的作用是让反应体系处于均匀状态，而石英冷井和冷凝管是保持该反应体系的温度稳定和防止溶液蒸发。高压汞灯(500W)作为光催化的光源，每隔30min取5mL光照悬浊溶液。该悬浊溶液经高速离心分离，得到的上清液是含有甲基橙的溶液，使用由Hatachi公司以商品名UV-4100可见分光光度计在波长464nm处测定该上清液的吸光度值，然后由甲基橙标准溶液绘制的标准曲线计算得到其甲基橙浓度。Pipette 300 mL, 20 mg L -1 methyl orange (MO) dye solution, respectively disperse 0.06 g of micro/nano Cu 2 O/ZnO composite materials prepared in Examples 1-9 as photocatalysts in the solution. Stir with magnetic force for 1 hour under the condition of avoiding light, so that the MO dye molecule reaches the adsorption-desorption equilibrium on the surface of the catalyst. The photocatalytic reaction was carried out in a 500mL cylindrical glass container fixed in the SGY-IB photochemical reactor. The reactor is equipped with a magnetic stirrer, a quartz cold well and a condenser. Among them, the function of the magnetic stirrer is to keep the reaction system in a uniform state, while the quartz cold well and the condenser tube are to keep the temperature of the reaction system stable and prevent the solution from evaporating. A high-pressure mercury lamp (500W) was used as a light source for photocatalysis, and 5 mL of the suspension solution for light was taken every 30 minutes. This suspension solution is through high-speed centrifugation, and the supernatant that obtains is the solution that contains methyl orange, uses the absorbance value that measures this supernatant at wavelength 464nm place by Hatachi company with trade name UV-4100 visible spectrophotometer, then The methyl orange concentration was calculated from the standard curve drawn by the methyl orange standard solution.
其实验结果列于图11中，图11(a)的纵坐标是甲基橙溶液的吸光度值，横坐标是光照时间，它表示MO降解率与时间的关系，说明每种样品的光催化活性随光照时间的延长而增强。The experimental results are listed in Figure 11. The ordinate of Figure 11(a) is the absorbance value of the methyl orange solution, and the abscissa is the light time, which represents the relationship between the MO degradation rate and time, illustrating the photocatalytic activity of each sample. Increased with prolonged exposure time.
图11(b)的纵坐标是终止浓度比初始浓度的负对数，横坐标是光照时间，图11(b)曲线表示甲基橙降解的反应动力学，遵循准一级反应动力学模型。The ordinate of Fig. 11(b) is the negative logarithm of the termination concentration compared to the initial concentration, and the abscissa is the light time. The curve of Fig. 11(b) represents the reaction kinetics of methyl orange degradation, following the pseudo-first-order kinetic model.
应用实施例2：本发明的高性能环境友好型海洋防污涂料挂板实验Application Example 2: Hanging board experiment of high-performance environment-friendly marine antifouling coating of the present invention
将45g浓度40重量％丙烯酸树脂的乙酸丁酯溶液、2.5g卵磷脂、10g氧化铁红、2.5g气相二氧化硅、40g本发明微/纳米Cu2O/ZnO复合材料进行混合，该混合物在由耐驰公司生产的的具有砂磨、分散、搅拌功能的篮式砂磨机中研磨20分钟，然后过100目筛网，得到本发明的高性能环境友好型海洋防污涂料。The butyl acetate solution of 45g concentration 40% by weight acrylic resin, 2.5g lecithin, 10g iron oxide red, 2.5g fumed silicon dioxide , 40g micro/nanometer Cu of the present invention O/ZnO composite material is mixed, and this mixture is in Grind for 20 minutes in a basket sand mill with sanding, dispersing and stirring functions produced by Netzsch, and then pass through a 100-mesh sieve to obtain the high-performance environment-friendly marine antifouling coating of the present invention.
为测试所述的海洋防污涂料的防污性能，参照国家标准GB/T5370-2007《防污漆样板浅海浸泡试验方法》，将上述防污涂料涂刷在板长250mm、宽150mm与厚2mm的低碳钢实验样板上，使用带槽的长方木条将这种实验样板两头用铁螺栓固定。将该实验样板挂在青岛市八号码头养殖场实验基地浸海实验1年，得到如下表1列出的实验结果。In order to test the antifouling performance of the marine antifouling paint, with reference to the national standard GB/T5370-2007 "Shoal Sea Immersion Test Method for Antifouling Paint Sample", the above antifouling paint was painted on the board with a length of 250mm, a width of 150mm and a thickness of 2mm. On the low-carbon steel experimental sample, use a slotted rectangular wooden strip to fix the two ends of the experimental sample with iron bolts. The experimental model was hung in the sea immersion experiment of Qingdao No. 8 Pier Farm Experiment Base for 1 year, and the experimental results listed in Table 1 below were obtained.
表1：本发明高性能环境友好型海洋防污涂料实验结果Table 1: Experimental results of high-performance environment-friendly marine antifouling coating of the present invention
市售Cu2O*：国药集团化学试剂有限公司。Commercially available Cu 2 O*: Sinopharm Chemical Reagent Co., Ltd.
空白板*：没有任何防污涂层。Blank board*: without any antifouling coating.
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