CN104327574A - 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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- CN104327574A CN104327574A CN201410515220.8A CN201410515220A CN104327574A CN 104327574 A CN104327574 A CN 104327574A CN 201410515220 A CN201410515220 A CN 201410515220A CN 104327574 A CN104327574 A CN 104327574A
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- matrix material
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- sodium hydroxide
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- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title abstract description 13
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title abstract 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title abstract 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 204
- 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
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 17
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 6
- 239000010949 copper Substances 0.000 claims description 129
- 239000011159 matrix material Substances 0.000 claims description 99
- 238000002156 mixing Methods 0.000 claims description 61
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 58
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 56
- 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 52
- 239000011248 coating agent Substances 0.000 claims description 47
- 238000000576 coating method Methods 0.000 claims description 47
- 238000003756 stirring Methods 0.000 claims description 34
- 239000004925 Acrylic resin Substances 0.000 claims description 30
- 239000011592 zinc chloride Substances 0.000 claims description 29
- 235000005074 zinc chloride Nutrition 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 238000000034 method 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
- 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 claims description 15
- 238000001782 photodegradation Methods 0.000 claims description 14
- 230000002829 reductive effect Effects 0.000 claims description 14
- 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
- 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 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-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
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- 239000000049 pigment Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 7
- 229920000178 Acrylic resin Polymers 0.000 claims description 6
- 229910002012 Aerosil® Inorganic materials 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 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
- 238000010992 reflux Methods 0.000 claims description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 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
- 229940043232 butyl acetate Drugs 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
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical class CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical class [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- OOVXWEQVEHIHSO-UHFFFAOYSA-N acetic acid ethene Chemical compound C=C.C=C.C=C.CC(O)=O OOVXWEQVEHIHSO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 3
- 230000007717 exclusion Effects 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
- 239000003973 paint Substances 0.000 abstract description 13
- 239000003054 catalyst Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 239000000463 material Substances 0.000 abstract description 3
- 239000000853 adhesive Substances 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000010183 spectrum analysis Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000001000 micrograph Methods 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 230000001699 photocatalysis Effects 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 239000013543 active substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000004070 electrodeposition Methods 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
- 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 2
- 229940012189 methyl orange Drugs 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
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012360 testing method Methods 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
- 101100518501 Mus musculus Spp1 gene Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 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
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000000703 high-speed centrifugation Methods 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
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000005855 radiation Effects 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
- 239000010959 steel Substances 0.000 description 1
- 239000000758 substrate Substances 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
- 239000002966 varnish Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- 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 specifically, the present invention relates to a kind of micro-/ nano Cu
2o/ZnO matrix material, also relates to described micro-/ nano Cu
2the preparation method of O/ZnO matrix material, also relates to described micro-/ nano Cu
2the purposes of O/ZnO matrix material.
[background technology]
Cu
2o is a kind of inorganic oxide, and it is the p-type semiconductor material that band gap is about 2.17eV, has higher uptake factor to visible ray.All have a wide range of applications in technical fields such as photochemical catalysis, novel solar battery, magnetic storing unit, biosensor and coating.Similar with other semiconductor light-catalysts, Cu
2o also also exists the poor problem of the catalytic effect that caused by the easy compound of light induced electron and hole.Research finds, preparing composite semiconductor is a kind of important method improving photocatalysis efficiency.
In recent years, Cu
2the main preparation method of O matrix material has the methods such as photochemical precipitation method, electrochemical deposition method, physical mixed method.Mittiga research group (A.Mittiga, E.Salza, F.Sarto, eta1.Heterojunctionsolarcellwith2%efficiencybasedonaCu
2osubstrate.Appl.Phys.Lett., 2006,88 (16), 163-502.) utilize two-step approach, thermooxidizing Cu sheet is prepared grain-size and is reached lmm
2, mobility is up to 100cm
2vs
-1cu
2o film, makes substrate deposition one deck ito thin film with this, thus prepares pn heterojunction solar battery, obtains the sunlight efficiency of conversion of about 2%; The people such as Cui (J.Cui, U.J.Glbson.Asimpletwo-step electrodepositionofCu
2o/ZnOnanopillarsolarcells.J.Phys.Chem.C., 2010,114 (14), 6408-6412.) two-step electrochemical deposition method is adopted to prepare nanometer Cu
2o/ZnO composite wood stock column.But the usual preparation process of these existing methods is complicated, and conditional request is harsh, significantly limit Cu
2the large-scale production of O matrix material and industrial application.
The present inventor, on the basis of summing up prior art, by lot of experiments, completes the present invention.The present invention adopts simple liquid phase reduction, when without any complementary organic additive or tensio-active agent, with copper sulfate, sodium hydroxide and glucose for raw material prepares micro-/ nano Cu
2o/ZnO matrix material.This synthetic method is simple, easy handling, the micro-/ nano Cu of synthesis
2o/ZnO matrix material can as catalyst degradation organic pollutant, again can as stain control agent composite high-performance environment-friendly type marine antifouling coating.
[summary of the invention]
[technical problem that will solve]
The object of this invention is to provide a kind of micro-/ nano Cu
2o/ZnO matrix material.
Another object of the present invention is to provide described micro-/ nano Cu
2the preparation method of O/ZnO matrix material.
Another object of the present invention is to provide described micro-/ nano Cu
2the purposes of O/ZnO matrix material.
[technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of micro-/ nano Cu
2the preparation method of O/ZnO matrix material.
The step of this preparation method is as follows:
A, prepare mixing solutions
Copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.025 ~ 2.000, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 0.5 ~ 2.0mol/L;
B, add sodium hydroxide
At normal temperatures, according to mol ratio 1:2 ~ 5 of copper sulfate and sodium hydroxide, the aqueous sodium hydroxide solution that concentration is 0.1 ~ 3.0mol/L is added in the mixing solutions that steps A obtains, then temperature 30 ~ 90 DEG C is heated to, then continue stirring 5 ~ 60min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
According to mol ratio 1:0.1 ~ 5.0 of copper sulfate and glucose, what obtain toward step B adds reductive agent glucose containing in the mixing solutions of sodium hydroxide, then, this reaction system is heated to temperature 40 ~ 100 DEG C, and be incubated 5 ~ 60min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material.
The invention still further relates to the micro-/ nano Cu adopting described preparation method to prepare
2o/ZnO matrix material.Described micro-/ nano Cu
2o/ZnO matrix material, its scantling is 0.1 ~ 5.0 μm.
The invention still further relates to described micro-/ nano Cu
2the purposes of O/ZnO matrix material in photodegradation organic pollutant.
The invention still further relates to described micro-/ nano Cu
2the purposes in high-performance environment-friendly type marine antifouling coating prepared by O/ZnO matrix material.
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 part auxiliary agent, 1 ~ 30 weight part pigment or filler and 1 ~ 50 weight part micro-/ nano Cu
2o/ZnO matrix material forms.
A preferred embodiment of the invention, described resin solution is by the resin that is selected from acrylic resin, zinc acrylate resin or acrylate resin and the solvent composition being selected from ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols.
According to another kind of preferred implementation of the present invention, the concentration of described resin solution is by weight 20 ~ 60%.
According to another kind of preferred implementation of the present invention, described zinc acrylate resin or acrylate resin adopt the synthesis of following method to obtain:
The preparation of I, prepolymer
The mixed solvent that 1000 ~ 1400 weight parts are made up of according to weight ratio 4:1 toluene and propyl carbinol is heated to reflux temperature, then the solution of 18 ~ 22 weight part Diisopropyl azodicarboxylates in 700 ~ 900 parts by weight of acrylic acid monomer mixtures is dripped, described Acrylic Acid Monomer mixture is made up of 104 parts by weight of acrylic acid, 161 parts by weight of methylmethacrylate, 320 parts by weight acetic acid ethene and 216 weight parts of methacrylic acid butyl esters, in dropping process, keep reflux; Drip rear continuation reaction 3.5 ~ 4.5 hours, obtain the acrylic polymer of micro-yellow clear;
The preparation of II, zinc acrylate resin or acrylate resin
The acrylic polymer prepared in step I by 150 weight parts, 11.5 weight part zinc hydroxides or 11.3 weight part copper hydroxides, 13.2 parts by weight, 27 weight part butylacetates mix with the mixed solvent that 10 weight parts use in step I, then react 5.5 ~ 6.5 hours under the condition of temperature 70 ~ 80 DEG C, then temperature is risen to 125 DEG C to dewater, question response mixture is transparent and exclusion distillates time terminate reaction, obtain transparent zinc acrylate resin or acrylate resin.
According to another kind of preferred implementation of the present invention, described pigment is red iron oxide, iron oxide yellow or titanium dioxide; Described filler is aerosil or talcum powder.
According to another kind of preferred implementation of the present invention, described auxiliary agent is Yelkin TTS or wilkinite.
In more detail the present invention will be described below.
The present invention relates to a kind of micro-/ nano Cu
2the preparation method of O/ZnO matrix material.
The step of this preparation method is as follows:
A, prepare mixing solutions
Copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.025 ~ 2.000, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 0.5 ~ 2.0mol/L.
In the present invention, described copper sulfate and mol ratio 1:0.025 ~ 2.000 of zinc chloride.If the mol ratio of zinc chloride is less than 0.025, in solution, obtain the ZnO of minute quantity
2 2-with a large amount of Cu (OH)
4 2-, now ZnO
2 2-to Cu
2the nucleation impact of O crystal is little; If the mol ratio of zinc chloride is higher than 2.000, then excessive in solution Zn
2+with OH
-reaction, inhibits Cu (OH)
4 2-generation; Therefore, the mol ratio of copper sulfate and zinc chloride is 1:0.025 ~ 2.000 is appropriate; Preferably 1:0.05 ~ 1.50; More preferably 1:0.30 ~ 1.00.
Preparing in mixing solutions process, needing abundant, Keep agitation, so that copper sulfate and zinc chloride fully dissolve completely.
B, add sodium hydroxide
At normal temperatures, according to mol ratio 1:2 ~ 5 of copper sulfate and sodium hydroxide, the aqueous sodium hydroxide solution that concentration is 0.1 ~ 3.0mol/L is added in the mixing solutions that steps A obtains, then temperature 30 ~ 90 DEG C is heated to, then continue stirring 5 ~ 60min, obtain a kind of mixing solutions containing sodium hydroxide.
In this step, the effect adding sodium hydroxide is to provide alkaline condition, makes the Cu in solution
2+with OH
-reaction forms Cu (OH)
4 2-solution, further by Reduction of Glucose.
In the present invention, described copper sulfate and the mol ratio of sodium hydroxide are 1:2 ~ 5.If the mol ratio of sodium hydroxide is less than 2, then can not get Cu (OH)
4 2-solution, finally inhibits Cu
2the nucleation of O crystal; If the mol ratio of sodium hydroxide is higher than 5, then remain excessive OH in solution
-, consume a large amount of raw materials; Therefore, the mol ratio of copper sulfate and sodium hydroxide is 1:2 ~ 5 is appropriate; Preferably 1:3.4 ~ 4.5; More preferably 1:3.8 ~ 4.2.
C, add glucose
According to mol ratio 1:0.1 ~ 5.0 of copper sulfate and glucose, what obtain toward step B adds reductive agent glucose containing in the mixing solutions of sodium hydroxide, then, this reaction system is heated to temperature 40 ~ 100 DEG C, and be incubated 5 ~ 60min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material.
In this step, the effect adding reductive agent glucose is lentamente by the Cu in solution
2+be reduced into Cu
+.
In the present invention, described copper sulfate and the mol ratio of glucose are 1:0.1 ~ 5.0.If the mol ratio of glucose is less than 0.1, then Cu
2+reduce insufficient; If the mol ratio of glucose is higher than 5.0, then remain a large amount of glucose in solution; Therefore, the mol ratio of copper sulfate and glucose is 1:0.1 ~ 5.0 is appropriate; Preferably 1:0.8 ~ 4.0; More preferably 1:1.6 ~ 0.30.
Adopt micro-/ nano Cu prepared by the inventive method
2o/ZnO matrix material has carried out conventional X-ray diffraction analysis and conventional scanning electron microscope analysis and energy spectrum analysis.
Described X-ray diffraction analysis condition is as follows:
Instrument: German Bruker company D8Advance type x-ray diffractometer.
Condition determination: CuK α (λ=1.5406
), sweep limit 15 °-85 °, scanning speed 4 ° of min
-1, graphite flake filtering, pipe pressure 40kV, electric current 40mA.
Measurement result is see accompanying drawing 1, and the result of this figure shows to obtain Cu
2o/ZnO composite structure.
Described scanning electron microscope analysis condition is as follows:
Instrument: Hitachi company S-4800 type field emission scanning electron microscope.
Condition determination: acceleration voltage 8 ~ 10kV.
Measurement result is see accompanying drawing 2 to 10, and the result of these accompanying drawings shows: with Zn
2+the change of consumption, product C u
2o/ZnO matrix material pattern changes.
Described energy spectrum analysis condition is as follows:
Instrument: Hitachi company S-4800 type field emission scanning electron microscope EDS analyzes.
Condition determination: acceleration voltage 8 ~ 10kV.
Measurement result is see accompanying drawing 5,7 and 8, and these results show to obtain Cu
2o/ZnO composite structure.
The invention still further relates to the micro-/ nano Cu adopting described preparation method to prepare
2o/ZnO matrix material.Known by the result of accompanying drawing 2 to 10, described micro-/ nano Cu
2the size of O/ZnO matrix material is 0.1 ~ 5.0 μm.
The invention still further relates to described micro-/ nano Cu
2the purposes of O/ZnO matrix material in photodegradation organic pollutant.
According to the mode that this specification sheets Application Example 1 describes, have studied micro-/ nano Cu of the present invention
2o/ZnO matrix material is as catalyzer, and visible ray is to the photodegradation of organic dye tropeolin-D, and it the results are shown in accompanying drawing 11.As can be seen from accompanying drawing 11, micro-/ nano Cu of the present invention
2o/ZnO matrix material is under the irradiation of visible ray, and photocatalytic activity strengthens along with the prolongation of light application time.Methyl orange degradation reaction kinetics follows first order reaction kinetics model.When copper zinc mol ratio is 1:0.5, product C u
2o/ZnO matrix material can reach 77.45% to the degradation rate of tropeolin-D under visible light.
In order to further illustrate micro-/ nano Cu of the present invention
2the photocatalysis performance of O/ZnO matrix material, uses polyvinylidene difluoride (PVDF) by micro-/ nano Cu of the present invention
2o/ZnO matrix material furnishing slurry, be coated in conductive glass FTO and prepare film forming as light anode, Ag/AgCl is as reference electrode, and Pt electrode, as to electrode, is assembled into virtual battery, adopts CHI660E type three-electrode electro Chemical workstation to test micro-/ nano Cu of the present invention
2the bode impedance chart of O/ZnO composite catalyst, calculate the electron lifetime of catalyzer, it the results are shown in Figure 12, and this figure clearly illustrates that the virtual battery of assembling is by Cu
2o/ZnO is as light anode, and when copper sulfate and zinc chloride mol ratio are 1:0.5, the photoelectron life-span, (τ) was the longest, best to the Photocatalytic Degradation Property of tropeolin-D.
The invention still further relates to described micro-/ nano Cu
2the purposes in high-performance environment-friendly type marine antifouling coating prepared by O/ZnO matrix material.
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 part auxiliary agent, 1 ~ 30 weight part pigment or filler and 1 ~ 50 weight part micro-/ nano Cu
2o/ZnO matrix material forms.
The concentration of described resin solution is by weight 20 ~ 60%.When the concentration of described resin solution exceedes this concentration range, all obviously can affect the anti-fouling effect of antifouling paint.Preferably, the concentration of described resin solution is by weight 30 ~ 50%, and more preferably, the concentration of described resin solution is by weight 36 ~ 45%.
Described resin solution is by the resin that is selected from acrylic resin, zinc acrylate resin or acrylate resin and the solvent composition being selected from ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols.
Described acrylic resin is product sold in the market, the acrylic resin such as sold by Changxing Chemical Industry Co Ltd.
Described zinc acrylate resin or acrylate resin adopt the synthesis of following method to obtain:
The preparation of I, prepolymer
The mixed solvent that 1000 ~ 1400 weight parts are made up of according to weight ratio 4:1 toluene and propyl carbinol is heated to reflux temperature, then the solution of 18 ~ 22 weight part Diisopropyl azodicarboxylates in 700 ~ 900 parts by weight of acrylic acid monomer mixtures is dripped, described Acrylic Acid Monomer mixture is made up of 104 parts by weight of acrylic acid, 161 parts by weight of methylmethacrylate, 320 parts by weight acetic acid ethene and 216 weight parts of methacrylic acid butyl esters, in dropping process, keep reflux; Drip rear continuation reaction 3.5 ~ 4.5 hours, obtain the acrylic polymer of micro-yellow clear.
The equipment that this prepolymer preparation process uses installs three mouthfuls of containers of whipping appts, condenser and thermometer, this equipment be normally used in chemical technology field, at extensive product sold in the market.
The preparation of II, zinc acrylate resin or acrylate resin
The acrylic polymer prepared in step I by 150 weight parts, 11.5 weight part zinc hydroxides or 11.3 weight part copper hydroxides, 13.2 parts by weight, 27 weight part butylacetates mix with the mixed solvent that 10 weight parts use in step I, then react 5.5 ~ 6.5 hours under the condition of temperature 70 ~ 80 DEG C, then temperature is risen to 125 DEG C to dewater, question response mixture is transparent and exclusion distillates time terminate reaction, obtain transparent zinc acrylate resin or acrylate resin.
The equipment that the equipment that this preparation process uses and step I use is identical.
Described ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols be all normally used in chemical technology field, at extensive product sold in the market.
In high-performance environment-friendly type marine antifouling coating of the present invention, described auxiliary agent has the effect of dispersion, anti-settling.Described auxiliary agent is Yelkin TTS or wilkinite.
Described Yelkin TTS or wilkinite be normally used in chemical technology field, at extensive product sold in the market, such as, by the Yelkin TTS of Zhengzhou Nai Ruite Company, the wilkinite sold by Zhejiang Fenghong New Material Co., Ltd..
In high-performance environment-friendly type marine antifouling coating of the present invention, the effect of described pigment is painted.Described pigment is red iron oxide, iron oxide yellow or titanium dioxide.
Described red iron oxide, iron oxide yellow or titanium dioxide be normally used in chemical technology field, at extensive product sold in the market, the red iron oxide of such as being sold by Shanghai Yipin Pigments Co., Ltd., iron oxide yellow, the titanium dioxide sold by the R-902 of du pont company.
In high-performance environment-friendly type marine antifouling coating of the present invention, described filler has the effect of filling.Described filler is aerosil or talcum powder.
Described aerosil or talcum powder be normally used in chemical technology field, at extensive product sold in the market, such as, the aerosil sold by Yantai Jia Hong Chemical Co., Ltd., reached the superfine talcum powder of superfine talcum powder Company by Yongfeng, Penglai City.
According to the present invention, micro-/ nano Cu
2the amount of O/ZnO matrix material is 1 ~ 50 weight part, the amount of other component is in described scope, and the amount of described resin solution lower than 20 weight part time, the film forming properties of antifouling paint then can be made to be deteriorated, if when the amount of described resin solution is higher than 60 weight part, then can reduce the antifouling property of antifouling paint, therefore, the amount of resin solution is 20 ~ 60 weight parts is suitable.
Similarly, micro-/ nano Cu
2the amount of O/ZnO matrix material is 1 ~ 50 weight part, the amount of other component is in described scope, and the amount of auxiliary agent lower than 1 weight part time, then can reduce the dispersiveness of antifouling paint, anti-settling performance, if when the amount of auxiliary agent is higher than 20 weight part, then can affect the film forming properties of antifouling paint, therefore, the amount of auxiliary agent is 1 ~ 20 weight part is suitable.
Micro-/ nano Cu
2the amount of O/ZnO matrix material is 1 ~ 50 weight part, the amount of other component is in described scope, and the amount of filler lower than 1 weight part time, then can reduce the anti-fouling effect of antifouling paint, if when the amount of filler is higher than 30 weight part, then can reduce the film-forming properties of antifouling paint, therefore, the amount of filler is 1 ~ 30 weight part is appropriate.
Preferably, described high-performance environment-friendly type marine antifouling coating is by 30 ~ 48 parts by weight resin solution, 5 ~ 14 weight part auxiliary agents, 8 ~ 22 weight part pigment or filler and 12 ~ 36 weight part micro-/ nano Cu
2o/ZnO matrix material forms.
More preferably, described high-performance environment-friendly type marine antifouling coating is by 35 ~ 42 parts by weight resin solution, 8 ~ 10 weight part auxiliary agents, 12 ~ 18 weight part pigment or filler and 18 ~ 30 weight part micro-/ nano Cu
2o/ZnO matrix material forms.
Marine biofouling is the biological phenomena recognized gradually after being engaged in Activities of Ocean, and the fight of the mankind and marine attaching organism has the history of more than 4,000 year.Marine fouling organism carrys out numerous harm to shipping industry and ocean industrial belt, preventing and kill off of marine fouling organism has been insoluble significant problem always since the mankind are engaged in Activities of Ocean, in order to reduce the harm that marine fouling organism is caused to greatest extent, brushing antifouling coating is method that is most economical, that effectively and generally adopt.
The performance of following standard method to high-performance environment-friendly type marine antifouling coating of the present invention is adopted to detect:
Dope viscosity assay method: GB/T1723-1993
Coating fineness assay method: GB/T1724-1979
Paint film adhesion assay method: GB/T1720-1979
By micro-/ nano Cu of the present invention
2o/ZnO matrix material is as the composite self polishing copolymer antifouling paint of stain control agent, the performance analysis of this coating has been carried out according to national standard, its medium viscosity (being coated with-4) cup, reach 85-92 (s), fineness is 50-55 (μm) and sticking power is 1 (level), this shows micro-/ nano Cu of the present invention
2o/ZnO matrix material is as the composite self polishing copolymer antifouling paint of stain control agent, and viscosity, fineness and sticking power three performance index all meet the basic demand of marine antifouling coating.
[beneficial effect]
The invention has the beneficial effects as follows: the present invention adopts simple liquid phase reduction, when without any complementary organic additive or tensio-active agent, with copper sulfate, zinc chloride, sodium hydroxide and glucose for raw material prepares micro-/ nano Cu
2o/ZnO matrix material, this preparation method is simple, easy handling, and productive rate is up to more than 96%, and the preparation process that it can make up in other preparation method's processes is numerous and diverse, and conditional request harshness waits restriction, also can make up Cu simultaneously
2the deficiency that O photocatalysis efficiency is low.Micro-/ nano Cu of the present invention
2o/ZnO matrix material has very good application prospect as photocatalyst with preparing in high-performance environment-friendly type marine antifouling coating.
[accompanying drawing explanation]
Fig. 1 is the micro-/ nano Cu of different copper sulfate and zinc chloride mol ratio
2o/ZnO matrix material x-ray diffraction pattern.
Fig. 2 is the micro-/ nano Cu that embodiment 1 prepares when copper sulfate and zinc chloride mol ratio are 1:0.025
2the electron scanning micrograph of O/ZnO matrix material.
Fig. 3 is the micro-/ nano Cu that embodiment 2 prepares when copper sulfate and zinc chloride mol ratio are 1:0.05
2the electron scanning micrograph of O/ZnO matrix material.
Fig. 4 is the micro-/ nano Cu that embodiment 3 prepares when copper sulfate and zinc chloride mol ratio are 1:0.15
2the electron scanning micrograph of O/ZnO matrix material.
Fig. 5 is the micro-/ nano Cu that embodiment 4 prepares when copper sulfate and zinc chloride mol ratio are 1:0.18
2the scanning electronic microscope of O/ZnO matrix material, energy spectrum analysis photo and x-ray photoelectron spectroscopy.
Fig. 6 is the micro-/ nano Cu that embodiment 5 prepares when copper sulfate and zinc chloride mol ratio are 1:0.25
2the electron scanning micrograph of O/ZnO matrix material.
Fig. 7 is the micro-/ nano Cu that embodiment 6 prepares when copper sulfate and zinc chloride mol ratio are 1:0.5
2the scanning electronic microscope of O/ZnO matrix material and energy spectrum analysis photo.
Fig. 8 is the micro-/ nano Cu that embodiment 7 prepares when copper sulfate and zinc chloride mol ratio are 1:0.8
2the scanning electronic microscope of O/ZnO matrix material and energy spectrum analysis photo.
Fig. 9 is the micro-/ nano Cu that embodiment 8 prepares when copper sulfate and zinc chloride mol ratio are 1:1.2
2the electron scanning micrograph of O/ZnO matrix material.
Figure 10 is the micro-/ nano Cu that embodiment 9 prepares when copper sulfate and zinc chloride mol ratio are 1:2
2the electron scanning micrograph of O/ZnO matrix material.
Figure 11 is micro-/ nano Cu of the present invention
2o/ZnO matrix material as catalyzer, at 5.5 hours radiation of visible light to degradation rate curve (a) of organic dye tropeolin-D and pseudo-first-order kinetic model (b) figure.
Figure 12 is that design virtual battery calculates micro-/ nano Cu of the present invention
2the catalytic life bode impedance chart of O/ZnO matrix material in organic pollutant.
[embodiment]
The present invention can be understood better by following embodiment.
Embodiment 1: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.025, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 1.0mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:4 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 1.0mol/L, be then heated to temperature 30 DEG C, then continue to stir 5min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:0.4 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 40 DEG C, and is incubated 13min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 96.5%.
According to the scanning electron microscope analysis method described in this specification sheets, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 2.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 2: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.05, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 0.5mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:3 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 0.6mol/L, be then heated to temperature 55 DEG C, then continue to stir 18min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:0.1 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 70 C, and is incubated 44min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 97.5%.
According to the scanning electron microscope analysis method described in this specification sheets, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 3.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 3: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.15, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 1.2mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:5 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 3.0mol/L, be then heated to temperature 75 DEG C, then continue to stir 43min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:4.3 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 95 DEG C, and is incubated 52min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 96.2%.
According to the scanning electron microscope analysis method described in this specification sheets, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 4.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 4: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.18, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 1.4mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:3.8 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 0.1mol/L, be then heated to temperature 50 C, then continue to stir 60min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:2.8 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 55 DEG C, and is incubated 29min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 98.2%.
According to the scanning electron microscope analysis described in this specification sheets and energy spectrum analysis method, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 5.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 5: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.25, stirring and dissolving, obtain a kind of copper concentration 1.6mol/L and copper zinc mixing solutions;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:4.5 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 2.1mol/L, be then heated to temperature 85 DEG C, then continue to stir 30min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:2 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 100 DEG C, and is incubated 5min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 96.6%.
According to the scanning electron microscope analysis method described in this specification sheets, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 6.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 6: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.5, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 1.0mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:4.2 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 1.5mol/L, be then heated to temperature 90 DEG C, then continue to stir 25min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:1.8 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 100 DEG C, and is incubated 21min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 97.4%.
According to the scanning electron microscope analysis described in this specification sheets and energy spectrum analysis method, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 7.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 7: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.8, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 0.8mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:2.5 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 2.5mol/L, be then heated to temperature 60 DEG C, then continue to stir 10min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:3.6 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 85 DEG C, and is incubated 35min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 98.0%.
According to the scanning electron microscope analysis described in this specification sheets and energy spectrum analysis method, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 8.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 8: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:1.2, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 1.8mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:5 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 1.2mol/L, be then heated to temperature 45 C, then continue to stir 56min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:5.0 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 73 DEG C, and is incubated 56min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 96.9%.
According to the scanning electron microscope analysis method described in this specification sheets, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 9.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, and the results are shown in Table 1 to use it to prepare the coating property of marine antifouling coating.
Embodiment 9: prepare micro-/ nano Cu
2o/ZnO matrix material
The implementation step of this embodiment is as follows:
A, prepare mixing solutions
Under continuous stirring, copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:2.0, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 2.0mol/L;
B, add sodium hydroxide
At normal temperatures, according to the mol ratio 1:2 of copper sulfate and sodium hydroxide, in the mixing solutions that steps A obtains, add the aqueous sodium hydroxide solution that concentration is 1.8mol/L, be then heated to temperature 65 DEG C, then continue to stir 28min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
Under the condition stirred, according to the mol ratio 1:1.0 of copper sulfate and glucose, add reductive agent glucose toward containing in the mixing solutions of sodium hydroxide of obtaining of step B, then, this reaction system is heated to temperature 95 DEG C, and is incubated 60min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material, its productive rate reaches 97.2%.
According to the scanning electron microscope analysis method described in this specification sheets, to micro-/ nano Cu prepared by the present embodiment
2o/ZnO matrix material is analyzed, and it the results are shown in accompanying drawing 10.
Micro-/ nano Cu prepared by the present embodiment
2the test-results of O/ZnO matrix material to the photodegradation of organic dye is listed in accompanying drawing 11, makes to use it as the composite antifouling paint of stain control agent, at Qingdao eight numbering head through the extra large link plate of reality after a while, investigates the antifouling property of coating.The results are shown in Table 1 for concrete link plate.
Application Example 1: micro-/ nano Cu of the present invention
2o/ZnO matrix material photodegradation organic dye is tested
The implementation step of this embodiment is as follows:
Pipette 300mL, 20mgL
-1tropeolin-D (MO) dye solution, the micro-/ nano Cu respectively prepared by 0.06g embodiment 1-9
2o/ZnO matrix material is dispersed in this solution as photocatalyst.Stir 1 hour at lucifuge condition lower magnetic force, make MO dye molecule reach adsorption-desorption balance at described catalyst surface.Light-catalyzed reaction is fixed in a 500mL cylindrical glass container in SGY-IB photochemical reactor to carry out.This reactor configurations magnetic stirring apparatus, quartzy cold well and prolong.Wherein the effect of magnetic stirring apparatus allows reaction system be in uniform state, and quartzy cold well and prolong keep the temperature-stable of this reaction system and prevent solution evaporation.High voltage mercury lamp (500W), as light-catalysed light source, gets 5mL illumination suspension solution every 30min.This suspension solution is separated through high speed centrifugation, the supernatant liquor obtained is the solution containing tropeolin-D, use the absorbance being measured this supernatant liquor by Hatachi company with trade(brand)name UV-4100 visible spectrophotometer at wavelength 464nm, the typical curve then drawn by tropeolin-D standardized solution calculates its tropeolin-D concentration.
Its experiment the results are shown in Figure 11, the ordinate zou of Figure 11 (a) is the absorbance of methyl orange solution, X-coordinate is light application time, and it represents MO degradation rate and the relation of time, illustrates that the photocatalytic activity of often kind of sample strengthens with the prolongation of light application time.
The ordinate zou of Figure 11 (b) is the negative logarithm stopping concentration ratio starting point concentration, and X-coordinate is light application time, and the reaction kinetics of Figure 11 (b) curve representation methyl orange degradation, follows pseudo-first order reaction kinetics model.
Application Example 2: high-performance environment-friendly type marine antifouling coating panel experiment of the present invention
By the butylacetate solution of 45g concentration 40 % by weight acrylic resin, 2.5g Yelkin TTS, 10g red iron oxide, 2.5g aerosil, 40g micro-/ nano Cu of the present invention
2o/ZnO matrix material mixes, this mixture produced by Nai Chi company have in the basket type sand mill of sand milling, dispersion, agitating function grind 20 minutes, then cross 100 eye mesh screens, obtain high-performance environment-friendly type marine antifouling coating of the present invention.
For testing the antifouling property of described marine antifouling coating, with reference to standard GB/T/T5370-2007 " antifouling varnish model shallow sea soak test method ", above-mentioned antifouling paint brushing is tested on model at the soft steel of the long 250mm of plate, wide 150mm and thick 2mm, uses the rectangular batten of trough of belt to be fixed by this experiment model two iron bolt.This experiment model is hung over numbering head plant of Qingdao City eight Experimental Base leaching sea experiment 1 year, obtain the experimental result listed as following table 1.
Table 1: high-performance environment-friendly type marine antifouling coating experimental result of the present invention
Commercially available Cu
2o*: Chemical Reagent Co., Ltd., Sinopharm Group.
Blank plate *: without any antifouling coating.
Claims (10)
1. a micro-/ nano Cu
2the preparation method of O/ZnO matrix material, is characterized in that the step of this preparation method is as follows:
A, prepare mixing solutions
Copper sulfate and zinc chloride are added in deionized water according to mol ratio 1:0.025 ~ 2.000, stirring and dissolving, obtain the copper zinc mixing solutions of a kind of copper concentration 0.5 ~ 2.0mol/L;
B, add sodium hydroxide
At normal temperatures, according to mol ratio 1:2 ~ 5 of copper sulfate and sodium hydroxide, the aqueous sodium hydroxide solution that concentration is 0.1 ~ 3.0mol/L is added in the mixing solutions that steps A obtains, then temperature 30 ~ 90 DEG C is heated to, then continue stirring 5 ~ 60min, obtain a kind of mixing solutions containing sodium hydroxide;
C, add glucose
According to mol ratio 1:0.1 ~ 5.0 of copper sulfate and glucose, what obtain toward step B adds reductive agent glucose containing in the mixing solutions of sodium hydroxide, then, this reaction system is heated to temperature 40 ~ 100 DEG C, and be incubated 5 ~ 60min at this temperature, be separated and obtain micro-/ nano Cu
2o/ZnO matrix material.
2. the preparation-obtained micro-/ nano Cu of preparation method according to claim 1
2o/ZnO matrix material, is characterized in that described micro-/ nano Cu
2the size of O/ZnO matrix material is 0.1 ~ 5.0 μm.
3. that obtain or the micro-/ nano Cu according to claim 2 of method according to claim 1
2the purposes of O/ZnO matrix material in photodegradation organic pollutant.
4. that obtain or the micro-/ nano Cu according to claim 2 of method according to claim 1
2the purposes in high-performance environment-friendly type marine antifouling coating prepared by O/ZnO matrix material.
5. a high-performance environment-friendly type marine antifouling coating, is characterized in that described marine antifouling coating is by 20 ~ 60 parts by weight resin solution, 1 ~ 20 weight part auxiliary agent, 1 ~ 30 weight part pigment or filler and 1 ~ 50 weight part micro-/ nano Cu
2o/ZnO matrix material forms.
6. high-performance environment-friendly type marine antifouling coating according to claim 5, is characterized in that described resin solution is by the resin that is selected from acrylic resin, zinc acrylate resin or acrylate resin and the solvent composition being selected from ethyl acetate, butylacetate, dimethylbenzene, toluene or butanols.
7. high-performance environment-friendly type marine antifouling coating according to claim 5, is characterized in that the concentration of described resin solution is by weight 20 ~ 60%.
8. high-performance environment-friendly type marine antifouling coating according to claim 5, is characterized in that zinc acrylate resin or acrylate resin adopt the synthesis of following method to obtain:
The preparation of I, prepolymer
The mixed solvent that 1000 ~ 1400 weight parts are made up of according to weight ratio 4:1 toluene and propyl carbinol is heated to reflux temperature, then the solution of 18 ~ 22 weight part Diisopropyl azodicarboxylates in 700 ~ 900 parts by weight of acrylic acid monomer mixtures is dripped, described Acrylic Acid Monomer mixture is made up of 104 parts by weight of acrylic acid, 161 parts by weight of methylmethacrylate, 320 parts by weight acetic acid ethene and 216 weight parts of methacrylic acid butyl esters, in dropping process, keep reflux; Drip rear continuation reaction 3.5 ~ 4.5 hours, obtain the acrylic polymer of micro-yellow clear;
The preparation of II, zinc acrylate resin or acrylate resin
The acrylic polymer prepared in step I by 150 weight parts, 11.5 weight part zinc hydroxides or 11.3 weight part copper hydroxides, 13.2 parts by weight, 27 weight part butylacetates mix with the mixed solvent that 10 weight parts use in step I, then react 5.5 ~ 6.5 hours under the condition of temperature 70 ~ 80 DEG C, then temperature is risen to 125 DEG C to dewater, question response mixture is transparent and exclusion distillates time terminate reaction, obtain transparent zinc acrylate resin or acrylate resin.
9. high-performance environment-friendly type marine antifouling coating according to claim 4, is characterized in that described pigment is red iron oxide, iron oxide yellow or titanium dioxide; Described filler is aerosil or talcum powder.
10. high-performance environment-friendly type marine antifouling coating according to claim 4, is characterized in that described auxiliary agent is Yelkin TTS or wilkinite.
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| CN106268831A (en) * | 2016-08-16 | 2017-01-04 | 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 |
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