CN115321581A - Photoresponse type cuprous oxide anti-fouling agent and preparation method thereof - Google Patents
Photoresponse type cuprous oxide anti-fouling agent and preparation method thereof Download PDFInfo
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 97
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 97
- 239000002519 antifouling agent Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 47
- 238000006722 reduction reaction Methods 0.000 claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 6
- 230000001404 mediated effect Effects 0.000 claims abstract description 4
- 238000009826 distribution Methods 0.000 claims abstract description 3
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 12
- 239000005750 Copper hydroxide Substances 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000000725 suspension Substances 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 8
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 8
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- 150000007529 inorganic bases Chemical class 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 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 description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims 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 claims description 2
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- 150000001879 copper Chemical class 0.000 claims 3
- 230000000694 effects Effects 0.000 abstract description 7
- -1 hydroxyl free radical Chemical class 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 238000007539 photo-oxidation reaction Methods 0.000 abstract description 3
- 239000013535 sea water Substances 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 2
- 230000003373 anti-fouling effect Effects 0.000 description 16
- 238000005260 corrosion Methods 0.000 description 7
- 230000001580 bacterial effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000003973 paint Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000000969 carrier Substances 0.000 description 5
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002516 radical scavenger Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000002189 fluorescence spectrum Methods 0.000 description 3
- 230000005764 inhibitory process Effects 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000001259 photo etching Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000003139 biocide Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000000843 powder Substances 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
- 238000009991 scouring Methods 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- DFNPRTKVCGZMMC-UHFFFAOYSA-M tributyl(fluoro)stannane Chemical compound CCCC[Sn](F)(CCCC)CCCC DFNPRTKVCGZMMC-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Paints Or Removers (AREA)
Abstract
The invention discloses a photoresponse type cuprous oxide antifouling agent and a preparation method thereof, wherein the photoresponse type cuprous oxide antifouling agent comprises cuprous oxide truncated octahedral micro-nano particles with special crystal faces exposed, each cuprous oxide micro-nano particle is formed by closing 6 (100) crystal faces and 8 (111) crystal faces, each (111) crystal face is adjacent to 3 (100) crystal faces, 36 edges and 24 vertexes are formed in total, the particle size distribution is 0.5-2 mu m, and the cuprous oxide micro-nano particles are prepared through a surfactant mediated wet chemical reduction strategy. Under the sunlight irradiation environment, cuprous oxide particles can rapidly separate surface photocarrier pairs (electron-hole, e) by virtue of the energy level difference between the (111) crystal planes and the (100) crystal planes ‑ ‑h + ) Not only inhibiting photooxidation reaction of photogenerated cavity, but also continuously catalyzing dissolved oxygen (O) in seawater 2 ) Water (H) 2 O) and hydroxide ion (OH) ‑ ) Etc. to generate oxyanion (. O) 2 ‑ ) And hydroxyl free radical (HO), and the like, so as to achieve the protection effect of killing fouling organisms.
Description
Technical Field
The invention relates to the technical field of marine antifouling, and particularly relates to a photoresponse type cuprous oxide antifouling agent and a preparation method thereof.
Background
The most effective technical scheme for solving the problem of marine biofouling is to coat antifouling paint on the surface of a ship, and cuprous oxide with broad-spectrum biocidal activity is generally used as a main antifouling agent. The waterline position between the light and heavy load lines of the ship is in the severe environment of sunlight exposure and seawater alternate soaking-scouring in a dry-wet manner, and the cuprous oxide antifouling agent in the antifouling paint at the position faces higher oxidation failure risk. This is mainly because cuprous oxide is susceptible to self-generation of photogenerated holes (h) under visible light irradiation + ) Oxidation and photo-etching occurs. The generation-transfer process of the cavity is significantly influenced by the structural morphology of the cuprous oxide. The conventionally used industrial cuprous oxide antifouling agent is micron-sized particles, has no regular morphology, and photogenerated carriers of the agent are more easily enriched on the surface to cause serious photo-corrosion oxidation, so that the antifouling paint performance of a waterline part is seriously deteriorated, and the antifouling failure risk of an underwater part is caused to a certain extent.
In order to solve the problem of failure of the cuprous oxide antifouling agent at the waterline part, the stability of the cuprous oxide in the illumination environment is urgently needed to be improved, and the key point is that the separation-transfer of the photon-generated carriers on the surface of the cuprous oxide is strengthened through structure regulation. To this end, the academic community has reached a certain consensus: the document j.phys.chem.c2009,113,14448 compares the stability of a series of cuprous oxide single crystal particles of different morphologies and indicates that an octahedral single crystal consisting entirely of (111) crystal planes has the most excellent photostability, thanks to the fact that it has (111) crystal planes with lower energy level positions, which is beneficial for the rapid separation of photogenerated holes. Nevertheless, cuprous oxide particles composed of a single crystal face still face the problem of oxidative corrosion due to the accumulation of photogenerated holes. Patent CN104591257B discloses cubic micro-nano cuprous oxide powder and a preparation method thereof. The obtained cubic cuprous oxide particles consist of (100) crystal faces, are easy to generate photo-oxidative corrosion under the irradiation of visible light as an antifouling agent, and cannot effectively solve the problem of failure of the antifouling agent at the ship waterline position. Fundamentally, the high-efficiency separation of the photo-generated holes on the cuprous oxide surface requires the introduction of energy level differences. For this reason, the prior art proposes binary heterojunction preparation strategies. Documents nat.Catal.2018, s41929-018-0077-6 respectively deposit heterojunction composite layers such as gallium oxide on the surface of the cuprous oxide nanowire by means of an electrochemical and single-atom deposition method; through the staggered matching of the energy band structures between the two, the separation of the current carriers on the surface of the cuprous oxide is promoted, so that the stability of the material in the photoelectrocatalysis process is improved. However, the preparation method of the heterojunction composite material is complicated and high in cost, and large-scale preparation for the antifouling field is difficult to perform. Therefore, the preparation of the cuprous oxide antifouling agent material with the intrinsic energy level difference is an effective strategy for solving the problem of failure of the antifouling agent at the ship waterline position.
At present, the industrial industry supplements and strengthens the use effect of the cuprous oxide antifouling agent at the ship waterline part by means of formula design measures such as compounding high-toxicity biocides and the like: the invention patents 201210494499.7 and 201710577196.4 both propose an antifouling agent system using tributyltin fluoride compounded with cuprous oxide and the like as marine waterline paint. It is noted that the organotin used has been globally banned by the international maritime organization in 2008 due to its extremely high bioaccumulation toxicity. In conclusion, the existing research cannot fundamentally solve the bottleneck problem that the cuprous oxide antifouling agent at the waterline part of the ship fails in advance due to photo-etching oxidation.
Disclosure of Invention
In view of the above, the invention aims to provide a photoresponse type cuprous oxide antifouling agent, which efficiently separates photoproduction cavities by means of energy level difference between crystal faces to inhibit corrosion and oxidation of cuprous oxide, so that the bottleneck problem of failure of the antifouling agent at the ship waterline position is solved. The cuprous oxide antifouling agent adopted by the prior art does not have a regular shape and cannot form energy level difference among crystal faces, so that photoproduction cavities are more easily enriched on the lower surface irradiated by visible light, and the antifouling paint at the waterline part is degraded and even loses efficacy due to serious photo-corrosion oxidation.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a photoresponse type cuprous oxide antifouling agent comprises cuprous oxide truncated octahedral micro-nano particles with special exposed crystal faces, wherein the cuprous oxide micro-nano particles are formed by closing 6 (100) crystal faces and 8 (111) crystal faces, each (111) crystal face is adjacent to 3 (100) crystal faces, 36 edges and 24 vertexes are total, the particle size distribution is 500 nm-2 microns, and the cuprous oxide micro-nano particles are prepared through a surfactant mediated wet chemical reduction strategy.
A preparation method of a photoresponse cuprous oxide antifouling agent is used for preparing the photoresponse cuprous oxide antifouling agent and comprises the following steps:
1) Dissolving soluble cupric salt in 80-4500 mL deionized water at the reaction temperature of 50-70 ℃, then adding inorganic base and polyvinylpyrrolidone surfactant, stirring at constant speed and reacting for 0.5-1.5 hours to obtain blue or blue-green copper hydroxide suspension;
2) Dissolving a reducing agent into 10-800 mL of deionized water, dropwise adding the reducing agent into the prepared copper hydroxide suspension, carrying out reduction reaction for 0.5-1 h at the temperature of 50-70 ℃, then carrying out centrifugal washing by using a washing solvent, and carrying out vacuum drying to obtain the truncated octahedral cuprous oxide micro/nano particles with special exposed crystal faces.
Further, the mole ratio of the cupric salt to the inorganic base in the step 1) is 1.
Further, the mole ratio of the cupric salt and the polyvinylpyrrolidone in the step 1) is 10-33.
Further, the molar ratio of the copper hydroxide to the reducing agent in step 2 is 1.
Further, the cupric salt is one or a combination of copper sulfate, copper chloride, copper acetate and copper nitrate.
Further, the inorganic base is one or a combination of sodium hydroxide and potassium hydroxide.
Further, the reducing agent is one or a combination of ascorbic acid, glucose and sodium sulfite.
Further, the washing solvent is one or a combination of methanol, ethanol and isopropanol.
Further, the vacuum drying temperature is 30-40 ℃, and the drying time is 12-24 hours.
Compared with the prior art, the photoresponse cuprous oxide antifouling agent and the preparation method thereof have the following advantages:
(1) The invention provides a photoresponse type cuprous oxide antifouling agent which is suitable for ship waterline positions and is used for obtaining truncated octahedral cuprous oxide micro-nano particles with special crystal face exposure based on a surfactant mediated wet chemical reduction strategy. Under the irradiation of sunlight, the photoresponse cuprous oxide particles can rapidly separate surfaces by virtue of energy level differences among different crystal planes to generate photon-generated carriers (electrons-holes, e) - -h + ) On one hand, the photooxidation reaction of photogenerated holes is inhibited, and on the other hand, the dissolved oxygen (O) in seawater is catalyzed 2 ) Water (H) 2 O) and hydroxide ion (OH) - ) Etc. to generate oxyanions (. O) 2- ) Active species such as hydroxyl radical (HO), etc. to kill marine fouling organisms attached to waterline parts, thereby exerting antifouling activity, besides, cuprous oxide can slow down the release of copper ions due to small particle size, and plays a role in long-acting sterilization.
(2) The photoresponse cuprous oxide antifouling agent prepared by the invention is suitable for various antifouling coating systems such as the existing abrasion type, self-polishing type, fouling release type and the like, and can be popularized and coated at the position of a ship waterline.
(3) The invention provides a preparation method of a photoresponse type cuprous oxide antifouling agent, which takes cupric salt as a copper source and polyvinylpyrrolidone as a structure directing agent, and prepares cuprous oxide micro-nano particles with special crystal face exposure through reduction by a reducing agent after reaction of the cupric salt and strong base.
Drawings
FIG. 1 is an electron scanning microscope image of conventional commercial grade cuprous oxide;
FIG. 2 is a scanning electron microscope photograph of photoresponsive cuprous oxide prepared according to example 1;
FIG. 3 is an X-ray diffraction pattern of photo-responsive cuprous oxide prepared according to example 1;
FIG. 4 is an infrared spectrum of photoresponsive cuprous oxide prepared in example 2;
FIG. 5 is the steady state fluorescence emission spectra of the photo-responsive cuprous oxide prepared in example 3 and conventional technical-grade cuprous oxide;
FIG. 6 is a graph showing the comparison of the inhibitory activity of the photo-responsive cuprous oxide prepared in example 1 before and after adding it to the active species scavenger;
FIG. 7 is a graph showing a comparison of bacterial inhibitory activity of conventional commercial-grade cuprous oxide before and after addition of an active species scavenger;
fig. 8 is a schematic view showing the mechanism of the photo-responsive antifouling of the photo-responsive cuprous oxide prepared in example 1.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
Example 1
Weighing 0.25g of copper sulfate pentahydrate and 2.75g of polyvinylpyrrolidone, stirring at 55 ℃, dissolving in 80mL of deionized water, weighing 1.68g of sodium hydroxide, and adding into the reaction solution to obtain blue or blue-green copper hydroxide suspension; then, 0.85g of ascorbic acid is weighed and dissolved in 10mL of deionized water, and then is added into the copper hydroxide suspension drop by drop, and reduction reaction is carried out for 0.5 hour at 55 ℃; and finally, washing and centrifugally separating the reduction product by using ethanol, and drying for 12 hours at 30 ℃ under a vacuum condition to prepare the photoresponse type cuprous oxide antifouling agent with the exposed special crystal face.
Example 2
Weighing 6.7g of copper chloride and 145.0g of polyvinylpyrrolidone, stirring at 70 ℃, dissolving in 4500mL of deionized water, weighing 75.0g of sodium hydroxide, and adding into the reaction solution to obtain blue or blue-green copper hydroxide suspension; subsequently, 45.0g of glucose is weighed and dissolved in 800mL of deionized water, and then is dropwise added into the copper hydroxide suspension for reduction reaction for 1 hour at 70 ℃; and finally, washing and centrifugally separating the reduction product by using isopropanol, and drying for 24 hours at 40 ℃ under a vacuum condition to prepare the photoresponse type cuprous oxide antifouling agent with the exposed special crystal face.
Example 3
Weighing 0.9g of copper acetate and 7.5g of polyvinylpyrrolidone, stirring at 60 ℃, dissolving in 500mL of deionized water, weighing 18.5g of potassium hydroxide, and adding into the reaction solution to obtain blue or blue-green copper hydroxide suspension; then, 26.3g of ascorbic acid is weighed and dissolved in 50mL of deionized water, and then is added into the copper hydroxide suspension drop by drop, and reduction reaction is carried out for 40 minutes at 60 ℃; and finally, washing and centrifugally separating the reduction product by using methanol, and drying for 12 hours at 35 ℃ under a vacuum condition to prepare the photoresponse type cuprous oxide antifouling agent with the exposed special crystal face.
Conventional technical grade cuprous oxide in this application was purchased from taxing smelting.
Performance testing
Fig. 1 and 2 are scanning electron microscope images of conventional technical-grade cuprous oxide and photoresponsive cuprous oxide prepared in example 1, respectively. As can be seen from fig. 1, the grain size difference of the cuprous oxide prepared by the conventional industrial grade is large, and a single cuprous oxide grain does not have a regular morphology, so that a special exposed crystal face and a crystal face energy level difference cannot be formed, and therefore, the cuprous oxide is easy to undergo photo-oxidation corrosion, and the antifouling effect at the ship waterline part is poor. As can be seen from fig. 2, the cuprous oxide prepared in example 1 has an average particle size of 0.5 to 2 μm, a clear edge angle, a regular shape, and a uniform size, and has a special crystal face exposed, that is, the cuprous oxide is in a truncated octahedron shape and is formed by closing 6 (100) crystal faces and 8 (111) crystal faces, each (111) crystal face is adjacent to 3 (100) crystal faces, there are 36 edges and 24 vertexes in total, and its shape and structure are significantly different from those of the conventional industrial-grade cuprous oxide.
Fig. 3 is an X-ray diffraction spectrum of the photo-responsive cuprous oxide prepared in example 1. As can be seen from FIG. 3, the (111)/(100) crystal face proportion of the prepared cuprous oxide is remarkably improved through X-ray diffraction characterization, and a special exposed crystal face is shown.
FIG. 4 shows photoresponsive cuprous oxide prepared in example 2An infrared spectrum. As can be seen from FIG. 4, the photoresponsive cuprous oxide antifouling agent shows a Cu (I) -O stretching vibration peak (628 cm) -1 )。
FIG. 5 is a graph showing the steady-state fluorescence emission spectra of the photo-responsive cuprous oxide prepared in example 3 and conventional technical-grade cuprous oxide. As can be seen from fig. 5, the photo-responsive cuprous oxide antifouling agent exhibits more excellent photocarrier separation effect. In particular, the steady-state fluorescence emission spectrum is used for characterizing the recombination luminescence phenomenon of photo-generated carrier pairs (electron-hole) generated by a material excited by a light source. Compared with the conventional industrial-grade cuprous oxide, the cuprous oxide in the embodiment 3 shows a significantly reduced fluorescence emission intensity, which indicates that the photo-generated holes and electrons can be rapidly transferred and the separation effect is enhanced.
FIGS. 6 and 7 are graphs comparing the bacterial inhibitory activity of the photo-responsive cuprous oxide prepared in example 1 and conventional technical-grade cuprous oxide before and after addition of the active species scavenger, respectively. As can be seen from FIG. 6, the photoresponsive cuprous oxide antifouling agent rapidly separates and consumes photogenerated holes (h +) under the irradiation of visible light, and generates hydroxyl radicals (HO) and oxyanions (O) 2- ) And the like. In particular, the active species capture assay is used to characterize the type and quantity of active species generated after a material is excited by visible light. Sodium oxalate, isopropanol and p-benzoquinone are respectively adopted as photogenerated holes (h) + ) Hydroxyl radical (OH), oxyanion (. O) 2- ) The method comprises the following steps of (1) waiting for capture agents of active species, and adding the capture agents into a bacterial (Escherichia coli) culture medium containing different types of cuprous oxide materials; the types of main photogenerated active species on the surface of the cuprous oxide are screened by comparing the descending trend of the bacterial inhibition activity. Compared with the conventional industrial-grade cuprous oxide shown in fig. 7, the cuprous oxide prepared in this embodiment 1 has a smaller reduction degree of bacterial inhibition activity after the hole scavenger is added, which indicates that a special crystal face is exposed to form a crystal face energy level difference, which is helpful for rapidly separating and transmitting a photo-generated hole generated on the surface of the cuprous oxide; meanwhile, the bacterial inhibition activity of the prepared photoresponse cuprous oxide is obviously reduced after the hydroxyl free radical and the oxygen anion scavenger are added, which shows thatThe special crystal face exposure is beneficial to the generation of active species such as hydroxyl radicals and oxyanions on the surface of the cuprous oxide.
Fig. 8 is a schematic view of the photo-responsive antifouling mechanism of the photo-responsive cuprous oxide prepared in example 1. As can be seen from fig. 8, under the irradiation of visible light, a photo-generated carrier is generated on the surface of cuprous oxide, and by virtue of the energy level difference between the (111) and (100) crystal planes, on one hand, photo-generated holes are efficiently separated and transmitted, so that the photo-corrosion of cuprous oxide is fundamentally inhibited; on the other hand, the photo-generated carriers are rapidly transmitted to an antifouling interface, and oxygen anions (O) are generated in a catalytic mode 2- ) Hydrogen peroxide (H) 2 O 2 ) And hydroxyl radical (OH) and other active species to kill fouling organisms attached to the waterline part of the ship, so that the long-acting photoresponse antifouling activity is exerted.
In conclusion, the photoresponse cuprous oxide with the special crystal face exposure is used as the antifouling agent, has simple synthesis process, is adapted to the existing antifouling paint formula system, and is suitable for antifouling application of ship water line positions in sunlight exposure and alternate dry and wet environments.
Although the present invention is disclosed above, the present invention is not limited thereto. Various changes and modifications may be effected therein by one skilled in the art without departing from the spirit and scope of the invention as defined in the appended claims.
Claims (10)
1. A photoresponse type cuprous oxide antifouling agent comprises cuprous oxide truncated octahedral micro-nano particles with special crystal faces exposed, and is characterized in that the cuprous oxide micro-nano particles are formed by closing 6 (100) crystal faces and 8 (111) crystal faces, each (111) crystal face is adjacent to 3 (100) crystal faces, 36 edges and 24 vertexes are formed in total, the particle size distribution is 0.5-2 mu m, and the cuprous oxide micro-nano particles are prepared through a surfactant mediated wet chemical reduction strategy.
2. A method for preparing a photoresponsive cuprous oxide antifouling agent, which is used for preparing the photoresponsive cuprous oxide antifouling agent according to claim 1, and is characterized by comprising the following steps:
1) Dissolving soluble divalent copper salt in 80-4500 mL deionized water at the reaction temperature of 50-70 ℃, then adding inorganic base and polyvinylpyrrolidone surfactant, and stirring at a constant speed for reaction for 0.5-1.5 hours to obtain blue or blue-green copper hydroxide suspension;
2) Dissolving a reducing agent in 10-800 mL of deionized water, dropwise adding the solution into the copper hydroxide suspension prepared in the step 1), carrying out reduction reaction for 0.5-1 h at the temperature of 50-70 ℃, then carrying out centrifugal washing by using a washing solvent, and carrying out vacuum drying to obtain the cuprous oxide truncated octahedral micro-nano particles with special crystal face exposure.
3. The method according to claim 2, wherein the molar ratio of the divalent copper salt to the inorganic base in step 1) is 1.
4. The method according to claim 2, wherein the molar ratio of the divalent copper salt to the polyvinylpyrrolidone in step 1) is 10 to 33.
5. The method according to claim 2, wherein the molar ratio of the copper hydroxide to the reducing agent in step 2 is 1.
6. The method of claim 2, wherein the cupric salt is one or a combination of copper sulfate, copper chloride, copper acetate and copper nitrate.
7. The preparation method according to claim 2, wherein the inorganic base is one or a combination of sodium hydroxide and potassium hydroxide.
8. The method of claim 2, wherein the reducing agent is one or a combination of ascorbic acid, glucose or sodium sulfite.
9. The method according to claim 2, wherein the washing solvent is one or a combination of methanol, ethanol and isopropanol.
10. The method according to claim 2, wherein the vacuum drying temperature is 30 to 40 ℃ and the drying time is 12 to 24 hours.
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