CN107446402A - Charge transfer type autoxidation reduced nano material, its preparation method and application and marine antifoulant and marine antifouling coating - Google Patents
Charge transfer type autoxidation reduced nano material, its preparation method and application and marine antifoulant and marine antifouling coating Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- 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
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2262—Oxides; Hydroxides of metals of manganese
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
- C08K3/36—Silica
Abstract
The invention discloses a kind of charge transfer type autoxidation reduced nano material, its preparation method and application and marine antifoulant and marine antifouling coating, it is related to marine anti-pollution technical field.The CT nano materials are the composite nano materials of doped or undoped rare earth element, and composite nano materials are mainly by MnO, TiO2, ZnO and SiO2Composition, and mol ratio is (1~5)：(1~15)：(1~3)：(1~15).The present invention alleviates conventional antifouling agents and easily enrichment, difficult degradation and the high deficiency of toxicity be present, and the antifouling phase imitates short, the unconspicuous defect of anti-fouling effect.The CT nano materials of the present invention are respectively provided with significant suppression adhesion effect to marine microorganism, marine alga and Macro-fouling Organismss at low concentrations, show the efficient, antifouling activity of wide spectrum, and have phobotaxis to marine growth without lethal, low-toxicity marine antifoulant can be used as to develop and apply.
Description
Technical field
The present invention relates to marine anti-pollution technical field, is received in particular to a kind of charge transfer type autoxidation reduction
Rice material, its preparation method and application and marine antifoulant and marine antifouling coating.
Background technology
Marine biofouling refers to the product of microorganism, vegetalitas biology and animality biology on artificial surface in ocean
Poly- phenomenon, various marine fouling organisms, such as microorganism, algae, barnacle, oyster, mussel, lime worm, Enteromorpha, ascidian, sea anemone
On the surfaces such as ship housing, marine structure, aquaculture net cage non-selectivity large area adhesion and deposition.Marine fouling organism
Attachment can be caused with being stained：(1) increase hull bottom roughness, cause ship resistance increase, energy consumption and discharge to aggravate, to ship
Oceangoing ship navigation brings high risks；(2) accelerate the structural members such as marine facility, building to be stained corrosion, significantly shorten their life-span；
(3) aquaculture net cage, mesh, the line clogging such as etting of fixation fishing are caused；(4) oceanographic instrumentation is damaged, causes instrument driver
Structure failure, distorted signals, performance reduce, or even potential safety hazard, cause huge economic losses.
At present, the attachment of marine fouling organism can effectively be suppressed or prevent by coating various marine antifouling coatings.Prevent ocean
Dirty coating is a kind of sapecial coating, is mainly made up of macromolecule resin, anti-fouling agent, color stuffing, solvent etc., wherein anti-fouling agent component
It can effectively suppress or prevent and treat the attachment of marine fouling organism, but with organic with high toxicity and the anti-fouling agent of teratogenesis
Tin compound is disabled by International Maritime Organization (IMO), and other anti-fouling agents such as cuprous oxide, OIT etc. are made extensively
With, however find in succession again these anti-fouling agents there is also easy enrichment, difficult degradation and toxicity are high the deficiencies of, marine environment is caused
Pollution.Therefore, there is an urgent need to research and develop the marine antifoulant of environment-friendly type at present.
A variety of Natural product antifoulants have been isolated to from the marine organisms such as sponge, coral and marine alga at present, there is life
Biodegradable and low toxin, but the most of Natural product antifoulants limited source found, in vivo content
Pettiness, and most of marine organisms are largely gathered with relatively difficult, therefore more difficult development and application.In recent years correlative study shows
Attachment of the nano material to microorganism, algae and cirrus class has good inhibition.Li Shanwen, Chen Meiling etc. are by nanometer two
Titanium oxide is added in the furan modified organosilicon acrylic resin synthesized, finds the nano-TiO added2Coating can be made is stained marine growth
Adhesion amount greatly reduces, and its anti-fouling effect is significantly improved.Qi Yuhong, Zhang Zhanping, Liu Hong have manufactured experimently serial nano TiO2/
FEVE fluororine-carbon coatings, study and find nano-TiO2Attachment to large-scale algae (water cloud algae) has obvious interception, can be with
As a kind of anti-pollution function additive of safety and environmental protection.Nano Silver is added polyampholyte/polyacrylamide by Ningbo material institute
Nanometer composite hydrogel is built in amine double-network hydrogel, it is found that small-size nano-silver imparts the excellent antibacterial of hydrogel, resisted
Algae antifouling property, while the sustained release of Nano Silver greatly extends the antifouling timeliness of this kind of composite.Patent of invention
In CN104403448A, using nano silver colloidal sol as anti-fouling agent, in patent of invention CN101531841A, with Cu2The hollow sub-micro balls of O
Individually or the nontoxic anti-fouling agent of embedding Cu2The hollow sub-micro balls of O use as anti-fouling agent.The Guo Zhangwei of Shanghai Ocean University
(2015) suppression that Nano Silver anti-fouling agent is prepared and its adhered to marine microorganism is have studied in its Master's thesis, prepared by design
Silica loads with Nano Silver and silicon dioxide coated nano money kind complex particle material, have studied it to Vibrio natriegen
The mechanism of the suppression of (Gram-negative bacteria) and bacillus subtilis (gram-positive bacteria), analyze the biocidal property of two kinds of materials
Energy and Antibacterial Mechanism.
Although some current nano materials are applied in anti-fouling agent, it is short generally to still suffer from antifouling phase effect, it is impossible to right
Marime fouling microorganism, algae and large ocean fouling organism have significant inhibition, it is impossible to fully meet it is high it is antifouling will
Ask, have much room for improvement in addition to the security of marine organisms.
In view of this, it is special to propose the present invention.
The content of the invention
An object of the present invention is that providing a kind of charge transfer type autoxidation reduced nano material is preventing ocean
Application in biodeterioration, charge transfer type autoxidation reduced nano material can suppress marime fouling microorganism, ocean algae
The attachment of class and large-scale Fouling Animals, it is environmentally friendly, marine anti-pollution field is can be applied to, is had a extensive future.
The second object of the present invention is to provide a kind of charge transfer type autoxidation reduced nano material, and the material is mixes
It is miscellaneous or undoped with rare earth element mainly by MnO, TiO2, ZnO and SiO2The composite nano materials of composition, and four mol ratio
For (1~5)：(1~15)：(1~3)：(1~15), the charge transfer type autoxidation reduced nano material of the composition is to being stained
Biology suppresses attachment activity with significant, and semi-inhibit attachment concentration (EC50 values) is below 10 μ g/mL, and display is efficient, wide spectrum
Antifouling activity.In addition, the charge transfer type autoxidation reduced nano material has phobotaxis to marine growth and without lethal,
Can be as the exploitation and application of low-toxicity marine antifoulant.
The third object of the present invention is to provide a kind of preparation of above-mentioned charge transfer type autoxidation reduced nano material
Method, for this method using being prepared using sol-gel process to composite nano materials, preparation condition is gentle, can realize point
Uniform Doped in sub- level.
The fourth object of the present invention is to provide a kind of comprising above-mentioned charge transfer type autoxidation reduced nano material
Marine antifoulant, charge transfer type autoxidation reduced nano material can not only use separately as anti-fouling agent, also can be with it
He compounds anti-fouling agent, strengthens its anti-fouling effect, is used alone or includes above-mentioned charge transfer type autoxidation reduced nano material
The anti-fouling significant effect of marine antifoulant of material, and safety and environmental protection.
The fifth object of the present invention is to provide a kind of comprising above-mentioned charge transfer type autoxidation reduced nano material
Marine antifouling coating, there is significant antifouling effect comprising antifouling paint made of charge transfer type autoxidation reduced nano material
Fruit.
In order to realize the above-mentioned purpose of the present invention, spy uses following technical scheme：
In a first aspect, the invention provides charge transfer type autoxidation reduced nano material to prevent marine biofouling
In application.
Further, on the basis of technical solution of the present invention, above-mentioned charge transfer type autoxidation reduced nano material is
The composite nano materials of doped or undoped rare earth element, composite nano materials are mainly by MnO, TiO2, ZnO and SiO2Composition, its
Middle MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~5)：(1~15)：(1~3)：(1~
15)；
Preferably, MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~4)：(5~15)：
(1~3)：(3~15)；
It is further preferred that MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO： SiO2=(1~3)：
(10~15)：(1~2)：(10~15).
Further, on the basis of technical solution of the present invention, the rare earth element of doping includes La and Ce, and rare earth element is mixed
Miscellaneous amount is 0.1~2wt%, and La and Ce mol ratio is La：Ce=1：(2~5)；
Preferably, the rare earth element of doping includes La and Ce, and the doping of rare earth element is 0.1~1 wt%, and La and
Ce mol ratio is La：Ce=1：(2~4)；
It is further preferred that the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.5~1wt%,
And La and Ce mol ratio is La：Ce=1：(2~3).
Second aspect, the invention provides a kind of charge transfer type autoxidation reduced nano material, and charge transfer type is certainly
Dynamic oxidation reduced nano material be doped or undoped rare earth element composite nano materials, composite nano materials mainly by MnO,
TiO2, ZnO and SiO2Composition, wherein MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~5)：
(1~15)：(1~3)：(1~15)；
Preferably, MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~4)：(5~15)：
(1~3)：(3~15)；
It is further preferred that MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO： SiO2=(1~3)：
(10~15)：(1~2)：(10~15).
Further, on the basis of technical solution of the present invention, the rare earth element of doping includes La and Ce, and rare earth element is mixed
Miscellaneous amount is 0.1~2wt%, and La and Ce mol ratio is La：Ce=1：(2~5)；
Preferably, the rare earth element of doping includes La and Ce, and the doping of rare earth element is 0.1~1 wt%, and La and
Ce mol ratio is La：Ce=1：(2~4)；
It is further preferred that the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.5~1wt%, and
La and Ce mol ratio is La：Ce=1：(2~3).
The third aspect, the invention provides a kind of preparation side of above-mentioned charge transfer type autoxidation reduced nano material
Method, using sol-gel process prepared by composite nano materials.
Specifically include：According to mol ratio n (Mn)：n(Ti)：n(Zn)：N (Si)=(1~5)：(1~15)：(1~3)：(1
~15) prepared by composite nano materials：(1) a certain amount of butyl titanate is added in absolute ethyl alcohol and is well mixed,
Obtain solution A；(2) a certain amount of zinc nitrate and manganese nitrate are weighed, adds absolute ethyl alcohol, is stirred to after being completely dissolved, is added successively
Enter water, tetraethyl orthosilicate and glacial acetic acid, and it is 2 to adjust pH, obtains solution B；(3) under agitation, that solution A is slowly dropped into B is molten
In liquid, after continuing 2~4h of stirring, 60~100 DEG C of dry 12h in vacuum drying chamber, powder, 400~900 DEG C of high temperature are ground into
2~6h is calcined, obtains composite nano materials.
Further, on the basis of technical solution of the present invention, the preparation of charge transfer type autoxidation reduced nano material
Method, comprise the following steps：
Composite nano materials are placed in the solution containing rare earth element and impregnated, through drying and being calcined after dipping, obtain electricity
Lotus transfevent autoxidation reduced nano material.
Further, on the basis of technical solution of the present invention, dipping uses ultrasonic immersing；
Preferably, the ultrasonic immersing time is 1~2h, more preferably 1.5~2h；
Preferably, drying temperature is 80~100 DEG C, more preferably 85~95 DEG C；
Preferably, sintering temperature is 500~800 DEG C, and more preferably 600~800 DEG C, roasting time is 5~8h, is entered
One step is preferably 5~7h.
Fourth aspect, the invention provides a kind of ocean for including above-mentioned charge transfer type autoxidation reduced nano material
Anti-fouling agent.
5th aspect, the invention provides a kind of ocean for including above-mentioned charge transfer type autoxidation reduced nano material
Antifouling paint.
Compared with the prior art, the present invention has the advantages that：
(1) there is the deficiencies of easily enrichment, difficult degradation and toxicity are high in traditional anti-fouling agent, and the antifouling phase imitates short, antifouling effect
Fruit unobvious defect, charge transfer type autoxidation reduced nano material are a kind of electric charge transmission type nanocatalysts, Neng Gouyin
Redox reaction is sent out, so as to suppress the attachment of marime fouling microorganism, marine algae and large-scale Fouling Animals, and to environment friend
It is good, available for marine antifoulant or marine antifouling coating etc. is prepared, possess the potentiality for being advantageously applied to marine anti-pollution field.
(2) charge transfer type autoxidation reduced nano material of the invention is mainly (1~5) by mol ratio：(1~
15)：(1~3)：MnO, the TiO of (1~15)2, ZnO and SiO2Composition, the charge transfer type autoxidation reduced nano of the composition
Material has to marine microorganism, the soft fouling organism marine alga in ocean and ocean Macro-fouling Organismss reticulate pattern barnacle at low concentrations
There is significant suppression adhesion effect, there is significant suppression attachment activity, semi-inhibit attachment concentration (EC50 values) to fouling organism
Below 10 μ g/mL, display is efficient, the antifouling activity of wide spectrum, and antifouling property protrudes.
(3) charge transfer type autoxidation reduced nano material of the invention there is phobotaxis to marine growth and without killing
Property, can be as the exploitation and application of low-toxicity marine antifoulant.Using charge transfer type autoxidation reduced nano material as anti-
Dirty agent, significant anti-fouling effect, and safety and environmental protection can be brought, prepare marine antifouling coating, real extra large hanging plate examination in conventional manner
Test result and show that it has prominent anti-marine biofouling effect, it is seen that charge transfer type autoxidation reduction of the invention is received
Rice material possesses the application potential as novel sea anti-fouling agent.The charge transfer type autoxidation reduced nano material of the present invention
Not only can one-component be used for the preparation of marine antifouling coating, can also be arranged in pairs or groups with other anti-fouling agents and play synergy, it is anti-to strengthen it
Dirty effect.
(4) preparation technology of charge transfer type autoxidation reduced nano material of the present invention uses sol-gel process,
Preparation method is simple, workable, and preparation condition is gentle, can realize the Uniform Doped on molecular level.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and is not construed as limiting the scope of the present invention.It is unreceipted specific in embodiment
Condition person, the condition suggested according to normal condition or manufacturer are carried out.Agents useful for same or the unreceipted production firm person of instrument, it is
The conventional products that can be obtained by commercially available purchase.
According to the first aspect of the invention, there is provided a kind of charge transfer type autoxidation reduced nano material is preventing
Application in marine biofouling.
Charge transfer type autoxidation reduced nano material (Charge Tranfer, CT nano material) is that a kind of electric charge passes
Defeated type nanocatalyst, it is the international newest fruits of nano anti-biotic material technology, there is remarkable antibacterial, superpower hydrophobic oil resistant
Property, self-cleaning properties and the characteristic such as nontoxic, special lattice structure can be formed, its specific crystal structure is the spinelle in six faces
Structure includes the perovskite structure of octahedral, and electric charge/electronics transfer can occur, can be played by heat energy independent of light merely
Powerful catalytic action.
Charge transfer type autoxidation reduced nano material in the present invention is typical but non-limiting purchased from the rich science and technology of platform
(Shenzhen) Co., Ltd.
The application includes but is not limited to preparing marine antifouling coating or anti-fouling agent etc., and CT nano materials are used in coating
Antifouling paint can be applied to artificial ocean facility surface by the usual manner such as impregnating, spraying or be coated with, its can be applied to carry out ring
Antifouling marine Artificial facilities are protected, are included but is not limited to：Ship, offshore oil and gas platform, buoy, harbour, bridge pier, dock, seawater
Pipeline, timber and net cage for sea farming.
Charge transfer type autoxidation reduced nano material has good antifouling activity, and energy is used as marine antifoulant
Significant anti-fouling effect, and safety and environmental protection are enough brought, possesses the application potential as novel sea anti-fouling agent, is added to ocean and prevents
In dirty coating, it can make coating that there is anti-marine biofouling effect.
There is the deficiencies of easily enrichment, difficult degradation and toxicity are high in traditional anti-fouling agent, and effect of antifouling phase is short, and anti-fouling effect is not
The defects of obvious.Because the transfer of charge transfer type autoxidation reduced nano material electric charge/electronics being capable of initiated oxidation reduction
Reaction, wall film is caused to perforate, and normal biochemical reaction in interference cell, so as to suppress marime fouling microorganism, marine algae
With the attachment of large-scale Fouling Animals, there is anti-stick dirty, antibacterial and anti-algae performance, and environmentally friendly well, possess well
The effect of anti-marine biofouling, there is good application prospect in marine biofouling is prevented.
In a preferred embodiment, charge transfer type autoxidation reduced nano material is doped or undoped dilute
The composite nano materials of earth elements, composite nano materials are mainly by MnO, TiO2, ZnO and SiO2Composition, wherein MnO, TiO2、
ZnO and SiO2Mol ratio be MnO：TiO2：ZnO： SiO2=(1~5)：(1~15)：(1~3)：(1~15).
MnO、TiO2, ZnO and SiO2Typical but non-limiting mol ratio is, for example, 1:1:1:1、 1:2:2:2、1:3:3:
3、1:12:2:15、1:4:1:12、1:5:2:12、1:6:3:5、1:4:1:12、2:15:1:12、 2:2:1:12、2:1:3:5、2:
5:1:15、3:15:1:12、3:10:3:12、4:15:1:10、4:1:3:5、5:15:1:12、 5:1:3:10、5:8:3:3 or 5:
6:1:6。
Composite nano materials are typical but non-limiting to be prepared using sol-gel process, specific preparation method
For：
According to mol ratio n (Mn)：n(Ti)：n(Zn)：N (Si)=(1~5)：(1~15)：(1~3)：(1~15) is to multiple
Nano material is closed to be prepared：(1) a certain amount of butyl titanate is added in absolute ethyl alcohol and be well mixed, obtain solution A；
(2) a certain amount of zinc nitrate and manganese nitrate are weighed, adds absolute ethyl alcohol, stirs to after being completely dissolved, sequentially adds water, positive silicic acid
Ethyl ester and glacial acetic acid, and it is 2 to adjust pH, obtains solution B；(3) under agitation, solution A is slowly dropped into B solution, continues to stir
After mixing 2~4h, 60~100 DEG C of dry 12h in vacuum drying chamber, powder is ground into, 400~900 DEG C of 2~6h of high-temperature calcination, is obtained
To composite nano materials.
This method mild condition, stable vitreosol system is formed in the solution, is slowly polymerize between micelle, formed three-dimensional
The gel of spacial framework, gel obtain composite nano materials after drying, sintering curing.
Using doped or undoped rare earth element mainly by MnO, TiO2, ZnO and SiO2The CT nano materials of composition, and
By adjusting the proportioning in composite nano materials between each nano-metal-oxide, it can obtain that lattice structure is more perfect to be received
Rice material, more preferable electric charge/electronics transfer is realized, the transfer velocity of CT nano materials electric charge/electronics of the component is fast, and catalysis is made
With strong, so as to be more prone to initiated oxidation reduction reaction, cell is interfered, it is strong to the inhibitory action of bacterium and microorganism,
There is significant suppression adhesion effect to bacterium, algae and Macro-fouling Organismss in ocean, there is excellent anti-marime fouling to imitate
Fruit, potentiality are had more in marine biofouling applied to preventing and treating.
Found through overtesting, the charge transfer type autoxidation reduced nano material of the composition is micro- to ocean at low concentrations
Biology, the soft fouling organism marine alga in ocean and ocean Macro-fouling Organismss reticulate pattern barnacle are respectively provided with significant suppression adhesion effect,
There is significant suppression attachment activity to fouling organism, semi-inhibit attachment concentration (EC50 values) shows height below 10 μ g/mL
Effect, the antifouling activity of wide spectrum, antifouling property protrude.In addition, the CT nano materials have phobotaxis to marine growth and without lethal,
Can be as the exploitation and application of low-toxicity marine antifoulant, more application prospect.
Preferably, MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~4)：(5~15)：
(1~3)：(3~15).
It is further preferred that MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO： SiO2=(1~3)：
(10~15)：(1~2)：(10~15).
It is found by experiment that, MnO, TiO2, ZnO and SiO2Mol ratio have for antifouling activity and influence, it is each by optimizing
Mol ratio between component, the CT nano materials can be made to obtain the highly efficient and antifouling activity of wide spectrum.
In a preferred embodiment, the rare earth element of doping includes La and Ce, and the doping of rare earth element is 0.1
~2wt%, and La and Ce mol ratio is La：Ce=1：(2~5).
Doping, which refers to using rare earth element as entirety, the gross mass of rare earth element, accounts for the quality percentage of composite nano materials
Than.
The doping of rare earth element is, for example, 0.1wt%, 0.2wt%, 0.5wt%, 1wt% or 2wt%.La's and Ce
Mol ratio is, for example, 1:2、1:3、1:4 or 1:5.
The rare earth element of doping can also include other rare earth elements, such as Pr etc. except La and Ce.
Rare earth doped element helps lend some impetus to electric charge/electronics transfer, so as to improve the catalytic action of CT nano materials, more has
Beneficial to initiated oxidation reduction reaction, so as to significantly improve the lethality to microorganism and marine organisms cell, CT nanometer materials are improved
The antifouling activity of material.By including MnO, TiO2, ZnO and SiO2Composite nano materials in adulterate La and Ce rare earth elements,
The attachment of marime fouling microorganism, marine algae and large-scale Fouling Animals can be significantly inhibited, is shown efficient, wide spectrum antifouling
Activity, it is rare earth doped after CT nano materials anti-marine biofouling effect it is more preferable, activity it is higher.
Preferably, the rare earth element of doping includes La and Ce, and the doping of rare earth element is 0.1~1 wt%, and La and
Ce mol ratio is La：Ce=1：(2~4).
It is further preferred that the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.5~1wt%,
And La and Ce mol ratio is La：Ce=1：(2~3).
By optimizing the mol ratio of the doping of rare earth element and the rare earth element of doping, CT nanometers can be further improved
The anti-fouling effect and antifouling activity of material.
As a preferred embodiment, charge transfer type autoxidation reduced nano material is rare earth doped element
Mainly by MnO, TiO2, ZnO and SiO2The composite nano materials of composition, wherein MnO, TiO2, ZnO and SiO2Mol ratio be
MnO：TiO2：ZnO：SiO2=2：15：1： 12；The rare earth element of doping is La and Ce, and the doping of rare earth element is 1wt%,
And La and Ce mol ratio is La：Ce=1：3.
According to the second aspect of the invention, there is provided a kind of charge transfer type autoxidation reduced nano material, to mix
Composite nano materials miscellaneous or undoped with rare earth element, composite nano materials are mainly by MnO, TiO2, ZnO and SiO2Composition, its
Middle MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~5)：(1~15)：(1~3)：(1~
15)。
MnO、TiO2, ZnO and SiO2Typical but non-limiting mol ratio is, for example, 1:1:1:1、 1:2:2:2、1:3:3:
3、1:12:2:15、1:4:1:12、1:5:2:12、1:6:3:5、1:4:1:12、2:15:1:12、 2:2:1:12、2:1:3:5、2:
5:1:15、3:15:1:12、3:10:3:12、4:15:1:10、4:1:3:5、5:15:1:12、 5:1:3:10、5:8:3:3 or 5:
6:1:6。
" mainly by " of the present invention, it is intended that it can also include other components in addition to the component, these other groups
Divide and assign charge transfer type autoxidation reduced nano material different characteristics.In addition, " mainly by " of the present invention,
It may be replaced by enclosed " for " or " Consists of ".
Composite nano materials are typical but non-limiting to be prepared using sol-gel process, specific preparation method
For：
According to mol ratio n (Mn)：n(Ti)：n(Zn)：N (Si)=(1~5)：(1~15)：(1~3)：(1~15) is to multiple
Nano material is closed to be prepared：(1) a certain amount of butyl titanate is added in absolute ethyl alcohol and be well mixed, obtain solution A；
(2) a certain amount of zinc nitrate and manganese nitrate are weighed, adds absolute ethyl alcohol, stirs to after being completely dissolved, sequentially adds water, positive silicic acid
Ethyl ester and glacial acetic acid, and it is 2 to adjust pH, obtains solution B；(3) under agitation, solution A is slowly dropped into B solution, continues to stir
After mixing 2~4h, 60~100 DEG C of dry 12h in vacuum drying chamber, powder is ground into, 400~900 DEG C of 2~6h of high-temperature calcination, is obtained
To composite nano materials.
This method mild condition, stable vitreosol system is formed in the solution, is slowly polymerize between micelle, formed three-dimensional
The gel of spacial framework, gel obtain composite nano materials after drying, sintering curing.
The CT nano materials of the present invention are mainly (1~5) by mol ratio：(1~15)：(1~3)：The MnO of (1~15),
TiO2, ZnO and SiO2Composition, the charge transfer type autoxidation reduced nano material of the composition is at low concentrations to the micro- life in ocean
Thing, the soft fouling organism marine alga in ocean and ocean Macro-fouling Organismss reticulate pattern barnacle are respectively provided with significant suppression adhesion effect, right
Fouling organism have it is significant suppress attachment activity, semi-inhibit attachment concentration (EC50 values) below 10 μ g/mL, display is efficient,
The antifouling activity of wide spectrum, antifouling property protrude.It is right meanwhile the CT nano materials have phobotaxis to marine growth and without lethal
Environment and marine organisms non-hazardous, more safety and environmental protection, can be as the exploitation and application of low-toxicity marine antifoulant.
In a preferred embodiment, MnO, TiO2, ZnO and SiO2Mol ratio be MnO： TiO2：ZnO：SiO2
=(1~4)：(5~15)：(1~3)：(3~15).
In a preferred embodiment, MnO, TiO2, ZnO and SiO2Mol ratio be MnO： TiO2：ZnO：SiO2
=(1~3)：(10~15)：(1~2)：(10~15).
By optimizing the mol ratio between each component, highly efficient and wide spectrum antifouling activity CT nanometer materials can be obtained
Material.
In a preferred embodiment, the rare earth element of doping includes La and Ce, and the doping of rare earth element is 0.1
~2wt%, and La and Ce mol ratio is La：Ce=1：(2~5).
Doping, which refers to using rare earth element as entirety, the gross mass of rare earth element, accounts for the quality percentage of composite nano materials
Than.
The doping of rare earth element is, for example, 0.1wt%, 0.2wt%, 0.5wt%, 1wt% or 2wt%.La's and Ce
Mol ratio is, for example, 1:2、1:3、1:4 or 1:5.
Described " rare earth element includes " means it in addition to the La and Ce, can also include other components, such as Pr etc.,
Described " rare earth element includes " may be replaced by enclosed " for " or " Consists of ".
Rare earth doped element helps lend some impetus to electric charge/electronics transfer, so as to improve the catalytic action of CT nano materials, more has
Beneficial to initiated oxidation reduction reaction, so as to further improve CT nano materials to microorganism and the lethality of marine organisms cell,
Improve the antifouling activity of CT nano materials.By including MnO, TiO2, ZnO and SiO2Composite nano materials in adulterate La and
Ce rare earth elements, the attachment of marime fouling microorganism, marine algae and large-scale Fouling Animals can be significantly inhibited, is shown more
Efficiently, the antifouling activity of wide spectrum, it is rare earth doped after CT nano materials anti-marine biofouling effect it is more preferable, activity it is higher.
Preferably, the rare earth element of doping includes La and Ce, and the doping of rare earth element is 0.1~1 wt%, and La and
Ce mol ratio is La：Ce=1：(2~4).
It is further preferred that the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.5~1wt%,
And La and Ce mol ratio is La：Ce=1：(2~3).
By optimizing the mol ratio of the doping of rare earth element and the rare earth element of doping, CT nanometers can be further improved
The anti-fouling effect and antifouling activity of material.
As a preferred embodiment, charge transfer type autoxidation reduced nano material is rare earth doped element
Mainly by MnO, TiO2, ZnO and SiO2The composite nano materials of composition, wherein MnO, TiO2, ZnO and SiO2Mol ratio be
MnO：TiO2：ZnO：SiO2=2：15：1： 12；The rare earth element of doping is La and Ce, and the doping of rare earth element is 1wt%,
And La and Ce mol ratio is La：Ce=1：3.
According to the third aspect of the present invention, there is provided a kind of above-mentioned charge transfer type autoxidation reduced nano material
Preparation method, using sol-gel process prepared by composite nano materials.
Sol-gel process be exactly by the compound containing high chemical active ingredient by solution, colloidal sol, gel and solidify, then
The method of the thermally treated oxide formed or other compound solids.
CT nano materials are prepared using sol-gel process, and method is simple to operation, and preparation condition is gentle, can be realized point
Uniform Doped in sub- level.
Composite nano materials are typical but non-limiting to be prepared by the following preparation method：
According to mol ratio n (Mn)：n(Ti)：n(Zn)：N (Si)=(1~5)：(1~15)：(1~3)：(1~15) is to multiple
Nano material is closed to be prepared：(1) a certain amount of butyl titanate is added in absolute ethyl alcohol and be well mixed, obtain solution A；
(2) a certain amount of zinc nitrate and manganese nitrate are weighed, adds absolute ethyl alcohol, stirs to after being completely dissolved, sequentially adds water, positive silicic acid
Ethyl ester and glacial acetic acid, and it is 2 to adjust pH, obtains solution B；(3) under agitation, solution A is slowly dropped into B solution, continues to stir
After mixing 2~4h, 60~100 DEG C of dry 12h in vacuum drying chamber, powder is ground into, 400~900 DEG C of 2~6h of high-temperature calcination, is obtained
To composite nano materials.
In a preferred embodiment, the preparation method bag of above-mentioned charge transfer type autoxidation reduced nano material
Include following steps：
Composite nano materials are placed in the solution containing rare earth element and impregnated, through drying and being calcined after dipping, obtain electricity
Lotus transfevent autoxidation reduced nano material.
Dry and roasting can use usual manner to carry out, such as drying is dried using baking oven, roasting uses Muffle furnace
It is calcined.
The preparation method of the rear-earth-doped CT nano materials of the present invention is using dipping combustion method, and technique is simple, operability
By force, cost is low, and product purity is high, granularity is small, and rare earth doped uniform, activity is high.
In a preferred embodiment, dipping uses ultrasonic immersing.
Using ultrasonic immersing rare earth element can be made more fully to be embedded into the lattice structure of composite nano materials, impregnated
Efficiency high, effect are good.
Preferably, the ultrasonic immersing time is 1~2h, more preferably 1.5~2h.
The typical but non-limiting ultrasonic immersing time is, for example, 1h, 1.5h or 2h.
Preferably, drying temperature is 80~100 DEG C, more preferably 85~95 DEG C.
Typical but non-limiting drying temperature is, for example, 80 DEG C, 90 DEG C or 100 DEG C.
Preferably, sintering temperature is 500~800 DEG C, and more preferably 600~800 DEG C, roasting time is 5~8h, is entered
One step is preferably 5~7h.
Typical but non-limiting sintering temperature is, for example, 500 DEG C, 600 DEG C, 700 DEG C or 800 DEG C.
Typical but non-limiting roasting time is, for example, 5h, 6h, 7h or 8h.
The preparation method of typical CT nano materials, is specifically included：With water by a certain amount of La (NO3)3·6H2O and Ce
(NO3)3·6H2O dissolves, by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2、ZnO
And SiO2In composite nano materials, dry, be placed in Muffle furnace at 80~100 DEG C after 1~2h of ultrasonic immersing, in 500~
5~8h is calcined at 800 DEG C, CT nano materials are made.
The doped or undoped rare earth element of the present invention is mainly (1~5) by mol ratio：(1~15)：(1~3)：(1~
15) MnO, TiO2, ZnO and SiO2The CT nano materials of composition have wide spectrum and significant to fouling organism at low concentrations
Suppress attachment activity, meanwhile, there is phobotaxis to marine growth without lethal, to environment and marine organisms non-hazardous, can make
Applied in standby marine antifouling coating or anti-fouling agent.
The application includes but is not limited to preparing marine antifouling coating or anti-fouling agent, and the CT nano materials are used in coating
Antifouling paint can be applied to artificial ocean facility surface by the usual manner such as impregnating, spraying or be coated with, its can be applied to carry out ring
Antifouling marine Artificial facilities are protected, are included but is not limited to：Ship, offshore oil and gas platform, buoy, harbour, bridge pier, dock, seawater
Pipeline, timber and net cage for sea farming.
According to the fourth aspect of the present invention, there is provided one kind includes above-mentioned charge transfer type autoxidation reduced nano material
The marine antifoulant of material.
As anti-fouling agent or it is added to using the CT nano materials that this is formed in existing anti-fouling agent, can be brought significant anti-
Dirty effect, it can not only be used separately as anti-fouling agent, can also be arranged in pairs or groups with other anti-fouling agents plays synergy, strengthens its antifouling effect
Fruit.
According to the fifth aspect of the present invention, there is provided one kind includes above-mentioned charge transfer type autoxidation reduced nano material
The marine antifouling coating of material.
The CT nano materials of the composition are added in marine antifouling coating as anti-fouling agent, are prepared ocean in conventional manner and are prevented
Dirty coating, real extra large board experiment show that it has prominent anti-ocean to marine antifouling coating by adding the agent of CT nano-material antifoulings
Biodeterioration effect.
The present invention is further illustrated below by specific embodiment and comparative example, it should be understood, however, that, these implementations
Example, which is only for being described in more detail, to be used, and is not to be construed as limiting the present invention in any form.It is of the present invention
Each raw material can pass through commercially available acquisition.
Composite nano materials in embodiment are prepared by the following method to obtain：
(1) according to mol ratio n (Mn)：n(Ti)：n(Zn)：N (Si)=(1~5)：(1~15)：(1~3)：(1~15)
A certain amount of butyl titanate is added in absolute ethyl alcohol and is well mixed, obtains solution A；(2) a certain amount of zinc nitrate is weighed
And manganese nitrate, absolute ethyl alcohol is added, stirs to after being completely dissolved, sequentially adds water, tetraethyl orthosilicate and glacial acetic acid, and adjust pH
For 2, solution B is obtained；(3) under agitation, solution A is slowly dropped into B solution, continued after stirring 4h, 100 in vacuum drying chamber
DEG C dry 12h, be ground into powder, 800 DEG C of high-temperature calcination 4h, obtain composite nano materials.
Embodiment 1
A kind of CT nano materials, it is by MnO, TiO doped with lanthanide-indueed shift2, ZnO and SiO2What is formed is compound
Nano material, the mol ratio of principal component is MnO：TiO2：ZnO：SiO2=2： 15：1：12, the codope of lanthanide-indueed shift
Measure as 1wt%, and both mol ratio La：Ce=1：3.
With water by a certain amount of La (NO3)3·6H2O and Ce (NO3)3·6H2O dissolvings (calculate the matter of salt according to doping
Amount), by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2, ZnO and SiO2Composite Nano
In material, dry, be placed in Muffle furnace at 100 DEG C after ultrasonic immersing 1h, 8h is calcined at 600 DEG C, CT nano materials are made.
Embodiment 2
A kind of CT nano materials, it is by MnO, TiO doped with lanthanide-indueed shift2, ZnO and SiO2What is formed is compound
Nano material, the mol ratio of principal component is MnO：TiO2：ZnO：SiO2=2： 5：1：5, the codope amount of lanthanide-indueed shift
For 0.1wt%, and both mol ratio La：Ce=1： 2.
With water by a certain amount of La (NO3)3·6H2O and Ce (NO3)3·6H2O dissolvings (calculate the matter of salt according to doping
Amount), by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2, ZnO and SiO2Composite Nano
In material, dry, be placed in Muffle furnace at 80 DEG C after ultrasonic immersing 1.5h, 5h is calcined at 800 DEG C, CT nanometer materials are made
Material.
Embodiment 3
A kind of CT nano materials, it is by MnO, TiO doped with lanthanide-indueed shift2, ZnO and SiO2What is formed is compound
Nano material, the mol ratio of principal component is MnO：TiO2：ZnO：SiO2=2： 1：1：1, the codope amount of lanthanide-indueed shift
For 0.5wt%, and both mol ratio La：Ce=1： 3.
With water by a certain amount of La (NO3)3·6H2O and Ce (NO3)3·6H2O dissolvings (calculate the matter of salt according to doping
Amount), by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2, ZnO and SiO2Composite Nano
In material, dry, be placed in Muffle furnace at 90 DEG C after ultrasonic immersing 2h, 8h is calcined at 500 DEG C, CT nano materials are made.
Embodiment 4
A kind of CT nano materials, it is by MnO, TiO doped with lanthanide-indueed shift2, ZnO and SiO2What is formed is compound
Nano material, the mol ratio of principal component is MnO：TiO2：ZnO：SiO2=2： 8：1：6, the codope amount of lanthanide-indueed shift
For 1wt%, and both mol ratio La：Ce=1： 4.
With water by a certain amount of La (NO3)3·6H2O and Ce (NO3)3·6H2O dissolvings (calculate the matter of salt according to doping
Amount), by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2, ZnO and SiO2Composite Nano
In material, dry, be placed in Muffle furnace at 90 DEG C after ultrasonic immersing 1h, 7h is calcined at 700 DEG C, CT nano materials are made.
Embodiment 5
A kind of CT nano materials, it is by MnO, TiO doped with lanthanide-indueed shift2, ZnO and SiO2What is formed is compound
Nano material, the mol ratio of principal component is MnO：TiO2：ZnO：SiO2=2： 10：1：5, the codope amount of lanthanide-indueed shift
For 1.5wt%, and both mol ratio La：Ce=1：5.
With water by a certain amount of La (NO3)3·6H2O and Ce (NO3)3·6H2O dissolvings (calculate the matter of salt according to doping
Amount), by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2, ZnO and SiO2Composite Nano
In material, dry, be placed in Muffle furnace at 80 DEG C after ultrasonic immersing 1.5h, 6h is calcined at 750 DEG C, CT nanometer materials are made
Material.
Embodiment 6
A kind of CT nano materials, it is by MnO, TiO doped with lanthanide-indueed shift2, ZnO and SiO2What is formed is compound
Nano material, the mol ratio of principal component is MnO：TiO2：ZnO：SiO2=2：3：1：10, the codope amount of lanthanide-indueed shift
For 1wt%, and both mol ratio La：Ce=1： 2.
With water by a certain amount of La (NO3)3·6H2O and Ce (NO3)3·6H2O dissolvings (calculate the matter of salt according to doping
Amount), by La (NO3)3·6H2O、Ce(NO3)3·6H2O mixed aqueous solution is impregnated into MnO, TiO2, ZnO and SiO2Composite Nano
In material, dry, be placed in Muffle furnace at 100 DEG C after ultrasonic immersing 2h, 6.5h is calcined at 650 DEG C, CT nanometer materials are made
Material.
Embodiment 7
A kind of CT nano materials, it is by MnO, TiO2, ZnO and SiO2The composite nano materials of composition, the mol ratio of principal component
For MnO：TiO2：ZnO：SiO2=2：15：1：12.
(1) according to mol ratio n (Mn)：n(Ti)：n(Zn)：N (Si)=2：15：1：12 add a certain amount of butyl titanate
Enter into absolute ethyl alcohol and be well mixed, obtain solution A；(2) a certain amount of zinc nitrate and manganese nitrate are weighed, adds absolute ethyl alcohol,
Stirring sequentially adds water, tetraethyl orthosilicate and glacial acetic acid to after being completely dissolved, and it is 2 to adjust pH, obtains solution B；(3) stirring
Mix down, solution A is slowly dropped into B solution, after continuing 2~4h of stirring, 60~100 DEG C of dry 12h in vacuum drying chamber, grinding
Into powder, 400~900 DEG C of 2~6h of high-temperature calcination, composite nano materials are obtained.
Embodiment 8
A kind of CT nano materials, wherein MnO, TiO2, ZnO and SiO2Mol ratio be MnO： TiO2：ZnO：SiO2=5：
1：3：2, remaining is same as Example 1.
Comparative example 1
A kind of CT nano materials, wherein MnO, TiO2, ZnO and SiO2Mol ratio be MnO： TiO2：ZnO：SiO2=6：
0.5：5：0.5, remaining is same as Example 1.
Comparative example 2
A kind of CT nano materials, wherein MnO, TiO2, ZnO and SiO2Mol ratio be MnO： TiO2：ZnO：SiO2=
0.5：20：0.5：20, remaining is same as Example 1.
Comparative example 3
The codope amount of a kind of CT nano materials, wherein lanthanide-indueed shift is 5wt%, and remaining is same as Example 1.
Comparative example 4
The codope amount of a kind of CT nano materials, wherein lanthanide-indueed shift is 0.05wt%, remaining and the phase of embodiment 1
Together.
Comparative example 5
A kind of mol ratio La of CT nano materials, wherein lanthanide-indueed shift：Ce=3：1, remaining and the phase of embodiment 1
Together.
Comparative example 6
A kind of marine antifoulant cuprous oxide.
Comparative example 7
A kind of marine antifoulant OIT.
Comparative example 8
A kind of marine antifoulant nano titanium oxide.
Comparative example 9
A kind of marine antifoulant Nano Silver.
Inhibitory action of the CT nano materials of test example 1 to marime fouling microorganism
By taking the CT nano materials of embodiment 1 as an example, inhibitory action of the research CT nano materials to marime fouling microorganism.
Test method：
The biological detection model of the miniature fouling organism in ocean uses most important miniature fouling organism-ocean in ocean dirty
Damage property bacterium.
Marine pseudomonas is inoculated in 2216E fluid nutrient mediums, bacterium is collected by centrifugation after overnight in shaking table culture, with nothing
Simultaneously suspension is made in bacterium seawer washing, bacterial concentration about 107~109Individual/mL.
The CT nano materials of embodiment 1 are first dissolved in 2216E fluid nutrient mediums, then by 0.1,1.0,10.0,
50.0th, 100.0 μ g/mL concentration mixes with obtained bacterial suspension, adds in culture dish.With the culture of refinement bacterium suspension
Ware is control group.Each experimental group is all provided with 3 parallel cups with control group, and 3h is cultivated at 30 DEG C, is gently washed repeatedly with antiseptic sea water
Wash culture dish.Culture dish is soaked with 4% formalin, with distilled water flushing, 5min is then dyed with 0.5 μ g/mL DAPI.
Take 10 visuals field to count at random under fluorescence microscope, obtain the attachment quantity of bacterium.
Result of the test：
Result of the test confirms that CT nano materials can significantly inhibit the attachment of marime fouling bacterium at low concentrations, and it half
It is only 3.32 ± 0.11 μ g/mL to suppress attachment concentration (EC50 values).
Inhibitory action of the CT nano materials of test example 2 to the soft fouling organism marine alga in ocean
By taking the CT nano materials of embodiment 1 as an example, suppression of the research CT nano materials to the soft fouling organism marine alga in ocean
Effect.
Test method：
The biological detection model of the soft fouling organism in ocean represents biological marine alga using it --- boat-shaped algae.Boat-shaped algae is commercially available
It is isolated in the aquatic institute algae kind storehouse of the Chinese Academy of Sciences, or from Shenzhen waters collection.
Boat-shaped algae is inoculated in Erdchreiber ' s culture mediums, the algae solution cultivated to exponential phase of growth is trained with algae
Nutrient solution is diluted to certain concentration, shakes up standby.
The CT nano materials of embodiment 1 are first dissolved in Erdchreiber ' s culture mediums, then by 0.5,5.0,
10.0th, 25,50 μ g/mL concentration mixes with obtained boat-shaped algae suspension, adds in culture dish.To add boat-shaped algae suspension
Culture dish is control group.Each experimental group and control group are all provided with 3 parallel cups, 20 DEG C, culture culture 3d under conditions of 30001x,
Culture dish is gently washed with antiseptic sea water repeatedly.Using the characteristic of chlorophyll autofluorescence, 10 are taken at random under fluorescence microscope
The individual visual field counts, and obtains the attachment quantity of boat-shaped algae.
Result of the test：
Result of the test confirms that CT nano materials can significantly inhibit the attachment of boat-shaped algae, the attachment of its semi-inhibit at low concentrations
Concentration (EC50Value) it is only 7.13 ± 0.36 μ g/mL.
Inhibitory action of the CT nano materials of test example 3 to large ocean fouling organism
By taking the CT nano materials of embodiment 1 as an example, inhibitory action of the research CT nano materials to large ocean fouling organism.
Test method：
The biological detection model of ocean Macro-fouling Organismss represents biological reticulate pattern barnacle using it.Reticulate pattern barnacle adult is in depth
Gather and obtain on the reef of ditch between fields city Bay in Shenzhen marine site, its cypris larva cultivates acquisition in laboratory.
The CT nano materials of embodiment 1 are dissolved in antiseptic sea water, 0.5,2.5,5,10 μ g/mL is configured to, takes respectively
Each solution of 10mL is added in culture dish, is separately taken 10mL antiseptic sea water to be added in blank culture dish, is set to corresponding control group,
Each experimental group is all provided with 3 parallel cups, every glass of addition cypris larva 30~80 with control group.After putting into cypris larva 48h, body is used
Stereomicroscope observes the adhesion condition of cypris larva.
Result of the test：
Result of the test confirms that CT nano materials can significantly inhibit the attachment of reticulate pattern barnacle at low concentrations, and it is big to ocean
The semi-inhibit attachment concentration EC50 of type fouling organism reticulate pattern barnacle is also only 10.58 ± 0.04 μ g/mL.
Test example 1~3 shows that CT nano materials are at low concentrations to marine microorganism, the soft fouling organism marine alga in ocean
Significant suppression adhesion effect is respectively provided with ocean Macro-fouling Organismss reticulate pattern barnacle, shows the efficient, antifouling activity of wide spectrum.
Environment friendly of the CT nano materials of test example 4 to large ocean fouling organism
After test example 3 is handled 3 days, reticulate pattern barnacle is transferred in fresh seawater, changes seawater daily, counts byssus number,
Observe byssus adhesive rate.As a result show, when CT nano materials concentration is less than 25ug/mL after 3 days, reticulate pattern barnacle byssus can recover
It is horizontal to control group.
It can thus be seen that CT nano materials have a phobotaxis without lethal, there is close friend to marine growth and extra large environment
Property.
The marine hanging plate test of the nano marine anti-fouling coating of application examples nano material containing CT
With reference to national standard《Anti-fouling paint model shallow sea soak test method》(GB/T 5370-2007), examine embodiment 1
~8 and comparative example 1~9 CT nano materials as antifouling efficiency of the marine antifoulant in Shenzhen sea area.
Using epoxy resin as film forming matter, add CT nano materials and be prepared into antifouling paint as anti-fouling agent, anti-fouling agent
Addition is the 1% of antifouling paint quality.Test group takes 6 pieces of test pieces, coating anti-pollution coating, not scribble antifouling paint
Conduct control, Yu Haiyang fouling organism vigorous summer carries out board experiment, in natural sea area hanging plate 1 month, calculates every piece
Fouling organism coverage on plate, averages.
As a result it is as shown in table 1.
The marine antifouling coating sea hanging plate test result of CT nano material of the table 1 containing embodiment and comparative example
As it can be seen from table 1 the biodeterioration on the test piece surface for finding to be coated with CT nano-material antifouling coating covers
Cover degree average out to 3.8-4.8%, substantially less than compares model, compares the biodeterioration coverage average out to 95.6% of model, table
Bright CT nano materials have good anti-fouling effect.
Embodiment 7 compared with Example 1, undoped with lanthanide-indueed shift in composite nano materials, as a result finds addition
There are the CT nano materials of rare earth element more preferable compared with the anti-fouling effect of the CT nano materials undoped with rare earth element, be coated with CT nanometers
The biodeterioration coverage on the test piece surface of material antifouling paint is smaller.
Embodiment 8 compared with Example 1, composite nano materials MnO, TiO2, ZnO and SiO2Mol ratio and embodiment 1 not
Together, the anti-fouling effect of the CT nano materials obtained is different, it is seen that the composite nano materials of different mol ratio can be to antifouling effect
Fruit has an impact.
Comparative example 1-2 compared with Example 1, composite nano materials MnO, TiO2, ZnO and SiO2Mol ratio and embodiment 1
Difference, the anti-fouling effect of obtained CT nano materials have declined, it is seen that unfavorable mol ratio can be prevented CT nano materials
Dirty effect has an impact.For comparative example 3 compared with embodiment 1, the doping of rare earth element is more, comparative example 4 compared with Example 1,
The doping of rare earth element is less, and the anti-fouling effect of CT nano materials is be not as good as embodiment 1, it is seen that rare earth doped amount mistake
It is more, negative effect can be played to the anti-fouling effect of CT nano materials.Comparative example 5 is compared with embodiment 1, lanthanide-indueed shift
Mol ratio it is different, La is more than Ce, and the anti-fouling effect of obtained CT nano materials is also be not as good as embodiment 1, it is seen that La's and Ce
Mol ratio also has certain influence to the anti-fouling effect of CT nano materials.
And it is coated with the biodeterioration covering on the test piece surface of the antifouling paint of the marine antifoulant of the 6-7 containing comparative example
Degree is obvious to become big, and cuprous oxide and isothiazolinone anti-fouling agent have Potential environmental risk, are coated with the 8-9's containing comparative example
The biodeterioration coverage on the test piece surface of the antifouling paint of nano material also becomes big, not as using CT nanometers material of the present invention
The good antifouling effect of the antifouling paint of material, it is seen that the anti-fouling effect of CT nano materials is notable.
As can be seen here, CT nano materials of the invention are at low concentrations to marine microorganism, the soft fouling organism sea in ocean
Algae and ocean Macro-fouling Organismss reticulate pattern barnacle are respectively provided with significant suppression adhesion effect, show efficient, the antifouling work of wide spectrum
Property；In addition, the recovery experiment to reticulate pattern barnacle also indicate that CT nano materials there is phobotaxis and without lethal, therefore, can conduct
Low-toxicity marine antifoulant is developed and application.Antifouling paint made of CT nano materials, shallow sea soak test result also indicate that it
With significant anti-fouling effect.CT nano materials provided by the invention, not only can one-component be used for marine antifouling coating preparation,
Also it can be compounded with other anti-fouling agents, strengthen its anti-fouling effect.
Although illustrate and describing the present invention with specific embodiment, but will be appreciated that without departing substantially from the present invention's
Many other change and modification can be made in the case of spirit and scope.It is, therefore, intended that wrap in the following claims
Include all such changes and modifications belonged in the scope of the invention.
Claims (10)
1. application of the charge transfer type autoxidation reduced nano material in marine biofouling is prevented.
2. according to the application described in claim 1, it is characterised in that the charge transfer type autoxidation reduced nano material is
The composite nano materials of doped or undoped rare earth element, composite nano materials are mainly by MnO, TiO2, ZnO and SiO2Composition, its
Middle MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~5)：(1~15)：(1~3)：(1~
15)；
Preferably, MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~4)：(5~15)：(1~
3)：(3~15)；
It is further preferred that MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~3)：(10~
15)：(1~2)：(10~15).
3. according to the application described in claim 2, it is characterised in that the rare earth element of doping includes La and Ce, rare earth element
Doping is 0.1~2wt%, and La and Ce mol ratio is La：Ce=1：(2~5)；
Preferably, the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.1~1wt%, and La and Ce rubs
Your ratio is La：Ce=1：(2~4)；
It is further preferred that the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.5~1wt%, and La with
Ce mol ratio is La：Ce=1：(2~3).
4. a kind of charge transfer type autoxidation reduced nano material, it is characterised in that the charge transfer type autoxidation is also
Former nano material is the composite nano materials of doped or undoped rare earth element, and composite nano materials are mainly by MnO, TiO2、ZnO
And SiO2Composition, wherein MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~5)：(1~15)：(1
~3)：(1~15)；
Preferably, MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~4)：(5~15)：(1~
3)：(3~15)；
It is further preferred that MnO, TiO2, ZnO and SiO2Mol ratio be MnO：TiO2：ZnO：SiO2=(1~3)：(10~
15)：(1~2)：(10~15).
5. according to the charge transfer type autoxidation reduced nano material described in claim 4, it is characterised in that the rare earth of doping
Element includes La and Ce, and the doping of rare earth element is 0.1~2wt%, and La and Ce mol ratio is La：Ce=1：(2~
5)；
Preferably, the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.1~1wt%, and La and Ce rubs
Your ratio is La：Ce=1：(2~4)；
It is further preferred that the rare earth element of doping includes La and Ce, the doping of rare earth element is 0.5~1wt%, and La with
Ce mol ratio is La：Ce=1：(2~3).
6. a kind of preparation method of the charge transfer type autoxidation reduced nano material described in claim 4 or 5, its feature exist
In being prepared using sol-gel process to composite nano materials.
7. according to the preparation method of the charge transfer type autoxidation reduced nano material described in claim 6, it is characterised in that
Comprise the following steps：
Composite nano materials are placed in the solution containing rare earth element and impregnated, through drying and being calcined after dipping, electric charge is obtained and turns
Shifting type autoxidation reduced nano material.
8. according to the preparation method of the charge transfer type autoxidation reduced nano material described in claim 7, it is characterised in that
Dipping uses ultrasonic immersing；
Preferably, the ultrasonic immersing time is 1~2h, more preferably 1.5~2h；
Preferably, drying temperature is 80~100 DEG C, more preferably 85~95 DEG C；
Preferably, sintering temperature is 500~800 DEG C, and more preferably 600~800 DEG C, roasting time is 5~8h, further
Preferably 5~7h.
A kind of 9. marine antifoulant of the charge transfer type autoxidation reduced nano material comprising described in claim 4 or 5.
10. a kind of marine anti-pollution of the charge transfer type autoxidation reduced nano material comprising described in claim 4 or 5 applies
Material.
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| CN111066816A (en) * | 2019-11-21 | 2020-04-28 | 浙江大学 | Preparation for treating fouling of coastal mussels, and use method and application thereof |
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