CN107446402B - Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint - Google Patents

Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint Download PDF

Info

Publication number
CN107446402B
CN107446402B CN201710767834.9A CN201710767834A CN107446402B CN 107446402 B CN107446402 B CN 107446402B CN 201710767834 A CN201710767834 A CN 201710767834A CN 107446402 B CN107446402 B CN 107446402B
Authority
CN
China
Prior art keywords
nano material
marine
transfer type
antifouling
charge transfer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201710767834.9A
Other languages
Chinese (zh)
Other versions
CN107446402A (en
Inventor
刘春花
梁岩
吴彬彬
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shenzhen Shen Tech Advanced Cci Capital Ltd
Original Assignee
Shenzhen Institute of Advanced Technology of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shenzhen Institute of Advanced Technology of CAS filed Critical Shenzhen Institute of Advanced Technology of CAS
Priority to CN201710767834.9A priority Critical patent/CN107446402B/en
Publication of CN107446402A publication Critical patent/CN107446402A/en
Application granted granted Critical
Publication of CN107446402B publication Critical patent/CN107446402B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • 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
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Plant Pathology (AREA)
  • Inorganic Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses a charge transfer type automatic redox nano material, a preparation method and application thereof, a marine antifouling agent and a marine antifouling paint, and relates to the technical field of marine antifouling. The CT nano material is a composite nano material doped or undoped with rare earth elements, and the composite nano material mainly comprises MnO and TiO2ZnO and SiO2The composition is characterized in that the molar ratio is (1-5): (1-15): (1-3): (1-15). The invention overcomes the defects of easy enrichment, difficult degradation and high toxicity of the traditional antifouling agent, and the defects of short antifouling period and unobvious antifouling effect. The CT nano material has obvious adhesion inhibition effect on marine microorganisms, seaweed and large fouling organisms under low concentration, shows high-efficiency and broad-spectrum antifouling activity, has evasion and no killing property on marine organisms, and can be developed and applied as a low-toxicity marine antifouling agent.

Description

Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint
Technical Field
The invention relates to the technical field of marine antifouling, in particular to a charge transfer type automatic redox nano material, a preparation method and application thereof, a marine antifouling agent and a marine antifouling paint.
Background
Marine biofouling refers to the accumulation of microorganisms, plant organisms and animal organisms on artificial surfaces in the sea, and various marine fouling organisms such as microorganisms, algae, barnacles, oysters, mussels, limestans, enteromorpha, sea squirts, sea anemones and the like are not selectively adhered and deposited on the surfaces of ship shells, marine buildings, culture net cages and the like in large areas. The attachment and fouling of marine fouling organisms can cause: (1) the roughness of the ship bottom is increased, the sailing resistance of the ship is increased, and the energy consumption and the emission are intensified, so that great harm is brought to the sailing of the ship; (2) the fouling and corrosion of structural members such as marine facilities, buildings and the like are accelerated, and the service lives of the structural members are obviously shortened; (3) causing the blockage of meshes and pipelines of the culture net cage, the fixed catching netting and the like; (4) damage to marine instruments results in failure of instrument transmission mechanisms, signal distortion, performance reduction, and even potential safety hazards, and huge economic loss is caused.
At present, the adhesion of marine fouling organisms can be effectively inhibited or prevented by coating various marine antifouling coatings. The marine antifouling paint is a special paint, mainly comprising macromolecular resin, antifouling agent, pigment and filler, solvent and the like, wherein the antifouling agent component can effectively inhibit or prevent the attachment of marine fouling organisms, but with the antifouling agent organotin compounds with high toxicity and teratogenesis being forbidden by the International Maritime Organization (IMO), other antifouling agents such as cuprous oxide, isothiazolinone and the like are widely used, however, the antifouling agents are also discovered in succession to have the defects of easy enrichment, difficult degradation, high toxicity and the like, and cause pollution to marine environment. Therefore, the development of an environmentally friendly marine antifouling agent is urgently needed.
At present, various natural antifouling products are separated from marine organisms such as sponges, corals, seaweeds and the like, and have the advantages of low biodegradability and toxicity and the like, but most of the found natural antifouling products have limited sources and little content in organisms, and most of the marine organisms are difficult to collect, so that the natural antifouling products are difficult to develop and apply. Related researches in recent years show that the nano material has a good inhibition effect on the attachment of microorganisms, algae and sprawl species. The plum-kindly, Chenmeiling and the like add nano titanium dioxide into the synthesized furan modified silicone-acrylic resin, and find that the added nano TiO2The adhesion of fouling marine organisms of the paint can be greatly reduced, and the antifouling effect is obviously improved. The Qiyuhong, Zhangping and Liuhong trial prepare a series of nano TiO2the/FEVE fluorocarbon coating is researched and found to be nano TiO2Has obvious effect of preventing the attachment of macroalgae (algae in the cloud), and can be used as a safe and environment-friendly antifouling additive. According to the Ningbo material, nano silver is added into the amphoteric polyelectrolyte/polyacrylamide double-network hydrogel to construct the nano composite hydrogel, the fact that the small-size nano silver endows the hydrogel with excellent antibacterial, anti-algae and antifouling performances is found, and meanwhile, the antifouling aging of the composite material is greatly prolonged due to the slow release of the nano silver. In patent CN104403448A, nano silver sol is used as antifouling agent, and in patent CN101531841A, Cu is used2O hollow sub-microsphere Cu alone or embedded with nontoxic antifouling agent2The O hollow submicron ball is used as an antifouling agent. Guo Zhang Wei of Shanghai oceanic university(2015) The preparation of nano-silver anti-fouling agent and the inhibition of the nano-silver anti-fouling agent on marine microorganism adhesion are researched in a master thesis, two composite particle materials of silica-loaded nano-silver and silica-coated nano-silver are designed and prepared, the inhibition mechanism of the nano-silver anti-fouling agent on vibrio natriegens (gram-negative bacteria) and bacillus subtilis (gram-positive bacteria) is researched, and the antibacterial performance and the antibacterial mechanism of the two materials are analyzed.
Although some nano materials are applied to antifouling agents at present, the antifouling period is still short, the nano materials cannot have a remarkable inhibiting effect on marine fouling microorganisms, algae and large marine fouling organisms, the high antifouling requirement cannot be completely met, and the safety on the marine organisms needs to be improved.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
One of the purposes of the invention is to provide the application of the charge transfer type automatic redox nano material in preventing fouling of marine organisms, wherein the charge transfer type automatic redox nano material can inhibit the attachment of marine fouling microorganisms, marine algae and large fouling animals, is environment-friendly, can be applied to the field of marine antifouling and has wide application prospect.
The other purpose of the invention is to provide a charge transfer type automatic oxidation reduction nano material, which is doped or undoped rare earth elements and mainly consists of MnO and TiO2ZnO and SiO2The composite nano material comprises the following components in a molar ratio of (1-5): (1-15): (1-3): (1-15), the charge transfer type automatic redox nano material has remarkable adhesion inhibition activity on fouling organisms, has half adhesion inhibition concentration (EC50 value) of less than 10 [ mu ] g/mL, and shows efficient and broad-spectrum antifouling activity. In addition, the charge transfer type auto-redox nano material has evasion and no killing property to marine organisms, and can be used for development and application of low-toxicity marine antifouling agents.
The invention also aims to provide a preparation method of the charge transfer type automatic redox nano material, which adopts a sol-gel method to prepare the composite nano material, has mild preparation conditions and can realize uniform doping on a molecular level.
The fourth purpose of the present invention is to provide a marine antifouling agent containing the charge transfer type auto-redox nano-material, wherein the charge transfer type auto-redox nano-material can be used as an antifouling agent alone, and can be compounded with other antifouling agents to enhance the antifouling effect, and the marine antifouling agent used alone or containing the charge transfer type auto-redox nano-material has a remarkable antifouling effect, and is safe and environment-friendly.
The fifth purpose of the present invention is to provide a marine antifouling paint containing the charge transfer type auto-redox nano-material, wherein the antifouling paint prepared from the charge transfer type auto-redox nano-material has a significant antifouling effect.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
in a first aspect, the present invention provides the use of charge transfer type auto-redox nanomaterials in the prevention of marine biofouling.
Further, on the basis of the technical scheme of the invention, the charge transfer type automatic oxidation-reduction nano material is a composite nano material doped or undoped with rare earth elements, and the composite nano material mainly comprises MnO and TiO2ZnO and SiO2Composition of, wherein MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝(1～5)：(1～15)：(1～3)：(1～15)；
Preferably MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝ (1～4)：(5～15)：(1～3)：(3～15)；
Further preferably MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO： SiO2＝(1～3)：(10～15)：(1～2)：(10～15)。
Further, on the basis of the technical scheme of the invention, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-2 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-5);
preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-4);
further preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.5-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-3).
In a second aspect, the invention provides a charge transfer type auto-redox nano-material, wherein the charge transfer type auto-redox nano-material is a composite nano-material doped or undoped with rare earth elements, and the composite nano-material mainly comprises MnO and TiO2ZnO and SiO2Composition of, wherein MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝(1～5)：(1～15)：(1～3)： (1～15)；
Preferably MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝ (1～4)：(5～15)：(1～3)：(3～15)；
Further preferably MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO： SiO2＝(1～3)：(10～15)：(1～2)：(10～15)。
Further, on the basis of the technical scheme of the invention, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-2 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-5);
preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-4);
further preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.5-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-3).
In a third aspect, the invention provides a method for preparing the charge transfer type auto-redox nano material, which adopts a sol-gel method to prepare the composite nano material.
The method specifically comprises the following steps: according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) preparing the composite nano material: (1) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
Further, on the basis of the technical scheme of the invention, the preparation method of the charge transfer type automatic oxidation-reduction nano material comprises the following steps:
and (3) soaking the composite nano material in a solution containing rare earth elements, and drying and roasting the soaked composite nano material to obtain the charge transfer type automatic redox nano material.
Further, on the basis of the technical scheme of the invention, ultrasonic impregnation is adopted for impregnation;
preferably, the ultrasonic dipping time is 1-2 h, and further preferably 1.5-2 h;
preferably, the drying temperature is 80-100 ℃, and further preferably 85-95 ℃;
preferably, the roasting temperature is 500-800 ℃, further preferably 600-800 ℃, and the roasting time is 5-8 hours, further preferably 5-7 hours.
In a fourth aspect, the present invention provides a marine antifouling agent comprising the charge transfer type auto-redox nanomaterial described above.
In a fifth aspect, the present invention provides a marine antifouling paint comprising the charge transfer type auto-redox nanomaterial described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) the traditional antifouling agent has the defects of easy enrichment, difficult degradation, high toxicity and the like, short antifouling period and unobvious antifouling effect, and the charge transfer type automatic redox nano material is a charge transfer type nano catalyst, can initiate redox reaction so as to inhibit the attachment of marine fouling microorganisms, marine algae and large fouling animals, is environment-friendly, can be used for preparing marine antifouling agents, marine antifouling coatings and the like, and has the potential of being well applied to the field of marine antifouling.
(2) The charge transfer type automatic oxidation-reduction nano material mainly comprises the following components in a molar ratio of (1-5): (1-15): (1-3): (1-15) MnO and TiO2ZnO and SiO2The charge transfer type automatic redox nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms reticulate barnacles under low concentration, has obvious adhesion inhibition activity on fouling organisms, has semi-inhibition adhesion concentration (EC50 value) below 10 mu g/mL, shows high-efficiency and broad-spectrum antifouling activity, and has outstanding antifouling performance.
(3) The charge transfer type auto-redox nano material has evasion and no killing property to marine organisms, and can be used for development and application of low-toxicity marine antifouling agents. The charge transfer type automatic redox nano material is used as an antifouling agent, so that the obvious antifouling effect can be brought, the marine antifouling paint is safe and environment-friendly, the marine antifouling paint is prepared by a conventional method, and the test result of a real sea hanging plate shows that the charge transfer type automatic redox nano material has the outstanding effect of preventing marine organism fouling, so that the charge transfer type automatic redox nano material has the application potential as a novel marine antifouling agent. The charge transfer type automatic redox nano material not only can be used for preparing marine antifouling paint in a single component, but also can be matched with other antifouling agents to play a synergistic effect, so that the antifouling effect is enhanced.
(4) The preparation process of the charge transfer type automatic oxidation-reduction nano material adopts a sol-gel method, has simple preparation method, strong operability and mild preparation conditions, and can realize uniform doping on the molecular level.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but it will be understood by those skilled in the art that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
According to a first aspect of the present invention, there is provided the use of a charge transfer type auto-redox nanomaterial in the prevention of marine biofouling.
The Charge transfer type auto-redox nano material (CT nano material) is a Charge transfer type nano catalyst, is the international latest achievement of nano antibacterial material technology, has the characteristics of excellent antibacterial property, super-strong hydrophobic oil resistance, self-cleaning property, no toxicity and the like, can form a special lattice structure, has a specific crystal structure of a hexahedral spinel structure including an octahedral perovskite structure, can generate Charge/electron transfer, and can play a strong catalytic action by only depending on heat energy and not depending on light.
The charge transfer type auto-redox nano-material in the present invention is typically but not limited to purchased from Taifu technology (Shenzhen) Limited.
The applications include but are not limited to preparing marine antifouling paint or antifouling agent, etc., the CT nano material can be used in paint to apply the antifouling paint to the surface of marine artificial facilities by conventional methods such as dipping, spraying or coating, and marine artificial facilities which can be applied to environmental protection antifouling, including but not limited to: ships, offshore oil and gas platforms, buoys, wharfs, piers, docks, seawater pipelines, wooden piles and mariculture net cages.
The charge transfer type automatic redox nano material has good antifouling activity, can bring remarkable antifouling effect when used as a marine antifouling agent, is safe and environment-friendly, has application potential as a novel marine antifouling agent, is added into marine antifouling paint, and can enable the paint to have the effect of preventing marine biofouling.
The traditional antifouling agent has the defects of easy enrichment, difficult degradation, high toxicity and the like, and has short antifouling period and unobvious antifouling effect. The charge transfer type automatic redox nano material can cause redox reaction due to charge/electron transfer, cause perforation of a wall film and interfere normal biochemical reaction in cells, so that attachment of marine fouling microorganisms, marine algae and large fouling animals is inhibited, and the material has good anti-fouling, antibacterial and anti-algae performances, is environment-friendly, has a good marine organism fouling prevention effect, and has a good application prospect in marine organism fouling prevention.
In a preferred embodiment, the charge transfer type automatic oxidation reduction nano material is a composite nano material doped or not doped with rare earth elements, and the composite nano material mainly consists of MnO and TiO2ZnO and SiO2Composition of, wherein MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO： SiO2＝(1～5)：(1～15)：(1～3)：(1～15)。
MnO、TiO2ZnO and SiO2Typical but non-limiting molar ratios are 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.
The composite nano material is typically but not limited to be prepared by a sol-gel method, and the specific preparation method comprises the following steps:
according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) preparing the composite nano material: (1) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
The method has mild conditions, forms a stable transparent sol system in the solution, slowly polymerizes among colloidal particles to form gel with a three-dimensional network structure, and dries, sinters and solidifies the gel to obtain the composite nano material.
Mainly composed of MnO and TiO by adopting doped or undoped rare earth elements2ZnO and SiO2The CT nano material has high charge/electron transfer speed and strong catalytic action, thereby easily initiating redox reaction, causing interference to cells, having strong inhibition effect on bacteria and microorganisms, having remarkable adhesion inhibition effect on bacteria, algae and large fouling organisms in the ocean, having excellent marine fouling prevention effect, and having more potential when being applied to preventing and treating marine fouling.
Tests show that the charge transfer type automatic redox nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms reticulate barnacles under low concentration, has obvious adhesion inhibition activity on fouling organisms, has half-inhibition adhesion concentration (EC50 value) below 10 mu g/mL, shows high-efficiency and broad-spectrum antifouling activity and has outstanding antifouling performance. In addition, the CT nano material has evasion and no killing property to marine organisms, can be used for development and application of a low-toxicity marine antifouling agent, and has a better application prospect.
Preferably MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝ (1～4)：(5～15)：(1～3)：(3～15)。
Further preferably MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO： SiO2＝(1～3)：(10～15)：(1～2)：(10～15)。
Through tests, MnO and TiO are found2ZnO and SiO2The molar ratio of (a) has an influence on the antifouling activity, and the CT nanomaterial can be obtained by optimizing the molar ratio of the componentsThe antifouling paint has high efficiency and broad-spectrum antifouling activity.
In a preferred embodiment, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-2 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-5).
The doping amount refers to the mass percentage of the total mass of the rare earth elements in the composite nano material by taking the rare earth elements as a whole.
The doping amount of the rare earth element is, for example, 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, or 2 wt%. The molar ratio of La and Ce is, for example, 1:2, 1:3, 1:4 or 1: 5.
The doped rare earth elements may contain other rare earth elements besides La and Ce, such as Pr and the like.
The rare earth element is doped to promote charge/electron transfer, so that the catalytic action of the CT nano material is improved, and the redox reaction is more favorably initiated, so that the killing power to microorganisms and marine organism cells is obviously improved, and the antifouling activity of the CT nano material is improved. By including MnO and TiO2ZnO and SiO2The composite nano material is doped with La and Ce rare earth elements, can obviously inhibit the attachment of marine fouling microorganisms, marine algae and large fouling animals, shows high-efficiency and broad-spectrum antifouling activity, and has better marine organism fouling prevention effect and higher activity after being doped with rare earth.
Preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-4).
Further preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.5-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-3).
The antifouling effect and antifouling activity of the CT nano material can be further improved by optimizing the doping amount of the rare earth elements and the molar ratio of the doped rare earth elements.
As a preferred embodiment, the charge transfer type automatic oxidation reduction nano material is mainly composed of MnO and TiO doped with rare earth elements2ZnO and SiO2Composite nano-particles of compositionMaterials of MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO22:15:1: 12; the doped rare earth elements are La and Ce, the doping amount of the rare earth elements is 1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: 3.
according to a second aspect of the present invention, there is provided a charge transfer type auto-redox nanomaterial which is a rare earth doped or undoped composite nanomaterial consisting essentially of MnO and TiO2ZnO and SiO2Composition of, wherein MnO, TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝(1～5)：(1～15)：(1～3)：(1～15)。
MnO、TiO2ZnO and SiO2Typical but non-limiting molar ratios are 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.
The term "consisting essentially of" as used herein means that it may include, in addition to the recited components, other components that impart different properties to the charge transfer type auto-redox nanomaterial. In addition, the term "consisting essentially of" as used herein may be replaced by "being" or "consisting of …" as used herein in the closed-loop fashion.
The composite nano material is typically but not limited to be prepared by a sol-gel method, and the specific preparation method comprises the following steps:
according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) preparing the composite nano material: (1) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
The method has mild conditions, forms a stable transparent sol system in the solution, slowly polymerizes among colloidal particles to form gel with a three-dimensional network structure, and dries, sinters and solidifies the gel to obtain the composite nano material.
The CT nano material mainly comprises the following components in a molar ratio of (1-5): (1-15): (1-3): (1-15) MnO and TiO2ZnO and SiO2The charge transfer type automatic redox nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms reticulate barnacles under low concentration, has obvious adhesion inhibition activity on fouling organisms, has semi-inhibition adhesion concentration (EC50 value) below 10 mu g/mL, shows high-efficiency and broad-spectrum antifouling activity, and has outstanding antifouling performance. Meanwhile, the CT nano material has evasion and no killing property on marine organisms, is harmless to the environment and marine organisms, is safer and more environment-friendly, and can be used for development and application of a low-toxicity marine antifouling agent.
In a preferred embodiment, MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝(1～4)：(5～15)：(1～3)：(3～15)。
In a preferred embodiment, MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO2＝(1～3)：(10～15)：(1～2)：(10～15)。
By optimizing the molar ratio among the components, the CT nano material with high efficiency and broad-spectrum antifouling activity can be obtained.
In a preferred embodiment, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-2 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-5).
The doping amount refers to the mass percentage of the total mass of the rare earth elements in the composite nano material by taking the rare earth elements as a whole.
The doping amount of the rare earth element is, for example, 0.1 wt%, 0.2 wt%, 0.5 wt%, 1 wt%, or 2 wt%. The molar ratio of La and Ce is, for example, 1:2, 1:3, 1:4 or 1: 5.
The "rare earth element including" means that it may include other components such as Pr and the like in addition to the La and Ce, and the "rare earth element including" may be replaced with a closed form of "being" or "consisting of …".
The rare earth element is doped to facilitate the charge/electron transfer, so that the catalytic action of the CT nano material is improved, the redox reaction is more favorably initiated, the killing power of the CT nano material on microorganisms and marine organism cells is further improved, and the antifouling activity of the CT nano material is improved. By including MnO and TiO2ZnO and SiO2The composite nano material is doped with La and Ce rare earth elements, can obviously inhibit the attachment of marine fouling microorganisms, marine algae and large fouling animals, and shows more efficient and broad-spectrum antifouling activity, and the CT nano material doped with rare earth has better marine organism fouling prevention effect and higher activity.
Preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.1-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-4).
Further preferably, the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.5-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-3).
The antifouling effect and antifouling activity of the CT nano material can be further improved by optimizing the doping amount of the rare earth elements and the molar ratio of the doped rare earth elements.
As a preferred embodiment, the charge transfer type automatic oxidation reduction nano material is mainly composed of MnO and TiO doped with rare earth elements2ZnO and SiO2Composite nano material of MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO22:15:1: 12; the doped rare earth elements are La and Ce, the doping amount of the rare earth elements is 1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: 3.
according to a third aspect of the present invention, there is provided a method for preparing the charge transfer type auto-redox nanomaterial, wherein the composite nanomaterial is prepared by a sol-gel method.
The sol-gel method is a method of solidifying a compound containing a high chemical activity component by a solution, a sol or a gel, and then thermally treating the solidified compound to obtain an oxide or other compound solid.
The CT nano material is prepared by adopting a sol-gel method, the method is simple and easy to operate, the preparation condition is mild, and uniform doping on a molecular level can be realized.
The composite nanomaterial is typically, but not limited to, obtained by the following preparation method:
according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) preparing the composite nano material: (1) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
In a preferred embodiment, the method for preparing the charge transfer type auto-redox nanomaterial comprises the following steps:
and (3) soaking the composite nano material in a solution containing rare earth elements, and drying and roasting the soaked composite nano material to obtain the charge transfer type automatic redox nano material.
Drying and baking can be carried out in a conventional manner, for example, drying is carried out by using an oven, and baking is carried out by using a muffle furnace.
The preparation method of the rare earth doped CT nano material adopts an immersion combustion method, and has the advantages of simple process, strong operability, low cost, high product purity, small granularity, uniform doping of rare earth elements and high activity.
In a preferred embodiment, the impregnation is carried out by ultrasonic impregnation.
The adoption of ultrasonic impregnation can enable the rare earth elements to be more fully embedded into the lattice structure of the composite nano material, and the impregnation efficiency is high and the effect is good.
Preferably, the ultrasonic immersion time is 1-2 h, and further preferably 1.5-2 h.
The ultrasonic immersion time is typically, but not limited to, 1h, 1.5h or 2h, for example.
Preferably, the drying temperature is 80 to 100 ℃, and more preferably 85 to 95 ℃.
The drying temperature is typically, but not limited to, for example, 80 ℃, 90 ℃ or 100 ℃.
Preferably, the roasting temperature is 500-800 ℃, further preferably 600-800 ℃, and the roasting time is 5-8 hours, further preferably 5-7 hours.
The firing temperature is typically, but not limited to, 500 deg.C, 600 deg.C, 700 deg.C or 800 deg.C, for example.
The calcination time is typically, but not limited to, for example, 5h, 6h, 7h or 8 h.
The preparation method of the typical CT nano material specifically comprises the following steps: adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2In the composite nanomaterial, the composite nanomaterial is ultrasonically immersed for 1-2 hours, then dried at 80-100 ℃, placed in a muffle furnace, and roasted at 500-800 ℃ for 5-8 hours to obtain the CT nanomaterial.
The doped or undoped rare earth elements mainly comprise the following components in a molar ratio of (1-5): (1-15): (1-3): (1-15) MnO and TiO2ZnO and SiO2The formed CT nano material has broad-spectrum and obvious adhesion inhibition activity on fouling organisms under low concentration, has evasion and no killing property on marine organisms, has no harm on environment and marine organisms, and can be applied to preparing marine antifouling paint or antifouling agent.
The applications include, but are not limited to, preparing marine antifouling paint or antifouling agent, the CT nano material is used in paint to apply the antifouling paint to the surface of marine artificial facilities by conventional methods such as dipping, spraying or coating, and marine artificial facilities to which environmental protection antifouling can be applied include, but not limited to: ships, offshore oil and gas platforms, buoys, wharfs, piers, docks, seawater pipelines, wooden piles and mariculture net cages.
According to a fourth aspect of the present invention, there is provided a marine antifouling agent comprising the above charge transfer type auto-redox nanomaterial.
The CT nano material with the composition can bring remarkable antifouling effect when being used as an antifouling agent or being added into the existing antifouling agent, not only can be used as the antifouling agent alone, but also can be matched with other antifouling agents to play a synergistic effect, so that the antifouling effect is enhanced.
According to a fifth aspect of the present invention, there is provided a marine antifouling paint comprising the above charge transfer type auto-redox nanomaterial.
The CT nano material is added into a marine antifouling paint as an antifouling agent, the marine antifouling paint is prepared by a conventional method, and a real sea hanging plate test shows that the marine antifouling paint has an outstanding marine biofouling prevention effect by adding the CT nano material antifouling agent.
The invention is further illustrated by the following specific examples and comparative examples, but it should be understood that these examples are for purposes of illustration only and are not to be construed as limiting the invention in any way. All the raw materials related to the invention can be obtained commercially.
The composite nano-material in the examples is prepared by the following method:
(1) according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH to 2 to obtain a solution B; (3) and slowly dropping the solution A into the solution B under stirring, continuously stirring for 4h, drying in a vacuum drying oven at 100 ℃ for 12h, grinding into powder, and calcining at the high temperature of 800 ℃ for 4h to obtain the composite nano material.
Example 1
A CT nano-material is prepared from MnO and TiO doped with rare-earth elements La and Ce2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO22:15:1:12, the co-doping amount of the rare earth elements La and Ce is 1 wt%, and the molar ratio of La: ce ═ 1: 3.
adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O (calculating the mass of the salt according to the doping amount), and adding La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2And (3) ultrasonically dipping the composite nano material for 1h, drying at 100 ℃, placing the composite nano material in a muffle furnace, and roasting at 600 ℃ for 8h to obtain the CT nano material.
Example 2
A CT nano-material is prepared from MnO and TiO doped with rare-earth elements La and Ce2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO22:5:1: 5, the co-doping amount of the rare earth elements La and Ce is 0.1 wt%, and the molar ratio of La: ce ═ 1: 2.
Adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O (calculating the mass of the salt according to the doping amount), and adding La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2And (3) ultrasonically dipping the composite nano material for 1.5h, drying at 80 ℃, placing in a muffle furnace, and roasting at 800 ℃ for 5h to obtain the CT nano material.
Example 3
CT nano materialThe material is doped with rare earth elements La and Ce and consists of MnO and TiO2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO22:1: 1:1, the co-doping amount of the rare earth elements La and Ce is 0.5 wt%, and the molar ratio of La: ce ═ 1: 3.
Adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O (calculating the mass of the salt according to the doping amount), and adding La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2And (3) ultrasonically dipping the composite nano material for 2 hours, drying the composite nano material at the temperature of 90 ℃, placing the composite nano material in a muffle furnace, and roasting the composite nano material for 8 hours at the temperature of 500 ℃ to obtain the CT nano material.
Example 4
A CT nano-material is prepared from MnO and TiO doped with rare-earth elements La and Ce2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO22: 8: 1:6, the co-doping amount of the rare earth elements La and Ce is 1 wt%, and the molar ratio of La: ce ═ 1: 4.
Adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O (calculating the mass of the salt according to the doping amount), and adding La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2And (3) ultrasonically dipping the composite nano material for 1h, drying at 90 ℃, placing in a muffle furnace, and roasting at 700 ℃ for 7h to obtain the CT nano material.
Example 5
A CT nano-material is prepared from MnO and TiO doped with rare-earth elements La and Ce2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO22: 10: 1:5, the co-doping amount of the rare earth elements La and Ce is 1.5 wt%, and the rare earth elements La and Ce are doped in the same amountThe molar ratio of La: ce ═ 1: 5.
adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O (calculating the mass of the salt according to the doping amount), and adding La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2And (3) ultrasonically dipping the composite nano material for 1.5h, drying at 80 ℃, placing in a muffle furnace, and roasting at 750 ℃ for 6h to obtain the CT nano material.
Example 6
A CT nano-material is prepared from MnO and TiO doped with rare-earth elements La and Ce2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO22: 3: 1:10, the co-doping amount of the rare earth elements La and Ce is 1 wt%, and the molar ratio of La: ce ═ 1: 2.
Adding a certain amount of La (NO) with water3)3·6H2O and Ce (NO)3)3·6H2Dissolving O (calculating the mass of the salt according to the doping amount), and adding La (NO)3)3·6H2O、Ce(NO3)3·6H2Impregnating mixed aqueous solution of O into MnO and TiO2ZnO and SiO2And (3) ultrasonically dipping the composite nano material for 2 hours, drying the composite nano material at the temperature of 100 ℃, placing the composite nano material in a muffle furnace, and roasting the composite nano material for 6.5 hours at the temperature of 650 ℃ to obtain the CT nano material.
Example 7
A CT nano-material is prepared from MnO and TiO2ZnO and SiO2The composite nano material comprises the following main components in a molar ratio of MnO: TiO 22：ZnO：SiO2＝2：15：1：12。
(1) According to the molar ratio n (Mn): n (Ti): n (Zn): n (si) ═ 2:15:1:12, adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
Example 8
A CT nano material, wherein MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO25:1:3: 2, the rest is the same as example 1.
Comparative example 1
A CT nano material, wherein MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO26: 0.5: 5: 0.5, the rest is the same as example 1.
Comparative example 2
A CT nano material, wherein MnO and TiO2ZnO and SiO2The molar ratio of (A) to (B) is MnO: TiO 22：ZnO：SiO20.5: 20: 0.5: 20, the rest is the same as example 1.
Comparative example 3
A CT nanomaterial in which the co-doping amount of rare earth elements La and Ce is 5 wt%, the rest being the same as in example 1.
Comparative example 4
A CT nanomaterial in which the co-doping amount of rare earth elements La and Ce is 0.05 wt%, the rest being the same as in example 1.
Comparative example 5
A CT nanomaterial, wherein the molar ratio of rare earth elements La and Ce is La: ce ═ 3:1, the rest is the same as example 1.
Comparative example 6
A marine antifouling agent cuprous oxide.
Comparative example 7
An isothiazolinone as marine antifoulant.
Comparative example 8
A marine antifouling agent nano titanium dioxide.
Comparative example 9
A marine antifouling agent, nanometer silver.
Test example 1 inhibitory Effect of CT nanomaterial on Marine fouling microorganism
Taking the CT nanomaterial of example 1 as an example, the inhibitory effect of the CT nanomaterial on marine fouling microorganisms was studied.
The test method comprises the following steps:
the biological detection model of the marine micro fouling organisms adopts the most important micro fouling organisms in the sea, namely marine fouling bacteria.
Inoculating Pseudomonas marini into 2216E liquid culture medium, shake culturing overnight, centrifuging to collect bacteria, washing with sterile seawater, and making into suspension with bacteria concentration of about 107～109one/mL.
The CT nanomaterial of example 1 was dissolved in 2216E liquid medium, mixed with the prepared bacterial suspension at concentrations of 0.1, 1.0, 10.0, 50.0, 100.0. mu.g/mL, and added to the petri dish. The culture dish added with the bacterial suspension is used as a control group. Each experimental group and control group were set with 3 parallel cups, incubated at 30 ℃ for 3h, and the petri dishes were repeatedly and gently washed with sterile seawater. The dishes were soaked in 4% formaldehyde solution, rinsed with distilled water, and then stained with 0.5. mu.g/mL of DAPI for 5 min. The number of attached bacteria was obtained by counting 10 fields at random under a fluorescence microscope.
And (3) test results:
the test result proves that the CT nano-material can obviously inhibit the attachment of marine fouling bacteria at low concentration, and the semi-inhibited attachment concentration (EC50 value) is only 3.32 +/-0.11 mu g/mL.
Test example 2 inhibiting action of CT nanomaterial on marine soft fouling organism seaweed
Taking the CT nano material of example 1 as an example, the inhibitory effect of the CT nano material on marine soft fouling organism algae was studied.
The test method comprises the following steps:
the biological detection model of marine soft fouling organisms adopts the biological alga, namely navicula. The Navicula algae can be purchased from the institute of aquatic algae seed bank of Chinese academy of sciences or collected and separated from Shenzhen sea area.
The navicula is inoculated in an Erdchreiber's culture medium, the algae liquid cultured to the exponential phase is diluted to a certain concentration by the algae culture liquid, and is shaken up for standby.
The CT nanomaterial of example 1 was dissolved in Erdchreiber's medium, mixed with the suspension of navicula at concentrations of 0.5, 5.0, 10.0, 25, 50 μ g/mL, and added to the petri dish. The culture dish containing the suspension of Navicula algae was used as a control. Each experimental group and control group were equipped with 3 parallel cups, cultured at 20 ℃ under 30001X for 3d, and the petri dishes were repeatedly and gently washed with sterile seawater. The attached quantity of navicula is obtained by counting 10 visual fields at random under a fluorescence microscope by utilizing the characteristic of chlorophyll autofluorescence.
And (3) test results:
the test result proves that the CT nano material can obviously inhibit the attachment of navicula at low concentration and semi-inhibit the attachment concentration (EC)50Value) was only 7.13. + -. 0.36. mu.g/mL.
Test example 3 inhibitory Effect of CT nanomaterial on Large-Scale Marine fouling organism
Taking the CT nanomaterial of example 1 as an example, the inhibitory effect of the CT nanomaterial on large marine fouling organisms was studied.
The test method comprises the following steps:
the biological detection model of the marine large fouling organisms is used for representing biological reticulate barnacles. The reticulate balanus adult is obtained by collecting on a Shenzhen bay reef in Shenzhen city, and the Jinxing larva is obtained by culturing in a laboratory.
Dissolving the CT nano material in the embodiment 1 in sterile seawater to prepare 0.5, 2.5, 5 and 10 mu g/mL, respectively adding 10mL of each solution into a culture dish, adding 10mL of sterile seawater into a blank culture dish, setting the blank culture dish as a corresponding control group, setting 3 parallel cups for each experimental group and the control group, and adding 30-80 Venus aureus larvae in each cup. After 48 hours of the star larvae being thrown in, the adhesion of the star larvae was observed by a stereomicroscope.
And (3) test results:
the test result proves that the CT nano material can obviously inhibit the adhesion of the balanus reticulatus at low concentration, and the semi-inhibiting adhesion concentration EC50 of the CT nano material to the balanus reticulatus of marine large fouling organisms is only 10.58 +/-0.04 mu g/mL.
Test examples 1-3 show that the CT nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms reticulate barnacles under low concentration, and shows high-efficiency and broad-spectrum antifouling activity.
Test example 4 environmental friendliness of CT nanomaterial to Large-sized Marine fouling organisms
Test example 3 after 3 days of treatment, the balanus reticulates were transferred to fresh seawater, the seawater was changed every day, the number of byssus was counted, and the byssus attachment rate was observed. The result shows that when the concentration of the CT nano material is less than 25ug/mL after 3 days, the balanus reticulatus byssus can be restored to the level of the control group.
Therefore, the CT nano material has evasion and no killing property and is friendly to marine organisms and marine environment.
Marine hanging plate test of nano marine antifouling paint applying CT nano material
Referring to the national standard 'shallow sea immersion test method of antifouling paint template' (GB/T5370-2007), the antifouling efficiency of the CT nano-materials of examples 1-8 and comparative examples 1-9 as a marine antifouling agent in the Shenzhen sea region is examined.
Epoxy resin is used as a film forming substance, CT nano material is added as an antifouling agent to prepare the antifouling paint, and the addition amount of the antifouling agent is 1 percent of the mass of the antifouling paint. The test group takes 6 test samples, coats antifouling paint, carries out the plate hanging test in summer with vigorous marine fouling organisms by taking the sample without the antifouling paint as a contrast, calculates the fouling organism coverage on each plate in 1 month of plate hanging in the natural sea area, and takes an average value.
The results are shown in Table 1.
TABLE 1 Marine antifouling paint marine slat test results containing CT nanomaterials of examples and comparative examples
Figure BDA0001393937840000211
Figure BDA0001393937840000221
As can be seen from Table 1, the biofouling coverage of the surface of the test sample coated with the antifouling paint containing the CT nano-material is found to be 3.8-4.8% on average, which is significantly lower than that of the control sample, and the biofouling coverage of the control sample is 95.6% on average, which indicates that the CT nano-material has a good antifouling effect.
Example 7 compared with example 1, rare earth elements La and Ce were not doped in the composite nanomaterial, and as a result, it was found that the CT nanomaterial added with the rare earth element had better antifouling effect than the CT nanomaterial not doped with the rare earth element, and the biofouling coverage of the surface of the test sample coated with the CT nanomaterial antifouling paint was smaller.
Example 8 compared to example 1, composite nanomaterials MnO, TiO2ZnO and SiO2The molar ratio of (a) to (b) was different from that in example 1, and the antifouling effect of the obtained CT nanomaterial was different, and it was found that composite nanomaterials having different molar ratios had an influence on the antifouling effect.
Comparative examples 1-2 composite nanomaterials MnO, TiO compared to example 12ZnO and SiO2The molar ratio of (A) was different from that in example 1, and the antifouling effect of the obtained CT nanomaterial was reduced, and it was found that an inappropriate molar ratio had an effect on the antifouling effect of the CT nanomaterial. Compared with the example 1, the doping amount of the rare earth element is more in the comparative example 3, compared with the example 1, the doping amount of the rare earth element is less in the comparative example 4, the antifouling effect of the CT nano material is not as good as that of the example 1, and the antifouling effect of the CT nano material is negatively influenced due to the excessive doping amount of the rare earth element. Compared with the example 1, the molar ratio of the rare earth elements La and Ce is different, La is more than Ce, the antifouling effect of the obtained CT nano material is not as good as that of the example 1, and the molar ratio of La and Ce also has a certain influence on the antifouling effect of the CT nano material.
The biofouling coverage of the surface of the test sample coated with the antifouling paint containing the marine antifouling agent of comparative examples 6 to 7 was significantly increased, and the cuprous oxide and the isothiazolinone antifouling agent had a potential environmental risk, and the biofouling coverage of the surface of the test sample coated with the antifouling paint containing the nanomaterial of comparative examples 8 to 9 was also increased, which is not as good as the antifouling effect of the antifouling paint using the CT nanomaterial of the present invention, and thus the antifouling effect of the CT nanomaterial was significant.
Therefore, the CT nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms reticulate barnacles under low concentration, and shows high-efficiency and broad-spectrum antifouling activity; in addition, the recovery experiment of the reticulate barnacle also shows that the CT nano material has evasion and no killing property, so that the CT nano material can be developed and applied as a low-toxicity marine antifouling agent. The result of shallow sea immersion test of the antifouling paint prepared from the CT nano material also shows that the antifouling paint has an obvious antifouling effect. The CT nano material provided by the invention not only can be used for preparing marine antifouling paint in a single component, but also can be compounded with other antifouling agents to enhance the antifouling effect.
While particular embodiments of the present invention have been illustrated and described, it would be obvious that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.

Claims (11)

1. The charge transfer type automatic oxidation reduction nano material is characterized in that the charge transfer type automatic oxidation reduction nano material is a composite nano material doped with rare earth elements, and the composite nano material mainly comprises MnO and TiO2ZnO and SiO2Composition is carried out; the doped rare earth elements comprise La and Ce, the doping amount of the rare earth elements is 0.5-1 wt%, and the molar ratio of La to Ce is La: ce ═ 1: (2-3);
the crystal structure of the charge transfer type automatic oxidation-reduction nano material is a hexahedral spinel structure comprising an octahedral perovskite structure, and the charge transfer type automatic oxidation-reduction nano material can play a catalytic role by only depending on heat energy and not depending on light;
the preparation method of the composite nano material by adopting a sol-gel method comprises the following steps: according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) preparing the composite nano material: (1) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
2. The method for preparing the charge transfer type auto-redox nano-material according to claim 1, wherein the sol-gel method is adopted to prepare the composite nano-material, and the method comprises the following steps: according to the molar ratio n (Mn): n (Ti): n (Zn): n (Si) is (1-5): (1-15): (1-3): (1-15) preparing the composite nano material: (1) adding a certain amount of tetrabutyl titanate into absolute ethyl alcohol, and uniformly mixing to obtain a solution A; (2) weighing a certain amount of zinc nitrate and manganese nitrate, adding absolute ethyl alcohol, stirring until the zinc nitrate and the manganese nitrate are completely dissolved, sequentially adding water, ethyl orthosilicate and glacial acetic acid, and adjusting the pH value to 2 to obtain a solution B; (3) and (3) slowly dropping the solution A into the solution B while stirring, continuously stirring for 2-4 h, drying for 12h at 60-100 ℃ in a vacuum drying oven, grinding into powder, and calcining for 2-6 h at high temperature of 400-900 ℃ to obtain the composite nano material.
3. The method for preparing a charge-transfer type auto-redox nanomaterial according to claim 2, comprising the steps of:
and (3) soaking the composite nano material in a solution containing rare earth elements, and drying and roasting the soaked composite nano material to obtain the charge transfer type automatic redox nano material.
4. The method for preparing a charge-transfer type auto-redox nanomaterial according to claim 3, wherein the impregnation is ultrasonic impregnation.
5. The method for preparing a charge transfer type auto-redox nanomaterial according to claim 4, wherein the ultrasonic immersion time is 1-2 hours.
6. The method for preparing a charge transfer type auto-redox nanomaterial according to claim 5, wherein the ultrasonic immersion time is 1.5-2 hours.
7. The method for preparing a charge-transfer type auto-redox nanomaterial according to claim 3, wherein the drying temperature is 80 to 100 ℃.
8. The method for preparing a charge-transfer type auto-redox nanomaterial according to claim 7, wherein the drying temperature is 85 to 95 ℃.
9. The method for preparing a charge transfer type auto-redox nano-material according to claim 3, wherein the calcination temperature is 500 to 800 ℃ and the calcination time is 5 to 8 hours.
10. A marine antifouling agent comprising the charge transfer type auto-redox nanomaterial of claim 1.
11. A marine antifouling paint comprising the charge transfer type auto-redox nanomaterial of claim 1.
CN201710767834.9A 2017-08-30 2017-08-30 Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint Active CN107446402B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710767834.9A CN107446402B (en) 2017-08-30 2017-08-30 Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710767834.9A CN107446402B (en) 2017-08-30 2017-08-30 Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint

Publications (2)

Publication Number Publication Date
CN107446402A CN107446402A (en) 2017-12-08
CN107446402B true CN107446402B (en) 2021-01-19

Family

ID=60494628

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710767834.9A Active CN107446402B (en) 2017-08-30 2017-08-30 Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint

Country Status (1)

Country Link
CN (1) CN107446402B (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110726804B (en) * 2019-07-11 2021-12-31 浙江省海洋开发研究院 Quick evaluation method for antifouling performance of bionic and low-surface-energy marine antifouling coating
CN111066816B (en) * 2019-11-21 2021-05-07 浙江大学 Preparation for treating fouling of coastal mussels, and use method and application thereof
CN116219578A (en) * 2023-04-07 2023-06-06 南通新帝克单丝科技股份有限公司 Production method of anti-shellfish algae large-diameter polyester monofilament

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1935366A (en) * 2006-09-09 2007-03-28 骆天荣 Nano photocatalytic environmental-protection material and its product
CN105176149A (en) * 2015-10-22 2015-12-23 广东美的厨房电器制造有限公司 Coating as well as preparation method and application thereof

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20030036223A (en) * 2000-06-14 2003-05-09 더 프록터 앤드 갬블 캄파니 Long lasting coatings for modifying hard surfaces and processes for applying the same
CN104592851B (en) * 2015-01-06 2017-02-22 西北大学 Biodegradable antifouling marine coating and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1935366A (en) * 2006-09-09 2007-03-28 骆天荣 Nano photocatalytic environmental-protection material and its product
CN105176149A (en) * 2015-10-22 2015-12-23 广东美的厨房电器制造有限公司 Coating as well as preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
电荷转移型自动氧化还原(CT)纳米催化剂在抗菌涂层中的性能研究;郭静等;<<涂料工业>>;20161231(第8期);第6-11页 *

Also Published As

Publication number Publication date
CN107446402A (en) 2017-12-08

Similar Documents

Publication Publication Date Title
Wu et al. Antibacterial behaviors of Cu2O particles with controllable morphologies in acrylic coatings
Liu et al. Research progress of environmentally friendly marine antifouling coatings
Jin et al. Recent advances in emerging integrated antifouling and anticorrosion coatings
Al-Fori et al. Antifouling properties of zinc oxide nanorod coatings
Kumar et al. Functional nanomaterials, synergisms, and biomimicry for environmentally benign marine antifouling technology
CN107446402B (en) Charge transfer type automatic redox nano material, preparation method and application thereof, marine antifouling agent and marine antifouling paint
CN107541117A (en) Nanometer fishing net waterborne anti-fouling coatings and its preparation method and application
CN102277025A (en) Sea antifouling coating
CN108047797B (en) Composite nano material, preparation method and application thereof
Li et al. Marine antifouling strategies: Emerging opportunities for seawater resource utilization
Archana et al. Review on impact of biofouling in aquafarm infrastructures
Li et al. Investigation on the efficiency of a silicone antifouling coating in controlling the adhesion and germination of Ulva prolifera micro-propagules on rafts
CN107573828B (en) Broad-spectrum antifouling paint for fishing nets and preparation method thereof
CN110358345B (en) Microcapsule type antifouling agent and preparation method thereof, antifouling coating and preparation method thereof
CN108329783B (en) Marine antifouling paint and preparation method thereof
Zhao et al. Antifouling based on biocides: From toxic to green
Ferreira-Vançato et al. Nanobiocides against marine biofouling
CN102093770B (en) Application of the myrica extract in marine antifouling coating is prepared
CN116179040A (en) Tin-free low-surface-energy self-polishing environment-friendly thick-paste type anti-fouling paint and preparation method and application thereof
Sam et al. Antifouling effects of silver nano particles synthesized from tropical seaweeds
JPH0565433A (en) Material for preventing adhesion of aquatic life
CN116324037A (en) Marine coating formulation
Zhao et al. Studies on nano-additive for the substitution of hazardous chemical substances in antifouling coatings for the protection of ship hulls.
Anil et al. Role of diatoms in marine biofouling
Ashraf Influence of Nanotechnology on Prevention of Biofouling in Aquaculture Cage Nets: Green Conducting Polymers and Their Significance in Case Studies

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right

Effective date of registration: 20240604

Address after: 518000 A-301, office building, Shenzhen Institute of advanced technology, No. 1068, Xue Yuan Avenue, Shenzhen University Town, Shenzhen, Guangdong, Nanshan District, China

Patentee after: Shenzhen shen-tech advanced Cci Capital Ltd.

Country or region after: China

Address before: No.1068, Xueyuan Avenue, Shenzhen University Town, Xili, Nanshan District, Shenzhen, Guangdong 518000

Patentee before: SHENZHEN INSTITUTES OF ADVANCED TECHNOLOGY

Country or region before: China

TR01 Transfer of patent right