CN108047797B - Composite nano material, preparation method and application thereof - Google Patents

Composite nano material, preparation method and application thereof Download PDF

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CN108047797B
CN108047797B CN201711209958.1A CN201711209958A CN108047797B CN 108047797 B CN108047797 B CN 108047797B CN 201711209958 A CN201711209958 A CN 201711209958A CN 108047797 B CN108047797 B CN 108047797B
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CN108047797A (en
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梁岩
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Shensi Laifu Shenzhen Technology Co ltd
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Shenzhen Zhongke Taifu Technology Co ltd
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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
    • 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
    • C08K2003/2289—Oxides; Hydroxides of metals of cobalt
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives

Abstract

The invention relates to the technical field of marine antifouling paint,in particular to a composite nano material. The composite nano material consists of MnO, CoO and TiO2The composition comprises the following components in a molar ratio of (1-15): (1-15): (1-100); the composite nano material is doped with transition metal elements and rare earth elements; the composite nanometer material is 100 wt%, the doped transition metal element is 0.1-5 wt%, and the doped RE element is 0.1-3 wt%. The composite nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms mussels under low concentration, and shows high-efficiency and broad-spectrum antifouling activity; the preparation process is simple, the operability is strong, the antifouling performance is outstanding, and the application prospect is wide.

Description

Composite nano material, preparation method and application thereof
Technical Field
The invention relates to the technical field of marine antifouling paint, and particularly relates to a composite nano material, and a preparation method and application thereof.
Background
With the increasing depth of human beings on the development and utilization of marine resources, the harm brought by marine biofouling has attracted high attention and wide attention of countries in the world. The marine environment is an environment with serious corrosion and biofouling. Marine biofouling refers to a phenomenon in which marine organisms such as microorganisms, plant organisms, and animal organisms in the sea adhere to the surface of a ship body or a marine structure and are destroyed. Statistically, the worldwide direct economic loss due to marine biofouling is as high as $ 300- > 500 billion annually. The major hazards of marine biofouling include: (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 aggravated, so that great harm is brought to the sailing of the ship. (2) The fouling and corrosion of structural members of marine facilities, buildings and the like are accelerated, and the service life of the structural members is obviously shortened. (3) Resulting in 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. Therefore, how to effectively inhibit marine biofouling becomes a key problem to be solved urgently for reasonable development and utilization of marine resources by human beings. At present, the commonly used protection methods mainly comprise an antifouling coating method, a method for generating hypochlorite by electrolyzing seawater, a heavy metal electrolysis method, a manual or mechanical cleaning method, a method for manufacturing a structure by adopting an antifouling material, a conductive coating method and the like. At present, the coating of antifouling paint on the surface of ship hull or marine structure to inhibit the adhesion and growth of marine fouling organisms is one of the most effective strategies for solving the fouling problem.
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 is a core component of an antifouling coating for inhibiting adhesion of fouling organisms. With the banned of organotin compounds as antifouling agents with high toxicity and teratogenicity 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 successively found to have the defects of easy enrichment, difficult degradation, high toxicity and the like, and cause pollution to the marine environment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a composite nano material which can inhibit the attachment of marine fouling microorganisms, marine algae and large fouling animals and has excellent antibacterial and anti-algae performances.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides a composite nanomaterial consisting of MnO, CoO and TiO2Composition is carried out; the MnO, CoO and TiO2The molar ratio of (1-15): (1-15): (1-100); the composite nano material is doped with transition metal elements and rare earth elements; the composite nano material is 100 percent by mass, the doped transition metal element is 0.1 to 5 percent by mass, and the doped rare earth element is 0.1 to 3 percent by mass.
In some embodiments, the transition metal element is selected from at least one of platinum or palladium; the rare earth element is at least one of zirconium, lanthanum or cerium.
In some embodiments, the method of preparing the composite nanomaterial comprises: s1, preparing a precursor MnO @ CoO @ TiO 2; s2, doping transition elements to obtain a composite nano material intermediate doped with transition metal elements; s3, doping rare earth elements.
In some embodiments, the precursor MnO @ CoO @ TiO2The preparation method comprises the following steps: weighing manganese salt and cobalt salt according to a proportion to prepare a solution A; slowly dropping titanium tetrachloride and NaOH solution into the solution A under stirring, continuously stirring for reaction for 2-6 h to obtain uniform transparent sol, filtering to obtain precipitate, and washing with deionized water; putting the precipitate into a vacuum drying oven at the temperature of 60-100 DEG CDrying for 6-12 h, then placing in a crucible, calcining for 4-12 h at 600-1000 ℃ under reducing atmosphere, and naturally cooling to room temperature.
In some embodiments, the concentration of the manganese salt in the solution A is 0.05mol/L to 1.0mol/L, and the concentration of the cobalt salt is 0.05mol/L to 1.0 mol/L; the concentration of the NaOH solution is 0.05 mol/L-2.0 mol/L.
In some embodiments, the rare earth element doping is by a direct addition method, including in the precursor MnO @ CoO @ TiO2In the preparation of (1), after preparing solution A, La (NO) was added with a small amount of deionized water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O in the solution A, and slowly dropping titanium tetrachloride and NaOH solution into the solution A under stirring.
In some embodiments, the transition element doping comprises: and (3) uniformly mixing the precursor prepared in the step (S1) with transition metal powder consisting of platinum and/or palladium according to the proportion (20-100): 1, tabletting, placing in a crucible, calcining at the high temperature of 1000-1500 ℃ for 1-6 h, and naturally cooling to the room temperature.
In some embodiments, the rare earth element doping is by solid state combustion, including adding La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Grinding and mixing O, transition metal powder and the precursor uniformly, tabletting, placing in a crucible, roasting at 500-800 ℃ for 5-8 h, and naturally cooling to room temperature.
In some embodiments, the rare earth element doping is performed by an immersion combustion method including adding La (NO) with a small amount of deionized water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Soaking the mixed water solution of O into the intermediate of the composite nanometer material doped with transition metal element, ultrasonically soaking for 1-2 h, vacuum drying at 60-100 deg.c, and final vacuum drying at 500-800 deg.cRoasting for 5-8 h.
In still another aspect, the present invention provides a use of the above composite nanomaterial for preparing a marine antifouling paint or a marine antifouling agent.
The invention has the beneficial effects that: the composite nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms mussels under low concentration, and shows high-efficiency and spectral antifouling activity; the marine antifouling paint has avoidance to marine organisms without obvious killing property, is environment-friendly, and can be developed and applied as a low-toxicity marine antifouling agent; the preparation process is simple, the operability is strong, the antifouling performance is outstanding, and the application prospect is wide. The composite nano material not only can be independently used as an antifouling agent to be applied to marine antifouling paint, but also can be matched with other antifouling agents to play a synergistic effect.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not to be construed as limiting the invention.
The composite nano material of the embodiment of the invention consists of MnO, CoO and TiO2Composition is carried out; wherein MnO, CoO and TiO2The molar ratio of (1-15): (1-15): (1-100); the composite nano material is doped with transition metal elements and rare earth elements; the mass percent of the doped transition metal element is 0.1-5%, and the mass percent of the doped rare earth element is 0.1-3% based on 100% of the composite nano material. The transition metal element is at least one of platinum or palladium; the rare earth element is at least one of zirconium, lanthanum or cerium. In a more preferred embodiment, the transition metal elements include both platinum and palladium.
The preparation method of the composite nano material of the specific embodiment of the invention comprises the following steps: s1 and precursor MnO @ CoO @ TiO2Preparing; s2, doping transition elements to obtain the intermediate of the composite nanometer material doped with the transition metal elements(ii) a S3, doping rare earth elements. The sequence of steps S2 and S3 is not particularly limited, and the doping with the transition element may be performed first, and then the doping with the rare earth element may be performed, or the doping with the transition element and the rare earth element may be performed together.
Specifically, a precursor MnO @ CoO @ TiO2The preparation method comprises the following steps: weighing manganese salt and cobalt salt according to a proportion to prepare a solution A, wherein the concentration of the manganese salt in the solution A is 0.05-1.0 mol/L, the concentration of the cobalt salt is 0.05-1.0 mol/L, and the manganese salt can be manganese nitrate, manganese dichloride and the like; the cobalt salt can be cobalt nitrate or cobalt dichloride; slowly dropping titanium tetrachloride and NaOH solution into the solution A under stirring, wherein the concentration of the NaOH solution is 0.05-2.0 mol/L, continuously stirring for reaction for 2-6 h to obtain uniform transparent sol, filtering to obtain precipitate, and washing for 3 times or more with deionized water; and (3) drying the precipitate for 6-12 h at the temperature of 60-100 ℃ in a vacuum drying oven, then placing the dried precipitate in a crucible, calcining the calcined precipitate for 4-12 h at the high temperature of 600-1000 ℃ in a reducing atmosphere, and naturally cooling the calcined precipitate to the room temperature.
In addition to the above method, the precursor MnO @ CoO @ TiO2Can also be prepared by other methods. Such as: with titanium tetrachloride (TiCl)4) Manganese dichloride (MnCl)2) Cobalt dichloride (CoCl)2) With urea (CO (NH)2)2) Ammonia water (NH)3.H2O), NaOH solution, etc. to produce composite colloid, washing with water or drying directly, and high temperature calcining to obtain the product2The precursor of the composite nanometer material, etc.
Specifically, the transition element doping comprises: and (2) uniformly mixing the precursor prepared in the step (S1) with transition metal powder consisting of platinum and/or palladium according to the mass ratio of (20-100) to 1, tabletting, placing in a crucible, calcining at the high temperature of 1000-1500 ℃ for 1-6 h, and naturally cooling to the room temperature.
The doping of the rare earth elements can adopt a direct addition method, a solid combustion method or an immersion combustion method, and the direct addition method has simple process steps; the composite nano material prepared by the solid combustion method and the impregnation combustion method has higher antibacterial and antifouling activity, and the nano material prepared by the impregnation combustion methodThe antibacterial and antifouling activity of the rice material is more prominent. When a direct addition method is adopted, the method comprises the steps of adding a precursor MnO @ CoO @ TiO @2In the preparation of (1), La (NO) was added with a small amount of deionized water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O into the solution A, and then carrying out subsequent operation. When the solid combustion method is adopted, La (NO) is added3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2And grinding and uniformly mixing the O, the transition metal powder and the precursor, and then carrying out subsequent operation. When the dipping combustion method is adopted, the method comprises the step of adding a small amount of deionized water to La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Soaking the mixed water solution of O into the composite nanometer material intermediate doped with transition metal elements, ultrasonically soaking for 1-2 h, vacuum drying at 60-100 ℃, putting into a muffle furnace, and roasting at 500-800 ℃ for 5-8 h to obtain the final composite nanometer material.
The composite nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms mussels under low concentration, shows high-efficiency and spectral antifouling activity, and can be developed and applied as a low-toxicity marine antifouling agent. The shallow sea immersion test result of the antifouling paint prepared from the composite nano material also shows that the antifouling paint has a remarkable antifouling effect. The composite 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.
The composite nano material can be applied to preventing marine biofouling, and the application includes but is not limited to preparing marine antifouling paint, marine antifouling agent and the like, wherein the marine antifouling paint contains the composite nano material, and the antifouling paint can be applied to the surface of marine artificial facilities by a conventional mode of dipping, spraying or coating and the like. In addition, the composite nanomaterial of the present invention can also be applied to marine artificial facilities for environmental protection and antifouling, including but not limited to: ships, offshore oil and gas platforms, buoys, wharfs, piers, docks, seawater pipelines, wooden piles, mariculture net cages and the like.
The following detailed description is given with reference to specific examples.
Example 1:
in a molar ratio n (Mn): n (Co): n (ti) ═ 1: 1: 1 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.05mol/L, Co (NO)3)2The concentration is 0.05 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 0.05mol/L into the solution A under stirring, continuously stirring for reaction for 2 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at 60 ℃, then is placed in a crucible, is calcined for 4 hours at the high temperature of 600 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the precursor MnO @ CoO @ TiO2。
Example 2:
in a molar ratio n (Mn): n (Co): n (ti) ═ 15: 9: 100 as the basis. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 1mol/L, Co (NO)3)2The concentration is 1 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 2mol/L into the solution A under stirring, continuously stirring for reacting for 6 hours to obtain uniform and transparent sol, filtering the precipitate, and washing for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at 100 ℃, then is placed in a crucible, is calcined for 12 hours at the high temperature of 1000 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the precursor MnO @ CoO @ TiO2。
Example 3:
in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed in proportion to prepare a solution A, wherein Mn (N)O3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the precursor MnO @ CoO @ TiO2。
Example 4:
step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: and (2) uniformly mixing the precursor prepared in the step (S1) with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the proportion of 1000:1, wherein the co-doping mass percentage of the transition elements of platinum (Pt) and palladium (Pd) is 0.1%, tabletting, placing in a crucible, calcining at 1500 ℃ for 1h, and naturally cooling to room temperature to obtain the intermediate of the composite nano material doped with the transition metal elements of platinum (Pt) and palladium (Pd).
Example 5:
step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, titanium tetrachloride was added with stirring to a concentration of 1.0Slowly dropping a mol/L NaOH solution into the solution A, continuously stirring and reacting for 4 hours to obtain uniform transparent sol, filtering the precipitate, and washing for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: and (2) uniformly mixing the precursor prepared in the step (S1) with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the ratio of 20:1, wherein the co-doping mass percentage of the transition elements platinum (Pt) and palladium (Pd) is 5%, tabletting, placing in a crucible, calcining at the high temperature of 1000 ℃ for 6 hours, and naturally cooling to the room temperature to obtain the intermediate of the composite nano material doped with the transition metal elements platinum (Pt) and palladium (Pd).
Example 6:
step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: and (2) uniformly mixing the precursor prepared in the step (S1) with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the proportion of 100:1, wherein the co-doping mass percentage of the transition elements platinum (Pt) and palladium (Pd) is 1%, tabletting, placing in a crucible, calcining at 1200 ℃ for 3h, and naturally cooling to room temperature to obtain the intermediate of the composite nano material doped with the transition metal elements platinum (Pt) and palladium (Pd).
Example 7:
a composite nanomaterial intermediate doped with transition metal platinum (Pt), wherein the doped transition element is platinum (Pt) and the doping percentage is 1%, the rest being the same as in example 6.
Example 8:
a composite nano-class material doped with transition elements (Pt, Pd) and rare-earth elements (Zr, La and Ce) and prepared from MnO, CoO and TiO2The composite nano material comprises the following main components in a molar ratio of MnO: and (3) CoO: TiO2210: 15: 50, the co-doping impurity content percentage of the transition element is 1 percent, and the co-doping mass percentage of the rare earth element is 1 percent. The rare earth element doping method is a dipping combustion method.
Step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: uniformly mixing the precursor prepared in the step S1 with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the ratio of 100:1, tabletting, placing in a crucible, calcining at 1200 ℃ for 3h, and naturally cooling to room temperature to obtain the transition metal element doped platinum (Pt) and palladium (Pd) containing MnO, CoO and TiO2The composite nanomaterial of (1).
Step S3: and (3) doping the rare earth element in the nano material intermediate prepared in the step S2 by adopting a dipping combustion method, which specifically comprises the following steps: adding La (NO) with small amount of water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2And (4) soaking the O mixed aqueous solution into the nano material intermediate prepared in the step S2, performing ultrasonic soaking for 2 hours, performing vacuum drying at 80 ℃, putting into a muffle furnace, roasting at 650 ℃ for 6 hours, and naturally cooling to room temperature to obtain the composite nano material.
Example 9:
a composite nanomaterial, wherein the mass percentage of rare earth element doping is 0.1%, and the rest is the same as that in example 8.
Example 10:
a composite nanomaterial in which the rare earth element doping is 3% by mass, the remainder being the same as in example 8.
Example 11:
a composite nano-class material doped with transition elements (Pt, Pd) and rare-earth elements (Zr, La and Ce) and prepared from MnO, CoO and TiO2The composite nano material comprises the following main components in a molar ratio of MnO: and (3) CoO: TiO2210: 15: 50, the co-doping impurity content percentage of the transition element is 1 percent, and the co-doping mass percentage of the rare earth element is 1 percent. The rare earth element doping method is a direct addition method.
Step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, weighing manganese nitrate, cobalt nitrate and La (NO) according to the proportion3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O, and preparing a solution A, wherein the concentration of Mn (NO3)2 is 0.5mol/L, Co (NO3)2 is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: and (3) uniformly mixing the precursor prepared in the step S1 with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the ratio of 100:1, tabletting, placing in a crucible, calcining at the high temperature of 1200 ℃ for 3h, and naturally cooling to the room temperature to obtain the composite nanomaterial.
Example 12:
a composite nano-class material doped with transition elements (Pt, Pd) and rare-earth elements (Zr, La and Ce) and prepared from MnO, CoO and TiO2The composite nano material comprises the following main components in a molar ratio of MnO: and (3) CoO: TiO2210: 15: 50, the co-doping impurity content percentage of the transition element is 1 percent, and the co-doping mass percentage of the rare earth element is 1 percent. The rare earth element doping method is a solid combustion method.
Step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: adding La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Grinding and mixing O, transition metal powder and the precursor uniformly, adding tablets, placing in a crucible, calcining at the high temperature of 1200 ℃ for 3h, and naturally cooling to room temperature to obtain the composite nanomaterial.
Example 13:
a composite nano-class material doped with transition elements (Pt, Pd) and rare-earth elements (Zr, La and Ce) and prepared from MnO, CoO and TiO2The composite nano material comprises the following main components in a molar ratio of MnO: and (3) CoO: TiO2 ═ 10: 15: 50 and co-doping mass of transition elementThe percentage is 1 percent, and the co-doping mass percentage of the rare earth elements is 1 percent. The rare earth element doping method is a dipping combustion method.
Step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: uniformly mixing the precursor prepared in the step S1 with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the ratio of 100:1, tabletting, placing in a crucible, calcining at 1200 ℃ for 3h, and naturally cooling to room temperature to obtain the transition metal element doped platinum (Pt) and palladium (Pd) containing MnO, CoO and TiO2The composite nanomaterial of (1).
Step S3: and (3) doping the rare earth element in the nano material intermediate prepared in the step S2 by adopting a dipping combustion method, which specifically comprises the following steps: adding La (NO) with small amount of water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2And (4) soaking the O mixed aqueous solution into the nano material intermediate prepared in the step S2, performing ultrasonic soaking for 1h, performing vacuum drying at 100 ℃, putting into a muffle furnace, roasting at 500 ℃ for 8h, and naturally cooling to room temperature to obtain the composite nano material.
Example 14:
a composite nano-class material doped with transition elements (Pt, Pd) and rare-earth elements (Zr, La, Ce) and composed of MnO, CoO, Ce, etc,TiO2The composite nano material comprises the following main components in a molar ratio of MnO: and (3) CoO: TiO2 ═ 10: 15: 50, the co-doping impurity content percentage of the transition element is 1 percent, and the co-doping mass percentage of the rare earth element is 1 percent. The rare earth element doping method is a dipping combustion method.
Step S1: in a molar ratio n (Mn): n (Co): n (ti) ═ 10: 15: 50 was carried out on the basis of the above-mentioned reaction. Firstly, manganese nitrate and cobalt nitrate are weighed according to proportion to prepare a solution A, wherein Mn (NO)3)2The concentration is 0.5mol/L, Co (NO)3)2The concentration is 0.5 mol/L; then, slowly dropping titanium tetrachloride and NaOH solution with the concentration of 1.0mol/L into the solution A under stirring, continuously stirring for reaction for 4 hours to obtain uniform and transparent sol, filtering the precipitate, and washing the precipitate for 3 times by using deionized water; finally, the obtained precipitate is dried in a vacuum drying oven at the temperature of 80 ℃, then is placed in a crucible, is calcined for 8 hours at the high temperature of 800 ℃ in the reducing atmosphere, and is naturally cooled to the room temperature, thus obtaining the product containing MnO, CoO and TiO2Precursors of three oxides.
Step S2: and (4) uniformly mixing the precursor prepared in the step S1 with transition metal powder consisting of platinum (Pt) and palladium (Pd) according to the ratio of 100:1, tabletting, placing in a crucible, calcining at the high temperature of 1200 ℃ for 3h, and naturally cooling to room temperature to obtain the composite nano material doped with transition metal elements of platinum (Pt) and palladium (Pd) and containing MnO, CoO and TiO 2.
Step S3: and (3) doping the rare earth element in the nano material intermediate prepared in the step S2 by adopting a dipping combustion method, which specifically comprises the following steps: adding La (NO) with small amount of water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2And (4) soaking the O mixed aqueous solution into the nano material intermediate prepared in the step S2, performing ultrasonic soaking for 2 hours, performing vacuum drying at 60 ℃, putting into a muffle furnace, roasting at 800 ℃ for 5 hours, and naturally cooling to room temperature to obtain the composite nano material.
Example 15:
a composite nanomaterial in which the doped rare earth element is zirconium (Zr), the remainder being the same as in example 8.
Comparative example 1
A marine antifouling agent cuprous oxide.
Comparative example 2
A marine antifouling agent nano titanium dioxide.
Performance testing
1. Inhibition effect of composite nano material on marine fouling microorganisms
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 the marine pseudomonas D2217 into 2216E liquid culture medium, carrying out shake culture overnight, centrifuging to collect bacteria, washing with sterile seawater, and preparing into suspension with the concentration of the bacteria reaching about 107-109/mL. The materials obtained in examples 1 to 15 and the antifouling agents of comparative examples 1 to 2 were dissolved in 2216E liquid medium, respectively, and then mixed with the prepared bacterial suspension at concentrations of 0.1, 1.0, 5.0, 15.0, 50.0. mu.g/mL, and added to a 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, as shown in table 1.
TABLE 1 half-inhibitory concentration of marine bacteria D2217 for each material
Figure BDA0001484398570000121
Figure BDA0001484398570000131
As can be seen from table 1, the composite nanomaterial of the present invention can significantly inhibit the adhesion of marine fouling bacteria D2217 at low concentration, and the antibacterial properties of the composite nanomaterials prepared in examples 8 to 15 are superior to those of the precursors prepared in examples 1 to 3, the intermediates prepared in examples 4 to 7, and the nano copper oxide and nano titanium dioxide materials in the comparative examples.
2. Inhibition effect of composite nano material on marine soft fouling organism seaweed
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 materials obtained in examples 1 to 15 and the antifouling agents of comparative examples 1 to 2 were dissolved in erdchreiberer's medium, respectively, and then mixed with the prepared navicula suspension at concentrations of 0.5, 5.0, 10.0, 25, 50 μ g/mL, and added to a petri dish. The culture dish containing the suspension of Navicula algae was used as a control. Each experimental group and control group were set with 3 parallel cups, cultured at 20 ℃ for 7 days under 30001X, and the petri dishes were repeatedly and gently washed with sterile seawater. Using the chlorophyll autofluorescence characteristics, 10 visual fields were randomly counted under a fluorescence microscope to obtain the attachment number of navicula, as shown in table 2.
TABLE 2 half-inhibiting concentration of each material to Navicula algae
Figure BDA0001484398570000132
Figure BDA0001484398570000141
The experimental results in table 2 confirm that the composite nanomaterial of the present invention can significantly inhibit the attachment of navicula at low concentration, and the anti-algae performance is significantly better than that of the nano copper oxide and nano titanium dioxide materials in the comparative examples, and the anti-algae performance of the composite nanomaterial prepared in examples 8-15 is also better than that of the precursors prepared in examples 1-3 and the intermediates prepared in examples 4-7.
3. Inhibition effect of composite nano material on large-scale marine fouling organisms
The biological detection model of marine large fouling organisms adopts a representative organism, namely common mussel. The adult Mytilus edulis is collected on a reef in the sea area of Qingdao city to obtain the adult Mytilus edulis, and the larva of the Mytilus edulis is cultured in a laboratory to obtain the adult Mytilus edulis. The materials obtained in examples 1-15 and the antifouling agents of comparative examples 1-2 were dissolved in sterile seawater respectively to prepare 0.5, 2.5, 5, 10. mu.g/mL, 10mL of each solution was added to a petri dish, 10mL of sterile seawater was added to a blank petri dish, and a corresponding control group was set, 3 parallel cups were provided for each experimental group and control group, and 30-80 larvae were added to each cup. The adhesion of the larvae was observed by a stereomicroscope 48h after the larvae were fed, and the results are shown in Table 3.
TABLE 3 half-inhibiting adhesion concentration of each material to Mytilus edulis
Serial number EC50/μg/mL Serial number EC50/μg/mL
Example 1 25.95±0.37 Example 10 5.92±0.20
Example 2 23.57±0.45 Example 11 6.88±0.24
Example 3 21.18±0.62 Example 12 7.16±0.19
Example 4 16.72±0.33 Example 13 6.13±0.25
Example 5 12.37±0.29 Example 14 5.96±0.26
Example 6 10.49±0.21 Example 15 6.55±0.22
Example 7 11.14±0.35 Comparative example 1 45.79±2.15
Example 8 5.58±0.24 Comparative example 2 1542.43±17.28
Example 9 7.24±0.27
The experimental results in table 3 confirm that the composite nano-material can significantly inhibit the adhesion of the mytilus edulis at low concentration, and that the inhibition effect of the materials prepared in examples 1-15, especially the composite nano-materials prepared in examples 8-15, on the mytilus edulis of a large fouling organism is significantly better than that of the nano-copper oxide and nano-titanium dioxide materials in the comparative example, and that the inhibition effect of the composite nano-materials prepared in examples 8-15 on the mytilus edulis of a large fouling organism is also better than that of the precursors prepared in examples 1-3 and the intermediates prepared in examples 4-7.
4. Environmental friendliness of composite nano material to large marine fouling organisms
And (3) treating the common mussels in the composite nano material solution for 3 days, transferring the common mussels into fresh seawater, replacing the seawater every day, counting byssus, and observing byssus attachment rate. The results show that the composite nano-materials prepared in examples 1 to 15 and the composite nano-material prepared in comparative example 2 can be recovered to the level of a control group when the concentration of the nano-titanium dioxide is less than 25ug/mL after 3 days, and the composite nano-material prepared in the invention is environment-friendly because the nano-copper oxide in comparative example 1 can not be completely recovered to the level of the control group (52%) when the nano-copper oxide is applied to the common mussel at the concentration of 25 ug/mL.
5. Marine hanging plate test of novel nano marine antifouling paint containing composite nano material
The antifouling efficiency of the composite nano material as a marine antifouling agent in the Shenzhen sea region is tested by referring to the national standard 'antifouling paint template shallow sea immersion test method' (GB/T5370-2007). Epoxy resin is used as a film forming substance, the nano antifouling paint prepared by the composite nano material of the embodiment and the marine antifouling agent of the comparative example are respectively added, and a hanging plate experiment is carried out in summer with vigorous marine fouling organisms, wherein a control group is the hanging plate experiment aiming at a blank plate, the fouling organism coverage on the plate is calculated in 3 months by hanging the plate in a natural sea area, and the result is shown in table 4.
TABLE 4 Marine antifouling paint marine suspending board test results prepared from the materials
Figure BDA0001484398570000151
As can be seen from the data in table 4, the biofouling coverage of the surface of the test sample coated with the antifouling paint of the composite nanomaterial of examples 8-15 is 5% on average, which is significantly lower than that of the antifouling paint sample plate, the comparative sample plate and the control sample prepared from the precursor and the intermediate nanomaterial of examples 1-7, especially significantly lower than that of the control sample (blank plate) which is 97.8% on average, indicating that the composite nanomaterial of the present invention has a good antifouling effect.
In conclusion, the composite nano material has obvious adhesion inhibition effect on marine microorganisms, marine soft fouling organisms seaweed and marine large fouling organisms Mytilus edulis under low concentration, and shows high-efficiency and spectral antifouling activity; in addition, the recovery experiment on the common mussel also shows that the composite nano material has evasion and no killing property, and 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 composite nano material also shows that the antifouling paint has an obvious antifouling effect. The composite 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.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (9)

1. An application of a composite nano material in preparing a marine antifouling paint or a marine antifouling agent is characterized in that,
the composite nano material is prepared from a precursor MnO @ CoO @ TiO2Element A and element B; the MnO, CoO and TiO2The molar ratio of (1-15):(1-15): (1-100); the precursor MnO @ CoO @ TiO2Doping with element A and element B; with the precursor MnO @ CoO @ TiO2The mass of the element A is 100 percent, the mass percent of the doped element A is 0.1 to 5 percent, and the mass percent of the doped element B is 0.1 to 3 percent;
the element A is a transition metal element, and the element B is at least one selected from zirconium, lanthanum or cerium.
2. Use of a composite nanomaterial according to claim 1, wherein the element a is selected from at least one of platinum or palladium.
3. The use of the composite nanomaterial of claim 1, wherein the composite nanomaterial is prepared by a method comprising:
s1 and precursor MnO @ CoO @ TiO2Preparing; s2, doping the element A to obtain a composite nano material intermediate doped with the element A; s3, doping element B.
4. The use of the composite nanomaterial of claim 3, wherein the precursor MnO @ CoO @ TiO2The preparation method comprises the following steps: weighing manganese salt and cobalt salt according to a proportion to prepare a solution A; slowly dropping titanium tetrachloride and NaOH solution into the solution A under stirring, continuously stirring for reaction for 2-6 h to obtain uniform transparent sol, filtering to obtain precipitate, and washing with deionized water; and (3) drying the precipitate for 6-12 h at the temperature of 60-100 ℃ in a vacuum drying oven, then placing the dried precipitate in a crucible, calcining the calcined precipitate for 4-12 h at the high temperature of 600-1000 ℃ in a reducing atmosphere, and naturally cooling the calcined precipitate to the room temperature.
5. The use of the composite nanomaterial of claim 4, wherein the concentration of the manganese salt in the solution A is 0.05mol/L to 1.0mol/L, and the concentration of the cobalt salt is 0.05mol/L to 1.0 mol/L; the concentration of the NaOH solution is 0.05 mol/L-2.0 mol/L.
6. As claimed in claim 3The application of the composite nano material is characterized in that the element B is doped by adopting a direct addition method, and the method comprises the step of adding a precursor MnO @ CoO @ TiO @2In the preparation of (1), after preparing solution A, La (NO) was added with a small amount of deionized water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O in the solution A, and slowly dropping titanium tetrachloride and NaOH solution into the solution A under stirring.
7. The use of the composite nanomaterial of claim 3, wherein the elemental A doping comprises: and (3) uniformly mixing the precursor prepared in the step (S1) with transition metal powder consisting of platinum and/or palladium in a mass ratio of (20-100): 1, tabletting, placing in a crucible, calcining at the high temperature of 1000-1500 ℃ for 1-6 h, and naturally cooling to room temperature.
8. Use of the composite nanomaterial of claim 3, wherein the element B doping is carried out by a solid-state combustion method comprising adding La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Grinding and mixing O, transition metal powder and the precursor uniformly, tabletting, placing in a crucible, roasting at 500-800 ℃ for 5-8 h, and naturally cooling to room temperature.
9. The use of the composite nanomaterial of claim 3, wherein the doping of element B is by immersion combustion comprising adding La (NO) with a small amount of deionized water3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Dissolving O to obtain La (NO)3)3·6H2O、Ce(NO3)3·6H2O、ZrOCl2·8H2Soaking the mixed water solution of O into the composite nanometer material intermediate doped with the element A, ultrasonically soaking for 1-2 h, vacuum drying at 60-100 ℃, and roasting at 500-800 ℃ for 5-8 h.
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