CN112500760B - polyaniline/MOF composite coating electrode material, and preparation method and application thereof - Google Patents

polyaniline/MOF composite coating electrode material, and preparation method and application thereof Download PDF

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CN112500760B
CN112500760B CN202010497124.0A CN202010497124A CN112500760B CN 112500760 B CN112500760 B CN 112500760B CN 202010497124 A CN202010497124 A CN 202010497124A CN 112500760 B CN112500760 B CN 112500760B
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polyaniline
epoxy resin
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CN112500760A (en
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王巍
李其原
冯荟蒙
陈守刚
李文
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Ocean University of China
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • 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
    • C08K2201/001—Conductive additives
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets

Abstract

The invention provides a polyaniline/MOF composite coating electrode material and a preparation method and application thereof, wherein the coating electrode material is prepared by combining A, B, C components according to the mass ratio of m (A component) to m (B component) to m (C component) of 1.5-2.5: 1-5: 800-. Wherein the A component is Polyaniline (PANI), and the B component is MOF structural material (Co/Co)4N-N), wherein the C component is an epoxy resin. According to the invention, the material with the MOF structure is doped to modify the polyaniline material, so that the electrochemical performance of the polyaniline material is improved, and the modified polyaniline material is used for modifying the epoxy resin base material. According to the invention, Q235 steel is taken as a research object, so that the corrosion protection performance of the epoxy resin base material is improved, and the corrosion resistance of the Q235 steel in a corrosion environment is effectively improved. Through experimental exploration on key material parts, a process route with the best performance is obtained.

Description

polyaniline/MOF composite coating electrode material, and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic polymer coating material synthesis, in particular to a polyaniline/MOF composite coating electrode material and a preparation method and application thereof.
Background
The rapid growth of socioeconomic is largely driven by the progress of industrial technology, which is derived from the innovation of new materials. However, corrosion is a challenge that prevents the rapid and sustainable use of materials, and despite the constant emergence of new materials, how to design long-term service materials remains a long-term challenge facing many practical projects.
Kinetically, the corrosion process is closely related to the presence and concentration of corrosive substances that determine whether the corrosion process is a chemical process and/or an electrochemical process. The presence of oxygen can lead to chemical corrosion, while water is critical for electrochemical corrosion, both of which can greatly affect the corrosion rate. The maximum protection against contact of external corrosive substances with metal substrates is of crucial importance for corrosion protection, and therefore the use of a physical barrier corrosion protection method, corrosion protection coatings, is of increasing interest in a variety of fields.
Polyaniline (PANI) is widely applied to the field of corrosion prevention by virtue of unique chemical, electrochemical and physical properties, so that polyaniline has infinite potential in the field of marine corrosion prevention. The PANI has the defects of poor dispersibility, poor adhesion with a metal structure, low solubility in an organic solvent and the like, so that the application of the PANI in the anticorrosive paint is greatly limited.
Disclosure of Invention
The invention aims at the defects of the prior art and provides a polyaniline/MOF composite coating electrode material, a preparation method and application thereof.
The innovation points of the invention are mainly as follows:
1. the polyaniline material has the anticorrosion mechanisms of barrier action, passivation action, anode protection action, electric field action and the like;
2. the MOF material has low conductivity or is difficult to conduct, but the MOF material is often carbonized after being calcined at high temperature, so that the structural conductivity is obviously improved; and by virtue of the stable self-structure and physicochemical properties, the porosity of the porous material is still higher, and the specific surface area is larger. The MOF material after high-temperature calcination and polyaniline are combined and applied to the field of corrosion protection, and the corrosion resistance of the coating is enhanced in multiple aspects by utilizing the high porosity and larger specific surface area of the MOF material, and the MOF material also has variable functional groups and adjustable pore size;
3. the polyaniline material is modified by the MOF material, so that the working area participating in corrosion protection of the polyaniline is increased, and in addition, the calcined MOF material has improved conductivity, capacitance and the like, so that the electrochemical performance of the polyaniline is improved, the electric field effect of the polyaniline is promoted, and the anti-corrosion effect of the polyaniline is improved;
4. the polyaniline/MOF composite coating electrode material is introduced into the traditional epoxy coating, so that the corrosion resistance of the epoxy coating is improved.
The technical scheme adopted by the invention for solving the technical problems is as follows:
1. the invention provides a polyaniline/MOF composite coating electrode material, which is prepared from A, B, C three components in mass ratio m (component A): m (B component): m (C component) = 1.5-2.5: 1-5: 800-1200;
wherein the component A is Polyaniline (PANI);
wherein the component B is MOF structural material (Co/Co)4N-N) from Co (NO)3)2·6H2O, oxidant and surfactant are synthesized in a solvent 1 and calcined according to certain process conditions to obtain the catalyst;
wherein the component C is epoxy resin.
Optionally, the solvent 1 in the component B is one or more of n-butanol, tetrahydrofuran, water, acetone, dichloromethane, methanol and carbon tetrachloride.
Optionally, the oxidant in the component B is one or more of potassium permanganate, ammonium persulfate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, hydrogen peroxide and hypochlorous acid.
Optionally, the surfactant in the component B is one or more of azobenzene imidazole, hexadecyl ammonium tribromide, ammonium laurate, dodecyl dimethyl ammonium bromide, stearic acid, fatty glyceride and benzalkonium chloride.
Optionally, the solvent 2 in the component C is one or more of n-butanol, water, dimethyl sulfoxide, benzene, xylene, pentane, isopropanol, chlorobenzene, propylene oxide, phenol, and acetonitrile.
2. The invention also provides a preparation method of the polyaniline/MOF composite coating electrode material, which comprises the steps of firstly synthesizing the component B, then synthesizing the component A modified by the component B, and then mixing the three components according to the mass ratio of m (A): m (B): m (c) = 1.5-2.5: 1-5: 800-1200 ratio mixing;
the method specifically comprises the following steps:
1) synthesizing a component B: firstly, synthesizing a precursor of the MOF structural material, namely ZIF-67, according to experimental design; then, selecting proper calcination conditions according to proper process conditions to calcine the precursor, and grinding the obtained MOF structural material into powder in a mortar for later use; the obtained MOF structural material interacts with the component A, so that the electrochemical performance of the component A is improved;
2) synthesis of B-modified a-component: firstly, adding a certain amount of prepared B into an aniline solution with a certain concentration, dropwise adding an oxidant and continuously stirring, then reacting for a proper time under an ice bath condition, regulating the pH value of a system to be neutral, then, centrifugally washing, and carrying out vacuum drying;
3) and (3) synthesizing a component C: and (2) mixing the modified component A and the modified component C according to the mass ratio m (A): m (c) = 1.5-2.5: the proportion of 800-1200 is uniform.
Optionally, the solvent 1 in the component B is one or more of n-butanol, tetrahydrofuran, water, acetone, dichloromethane, methanol and carbon tetrachloride.
The oxidant in the component B is one or more of potassium permanganate, ammonium persulfate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, hydrogen peroxide and hypochlorous acid;
the surfactant in the component B is one or more of azobenzene imidazole, hexadecyl ammonium tribromide, ammonium laurate, dodecyl dimethyl ammonium bromide, stearic acid, fatty glyceride and benzalkonium chloride.
3. The invention also provides application of the polyaniline/MOF composite coating electrode material, wherein the prepared composite coating electrode material is coated on the surface of an epoxy resin working electrode, and is kept stand and cured for 12 hours in a ventilation place to prepare the polyaniline/MOF/epoxy resin working electrode.
Optionally, the epoxy resin working electrode is prepared by the following steps:
1) cutting the PVC plastic pipe into a plurality of sections at a distance of 15-20mm, and polishing the PVC pipe smoothly on a pre-grinding machine; after the PVC pipe is strictly sealed, cutting off the insulating surface skin of the metal wire to 5-8 cm; the part is exposed and is polished by sand paper for standby;
2) polishing a Q235 steel sheet on sand paper, then spreading soldering tin wires on the polished carbon steel sheet, and welding metal wires and the soldering tin wires by using an electric soldering iron;
3) mixing an epoxy resin: polyamide: solvent 2= 7-9: 3-5: preparing epoxy resin for encapsulation according to the mass ratio of 0.5-1.5, and centrifuging; filling and sealing the centrifuged epoxy resin between the fixed electrode and the PVC pipe, and standing for 24 hours until the epoxy resin just overflows;
4) and (3) grinding the dried electrode on a pre-grinding machine by using sand paper to expose the Q235 carbon steel sheet, and coating ethanol on the steel sheet to prevent corrosion to prepare the epoxy resin working electrode.
Optionally, the solvent 2 in the step 3) is one or more of n-butanol, water, dimethyl sulfoxide, benzene, xylene, pentane, isopropanol, chlorobenzene, propylene oxide, phenol and acetonitrile.
Compared with the prior art, the preparation of the polyaniline/MOF composite coating electrode material and the synthesis method and the application of the modified epoxy coating have the following beneficial effects:
1. the coating combines the traditional epoxy resin material with the novel material for use, has novel application and provides a new idea for improving the performance of the traditional material.
2. Compared with a pure epoxy resin coating, the polyaniline/MOF/epoxy resin coating has more excellent corrosion resistance and corrosion resistance, and has wide application and market values in future marine anticorrosive coatings.
Drawings
FIG. 1 shows the synthesis of PANI-Co/Co in accordance with an embodiment of the present invention4An infrared spectrogram of N-NC;
FIG. 2 shows the PANI-Co/Co synthesized in accordance with one embodiment of the present invention4N-NC and PANI, Co4XRD contrast of N standard card;
FIG. 3 is a SEM of a ZIF-67 precursor synthesized in accordance with an embodiment of the present invention;
FIG. 4 shows an example of the synthesis of a MOF structural material Co/Co4Scanning electron microscope photos of N-NC;
FIG. 5 shows an example of the synthesis of a MOF structural material Co/Co4A transmission electron microscope photo of N-NC;
FIG. 6 is a scanning electron microscope photograph of a polyaniline/MOF composite coating electrode material with a reaction time of 1h according to an embodiment of the present invention;
FIG. 7 is a scanning electron microscope photograph of a polyaniline/MOF composite coating electrode material with a reaction time of 3 hours according to an embodiment of the present invention;
FIG. 8 is a scanning electron micrograph of a polyaniline/MOF composite coating electrode material with a reaction time of 6h according to an embodiment of the present invention;
FIG. 9 is a scanning electron micrograph of a polyaniline/MOF composite coating electrode material with a reaction time of 12h according to an embodiment of the present invention;
FIG. 10 shows PANI-Co/Co synthesized in accordance with example two of the present invention4Obtaining an X-ray energy spectrum analysis chart by N-NC-10 mg;
FIG. 11 shows pure Co/Co in example two of the present invention4N of N-NC2Physical adsorption analysis test chart 11;
FIG. 12 shows PANI-Co/Co of example two4N-NC-10mg of N2Physical adsorption analysis test chart;
FIG. 13 shows four different Co/Co ratios in example two of the present invention4Nyquist plot versus N-NC content epoxy coating;
FIG. 14 shows four different Co/Co ratios in example two of the present invention4Bode plot comparison of epoxy coatings with N-NC content; FIG. 15 shows four different Co/Co ratios in the third and second embodiments of the present invention4Phase angle diagrams of epoxy coatings with N-NC content are compared.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a polyaniline/MOF composite coating electrode material, which is prepared from A, B, C three components in mass ratio m (component A): m (B component): m (C component) = 1.5-2.5: 1-5: 800-1200;
wherein the component A is Polyaniline (PANI);
wherein the component B is MOF structural material (Co/Co)4N-N) from Co (NO)3)2·6H2O, oxidant and surfactant are synthesized in a solvent 1 and calcined according to certain process conditions to obtain the catalyst;
wherein the component C is epoxy resin.
Optionally, the solvent 1 in the component B is one or more of n-butanol, tetrahydrofuran, water, acetone, dichloromethane, methanol and carbon tetrachloride.
Optionally, the oxidant in the component B is one or more of potassium permanganate, ammonium persulfate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, hydrogen peroxide and hypochlorous acid.
Optionally, the surfactant in the component B is one or more of azobenzene imidazole, hexadecyl ammonium tribromide, ammonium laurate, dodecyl dimethyl ammonium bromide, stearic acid, fatty glyceride and benzalkonium chloride.
Optionally, the solvent 2 in the component C is one or more of n-butanol, water, dimethyl sulfoxide, benzene, xylene, pentane, isopropanol, chlorobenzene, propylene oxide, phenol, and acetonitrile.
The invention discloses a preparation method of a polyaniline/MOF composite coating electrode material, which comprises the following steps: firstly synthesizing a component B, and then synthesizing the component B according to the mass ratio m (component A): m (B component): = 1.5-2.5: 1-5, synthesizing a component A modified by B, and then mixing the modified component A and the modified component C according to the mass ratio of m (A): m (c) = 1.5-2.5: 800-1200 ratio mixing;
the method specifically comprises the following steps:
1) synthesizing a component B: firstly, synthesizing a precursor of the MOF structural material, namely ZIF-67, according to experimental design; then, selecting proper calcination conditions according to proper process conditions to calcine the precursor, and grinding the obtained MOF structural material into powder in a mortar for later use;
2) synthesis of B-modified a-component: firstly, adding a certain amount of prepared B into an aniline solution with a certain concentration, dropwise adding an oxidant and continuously stirring, then reacting for a proper time under an ice bath condition, regulating the pH value of a system to be neutral, then, centrifugally washing, and carrying out vacuum drying;
3) and (3) synthesizing a component C: and (2) mixing the modified component A and the modified component C according to the mass ratio m (A): m (c) = 1.5-2.5: the proportion of 800-1200 is uniform.
Optionally, the solvent 1 in the component B is one or more of n-butanol, tetrahydrofuran, water, acetone, dichloromethane, methanol and carbon tetrachloride.
The oxidant in the component B is one or more of potassium permanganate, ammonium persulfate, potassium dichromate, potassium chlorate, concentrated sulfuric acid, hydrogen peroxide and hypochlorous acid;
the surfactant in the component B is one or more of azobenzene imidazole, hexadecyl ammonium tribromide, ammonium laurate, dodecyl dimethyl ammonium bromide, stearic acid, fatty glyceride and benzalkonium chloride.
And coating the prepared composite coating electrode material on the surface of an epoxy resin working electrode, and standing and curing in a ventilation position to prepare the polyaniline/MOF/epoxy resin working electrode.
Optionally, the epoxy resin working electrode is prepared by the following steps:
1) cutting the PVC plastic pipe into a plurality of sections at a distance of 15-20mm, and polishing the PVC pipe smoothly on a pre-grinding machine; after the PVC pipe is strictly sealed, cutting off the insulating surface skin of the metal wire to 5-8 cm; the part is exposed and is polished by sand paper for standby;
2) polishing a Q235 steel sheet on sand paper, then spreading soldering tin wires on the polished carbon steel sheet, and welding metal wires and the soldering tin wires by using an electric soldering iron;
3) mixing an epoxy resin: polyamide: solvent 2= 7-9: 3-5: preparing epoxy resin for encapsulation according to the mass ratio of 0.5-1.5, and centrifuging; filling and sealing the centrifuged epoxy resin between the fixed electrode and the PVC pipe, and standing for 24 hours until the epoxy resin just overflows;
4) and (3) grinding the dried electrode on a pre-grinding machine by using sand paper to expose the Q235 carbon steel sheet, and coating ethanol on the steel sheet to prevent corrosion to prepare the epoxy resin working electrode.
Optionally, the solvent 2 in the step 3) is one or more of n-butanol, water, dimethyl sulfoxide, benzene, xylene, pentane, isopropanol, chlorobenzene, propylene oxide, phenol and acetonitrile.
The invention is illustrated by taking polyaniline/MOF/epoxy resin working electrodes synthesized by different formulas as an example.
Example one
The polyaniline/MOF composite coating electrode material is synthesized from a component A, a component B and a component C;
the method comprises the following specific steps:
1) synthesizing a component B: dissolve 1160mg Co (NO) in 40mL deionized water3)2·6H2O and 20mg CTAB, and rapidly stirring; quickly dissolving the solution in a mixed solution consisting of 18160mg of 2-methylimidazole and 280mL of deionized water, and violently stirring at normal temperature for 6 hours; centrifuging the precipitate and washing with ethanol for 3 times until the precipitate is clear; and placing the precipitate in a vacuum drying oven for 12 hours to prepare a ZIF-67 precursor.
Putting the prepared ZIF-67 precursor into a porcelain boat, and putting the porcelain boat into a tube furnaceAt 5 deg.C/min-1Is heated to 900 ℃ and is in N2Deeply heat treating for 2 hours in the atmosphere; slowly cooling the fired material to room temperature to obtain Co/Co4N-NC; mixing Co with Co4The N-NC was ground into powder in a mortar.
2) Synthesis of B-modified a-component: 10mg of prepared Co/Co4Adding N-NC into a beaker in which 23.3mg of aniline is dissolved in 20mL of aqueous solution, performing ultrasonic dispersion in an ice-water bath for 30min, and repeatedly preparing four samples; dropwise adding 20mL of aqueous solution dissolved with 228mg of ammonium persulfate into the four solutions by using a separating funnel, finishing dropping for 20min, and violently stirring in an ice-water bath for 30 min; stopping stirring, standing the four samples in ice water bath for reaction for 1h, 3h, 6h and 12h respectively, and synthesizing PANI-Co/Co with different reaction times4N-NC samples; adjusting the pH of the precipitate to be neutral, centrifuging and washing for 3 times by using ethanol until the precipitate is clear; the precipitate is placed in a vacuum drying oven for 12h to obtain PANI-Co/Co4N-NC composite coating electrode material, and is named as PANI-Co/Co in sequence4N-NC-1h、PANI-Co/Co4N-NC-3h、PANI-Co/Co4N-NC-6h、PANI-Co/Co4N-NC-12h。
3) And (5) manufacturing an epoxy resin working electrode. Cutting the PVC plastic pipe into a plurality of sections at a distance of 15-20mm, and polishing the PVC pipe smoothly on a pre-mill by using abrasive paper with the granularity of 800; after the PVC pipe is strictly sealed, the insulating surface skin of the metal wire is cut off by about 5-8 cm; the part is exposed and is polished by using sand paper with the granularity of 800 for standby; polishing a Q235 steel sheet on sand paper, then spreading soldering tin wires on the polished carbon steel sheet, and welding metal wires and the soldering tin wires by using an electric soldering iron; mixing an epoxy resin: polyamide: solvent (n-butanol: xylene) = 8: 4: 1 (3: 7) and centrifuging after epoxy resin for encapsulation is prepared; filling and sealing the centrifuged epoxy resin between the fixed electrode and the PVC pipe, and standing for 24 hours until the epoxy resin just overflows; and (3) grinding the dried electrode on a pre-grinding machine by using sand paper with the granularity of 800 to expose the Q235 carbon steel sheet, and coating ethanol on the steel sheet to prevent corrosion. And preparing the epoxy resin working electrode.
4) And (3) synthesizing a component C: from PANI-Co/Co, respectively4N-NC-1h、PANI-Co/Co4N-NC-3h、PANI-Co/Co4N-NC-6h、PANI-Co/Co4And taking 10mg of sample in N-NC-12h, adding the sample into 5g of epoxy resin coating, and performing ultrasonic dispersion uniformly.
5) And uniformly coating the composite coating on the surface of the epoxy resin electrode, and standing the epoxy resin working electrode coated with the composite coating in a fume hood for 24 hours to prepare the polyaniline/MOF/epoxy resin working electrode.
And (3) performing characterization test on the obtained composite coating:
synthetic PANI-Co/Co4The infrared spectrum of N-NC is shown in FIG. 1. From the figure, it can be found that the C-H stretching vibration peak of the benzene ring is 2920cm-1Two single-substituted in-plane bending vibration peaks of the benzene ring are respectively positioned at 826cm-1And 690cm-1(ii) a Two characteristic peaks of benzene ring are respectively positioned at 1608cm-1And 1541cm-1Wherein 1608cm-1The characteristic peak of the benzene ring of (a) is the absorption vibration of the quinoid structure Q = N; 1541cm-1The characteristic peak of the benzene ring is the characteristic absorption vibration of a benzene structure N-B-N; the aromatic amine Ar-N has two absorption peaks which are respectively positioned at 1406cm-1And 1217cm-1(ii) a -NH has a stretching vibration peak of 3420cm-1The absorption peak of (1). The remaining hetero-peaks may be Co/Co4A micro-scale stretching vibration peak in an organic frame in an N-NC structure. This is essentially consistent with the IR spectrum of the eigenstate PANI, indicating that PANI-Co/Co4The structure of PANI exists in N-NC.
Synthetic PANI-Co/Co4N-NC and PANI, Co4The XRD contrast pattern of the N standard card is shown in fig. 2. The peak in the XRD pattern is mainly the characteristic diffraction peak of PANI, Co/Co4The N-NC peak was relatively weak because the test sample was PANI-Co/Co4N-NC-10mg，Co/Co4The content of N-NC is less, and the vast majority of the N-NC is PANI. At the 2 theta of 21.78 degrees, a strong and sharp characteristic diffraction peak of PANI appears, and at 16.14 degrees and 24.98 degrees, characteristic diffraction peaks with weak PANI can be found respectively, which indicates that PANI has a certain crystal structure. It was observed that characteristic diffraction peaks of Co element appear at 43.86 ° and 49.96 °, which is consistent with the Co standard card (15-0806) comparison; appear at 43.12 ° and 48.65 °Co4Characteristic diffraction peak of N, this is in contrast to Co4N standard card (41-0943) comparison. Therefore, the synthesized composite coating electrode material can be judged to be PANI-Co/Co4The structure of N-NC.
The scanning electron microscope photo of the ZIF-67 precursor is shown in FIG. 3, the ZIF-67 precursor is in a nano-scale cubic shape, the shape is regular and smooth, the particle size is uniform, the average particle size is distributed between 400nm and 500nm, and the particles are uniformly dispersed.
Synthetic MOF structural material Co/Co4The SEM of N-NC is shown in FIG. 4. Co/Co4N-NC is also in the shape of a nano-scale cube, and the particle size is uniformly distributed between 400 and 600nm, which is consistent with the morphology of the ZIF-67 precursor. The white spots in the figure should be observed to be Co/Co4N-NC surfaces Co and Co4The original structure of the ZIF-67 precursor is not destroyed by the high-temperature calcination of the N nanoparticles at 900 ℃.
Synthetic MOF structural material Co/Co4The transmission electron micrograph of N-NC is shown in FIG. 5. The black spots are Co and Co4N nanoparticles, large amounts of Co and Co4The N nano particles are uniformly embedded in the carbon nano cubic frame. Estimated after magnification observation, Co/Co4The N-NC surface may form a small amount of carbon nanotubes
Scanning electron micrographs of the polyaniline/MOF composite coating electrode materials with different reaction times are shown in FIGS. 6-9. Standing in ice water bath for 1 hr to obtain fibrous rod-like structure (FIG. 6), Co/Co4N-NC nanometer particles are evenly attached to the rodlike polyaniline fibers; standing in ice water bath for 3 hr to obtain uniform and round polyaniline rod-like structure (FIG. 7), Co/Co4N-NC is uniformly adsorbed on the surface of the polyaniline rod-shaped structure; the polyaniline is kept stand in ice-water bath for 6h to form a reticular polyaniline structure (figure 8), and most of Co/Co4The N-NC is coated by the nodular polyaniline; standing in ice water bath for 12 hr to form a ball-shaped polyaniline structure (FIG. 9), Co/Co4The N-NC nanometer particles are completely coated by the clustered polyaniline.
Example two
The polyaniline/MOF composite coating electrode material is synthesized from a component A, a component B and a component C;
the method comprises the following specific steps:
1) synthesizing a component B: dissolve 1160mg Co (NO) in 40mL deionized water3)2·6H2O and 20mg CTAB, and rapidly stirring; quickly dissolving the solution in a mixed solution consisting of 18160mg of 2-methylimidazole and 280mL of deionized water, and violently stirring at normal temperature for 6 hours; centrifuging the precipitate and washing with ethanol for 3 times until the precipitate is clear; and placing the precipitate in a vacuum drying oven for 12 hours to prepare a ZIF-67 precursor.
The prepared ZIF-67 precursor is placed in a porcelain boat and put in a tube furnace at the speed of 5 ℃/min-1Heating to 900 ℃ and carrying out deep heat treatment for 2h under the atmosphere of N2; slowly cooling the fired material to room temperature to obtain Co/Co4N-NC; mixing Co with Co4The N-NC was ground into powder in a mortar.
2) Synthesis of B-modified a-component: 10mg, 30mg and 50mg of prepared Co/Co4Adding N-NC into three beakers respectively containing 20mL of aqueous solution of 23.3mg of aniline, and ultrasonically dispersing in an ice-water bath for 30 min; dropwise adding 20mL of aqueous solution dissolved with 228mg of ammonium persulfate into the three solutions by using a separating funnel, finishing dropping for 20min, and violently stirring in an ice-water bath for 30 min; stopping stirring, and standing in an ice-water bath for reaction for 12 hours; adjusting the pH of the precipitate to be neutral, centrifuging and washing for 3 times by using ethanol until the precipitate is clear; the precipitate is placed in a vacuum drying oven for 12h to obtain PANI-Co/Co4The N-NC composite coating electrode material is named as PANI-Co/Co in sequence4N-NC-10mg、PANI-Co/Co4N-NC-30mg、PANI-Co/Co4N-NC-50mg。
3) And (5) manufacturing an epoxy resin working electrode. Cutting the PVC plastic pipe into a plurality of sections at a distance of 15-20mm, and polishing the PVC pipe smoothly on a pre-mill by using abrasive paper with the granularity of 800; after the PVC pipe is strictly sealed, the insulating surface skin of the metal wire is cut off by about 5-8 cm; the part is exposed and is polished by using sand paper with the granularity of 800 for standby; polishing a Q235 steel sheet on sand paper, then spreading soldering tin wires on the polished carbon steel sheet, and welding metal wires and the soldering tin wires by using an electric soldering iron; mixing an epoxy resin: polyamide: solvent (n-butanol: xylene) = 8: 4: 1 (3: 7) and centrifuging after epoxy resin for encapsulation is prepared; filling and sealing the centrifuged epoxy resin between the fixed electrode and the PVC pipe, and standing for 24 hours until the epoxy resin just overflows; and (3) grinding the dried electrode on a pre-grinding machine by using sand paper with the granularity of 800 to expose the Q235 carbon steel sheet, and coating ethanol on the steel sheet to prevent corrosion. And preparing the epoxy resin working electrode.
4) And (3) synthesizing a component C: from PANI-Co/Co, respectively4N-NC-10mg、PANI-Co/Co4N-NC-30mg、PANI-Co/Co410mg of the sample is taken from N-NC-50mg and added into 5g of epoxy resin coating, and the ultrasonic dispersion is uniform.
5) And uniformly coating the composite coating on the surface of the epoxy resin electrode, and standing the epoxy resin working electrode coated with the composite coating in a fume hood for 24 hours to prepare the polyaniline/MOF/epoxy resin working electrode.
And (3) carrying out performance test on the obtained composite coating:
with PANI-Co/Co4The X-ray energy spectrum analysis of N-NC-10mg is shown in FIG. 10. Fig. 10 (c-e) are mapping images of C, N, Co elements, respectively, of the corresponding X-ray spectral analysis. Taking a square area on the rod-shaped polyaniline, wherein Co/Co is adsorbed4N-NC nanoparticles. From the EDS spectrum of fig. 10, it can be seen that the relative contents of the elements, C, O, N, Co, and S are 44.12%, 32.39%, 21.62%, 0.95%, and 0.92%, respectively. Wherein C, N, Co is PANI-Co/Co4The main elements of the N-NC-NC are formed. The O element is from Co/Co4The oxygen-containing functional group in the N-NC structure, and the S element are impurity elements. Therefore, C, N, Co, etc. are the main elements in accordance with PANI-Co/Co4The element composition of N-NC.
Pure Co/Co4N of N-NC2Physical adsorption assay the physical adsorption assay is shown in FIG. 11, PANI-Co/Co4N-NC-10mg of N2The physisorption analysis test is shown in fig. 12. With pure Co/Co4N-NC comparison, Co/Co4After N-NC and PANI are compounded, N2The adsorption amount is obviously reduced, which shows that PANI-Co/Co4The number of holes of the N-NC surface is obviously reduced. PANI and Co/Co4N-NC connected together to allow free entry of electronsInto Co/Co4The inner surface of the N-NC improves the electrochemical performance of the material and is beneficial to corrosion prevention.
Electrochemical impedance analysis tests of polyaniline/MOF/epoxy working electrodes prepared with different MOF material contents are shown in fig. 13-15. From FIG. 13 four different Co/Co4As can be seen in the Nyquist plot of the epoxy coating at N-NC content, the four curves are all semicircular above the solid axis. The capacitive reactance arcs in the figure are arranged in size: PANI-Co/Co blank sample4N-NC-10mg＜PANI-Co/Co4N-NC-30mg＜ PANI-Co/Co4N-NC-50 mg. The modification PANI-Co/Co can be seen4The sample of the N-NC epoxy coating has a capacitive arc radius 4-5 orders of magnitude greater than that of the unmodified blank, and Co/Co is added4The larger the quality of the N-NC is, the larger the capacitive arc is, and the better the protective effect of the finish coating on 925 carbon steel is.
From the Bode plot of fig. 14, it can be found that the magnitude of the impedance value | Z | at 0.01Hz (low frequency region) is arranged as: PANI-Co/Co blank sample4N-NC-10mg＜PANI-Co/Co4N-NC-30mg＜ PANI-Co/Co4N-NC-50mg。PANI-Co/Co4The low-frequency zone impedance of N-NC-50mg is as high as 2.74 multiplied by 1010 Omega, impedance (4.25X 10) of unmodified blank6Ω) 4 orders of magnitude greater; middle and high frequency region (100-10)3Omega) of, PANI-Co/Co4N-NC-50mg has the relatively highest resistance value, which indicates that a compact and firm protective layer is formed on the surface of the Q235 steel. Thus, PANI-Co/Co4The N-NC epoxy resin coating has obvious anticorrosion effect.
FIG. 15 phase angle diagram shows PANI-Co/Co4N-NC-10mg、 PANI-Co/Co4N-NC-30mg、 PANI-Co/Co4The phase angle of the three modified samples of N-NC-50mg is obviously increased, the highest angle is nearly 90 degrees in a high frequency region, and a wider relaxation platform is arranged in a middle-high frequency region. This is due to PANI-Co/Co4The N-NC epoxy resin coating completely covers the surface of the Q235 steel, so that the coating mainly shows capacitance in a high-frequency area. The capacitance of the coating is influenced by the phase angle, and the larger the phase angle is, the stronger the capacitance of the coating is, and the stronger the barrier effect on the erosion ions is.
Thus, it is possible to provideIn summary, the phase angle diagram is consistent with the analysis of the Bode diagram and the Nyquist diagram, which shows that the anticorrosion performance is ordered as: PANI-Co/Co4N-NC-50mg＞PANI-Co/Co4N-NC-30mg＞PANI-Co/Co4N-NC-10mg > blank.
EXAMPLE III
The difference between the third embodiment and the first embodiment is that the composite coating electrode material is prepared by the following components in mass ratio m (A component): m (B component): m (C component) = 1.5: 1: 800 in proportion;
and 3) when the epoxy resin working electrode is manufactured, the following steps are performed by using epoxy resin: polyamide: solvent 2= 7: 3: the potting epoxy resin was disposed at a mass ratio of 0.5 and centrifuged.
Example four
The fourth example is the same as the first example, except that the composite coating electrode material is prepared by mixing the following components in mass ratio m (A component): m (B component): m (C component) = 2.5: 5: 1200 in proportion.
And 3) when the epoxy resin working electrode is manufactured, the following steps are performed by using epoxy resin: polyamide: solvent 2= 8: 4: 1, epoxy resin for potting was disposed in a mass ratio of 1, and then centrifuged.
EXAMPLE five
The fifth embodiment is the same as the first embodiment, except that the composite coating electrode material comprises the following components in mass ratio m (A component): m (B component): m (C component) = 2: 3: 1000 in proportion.
And 3) when the epoxy resin working electrode is manufactured, the following steps are performed by using epoxy resin: polyamide: solvent 2= 9: 5: 1.5 the potting epoxy resin was prepared and centrifuged.
While the preferred embodiments of the present application have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all alterations and modifications as fall within the scope of the application.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present application without departing from the spirit and scope of the application. Thus, if such modifications and variations of the present application fall within the scope of the claims of the present application and their equivalents, the present application is intended to include such modifications and variations as well.
In addition to the technical features described in the specification, the technology is known to those skilled in the art.

Claims (5)

1. A polyaniline/MOF composite coating electrode material is characterized in that the preparation method of the composite coating electrode is as follows: firstly synthesizing a component B, and then synthesizing the component B according to the mass ratio m (component A): m (B component): = 1.5-2.5: 1-5, synthesizing a component A modified by B, and then mixing the modified component A and the modified component C according to the mass ratio of m (A): m (c) = 1.5-2.5: 800-1200 ratio mixing;
the method specifically comprises the following steps:
1) synthesizing a component B: firstly, synthesizing a precursor of the MOF structural material, namely ZIF-67, according to experimental design; then, selecting proper calcination conditions according to proper process conditions to calcine the precursor, and grinding the obtained MOF structural material into powder in a mortar for later use;
the calcining process comprises the following steps: the prepared ZIF-67 precursor is placed in a porcelain boat and is put in a tube furnace at the temperature of 5 ℃ for min-1Is heated to 900 ℃ and is in N2Deeply heat treating for 2 hours in the atmosphere; slowly cooling the fired material to room temperature to obtain Co/Co4N-NC; mixing Co with Co4Grinding N-NC into powder in a mortar;
2) synthesis of B-modified a-component: firstly, adding a certain amount of prepared B into an aniline solution with a certain concentration, dropwise adding an oxidant and continuously stirring, then reacting for a proper time under an ice bath condition, regulating the pH value of a system to be neutral, then, centrifugally washing, and carrying out vacuum drying;
3) and (3) synthesizing a component C: and (2) mixing the modified component A and the modified component C according to the mass ratio m (A): m (c) = 1.5-2.5: the proportion of 800-1200 is uniform.
2. The preparation method of the polyaniline/MOF composite coating electrode material as claimed in claim 1, wherein the preparation method comprises the following steps: firstly synthesizing a component B, and then synthesizing the component B according to the mass ratio m (component A): m (B component): = 1.5-2.5: 1-5, synthesizing a component A modified by B, and then mixing the modified component A and the modified component C according to the mass ratio of m (A): m (c) = 1.5-2.5: 800-1200 ratio mixing;
the method specifically comprises the following steps:
1) synthesizing a component B: firstly, synthesizing a precursor of the MOF structural material, namely ZIF-67, according to experimental design; then, selecting proper calcination conditions according to proper process conditions to calcine the precursor, and grinding the obtained MOF structural material into powder in a mortar for later use;
the calcining process comprises the following steps: the prepared ZIF-67 precursor is placed in a porcelain boat and is put in a tube furnace at the temperature of 5 ℃ for min-1Is heated to 900 ℃ and is in N2Deeply heat treating for 2 hours in the atmosphere; slowly cooling the fired material to room temperature to obtain Co/Co4N-NC; mixing Co with Co4Grinding N-NC into powder in a mortar;
2) synthesis of B-modified a-component: firstly, adding a certain amount of prepared B into an aniline solution with a certain concentration, dropwise adding an oxidant and continuously stirring, then reacting for a proper time under an ice bath condition, regulating the pH value of a system to be neutral, then, centrifugally washing, and carrying out vacuum drying;
3) and (3) synthesizing a component C: and (2) mixing the modified component A and the modified component C according to the mass ratio m (A): m (c) = 1.5-2.5: the proportion of 800-1200 is uniform.
3. The preparation method of the polyaniline/MOF composite coating electrode material as claimed in claim 2, wherein the prepared composite coating electrode material is coated on the surface of an epoxy resin working electrode, and is kept still and cured in a ventilated place to prepare the polyaniline/MOF/epoxy resin working electrode.
4. The application of the polyaniline/MOF composite coating electrode material as claimed in claim 1, wherein the epoxy resin working electrode is prepared by the following steps:
1) cutting the PVC plastic pipe into a plurality of sections at a distance of 15-20mm, and polishing the PVC pipe smoothly on a pre-grinding machine; after the PVC pipe is strictly sealed, cutting off the insulating surface skin of the metal wire to 5-8 cm; the part is exposed and is polished by sand paper for standby;
2) polishing a Q235 steel sheet on sand paper, then spreading soldering tin wires on the polished carbon steel sheet, and welding metal wires and the soldering tin wires by using an electric soldering iron;
3) mixing an epoxy resin: polyamide: solvent = 7-9: 3-5: preparing epoxy resin for encapsulation according to the mass ratio of 0.5-1.5, and centrifuging; filling and sealing the centrifuged epoxy resin between the fixed electrode and the PVC pipe, and standing for 24 hours until the epoxy resin just overflows;
4) and (3) grinding the dried electrode on a pre-grinding machine by using sand paper to expose the Q235 carbon steel sheet, and coating ethanol on the steel sheet to prevent corrosion to prepare the epoxy resin working electrode.
5. The application of the polyaniline/MOF composite coating electrode material as claimed in claim 4, wherein the solvent in step 3) is one or more of n-butanol, water, dimethyl sulfoxide, benzene, xylene, pentane, isopropanol, chlorobenzene, propylene oxide, phenol and acetonitrile.
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