Two-dimensional ordered conductive polymer film as well as synthesis method and application thereof

Abstract

The invention provides a two-dimensional ordered conductive polymer film as well as a synthesis method and application thereof. The synthesis method comprises the following steps: adding an oxidant solution into a reaction container, then adding a monomer solution while stirring, and fully and uniformly mixing to obtain a reaction solution; taking a substrate material, placing the substrate material in parallel to the liquid level of the reaction liquid, enabling the substrate material to float on the liquid level of the reaction liquid, then standing and reacting for a period of time, and attaching the substrate material on an interface where the liquid level of the reaction liquid is in contact with the substrate material to generate a uniform two-dimensional ordered conductive polymer film. The method is suitable for preparation of ordered conductive macromolecules subjected to oxidation-reduction polymerization, and has very high universality. The prepared conductive polymer film has excellent photo-thermal conversion performance, and has wide application prospects in the fields of smart buildings, energy management and the like.

Description

Technical Field

[0001] The present invention belongs to the field of preparation of conductive polymers, and specifically includes a two-dimensional ordered conductive polymer thin film, a synthesis method thereof, and an application thereof. Background Art

[0002] Conductive polymer materials are a type of polymer composite material with conductive functions, which have the characteristics of low density, easy processing, corrosion resistance, and large-area film formation. They can be used as substitutes for various metal materials and inorganic conductive materials, and have great application potential in many frontier fields such as semiconductors, energy conversion, and biomedicine. However, the practical application of conductive polymers faces great challenges due to the entropy-driven molecular chain distortion and entanglement during the synthesis process, resulting in poor consistency of materials and devices and unsatisfactory long-term stability of devices. To solve this problem, researchers have tried a series of methods to construct ordered conductive polymers, prepare polymer crystals or low-dimensional nanomaterials. One of the most concerned and effective solutions is to achieve the two-dimensionalization of conductive polymers by providing a restricted reaction space and a controlled reaction rate, mainly based on mechanisms such as nano-space confinement (such as water-oil interface polymerization), interface-induced assembly (such as constructing a two-dimensional template), and epitaxial growth (such as single crystal transformation).

[0003] The water-oil interface polymerization method synthesizes nanowires or nanofibers in many cases. As the polymerization reaction proceeds, the polymer moves downward into the liquid phase, and the product is difficult to transfer. Whether it is constructing a two-dimensional soft template (such as graphene) to make the polymer grow along the template or constructing a hard template in the two-dimensional space between solids to limit the growth space of the polymer, it brings the trouble of constructing and removing the template, greatly increasing the complexity and challenge of the reaction. In addition, the heterogeneous structure obtained by the soft template method makes it difficult to separate the polymer and the template, which is not conducive to studying the properties of the polymer itself. The reaction processes of the above synthesis methods are extremely uncontrollable, and the products are mostly disordered polymers, which to a certain extent limits the exertion of the excellent properties of conductive polymers. The epitaxial growth method has very strict requirements for reaction conditions and the product yield is small. More importantly, there is currently a lack of a method for large-area preparation of two-dimensional ordered conductive polymers, which is the biggest challenge in the polymer field, especially the practical application of conductive polymers. Summary of the Invention

[0004] Aiming at the above problems existing in the prior art, the first object of the present invention is to provide a synthesis method for large-area preparation of two-dimensional ordered conductive polymer thin films. Based on the principle of solid-liquid interface confinement, this synthesis method can quickly and efficiently synthesize large-area two-dimensional ordered conductive polymer thin films. During the whole synthesis process, there is no need to separately construct a confinement space or introduce a two-dimensional template. The oligomers generated by the polymerization reaction are only orderly anchored at the interface by relying on the interaction with water and the substrate, which not only simplifies the preparation process but also breaks through the limitations brought by the template.

[0005] The second object of the present invention is to provide a two-dimensional ordered conductive polymer film synthesized using the above-mentioned synthesis method.

[0006] The third object of the present invention is to provide an application of the two-dimensional ordered conductive polymer film as described above in the field of photothermal conversion.

[0007] To achieve the above first object, the technical solution adopted by the present invention includes:

[0008] The present invention discloses a synthesis method for preparing a two-dimensional ordered conductive polymer film on a large area, comprising the following steps:

[0009] Add the oxidant solution into the reaction container, then add the monomer solution while stirring, and mix thoroughly to obtain a reaction solution;

[0010] The substrate material is placed parallel to the surface of the reaction liquid and floated on the surface of the reaction liquid. After being allowed to react for a period of time, a uniform two-dimensional ordered conductive polymer film is formed by adhering to the substrate material at the interface where the reaction liquid surface contacts the substrate material.

[0011] The present invention is based on a solid-liquid interface confined reaction inspired by the biomineralization process, and can realize the ordered assembly of two-dimensional conductive polymers of any size on any substrate. The monomer and the oxidant undergo a polymerization reaction in the reaction solution, and the generated oligomeric substance is light and has a low solubility in water. It will float to the interface between the reaction liquid surface and the substrate material. Under the hydrogen bonds formed with water and the π-π interaction with the substrate material, the oligomers are regularly arranged at the interface and further polymerized to form a two-dimensional ordered polymer. Different from the traditional liquid-liquid interface and gas-liquid interface, under the gravity of the solid phase substrate, the contact between the solid and the liquid is more fitted, which is conducive to better construction of the confined space. In addition, oligomers with longer molecular chains or self-aggregation in the solution settle at the bottom of the solution due to the gravity effect, and small molecules such as dimers float to the surface. This spontaneous flotation process realizes the effective screening of the assembly precursor, which lays the foundation for realizing the ordered structure of the conductive polymer. The present invention can prepare two-dimensional ordered conductive polymer films of various sizes and shapes according to the needs of practical applications, which are not specifically limited in the present invention.

[0012] Furthermore, the monomers contained in the monomer solution are selected from one or more of pyrrole, aniline, acetylene, phenylacetylene, p-phenylene, p-phenyleneethylene, fluorene, carbazole, and thiophene.

[0013] Furthermore, the oxidant contained in the oxidant solution of the present invention is a commonly used oxidant in the art, including but not limited to one or more of ammonium persulfate, potassium persulfate, ferric chloride, ferric sulfate, ferric nitrate, copper chloride, potassium iodate, potassium permanganate, potassium dichromate, hydrogen peroxide, cerium sulfate, silver nitrate, ferric perchlorate, chloroauric acid, potassium ferricyanide, and benzoyl peroxide.

[0014] Furthermore, the concentration of the oxidant solution is 5 - 200 mmol / L; in a specific embodiment, according to the different oxidation capabilities of the oxidants, the concentration of the oxidants that meet the requirements of the polymerization reaction of the present invention needs to be further specified. For example, ammonium persulfate and potassium persulfate are suitable at a concentration of 5 - 10 mmol / L, potassium permanganate, hydrogen peroxide, benzoyl peroxide, cerium sulfate, and chloroauric acid are suitable at a concentration of 10 - 20 mmol / L, potassium iodate, potassium dichromate, and ferric perchlorate are suitable at a concentration of 20 - 50 mmol / L, ferric chloride, ferric sulfate, ferric nitrate, potassium ferricyanide, and silver nitrate are suitable at a concentration of 80 - 160 mmol / L, and copper chloride is suitable at a concentration of 150 - 200 mmol / L.

[0015] Furthermore, the concentration of the monomer solution is 50 - 200 mmol / L; exemplarily, the concentration of the monomer solution can be 50 mmol / L, 60 mmol / L, 70 mmol / L, 80 mmol / L, 90 mmol / L, 100 mmol / L, 110 mmol / L, 120 mmol / L, 130 mmol / L, 140 mmol / L, 150 mmol / L, 160 mmol / L, 170 mmol / L, 180 mmol / L, 190 mmol / L, or 200 mmol / L, etc.

[0016] Furthermore, the molar ratio of the oxidant contained in the oxidant solution to the monomer contained in the monomer solution is 1:10 - 10:1; exemplarily, it can be 1:10, 1:9, 1:8, 1:7, 1:6, 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1, etc.

[0017] Furthermore, the liquid level height formed by the reaction solution in the reaction vessel affects the spontaneous flotation process of the polymerization product, thereby affecting the amount and composition of the substances floating to the interface. If the liquid level height is too low, effective screening cannot be formed, and the reaction precursors floating to the interface are insufficient, making it difficult to form a film and affecting the film uniformity. If the liquid level height is too high, there are too many oligomers floating to the interface, resulting in a relatively thick film. In the present invention, the liquid level height should be controlled at 0.5 - 3 cm; exemplarily, the liquid level height can be 0.5 cm, 1 cm, 1.5 cm, 2 cm, 2.5 cm, or 3 cm, etc., and the volume of the reaction vessel or the reaction solution can be correspondingly adjusted according to the volume of the reaction solution or the volume of the reaction vessel.

[0018] Furthermore, the substrate material includes, but is not limited to, materials with a flat surface such as polyethylene terephthalate sheet (PET sheet), polymethyl methacrylate sheet (PMMA sheet), polypropylene sheet (PP sheet), polydimethylsiloxane sheet (PDMS sheet), polystyrene sheet (PS sheet), silicon wafer, silicon dioxide wafer, copper foil, aluminum foil, stainless steel foil, graphite paper, carbon cloth, etc., and can also be materials with an uneven surface such as wooden blocks, leaves, porous foams, plastic bottles, etc., as long as the substrate material can float in the reaction solution.

[0019] Furthermore, the reaction vessel can be common plastic trays, enamel trays, petri dishes, beakers, etc. in the laboratory, or other containers with irregular shapes. The reaction area can be of any shape, and the shape of the reaction area determines the shape of the two-dimensional conductive polymer film on the substrate material.

[0020] Furthermore, the reaction can be carried out at 0 - 25 °C, and usually, the preparation can be completed at room temperature. Exemplarily, it can be 0 °C, 5 °C, 10 °C, 15 °C, 20 °C, or 25 °C, etc.; the reaction time is set to 0.5 - 3 h. Too long or too short reaction time is not conducive to film formation. Exemplarily, it can be 0.5 h, 1 h, 1.5 h, 2 h, 2.5 h, or 3 h, etc.

[0021] To achieve the above second object, the technical solution adopted by the present invention includes:

[0022] The present invention discloses a two-dimensional ordered conductive polymer film synthesized by the synthesis method as described above. The two-dimensional ordered conductive polymer film is highly ordered and has a thickness of about 20 - 100 nm.

[0023] According to the bottom size and shape of the reaction vessel and the size and shape of the flat surface of the substrate material, large-area two-dimensional ordered conductive polymer films of any size can be prepared, such as 30×65 cm 2 etc.

[0024] To achieve the above-mentioned third object, the technical solution adopted by the present invention includes:

[0025] The present invention discloses an application of the two-dimensional ordered conductive polymer film as described above in the field of photothermal conversion.

[0026] Advantages of the present invention:

[0027] The present invention provides a synthesis method of a two-dimensional ordered conductive polymer film. In this synthesis method, by controlling process conditions such as the concentration of the oxidant solution, the concentration of the monomer solution, the liquid level height of the reaction solution, and the reaction time, a large-area two-dimensional ordered conductive polymer film can be rapidly prepared. At the current laboratory stage, a size of 30×65 cm 2 can be achieved, with a thickness of 20 - 100 nm. Theoretically, a two-dimensional ordered conductive polymer film with a larger size can be obtained by using a larger reaction vessel and substrate material.

[0028] The two-dimensional ordered conductive polymer film obtained by the present invention has excellent photothermal conversion performance and high long-term stability. Under infrared light irradiation with a wavelength of 808 nm and a power density of 0.7 W cm -2 , the surface temperature can reach 140 °C, and there is almost no attenuation within 170 days. Under sunlight, the surface temperature of the two-dimensional ordered conductive polymer film can approach 100 °C, demonstrating its great potential application value in the fields of intelligent buildings, energy management, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] The following further details the specific embodiments of the present invention with reference to the accompanying drawings.

[0030] Figure 1 Shows a physical picture during the process of preparing the polypyrrole film in Example 1.

[0031] Figure 2 Shows a physical picture of the polypyrrole film prepared in Example 1 observed under sunlight.

[0032] Figure 3 Shows the X-ray diffraction pattern of the polypyrrole film prepared in Example 1.

[0033] Figure 4 Shows a physical picture of the polypyrrole film on the surface of the reaction solution prepared in Comparative Example 1.

[0034] Figure 5 Shows a physical picture of the polypyrrole film prepared on PET in Comparative Example 1.

[0035] Figure 6 Shows the polypyrrole film prepared on a coverslip in Comparative Example 2 observed under a metallurgical microscope.

[0036] Figure 7 The physical picture of the polypyrrole film on the surface of the reaction solution prepared in Comparative Example 3 is shown.

[0037] Figure 8 The physical picture of the polypyrrole film prepared on a cover glass in Comparative Example 3 is shown.

[0038] Figure 9 The X-ray diffraction pattern of the polypyrrole film prepared in Comparative Example 3 is shown.

[0039] Figure 10 The physical picture of the polypyrrole film prepared in Comparative Example 4 is shown.

[0040] Figure 11 The physical picture of the polypyrrole film on the surface of the reaction solution prepared in Comparative Example 5 is shown.

[0041] Figure 12 The physical picture of the polypyrrole film prepared on a copper foil in Comparative Example 5 is shown.

[0042] Figure 13 The physical picture of the polypyrrole film prepared on PET in Example 2 is shown.

[0043] Figure 14 The physical picture of the polypyrrole film prepared on a leaf in Example 3 is shown.

[0044] Figure 15 The physical picture of the polypyrrole film prepared on foam in Example 4 is shown.

[0045] Figure 16 The physical picture of the substrate material PET vial in Example 5 is shown.

[0046] Figure 17 The physical picture of the polypyrrole film prepared on the curved surface of the PET vial in Example 5 is shown.

[0047] Figure 18 The physical picture of the polyaniline thin film prepared on PMMA in Example 6 is shown.

[0048] Figure 19 The infrared thermal imaging pictures of the polypyrrole film prepared in Example 1 under the irradiation of 808 nm infrared light with different powers are shown.

[0049] Figure 20 The temperature change curves of the polypyrrole film prepared in Example 1 under the irradiation of 808 nm infrared light with different powers before and after 170 days are shown.

[0050] Figure 21 The surface temperature change of the polypyrrole film prepared in Example 1 pasted in a transparent PMMA box under sunlight irradiation is shown, where Figure 21(a) is a photograph of a polypyrrole film attached to a transparent PMMA box for field testing, and (b) is the surface temperature change of the polypyrrole film. DETAILED DESCRIPTION

[0051] In order to more clearly illustrate the present invention, the present invention is further described below in conjunction with preferred embodiments and drawings. It should be clear that the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0052] In addition, unless otherwise specified, the raw materials used in the present invention can be obtained commercially, and any range recorded in the present invention includes the end value and any numerical value between the end values ​​and any sub-range formed by the end value or any numerical value between the end values.

[0053] Example 1

[0054] Spread 1600 mL of 5 mmol / L ammonium persulfate aqueous solution on a 35×70×4.5 cm 3 The regular reaction vessel is formed so as to completely cover the bottom surface of the reaction area;

[0055] 40 mL of 150 mmol / L pyrrole aqueous solution was slowly and evenly added into the above reaction container. The pyrrole aqueous solution can be stirred while being added to prevent excessive pyrrole concentration in a local area. After the addition of the pyrrole aqueous solution, the ammonium persulfate aqueous solution and the pyrrole aqueous solution were stirred to mix evenly. After standing and stabilizing, a reaction solution with a liquid level of 0.67 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of the liquid level of the reaction solution caused by external changes, such as moving the reaction container, tilting the reaction container, stirring the reaction solution, etc.

[0056] After the liquid level of the reaction solution stabilizes, take a 30×65cm 2 A transparent PET sheet is placed parallel to the reaction solution. Under the action of the solution surface force and buoyancy, the entire PET sheet will float on the surface of the reaction solution.

[0057] The reaction was allowed to stand at room temperature for 1 hour. After the reaction was completed, it was observed that a uniform polypyrrole film was formed on the interface between the reaction liquid and the PET sheet. Figure 1 As shown, slowly pull the PET sheet upward to completely separate it from the surface of the reaction solution. Observe its uniformity and transparency under sunlight. Figure 2 , size 30×65cm 2 , with a thickness of about 20-30nm.

[0058] Figure 3XRD pattern of polypyrrole film. It can be seen from the figure that there are five obvious diffraction peaks (9.2°, 12.0°, 23.8°, 35.9°, 48.4°), indicating that the polypyrrole film prepared by this method has good crystallinity and high degree of order.

[0059] Comparative Example 1

[0060] Lay 1600 mL of ammonium persulfate aqueous solution with a concentration of 5 mmol / L flat in a 35×70×4.5 cm 3 regular reaction vessel so that it completely covers the bottom surface of the reaction area;

[0061] Add 40 mL of pyrrole aqueous solution with a concentration of 150 mmol / L while stirring to make the ammonium persulfate aqueous solution and pyrrole aqueous solution mix evenly. After standing and stabilizing, a reaction solution with a liquid level height of 0.67 cm is obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid level height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0062] After the liquid level height of the reaction solution is stable, take a 30×65 cm 2 transparent PET sheet and place it parallel on the reaction solution. Under the action of solution surface force and buoyancy, the whole PET sheet will float on the liquid surface of the reaction solution.

[0063] Let it stand and react at room temperature for 0.5 h. A film begins to form on the surface of the reaction solution. After continuing the reaction for 4 h, there is a significantly thicker polypyrrole film on both the surface of the reaction solution and the PET substrate, as shown in Figure 4 and Figure 5 shown. The reason is that the reaction time is too long and the film formed is thicker.

[0064] Comparative Example 2

[0065] Lay 1600 mL of ammonium persulfate aqueous solution with a concentration of 1 mmol / L flat in a 35×70×4.5 cm 3 regular reaction vessel so that it completely covers the bottom surface of the reaction area;

[0066] Add 40 mL of pyrrole aqueous solution with a concentration of 30 mmol / L while stirring. Stir to make the ammonium persulfate aqueous solution and pyrrole aqueous solution mix evenly. After standing and stabilizing, a reaction solution with a liquid level height of 0.67 cm is obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid level height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0067] After the liquid level height of the reaction solution is stable, take a 2×2 cm 2 transparent cover glass and place it parallel on the reaction solution. Under the action of solution surface force and buoyancy, the whole cover glass will float on the liquid surface of the reaction solution.

[0068] After standing and reacting at room temperature for 1 h, there was no obvious reaction phenomenon. After reacting for 5 h, the cover glass was taken out. Under a metallurgical microscope magnified 400 times, it was observed that polypyrrole films grew only in some areas on the surface of the cover glass, as Figure 6 shown. The reason is that the concentrations of ammonium persulfate aqueous solution and pyrrole aqueous solution are too low to form a film.

[0069] Comparative Example 3

[0070] 80 mL of ammonium persulfate aqueous solution with a concentration of 50 mmol / L was spread flat in a regular reaction vessel with a bottom radius of 4.5 cm and a height of 3 cm, so as to completely cover the bottom of the reaction area;

[0071] 2 mL of pyrrole aqueous solution with a concentration of 1500 mmol / L was added while stirring to make the ammonium persulfate aqueous solution and pyrrole aqueous solution mix evenly. After standing and stabilizing, a reaction solution with a liquid level height of 1.29 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid level height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0072] After the liquid level height of the reaction solution was stable, a 2×2 cm 2 transparent cover glass was taken and placed parallel on the reaction solution. Under the action of surface force and buoyancy of the solution, the whole cover glass would float on the liquid surface of the reaction solution.

[0073] After standing and reacting at room temperature for 10 min, the solution obviously turned black. The polypyrrole film formed after reacting for 1 h was relatively thick, as Figure 7 and Figure 8 shown. Figure 9 is the XRD pattern of the corresponding polypyrrole film, which is in a disordered state. The reason is that the concentrations of ammonium persulfate aqueous solution and pyrrole aqueous solution are too high, the reaction is too fast, and the formed film is relatively thick.

[0074] Comparative Example 4

[0075] 240 mL of ammonium persulfate aqueous solution with a concentration of 5 mmol / L was spread flat in a regular reaction vessel with a bottom radius of 5 cm and a height of 10 cm, so as to completely cover the bottom of the reaction area;

[0076] 6 mL of pyrrole aqueous solution with a concentration of 150 mmol / L was added while stirring to make the ammonium persulfate aqueous solution and pyrrole aqueous solution mix evenly. After standing and stabilizing, a reaction solution with a liquid level height exceeding 3 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid level height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0077] After the liquid level height of the reaction solution was stable, a 3×5 cm 2A transparent PET sheet is placed parallel on the reaction solution. Under the action of the solution surface force and buoyancy, the entire PET sheet will float on the liquid surface of the reaction solution.

[0078] Let it stand and react at room temperature for 1 h. After the reaction is completed, slowly lift the PET sheet upward so that it completely leaves the surface of the reaction solution. It is observed that a relatively thick polypyrrole film adheres to the PET sheet at the interface between the liquid surface of the reaction solution and the PET sheet, and the color is relatively deep, as Figure 10 shown.

[0079] Comparative Example 5

[0080] Pour 80 mL of an aqueous ammonium persulfate solution with a concentration of 5 mmol / L flatly into a regular reaction vessel with a bottom radius of 9 cm and a height of 9 cm, so that it completely covers the bottom of the reaction area;

[0081] While stirring, add 2 mL of an aqueous pyrrole solution with a concentration of 150 mmol / L to make the aqueous ammonium persulfate solution and the aqueous pyrrole solution mix evenly. After standing and stabilizing, a reaction solution with a liquid surface height lower than 0.5 cm is obtained. In the subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid surface height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0082] After the liquid surface height of the reaction solution is stable, take a 3×3 cm 2 copper foil and place it parallel on the reaction solution. Under the action of the solution surface force and buoyancy, the entire copper foil sheet will float on the liquid surface of the reaction solution.

[0083] Let it stand and react at room temperature for 1 h. After the reaction is completed, slowly lift the copper foil sheet upward so that it completely leaves the surface of the reaction solution. It is found that there is a relatively fragmented polypyrrole film on the surface of the reaction solution, and only some relatively fragmented polypyrrole films are formed on the copper foil sheet, as Figure 11 and Figure 12 shown.

[0084] Example 2

[0085] Pour 40 mL of an aqueous ammonium persulfate solution with a concentration of 5 mmol / L flatly into a regular reaction vessel with a bottom radius of 3 cm and a height of 5 cm, so that it completely covers the bottom of the reaction area;

[0086] While stirring, add 1 mL of an aqueous pyrrole solution with a concentration of 150 mmol / L to make the aqueous ammonium persulfate solution and the aqueous pyrrole solution mix evenly. After standing and stabilizing, a reaction solution with a liquid surface height of 1.45 cm is obtained. In the subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid surface height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0087] After the liquid surface height of the reaction solution is stable, take a 3×3 cm 2A transparent PET sheet was placed parallel on the reaction solution, making the entire PET sheet in complete contact with the liquid surface. Under the action of the surface force and buoyancy of the solution.

[0088] The reaction was allowed to stand for 1 h in an ice bath (0 °C). After the reaction ended, the PET sheet was slowly lifted upward to completely separate it from the surface of the reaction solution. It was observed that a uniform polypyrrole film adhered to the PET sheet at the interface between the liquid surface of the reaction solution and the PET sheet. See Figure 13 .

[0089] Example 3

[0090] 40 mL of an aqueous solution of ammonium persulfate with a concentration of 5 mmol / L was spread flat in a regular reaction vessel with a bottom radius of 4.5 cm and a height of 2 cm, so as to completely cover the bottom of the reaction area;

[0091] 1 mL of an aqueous solution of pyrrole with a concentration of 150 mmol / L was added while stirring to mix the aqueous solution of ammonium persulfate and the aqueous solution of pyrrole evenly. After standing and stabilizing, a reaction solution with a liquid surface height of 0.64 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid surface height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0092] After the liquid surface height of the reaction solution was stable, a 1×3 cm 2 leaf was placed parallel on the reaction solution. Under the action of the surface force and buoyancy of the solution, the whole leaf floated on the liquid surface of the reaction solution.

[0093] The reaction was allowed to stand for 1 h at room temperature. After the reaction ended, the leaf was slowly lifted upward to completely separate it from the surface of the reaction solution. It was observed that a uniform polypyrrole film adhered to the leaf at the interface between the liquid surface of the reaction solution and the leaf, as Figure 14 shown.

[0094] Example 4

[0095] 40 mL of an aqueous solution of ammonium persulfate with a concentration of 5 mmol / L was spread flat in a regular reaction vessel with a bottom radius of 4.5 cm and a height of 2 cm, so as to completely cover the bottom of the reaction area;

[0096] 1 mL of an aqueous solution of pyrrole with a concentration of 150 mmol / L was added while stirring to mix the aqueous solution of ammonium persulfate and the aqueous solution of pyrrole evenly. After standing and stabilizing, a reaction solution with a liquid surface height of 0.64 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid surface height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0097] After the liquid level of the reaction solution stabilized, a piece of foam with an uneven bottom and small holes was taken and placed parallel on the reaction solution. Under the action of the surface force and buoyancy of the solution, the foam floated on the liquid surface of the reaction solution.

[0098] The reaction was allowed to stand at room temperature for 1 h. After the reaction ended, the foam was slowly lifted upward to completely separate it from the surface of the reaction solution. It was observed that a uniform polypyrrole film was formed adhering to the foam at the interface between the liquid surface of the reaction solution and the foam. No film was formed on the part of the foam that was not in contact with the liquid surface, as Figure 15 shown.

[0099] Example 5

[0100] 40 mL of an aqueous solution of ammonium persulfate with a concentration of 5 mmol / L was spread flat in a regular reaction vessel with a bottom radius of 4.5 cm and a height of 2 cm, so as to completely cover the bottom of the reaction area;

[0101] 1 mL of an aqueous solution of pyrrole with a concentration of 150 mmol / L was added while stirring to mix the aqueous solution of ammonium persulfate and the aqueous solution of pyrrole evenly. After standing and stabilizing, a reaction solution with a liquid level height of 0.64 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid level height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0102] After the liquid level of the reaction solution stabilized, a small PET bottle with a bottom diameter of 3.2 cm and a bottle height of 5.8 cm (as Figure 16 shown) was taken and placed parallel (with the curved surface facing down) on the reaction solution. Under the action of the surface force and buoyancy of the solution, the small bottle floated on the liquid surface of the reaction solution.

[0103] The reaction was allowed to stand at room temperature for 1 h. After the reaction ended, the small bottle was slowly lifted upward to completely separate it from the surface of the reaction solution. It was observed that a uniform polypyrrole film was formed adhering to the small bottle at the interface between the liquid surface of the reaction solution and the curved surface of the small bottle, as Figure 17 shown.

[0104] Example 6

[0105] 40 mL of an aqueous solution of ferric chloride with a concentration of 100 mmol / L was spread flat in a regular reaction vessel with a bottom radius of 4.5 cm and a height of 2 cm, so as to completely cover the bottom of the reaction area;

[0106] 40 mL of a hydrochloric acid solution of aniline with a concentration of 50 mmol / L (the concentration ratio of aniline to hydrochloric acid is 1:1) was added while stirring to mix the aqueous solution of ferric chloride and the hydrochloric acid solution of aniline evenly. After standing and stabilizing, a reaction solution with a liquid level height of 1.26 cm was obtained. In subsequent steps, attention should be paid to reducing the disturbance of external changes to the liquid level height of the reaction solution, such as moving the reaction vessel, tilting the reaction vessel, stirring the reaction solution, etc.

[0107] After the liquid level height of the reaction solution is stable, take a 5×5 cm 2 transparent PMMA sheet and place it parallel on the reaction solution. Under the action of the surface force and buoyancy of the solution, the entire PMMA sheet will float on the liquid surface of the reaction solution.

[0108] Let it stand for reaction at room temperature for 1 h. After the reaction is completed, slowly lift the PMMA sheet upward to completely separate it from the surface of the reaction solution. It is observed that a uniform polyaniline thin film adheres to the PMMA sheet at the interface between the liquid surface of the reaction solution and the PMMA sheet. See Figure 18 .

[0109] Test example

[0110] Carry out infrared thermal imaging test on the polypyrrole thin film obtained in Example 1. The results are shown in Figure 19 . Under the irradiation of infrared light with a wavelength of 808 nm and a power density of 0.7 W cm -2 , the surface temperature of the polypyrrole thin film can reach 140 °C and there is almost no attenuation within 170 days. As shown in Figure 20 . If the polypyrrole thin film is pasted in a transparent PMMA box and irradiated under sunlight, the surface temperature of the polypyrrole thin film can be close to 100 °C. As shown in Figure 21 , which shows that it has great potential application value in the fields of intelligent buildings, energy management, etc.

[0111] This synthesis method has high versatility and provides a new concept for realizing the large-scale orderly preparation of other light organic materials with a synthesis path similar to that of pyrrole. For example, put the raw materials of the polyimide thin film (ethanol solution of maleic anhydride and ethanol solution of diethyltoluenediamine) into a reaction container and place a layer of PP sheet on the liquid surface. After a period of time, a uniform polyimide thin film will also be obtained at the interface, which provides a positive reference for solving the long-term stability of large devices based on light organic or organic-inorganic composite materials such as conductive polymers and MOFs and their extensive applications in frontier fields such as energy.

[0112] Obviously, the above-mentioned embodiments of the present invention are only examples for clearly explaining the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made on the basis of the above description. It is impossible to list all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. A synthesis method for preparing a two-dimensional ordered conductive polymer thin film on a large area, characterized in that, It includes the following steps: Add the oxidant solution into the reaction vessel, and then add the monomer solution while stirring. After fully mixing evenly, obtain the reaction solution; Place the substrate material parallel to the liquid surface of the reaction solution and make it float on the liquid surface of the reaction solution. Then, after standing and reacting for a period of time, a uniform two-dimensional ordered conductive polymer film is formed on the substrate material at the interface where the liquid surface of the reaction solution contacts the substrate material.

2. The synthesis method according to claim 1, wherein The monomer contained in the monomer solution is selected from one or more of pyrrole, aniline, acetylene, phenylacetylene, p-phenylene, p-phenylene vinylene, fluorene, carbazole, and thiophene.

3. The synthesis method according to claim 1, characterized in that The oxidant contained in the oxidant solution is selected from one or more of ammonium persulfate, potassium persulfate, ferric chloride, ferric sulfate, ferric nitrate, copper chloride, potassium iodate, potassium permanganate, potassium dichromate, hydrogen peroxide, cerium sulfate, silver nitrate, ferric perchlorate, chloroauric acid, potassium ferricyanide, and benzoyl peroxide.

4. The synthesis method according to claim 1, characterized in that, The concentration of the oxidant solution is 5 - 200 mmol / L; the concentration of the monomer solution is 50 - 200 mmol / L.

5. The synthesis method according to claim 1, characterized in that, The molar ratio of the oxidant contained in the oxidant solution to the monomer contained in the monomer solution is 1:10 - 10:

1.

6. The synthesis method according to claim 1, characterized in that, The reaction temperature of the standing reaction is 0 - 25 °C, and the reaction time is 0.5 - 3 h.

7. The synthesis method according to claim 1, characterized in that, The liquid level height formed by the reaction solution in the reaction vessel is 0.5 - 3 cm.

8. The synthesis method according to claim 1, characterized in that, The substrate material is selected from one or more of polyethylene terephthalate sheets, polymethyl methacrylate sheets, polypropylene sheets, polydimethylsiloxane sheets, polystyrene sheets, silicon wafers, silicon dioxide wafers, copper foils, aluminum foils, stainless steel foils, graphite papers, carbon cloths, cover glasses, wooden blocks, leaves, porous foams, and plastic bottles.

9. The two-dimensional ordered conductive polymer thin film synthesized by the synthesis method according to any one of claims 1-8, characterized in that, The thickness of the two-dimensional ordered conductive polymer film is 20 - 100 nm.

10. Application of the two-dimensional ordered conductive polymer film according to claim 9 in the field of photothermal conversion.

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