A controllable template-free preparation technique of zwitterionic functionalized conductive polymer nanofilms

Abstract

The purpose of this invention is to provide a controllable template-free preparation technique to solve the current assembly problem of zwitterionic functionalized conductive polymer nanofilms. This invention employs the following technical solution: a template-free assembly technique using an organic solvent-phase-separation solvent system. Based on the difference in solubility of conductive polymer monomers, the phase-separation solvent is used as a "template-like" agent to induce the directional assembly of monomers; simultaneously, a reverse surfactant is used to promote the dissolution of the zwitterionic conductive polymer monomers; furthermore, by rapidly mixing, lowering the temperature, and introducing hydrophobic stable structural units, the damage to the heterogeneous compatibilizer "template-like" agent by the zwitterionic functionalized conductive polymer monomers and the reverse surfactant is reduced, ultimately achieving template-free assembly of zwitterionic functionalized conductive polymer nanofilms.

Description

Technical Field

[0001] This invention belongs to the field of functional materials technology, specifically relating to the preparation technology of functionalized conductive polymer nanomaterials. Background Technology

[0002] Zwitterionic-modified conductive polymer nanomaterials have important applications in the field of electrochemical biosensing. Their surface nanostructures can increase the specific surface area for charge exchange and molecular exchange, effectively improving detection sensitivity; the introduction of zwitterionic groups can effectively resist the adhesion of non-specific biomolecules, enabling highly selective detection in complex bodily fluid environments.

[0003] Currently, existing methods for preparing functionalized conductive polymer nanomaterials mainly rely on template-based and template-free methods. Template-based methods utilize existing nanomaterials to impart specific nanomorphic structures to functionalized conductive polymer films, allowing for the adjustment of morphological parameters. However, these methods suffer from complexity and high cost, and the removal of the template may damage the polymer structure and properties (Advanced Functional Materials, 2013, 23: 3212-3219). Compared to template-based methods, template-free techniques leverage non-covalent forces such as π-π stacking, dipole-dipole interactions, hydrophobic interactions, van der Waals forces, hydrogen bonds, electrostatic interactions, and ionic dipole interactions between structural units. This enables the spontaneous formation of anisotropic aggregates or oriented structures, offering advantages such as simple processing methods, low cost, and in-situ preparation. For example, researchers have achieved template-free electrochemical in-situ preparation of nanotubular conductive polymer films by adjusting the polymerization temperature (Acs Nano, 2012, 6: 3018-3026). Alternatively, by introducing trace amounts of water templates into organic electrochemical solvents, electrochemical in-situ preparation of conductive polymers with nanotube morphologies has been achieved (J. Colloid Interface Sci., 2021, 590: 260-267.). However, existing template-free assembly techniques cannot achieve controllable adjustment of nanostructure parameters such as density and diameter. Furthermore, for highly polar zwitterionic conductive polymers, they are readily soluble in water but insoluble in organic electrochemical solvents, leading to the failure of the water template. Therefore, current template-free preparation techniques for functionalized conductive polymers cannot achieve the controllable preparation of zwitterionic functionalized conductive polymer nanomaterials.

[0004] In summary, a novel template-free micro / nano assembly technology is needed to achieve in-situ preparation of zwitterionic functionalized conductive polymer nanomaterials and controllable adjustment of the nanostructure parameters of the materials. Summary of the Invention

[0005] The purpose of this invention is to provide a controllable template-free preparation technology to solve the current assembly problem of zwitterionic functionalized conductive polymer nanofilms.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] This template-free assembly technique, employing an organic solvent-phase-solvent system, leverages the differences in solubility of conductive polymer monomers, using the phase-solvent solvent as a "template-like" to induce the directional assembly of monomers. Simultaneously, a reverse surfactant is introduced into the organic solvent to promote the dissolution of the zwitterionic conductive polymer monomers. Furthermore, the heterogeneous compatibilizer, zwitterionic functionalized conductive polymer monomers, and reverse surfactant are dissolved separately in organic electrochemical solvents with the same electrolyte concentration. These are rapidly mixed before electrochemical polymerization. Further methods, such as lowering the polymerization temperature and introducing hydrophobic stable structural units, are used to reduce the damage to the "template-like" effect of the zwitterionic functionalized conductive polymer monomers and reverse surfactants on the heterogeneous compatibilizer.

[0008] The present invention relates to zwitterionic functionalized conductive polymer nanofilms and their controllable template-free preparation technology, characterized in that: the zwitterionic functionalized conductive polymer nanofilms are composed of conductive polymers consisting of units of formula (I):

[0009]

[0010] (I)

[0011] In the general structural formula (Ⅰ): These are the groups that constitute the main chain of the conductive polymer. , , , , Any one of its derivatives; -R1 is any one of -OH and -COOH, -R2 is , , Any one of its derivatives; the ratio of m to n is 1:(1-5);

[0012] The zwitterionic functionalized conductive polymer nanofilms involved in this invention are characterized by having a nanotube structure with a nanotube density ranging from 0 to 2 × 10⁻⁶. 6 pcs / mm 2 The length ranges from 0 to 3000 nm, and the diameter ranges from 0 to 1000 nm;

[0013] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: preparation is carried out using a three-electrode system electrochemical polymerization method;

[0014] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: in the three-electrode system electrochemical polymerization method, the electrochemical solution is composed of organic solvent, heterogeneous solvent, electrolyte, surfactant, and polymer monomer;

[0015] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: the electrochemical solution is composed of an organic solvent, a heterogeneous solvent, an electrolyte, a surfactant, and a polymer monomer;

[0016] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: the organic solvent is any one of dichloroethane and chloroform; the heterogeneous solvent is any one of water, ethylene glycol, and glycerol; the electrolyte is any one of tetrabutylammonium hexafluorophosphate and tetrabutylammonium perchlorate; and the surfactant is any one of sodium dioctyl sulfosuccinate and sodium dodecyl sulfate.

[0017] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: the electrochemical solution is obtained by mixing an organic solvent containing electrolytes, surfactants, and polymer monomers with the same organic solvent containing heterogeneous solvents;

[0018] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: two organic solutions are prepared at a temperature of -10~25°C. o Under condition C, the mixture is shaken for 1~60s after mixing.

[0019] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: the three-electrode system electrochemical polymerization method can adjust the density, length, and diameter of nanotubes by adjusting the content of heterogeneous compatibilizer, polymerization time, and water contact angle of the conductive substrate;

[0020] The present invention relates to a controllable template-free preparation technology for zwitterionic functionalized conductive polymer nanofilms, characterized in that: during the adjustment of nanotube density, length, and diameter, the ratio of heterogeneous solvent volume to the total volume of electrochemical solution is 0‰~5‰; the polymerization time is 0~60s; and the water contact angle of the conductive substrate is 0°~180°. Attached Figure Description

[0021] To more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are merely exemplary, and those skilled in the art can derive other embodiments based on the provided drawings without creative effort.

[0022] The structures, proportions, sizes, etc. illustrated in this specification are only for the purpose of assisting those skilled in the art in understanding and reading the content disclosed herein, and are not intended to limit the conditions under which the present invention can be implemented. Therefore, they have no substantial technical significance. Any modifications to the structure, changes in the proportions, or adjustments to the size, without affecting the effects and objectives that the present invention can produce, should still fall within the scope of the technical content disclosed in the present invention.

[0023] Figure 1 These are scanning electron micrographs of polymers with different monomer ratios in Examples 1-3 of the present invention.

[0024] Figure 2 These are scanning electron micrographs of polymers at different temperatures in Examples 4-7 of this invention.

[0025] Figure 3 These are scanning electron micrographs of polymers with different nanotube densities in Examples 8-13 of this invention.

[0026] Figure 4 These are scanning electron micrographs of polymers with different nanotube lengths in Examples 14-16 of this invention.

[0027] Figure 5 These are the contact angles of substrates with different wettability in Examples 17-22 of this invention.

[0028] Figure 6 These are scanning electron micrographs of polymers with different nanotube diameters in Examples 17-22 of this invention. Detailed Implementation

[0029] To more clearly illustrate the present invention, the following description, in conjunction with preferred embodiments and accompanying drawings, further explains the invention. Similar components in the drawings are indicated by the same reference numerals. Those skilled in the art should understand that the specific description below is illustrative rather than restrictive and should not be construed as limiting the scope of protection of the present invention.

[0030] Example 1

[0031] In this embodiment, see Figure 1 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0032] Electropolymerization was performed using a three-electrode system with constant potential. 1 mmol of zwitterionic functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to -10℃ for later use.

[0033] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to -10°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 1 As shown in a, there is no obvious surface morphology.

[0034] Example 2

[0035] In this embodiment, see Figure 1 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0036] Electropolymerization was performed using a three-electrode system with constant potential. 0.9 mmol of zwitterionic functionalized conductive polymer monomer, 0.1 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to -10 °C for later use.

[0037] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to -10°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 1 As shown in b, the surface is almost flat, with only a slightly raised shape.

[0038] Example 3

[0039] In this embodiment, see Figure 1 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0040] Electropolymerization was performed using a three-electrode system with constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to -10 °C for later use.

[0041] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to -10°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 1 As shown in c, it has a uniform nanotube morphology.

[0042] Example 4

[0043] In this embodiment, see Figure 2 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0044] Electropolymerization was performed using a three-electrode system with constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to -10 °C for later use.

[0045] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to -10°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 2 As shown in figure a, it has a uniform nanotube morphology.

[0046] Example 5

[0047] In this embodiment, see Figure 2 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0048] Electropolymerization was performed using a three-electrode system with constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to 0 °C for later use.

[0049] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to 0°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 2 As shown in b, it exhibits a porous thin film structure.

[0050] Example 6

[0051] In this embodiment, see Figure 2 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0052] Electropolymerization was performed using a three-electrode system with constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to 10 °C for later use.

[0053] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to 10°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 2 As shown in c, it exhibits a porous thin film structure.

[0054] Example 7

[0055] In this embodiment, see Figure 2 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0056] Electropolymerization was performed using a three-electrode system with constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to 20 °C for later use.

[0057] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to 20°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 2 As shown in d, it has a slightly raised mesh structure.

[0058] Example 8

[0059] In this embodiment, see Figure 3 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0060] Electropolymerization was performed using a three-electrode system with constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 10 ml of anhydrous dichloromethane were added to the sample vial, stirred evenly, and then cooled to -10 °C for later use.

[0061] During polymerization, a circulating cooling pump is used to cool the electrolytic cell to -10°C, with indium tin oxide glass as the working electrode and Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, polymerization was performed at a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode). The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 3 As shown in a, there is no obvious surface morphology.

[0062] Example 9

[0063] In this embodiment, see Figure 3 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0064] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 10 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0065] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 30 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 3 As shown in b, the surface has a spherical raised structure.

[0066] Example 10

[0067] In this embodiment, see Figure 3 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0068] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 20 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0069] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... +Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 30 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 3 As shown in c, it has a uniform nanotube morphology, and the average density of the nanotubes is 4.1 × 10⁻⁶. 5 pcs / mm 2 .

[0070] Example 11

[0071] In this embodiment, see Figure 3 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0072] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfosuccinate (1.25 mmol), 30 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0073] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 30 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 3 As shown in d, it has a uniform nanotube morphology, and the average nanotube density is 6.4 × 10⁻⁶. 5 pcs / mm 2 .

[0074] Example 12

[0075] In this embodiment, see Figure 3 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0076] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0077] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 30 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 3 As shown in figure e, it has a uniform nanotube morphology with an average nanotube density of 9.6 × 10⁻⁶. 5 pcs / mm 2 .

[0078] Example 13

[0079] In this embodiment, see Figure 3 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0080] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 50 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0081] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... +Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 30 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 3 As shown in f, it has a uniform nanotube morphology, and the average nanotube density is 1.7 × 10⁻⁶. 6 pcs / mm 2 .

[0082] Example 14

[0083] In this embodiment, see Figure 4 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0084] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0085] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 15 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 4 As shown in b, it has a uniform nanotube morphology with an average nanotube length of 89.14 nm.

[0086] Example 15

[0087] In this embodiment, see Figure 4 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0088] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0089] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, polymerization was performed for 30 seconds using a constant potential method; the polymerization voltage was 1.4V (relative to the Ag / Ag+ electrode); a conductive polymer was electrochemically deposited on the surface of indium tin oxide glass to obtain the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows. Figure 4 As shown in c, it has a uniform nanotube morphology with an average nanotube length of 404.13 nm.

[0090] Example 16

[0091] In this embodiment, see Figure 4 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0092] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0093] During polymerization, the electrolytic cell is cooled to -10°C using a circulating cooling pump. Two solutions are mixed and stirred for 60 seconds before use. Indium tin oxide glass is used as the working electrode, with Ag / Ag... +Using a platinum electrode as the reference electrode and a constant potential method for 60 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 4 As shown in d, it has a uniform nanotube morphology with an average nanotube length of 1391.20 nm.

[0094] Example 17

[0095] In this embodiment, see Figure 6 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0096] Substrate wettability was adjusted using a coating. 17.2 mg of hydroxyl-functionalized EDOT (1 mmol), 106 mg of lithium perchlorate (10 mmol), 144 mg of sodium dodecyl sulfate (5 mmol), and 10 ml of water were added to an electrolytic cell. Indium tin oxide (ITO) glass was used as the working electrode, Ag / AgCl as the reference electrode, and a platinum electrode as the counter electrode. Cyclic voltammetry was used for one scan. The scan voltage ranged from -0.6 to 1.13 V (relative to the Ag / AgCl electrode). The substrate was electrochemically polymerized and deposited on the ITO glass surface, with a contact angle as shown in the figure. Figure 5 The average value shown in figure a is 70.2°.

[0097] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0098] During polymerization, the electrolytic cell was cooled to -10°C using a circulating cooling pump. Two solutions were mixed and stirred for 60 seconds before use. Indium tin oxide glass with adjusted substrate wettability was used as the working electrode, with Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 6As shown in figure a, it has a uniform nanotube morphology with an average nanotube diameter of 249.39 nm.

[0099] Example 18

[0100] In this embodiment, see Figure 6 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0101] Substrate wettability was adjusted using a coating. 33.7 mg of phosphocholine-functionalized EDOT (1 mmol), 342 mg of tetrabutylammonium perchlorate (10 mmol), 473.6 mg of sodium dioctyl sulfosuccinate (5 mmol), and 10 ml of acetonitrile were added to the electrolytic cell. Indium tin oxide glass was used as the working electrode, and Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, a cyclic voltammetry scan was performed; the scan voltage was -0.6 to 1.2 V (relative to Ag / Ag). + Electrode); a substrate was obtained by electrochemical polymerization deposition on an indium tin oxide glass surface, with a contact angle as shown. Figure 5 The average value shown in b is 18.97°.

[0102] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0103] During polymerization, the electrolytic cell was cooled to -10°C using a circulating cooling pump. Two solutions were mixed and stirred for 60 seconds before use. Indium tin oxide glass with adjusted substrate wettability was used as the working electrode, with Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 6 As shown in b, it has a uniform nanotube morphology with an average nanotube diameter of 343.12 nm.

[0104] Example 19

[0105] In this embodiment, see Figure 6 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0106] Substrate wettability was adjusted using a coating. 5.7 mg butyl-functionalized EDOT (0.25 mmol), 25.3 mg phosphoric acid-functionalized EDOT (0.75 mmol), 342 mg tetrabutylammonium perchlorate (10 mmol), 473.6 mg sodium dioctyl sulfosuccinate (5 mmol), and 10 ml acetonitrile were added to the electrolytic cell. Indium tin oxide glass was used as the working electrode, and Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, a cyclic voltammetry scan was performed; the scan voltage was -0.6 to 1.2 V (relative to Ag / Ag). + Electrode); a substrate was obtained by electrochemical polymerization deposition on an indium tin oxide glass surface, with a contact angle as shown. Figure 5 The average value shown in c is 24.54°.

[0107] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0108] During polymerization, the electrolytic cell was cooled to -10°C using a circulating cooling pump. Two solutions were mixed and stirred for 60 seconds before use. Indium tin oxide glass with adjusted substrate wettability was used as the working electrode, with Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 6 As shown in c, it has a uniform nanotube morphology with an average nanotube diameter of 299.82 nm.

[0109] Example 20

[0110] In this embodiment, see Figure 6 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0111] Substrate wettability was adjusted using a coating. 11.4 mg butyl-functionalized EDOT (0.5 mmol), 16.9 mg phosphoric acid-functionalized EDOT (0.5 mmol), 342 mg tetrabutylammonium perchlorate (10 mmol), 473.6 mg sodium dioctyl sulfosuccinate (5 mmol), and 10 ml acetonitrile were added to the electrolytic cell. Indium tin oxide glass was used as the working electrode, and Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, a cyclic voltammetry scan was performed; the scan voltage was -0.6 to 1.2 V (relative to Ag / Ag). + Electrode); a substrate was obtained by electrochemical polymerization deposition on an indium tin oxide glass surface, with a contact angle as shown. Figure 5 The average value shown in d is 42.60°.

[0112] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0113] During polymerization, the electrolytic cell was cooled to -10°C using a circulating cooling pump. Two solutions were mixed and stirred for 60 seconds before use. Indium tin oxide glass with adjusted substrate wettability was used as the working electrode, with Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 6 As shown in d, it has a uniform nanotube morphology with an average nanotube diameter of 249.39 nm.

[0114] Example 21

[0115] In this embodiment, see Figure 6 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0116] Substrate wettability was adjusted using a coating. 17.1 mg butyl-functionalized EDOT (0.75 mmol), 8.4 mg phosphoric acid-functionalized EDOT (0.25 mmol), 342 mg tetrabutylammonium perchlorate (10 mmol), 473.6 mg sodium dioctyl sulfosuccinate (5 mmol), and 10 ml acetonitrile were added to the electrolytic cell. Indium tin oxide glass was used as the working electrode, and Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, a cyclic voltammetry scan was performed; the scan voltage was -0.6 to 1.2 V (relative to Ag / Ag). + Electrode); a substrate was obtained by electrochemical polymerization deposition on an indium tin oxide glass surface, with a contact angle as shown. Figure 5 The average value shown in e is 112.15°.

[0117] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0118] During polymerization, the electrolytic cell was cooled to -10°C using a circulating cooling pump. Two solutions were mixed and stirred for 60 seconds before use. Indium tin oxide glass with adjusted substrate wettability was used as the working electrode, with Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 6 As shown in e, it has a uniform nanotube morphology with an average nanotube diameter of 127.53 nm.

[0119] Example 22

[0120] In this embodiment, see Figure 6 A method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilm materials includes the following steps:

[0121] Substrate wettability was adjusted using a coating. 22.8 mg butyl-functionalized EDOT (1 mmol), 342 mg tetrabutylammonium perchlorate (10 mmol), 473.6 mg sodium dioctyl sulfosuccinate (5 mmol), and 10 ml acetonitrile were added to the electrolytic cell. Indium tin oxide glass was used as the working electrode, and Ag / Ag... + Using a platinum electrode as the counter electrode and a reference electrode as the reference electrode, a cyclic voltammetry scan was performed; the scan voltage was -0.6 to 1.2 V (relative to Ag / Ag). + Electrode); a substrate was obtained by electrochemical polymerization deposition on an indium tin oxide glass surface, with a contact angle as shown. Figure 5 The average value shown in f is 176.01°.

[0122] Electropolymerization was performed using a three-electrode system with a constant potential. 0.75 mmol of zwitterionic functionalized conductive polymer monomer, 0.25 mmol of hydroxyl functionalized conductive polymer monomer, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), and 5 ml of anhydrous dichloromethane were added to a sample vial. In another sample vial, 387 mg of tetrabutylammonium hexafluorophosphate (10 mmol), 55.6 mg of sodium dioctyl sulfonate (1.25 mmol), 40 μl of water, and 5 ml of anhydrous dichloromethane were added. Both solutions were stirred thoroughly and then cooled to -10°C for later use.

[0123] During polymerization, the electrolytic cell was cooled to -10°C using a circulating cooling pump. Two solutions were mixed and stirred for 60 seconds before use. Indium tin oxide glass with adjusted substrate wettability was used as the working electrode, with Ag / Ag... + Using a platinum electrode as the reference electrode and a constant potential method for 30 seconds, a polymerization voltage of 1.4V (relative to the Ag / Ag+ electrode) was employed. The conductive polymer was electrochemically deposited on the indium tin oxide glass surface, yielding the desired anti-corrosion and anti-fouling conductive polymer coating. The surface morphology of the conductive polymer used in this embodiment is as follows: Figure 6 As shown in f, the film appears to be nearly flat.

[0124] As can be seen from Examples 1-22 of this invention, zwitterionic functionalized conductive polymer nanofilms can be obtained directly by electropolymerization in an organic solvent containing a phase-separating solvent using a constant potential method. The monomer ratio and polymerization temperature in the polymer determine whether a uniform nanotube morphology is generated. The methods in the above examples achieve controllable nanotube density by controlling the content of the phase-separating solvent in the solution; controllable nanotube length by controlling the polymerization time; and controllable nanotube diameter by controlling the wettability of the substrate. This method has a simple preparation process, wide applications, and high application prospects.

[0125] The embodiments of the present invention have been described above in conjunction with the accompanying drawings. However, the present invention is not limited to the above embodiments. Various changes can be made according to the purpose of the invention. Any changes, modifications, substitutions, combinations or simplifications made based on the spirit and principle of the technical solution of the present invention shall be equivalent substitutions. As long as they meet the purpose of the invention and do not deviate from the technical principle and inventive concept of the zwitterionic functionalized conductive polymer nanofilm of the present invention, they shall fall within the protection scope of the present invention.

Claims

1. A controllable template-free method for preparing zwitterionic functionalized conductive polymer nanofilms, characterized in that: This preparation method uses a heterogeneous solvent as a "template" for in-situ electrochemical polymerization with three electrodes; the electrochemical solution includes an organic solvent, a heterogeneous solvent, an electrolyte, a surfactant, and a polymer monomer. The resulting zwitterionic functionalized conductive polymer nanofilm is composed of conductive polymer (I) units: （Ⅰ） In the general structural formula (Ⅰ): These are the groups that constitute the main chain of the conductive polymer. , , , , Any one of them; -R1 is any one of -OH and -COOH, -R2 is , Any one of the following; the ratio of m to n is 1:(1-5); the zwitterionic functionalized conductive polymer nanofilm has a nanotube structure, and the nanotube density ranges from 0 to 2×10⁻⁶. 6 pcs / mm 2 The length ranges from 0 to 3000 nm, and the diameter ranges from 0 to 1000 nm.

2. The method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilms according to claim 1, characterized in that: The organic solvent in the electrochemical solution is any one of dichloroethane and chloroform; the heterogeneous solvent is any one of water, ethylene glycol, and glycerol; the electrolyte is any one of tetrabutylammonium hexafluorophosphate and tetrabutylammonium perchlorate; and the surfactant is any one of sodium dioctyl sulfosuccinate and sodium dodecyl sulfate.

3. The method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilms according to claim 1, characterized in that: The electrochemical solution is obtained by mixing an organic solvent containing electrolytes, surfactants, and polymer monomers with the same organic solvent containing heterogeneous solvents.

4. The method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilms according to claim 1, characterized in that: Electrochemical solutions at temperatures ranging from -10 to 25°C o Under condition C, the mixture is shaken for 1-60 seconds after mixing.

5. The method for controllable template-free preparation of zwitterionic functionalized conductive polymer nanofilms according to claim 1, characterized in that: By adjusting the heterogeneous solvent content, polymerization time, and water contact angle of the conductive substrate, the density, length, and diameter of nanotubes in the thin film can be controlled. The ratio of the heterogeneous solvent volume to the total volume of the electrochemical solution is 0‰ to 5‰; the polymerization time is 0 to 60 seconds; and the water contact angle of the conductive substrate is 0° to 180°.

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