Preparation method and application of a triphenylamine-based copper coordination polymer film

Abstract

The application discloses a preparation method and application of a triphenylamine-based copper coordination polymer film, and belongs to the technical field of electrochromic materials. The application takes redox active ligand 4,4',4'',4'''-(1,4-phenylenebis(nitrogen tri-radical)) tetrabenzoic acid as an electroactive source, takes copper ions as a coordination metal, and obtains a triphenylamine-based copper coordination polymer through an electrochemical deposition method. Since the triphenylamine organic matter has a large pi conjugated system and reversible intrinsic redox activity, the prepared triphenylamine-based copper coordination polymer film has the advantages of fast response speed, long cycle life and better electrochromic performance. The electrochemical deposition method is used to prepare the triphenylamine-based copper coordination polymer film, the film is not damaged during the preparation process, the preparation process is simple and easy to implement, and the film has good performance.

Description

Technical Field

[0001] This invention belongs to the field of electrochromic materials technology, and particularly relates to a method for preparing a triphenylamine-based copper coordination polymer film and its application. Background Technology

[0002] Electrochromic materials are intelligent materials that can undergo stable and reversible changes in optical properties (such as color and transmittance) under the stimulation of an applied electric field or current. As the core component of electrochromic devices, they have significant application value in fields such as smart windows, displays, and anti-glare rearview mirrors. These materials are mainly divided into two categories: inorganic and organic. Inorganic electrochromic materials (such as transition metal oxides like tungsten oxide and nickel oxide) have advantages such as good environmental stability and strong memory effect, but they generally suffer from defects such as high color-changing voltage, limited color range, and slow response. Organic electrochromic materials (such as violet derivatives and conductive polymers) have advantages such as rich colors, fast response, and wide transmittance adjustment range, but they face challenges such as weak adhesion to the substrate, poor cycle stability, and difficult processing. Currently, single-type electrochromic materials are insufficient to meet the growing demand for intelligent and diversified applications. In addition, the dense thin film structure formed by traditional preparation processes results in a limited interface between the material and the electrolyte and excessively long ion diffusion paths, which severely restricts the full realization of electrochromic performance and has become a key problem that urgently needs to be solved in this field.

[0003] Metal-organic coordination polymers (MOCMs) are multifunctional framework materials formed by the self-assembly of polyhedral organic linkers and metal ions. Electroactive MOCMs, in particular, possess the dual advantages of large specific surface area and high redox activity, making them highly advantageous for constructing highly sensitive electrochemical sensors. However, traditional signal molecule loading methods are limited by the pore size effect and steric hindrance of MOCMs, leading to complex experimental procedures. Therefore, researchers are working to develop intrinsically electroactive MOCMs that can achieve sensing functions through the redox properties of the metal center or the organic ligand itself. However, currently reported endogenously redox-active MOCMs mainly rely on variable-valence metal ions such as copper and cobalt, which pose a risk of framework instability due to oxidation state changes.

[0004] Therefore, there is an urgent need to develop a novel metal-organic coordination polymer material with fast response speed, long cycle life, and superior electrochromic properties to solve the above-mentioned technical problems. Summary of the Invention

[0005] To address the aforementioned technical problems, this invention proposes a method for preparing a triphenylamine-based copper coordination polymer thin film and its application. The triphenylamine-based copper coordination polymer thin film provided by this invention has the advantages of fast response speed, long cycle life, and superior electrochromic properties.

[0006] To achieve the above object, the present application provides the following technical solutions.

[0007] The present application provides a triphenylamine-based copper coordination polymer film, taking 4,4', 4'', 4'' '- (1, 4-phenylene bis (azatriyl)) tetrabenzoic acid as a ligand and copper ions as a metal coordination center, and being synthesized by an electrochemical deposition method.

[0008] Technical principle: taking the redox active ligand 4,4', 4'', 4'' '- (1, 4-phenylene bis (azatriyl)) tetrabenzoic acid as an electroactive source and copper ions as a coordination metal, a triphenylamine-based copper coordination polymer is obtained by an electrochemical deposition method. Due to the large pi conjugated system and reversible intrinsic redox activity of triphenylamine organic matter, the prepared triphenylamine-based copper coordination polymer film has the advantages of fast response speed, long cycle life and better electrochromic performance.

[0009] Further, the molar ratio of the copper ions to 4,4', 4'', 4'' '- (1, 4-phenylene bis (azatriyl)) tetrabenzoic acid is (2.5-4): 1.

[0010] The present application provides a preparation method of the triphenylamine-based copper coordination polymer film as described in the above technical solution, comprising the following steps:

[0011] (1) dissolving copper salt and potassium salt in an inorganic solvent to obtain a copper-containing electrolyte;

[0012] (2) taking the copper-containing electrolyte obtained in step (1) as an electrolyte, taking conductive glass as a working electrode, and performing electrodeposition to obtain conductive glass with a copper nanoparticle film attached;

[0013] (3) dissolving 4,4', 4'', 4'' '- (1, 4-phenylene bis (azatriyl)) tetrabenzoic acid and tetrabutylammonium perchlorate in a mixed solvent to obtain a coordination polymer organic end electrolyte;

[0014] (4) taking the coordination polymer organic end electrolyte obtained in step (3) as an electrolyte, taking the conductive glass with the copper nanoparticle film attached obtained in step (2) as a working electrode, and performing electrodeposition to obtain the triphenylamine-based copper coordination polymer film.

[0015] Further, in step (1), the copper salt is selected from at least one of copper nitrate, copper sulfate, copper chloride and copper acetate.

[0016] Further, in step (1), the potassium salt is potassium sulfate.

[0017] Further, in step (1), the concentration of the copper salt in the copper-containing electrolyte is 5 mmol / L, and the concentration of the potassium salt is 0.1 mol / L.

[0018] Further, in step (2), the electrodeposition is carried out under a constant potential of -0.6 to -0.4 V; the electrodeposition time is 5 to 25 min.

[0019] Further, in step (3), the concentration of 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid in the coordination polymer organic end electrolyte is 1.25 to 1.87 mmol / L, and the concentration of tetrabutylammonium perchlorate is 5 to 7.5 mmol / L.

[0020] Further, in step (4), the electrodeposition is carried out under a constant potential of 1 to 1.2 V; the electrodeposition time is 5 to 25 min.

[0021] The application also provides a use of the triphenylamine-based copper coordination polymer film in the preparation of a rigid or flexible device with an electrochromic function.

[0022] Compared with the prior art, the application has the following advantages and technical effects:

[0023] The application adopts an electrochemical deposition method to prepare a high-stability electroactive triphenylamine-based copper coordination polymer, selects a carboxylic acid ligand 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid as an organic ligand, the ligand has a certain flexibility, can appear in different structures in a suitable configuration according to a specific environment, and thus can construct a complex with various structures and functions; the ligand contains multiple carboxyl groups, can be coordinated with metal ions, and is easy to construct a novel coordination polymer; and the ligand structure contains multiple aromatic rings with a conjugated skeleton structure, which can enhance the stability of a coordination polymer skeleton constructed by the aromatic rings.

[0024] The application first designs a triphenylamine-based coordination polymer synthesized by coordinating a redox-active ligand 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid with a Cu transition metal as an electroactive source, and the prepared triphenylamine-based copper coordination polymer film is expected to solve the problems of slow response speed, short cycle life and poor electrochromism of existing electrochromic materials. The triphenylamine-based coordination polymer assembled by the redox-active ligand has high stability, can be directly applied to an electrochemical aptamer sensor, avoids any post-treatment and addition of a redox mediator, overcomes the disadvantage that a common coordination polymer material is in a powder form and is difficult to process, and has the advantages of a simple method, high loading rate and easy production expansion.

[0025] The triphenylamine-based copper coordination polymer thin film is prepared by an electrochemical deposition method, the electrochemical deposition method can prepare a thin film with a porous structure, shortens an ion diffusion path, thereby significantly improving response speed of the thin film, and the thin film is not damaged during preparation, the preparation process is simple and easy to implement, and the thin film has good performance. BRIEF DESCRIPTION OF DRAWINGS

[0026] The accompanying drawings, which form a part of the present application, are used to provide further understanding of the application, and serve as an explanation of the illustrative embodiments of the present application, and are not used to define the present application. In the drawings:

[0027] Figure 1 A real photo of electrochromism of the triphenylamine-based copper coordination polymer thin film prepared for Example 1;

[0028] Figure 2 A cyclic voltammetry characteristic curve (CV) of the triphenylamine-based copper coordination polymer thin film prepared for Example 1;

[0029] Figure 3 An optical contrast (△T) image of the triphenylamine-based copper coordination polymer thin film prepared for Example 1;

[0030] Figure 4 A response time image of the triphenylamine-based copper coordination polymer thin film prepared for Example 1;

[0031] Figure 5 A current response image of the triphenylamine-based copper coordination polymer thin film prepared for Example 1 when square wave voltages of 30s / step, 0V and 30s / step, 1.2V are applied;

[0032] Figure 6 A transmittance change image of the triphenylamine-based copper coordination polymer thin film prepared for Example 1 under square wave voltages of 30s / step, 0V and 30s / step, 1.2V, and the thin film is cycled 10 times at a wavelength of 643nm;

[0033] Figure 7 A coloring efficiency image of the triphenylamine-based copper coordination polymer thin film prepared for Example 1 at a wavelength of 643nm;

[0034] Figure 8 A CIE chromaticity diagram of the triphenylamine-based copper coordination polymer thin film prepared for Example 1 at 0V and 1.2V. DETAILED DESCRIPTION

[0035] With reference to the accompanying drawings, the technical solutions in the embodiments of the present application will be described clearly and completely. Obviously, the described embodiments are only a part of the embodiments of the present application, rather than all the embodiments of the present application. Based on the embodiments in the present application, all the other embodiments obtained by a person of ordinary skill in the art without creative effort belong to the protection scope of the present application.

[0036] In order to make the above objectives, characteristics and advantages of the present application more apparent, the present application will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0037] The triphenylamine-based copper coordination polymer thin film is synthesized by an electrochemical deposition method, using 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid as a ligand and copper ions as a metal coordination center.

[0038] In a preferred embodiment, the structural formula of the 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid is as follows: The present application uses 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid as a ligand. Triphenylamine organic matter is an ideal electroactive building unit due to its large pi conjugated system and reversible intrinsic redox activity. By coordinating the triphenylamine organic ligand and the transition metal ion copper ion, an electroactive metal organic coordination polymer material with high stability is prepared, which breaks through the technical bottlenecks of existing materials such as slow response, poor cycle stability and insufficient electrochromic performance.

[0039] In a preferred embodiment, the molar ratio of the copper ions to the 4,4',4'',4'''-(1,4-phenylenebis(triazinyl)) tetrabenzoic acid is (2.5-4):1.

[0040] The present application provides a preparation method of the triphenylamine-based copper coordination polymer thin film as described in the above technical solution, including the following steps:

[0041] (1) Dissolve a copper salt and a potassium salt in an inorganic solvent to obtain a copper-containing electrolyte;

[0042] (2) taking the copper-containing electrolyte obtained in step (1) as an electrolyte, and taking conductive glass as a working electrode, electrodepositing to obtain conductive glass with a copper nanoparticle film attached thereto;

[0043] (3) dissolving 4,4',4",4"'-(1,4-phenylenebis(triazinyl))tetraphthalic acid and tetrabutylammonium perchlorate in a mixed solvent to obtain a coordination polymer organic end electrolyte;

[0044] (4) taking the coordination polymer organic end electrolyte obtained in step (3) as an electrolyte, and taking the conductive glass with the copper nanoparticle film attached thereto obtained in step (2) as a working electrode, electrodepositing to obtain the triphenylamine-based copper coordination polymer film.

[0045] In a preferred embodiment, in step (1), the copper salt is selected from at least one of copper nitrate, copper sulfate, copper chloride and copper acetate; the potassium salt is selected from potassium sulfate; and the inorganic solvent is selected from deionized water.

[0046] In a preferred embodiment, in step (1), the concentration of the copper salt in the copper-containing electrolyte is 5 mmol / L, and the concentration of the potassium salt is 0.1 mol / L. Potassium sulfate in the copper-containing electrolyte is a strong electrolyte and is completely dissociated into K + and SO4 2- ions in water, which can significantly increase the ion concentration of the electrolyte and thus improve the conductivity. High conductivity can reduce the energy consumption (reduce the cell voltage) in the electrolysis process, make the current distribution more uniform, and improve the uniformity of the deposited layer.

[0047] In a preferred embodiment, in step (2), the conductive glass is selected from FTO conductive glass; the size of the conductive glass is 2x5 cm 2 ; and the process further comprises the steps of cleaning and drying the conductive glass before electrodepositing; the cleaning process specifically comprises: sequentially ultrasonically cleaning the conductive glass in deionized water, ethanol and acetone solution for 15 min; and the drying temperature is 60℃, and the equipment is an oven.

[0048] In a preferred embodiment, in step (2), the electrodepositing is performed under a constant potential condition, the constant potential is -0.6 to -0.4 V (vs. Ag / AgCl), and is further preferably -0.6 to -0.5 V (vs. Ag / AgCl); the electrodepositing time is 5 to 25 min, and is further preferably 10 to 20 min; and the electrodepositing is performed in a three-electrode mode, with a 10 mm x 10 mm x 0.2 mm platinum sheet as a counter electrode and a saturated silver / silver chloride electrode as a reference electrode. The constant potential and the deposition time of the copper nanoparticle film obtained by electrodepositing will significantly affect the morphology, size, distribution of the nanoparticles, and the thickness and conductivity of the film.

[0049] In the preferred embodiment, in step (3), the concentration of 4,4',4'',4'''-(1,4-phenylenebis(azatriyl)) tetrabenzoic acid in the coordination polymer organic end electrolyte is 1.25-1.87 mmol / L, and the concentration of tetrabutylammonium perchlorate is 5-7.5 mmol / L; the mixed solvent is N,N-dimethylformamide and deionized water, and the volume ratio of N,N-dimethylformamide and deionized water is 7:3. The tetrabutylammonium perchlorate in the coordination polymer organic end electrolyte can be completely dissociated into tetrabutylammonium cation (TBA + ) and perchlorate anion (ClO4 - ) in N,N-dimethylformamide, which significantly increases the ion concentration and reduces the solution resistance.

[0050] In the preferred embodiment, in step (4), the electrodeposition is carried out under a constant potential condition, and the constant potential is 1-1.2 V (vs. Ag / AgCl), and is further preferably 1.2 V (vs. Ag / AgCl); the electrodeposition time is 5-25 min, and is further preferably 10-20 min; the electrodeposition is carried out in a three-electrode mode, and a 10 mm x 10 mm x 0.2 mm platinum sheet is used as the counter electrode, and a saturated silver / silver chloride electrode is used as the reference electrode. The constant potential and the deposition time of the electrodeposited triphenylamine-based copper coordination polymer thin film can significantly affect the morphology, size, distribution of the nanoparticles, and the thickness and conductivity of the thin film.

[0051] The application further provides a use of the triphenylamine-based copper coordination polymer thin film as described in the above technical solution in the preparation of a rigid or flexible device with an electrochromic function.

[0052] In the embodiment of the application, room temperature refers to "25±2℃".

[0053] Unless otherwise specified, the raw materials in the embodiment of the application are obtained by a commercial route.

[0054] Embodiment 1

[0055] A preparation method of a triphenylamine-based copper coordination polymer thin film, and the specific steps are as follows:

[0056] (1) Prepare FTO conductive glass with a size of 2 x 5 cm 2 , and ultrasonically clean the FTO conductive glass in deionized water, ethanol and acetone solution for 15 min, respectively, and then place the FTO conductive glass in an oven at 60℃ for drying, and reserve it for use;

[0057] (2) using an electronic balance to weigh 0.1247 g of copper sulfate pentahydrate and 1.7301 g of potassium sulfate; dissolving the weighed copper sulfate pentahydrate and potassium sulfate in 100 mL of deionized water, stirring at a speed of 500 r / min for 30 min by using a magnetic stirrer to obtain a copper-containing electrolyte; wherein the concentration of copper salt in the copper-containing electrolyte is 5 mmol / L, and the concentration of potassium salt is 0.1 mol / L;

[0058] (3) placing the copper-containing electrolyte obtained in step (2) in a 150 mL electrolytic cell, using the FTO glass cleaned in step (1) as a working electrode, a 10 mm x 10 mm x 0.2 mm platinum sheet as a counter electrode, and a saturated silver / silver chloride electrode as a reference electrode, and performing electrodeposition work for 20 min at a constant potential of -0.5 V (vs. Ag / AgCl) by using an electrochemical system to obtain FTO glass with a copper nanoparticle film attached thereto.

[0059] (4) using an electronic balance to weigh 0.0735 g of 4,4',4”,4”'-(1,4-phenylenebis(azatriyl)) tetrabenzoic acid and 0.1709 g of tetrabutylammonium perchlorate; dissolving the weighed 4,4',4”,4”'-(1,4-phenylenebis(azatriyl)) tetrabenzoic acid and tetrabutylammonium perchlorate in a mixed solvent of 70 mL of N,N-dimethylformamide and 30 mL of deionized water, stirring at a speed of 500 r / min for 30 min by using a magnetic stirrer to obtain a coordination polymer organic end electrolyte; wherein the concentration of 4,4',4”,4”'-(1,4-phenylenebis(azatriyl)) tetrabenzoic acid in the coordination polymer organic end electrolyte is 1.25 mmol / L, and the concentration of tetrabutylammonium perchlorate is 5 mmol / L;

[0060] (5) placing the coordination polymer organic end electrolyte obtained in step (4) in a 150 mL electrolytic cell, using the FTO glass with a copper nanoparticle film attached thereto obtained in step (3) as a working electrode, a 10 mm x 10 mm x 0.2 mm platinum sheet as a counter electrode, and a saturated silver / silver chloride electrode as a reference electrode, and performing electrodeposition work for 10 min at a constant potential of 1.2 V (vs. Ag / AgCl) by using an electrochemical system to obtain a triphenylamine-based copper coordination polymer film.

[0061] Example 2

[0062] A preparation method of a triphenylamine-based copper coordination polymer film, which is different from example 1 in that in step (4), 0.1102 g of 4,4',4",4"'-(1,4-phenylenebis(azatriyl))tetrabenzoic acid and 0.2563 g of tetrabutylammonium perchlorate are weighed by an electronic balance, the concentration of 4,4',4",4"'-(1,4-phenylenebis(azatriyl))tetrabenzoic acid in the coordination polymer organic end electrolyte is 1.87 mmol / L, and the concentration of tetrabutylammonium perchlorate is 7.5 mmol / L; the others are the same as in example 1.

[0063] Example 3

[0064] A preparation method of a triphenylamine-based copper coordination polymer film, which is different from example 1 in that in step (3), the electrochemical system is electrodeposited for 10 min, and the others are the same as in example 1.

[0065] Performance test

[0066] 1. Electrochromic performance: In a three-electrode system, a pure platinum wire is used as a counter electrode, a pure silver wire is used as a reference electrode, and the triphenylamine-based copper coordination polymer film prepared in example 1 is used as a working electrode, and the test is carried out in a 1M LiClO4 / PC electrolyte. The test results are shown in Figure 1 .

[0067] Figure 1 It is the electrochromic real picture of the triphenylamine-based copper coordination polymer film prepared in example 1. From Figure 1 it can be seen that after applying a voltage of +1.2V, the color of the film changes from yellow to green, the response time is relatively fast, and the film performance is stable during the test, and the color change is uniform.

[0068] 2. Electrochemical performance: In a three-electrode system, a silver wire electrode is used as a reference electrode, a platinum wire electrode is used as a counter electrode, and the triphenylamine-based copper coordination polymer film prepared in example 1 is used as a working electrode, and 1M LiClO4 / PC is used as an electrolyte. The test is carried out by cyclic voltammetry (CV) at a scan rate of 0.02V / s in the range of 0~+1.2V. The test results are shown in Figure 2 .

[0069] Figure 2 It is the cyclic voltammetry characteristic curve (CV) of the triphenylamine-based copper coordination polymer film prepared in example 1, which characterizes the electrochemical performance of the electrochromic film. From Figure 2 it can be seen that the triphenylamine-based copper coordination polymer film prepared in example 1 shows a large closed area and two pairs of reversible redox peaks, indicating that the film has electrochemical activity and reversible cycling performance.

[0070] 3. Optical properties

[0071] In order to study the optical properties of the triphenylamine-based copper coordination polymer thin film under different voltages, the spectral electrochemical behavior of the thin film was studied by using a UV-visible spectrometer and an electrochromic cycle tester, and the results are shown in Figure 3 .

[0072] Figure 3 The optical contrast (△T) graph of the triphenylamine-based copper coordination polymer thin film prepared in Example 1. Figure 3 The results in Example 1 show that when a positive voltage is applied, the optical transmittance of the triphenylamine-based copper coordination polymer thin film sharply decreases in the wavelength range of 420-750 nm, showing a reversible process between yellow and dark green, which is caused by the reversible redox couple under the electrochemical bias.

[0073] 4. Response time

[0074] The electrochromic switching speed of the triphenylamine-based copper coordination polymer thin film was evaluated at a wavelength of 648.0 nm. The time required for the optical transmittance change to reach an optical contrast of 43.5% was defined as the response time, and the results are shown in Figure 4 .

[0075] Figure 4 The response time graph of the triphenylamine-based copper coordination polymer thin film prepared in Example 1. Figure 4 The results in Example 1 show that the coloring / bleaching response time (tc / tb) of the triphenylamine-based copper coordination polymer thin film is 8.9 s / 6.7 s, respectively, and since the electrochemical response of the thin film is fast, it shows a shorter coloring time and bleaching time.

[0076] Figure 5 The current response graph of the triphenylamine-based copper coordination polymer thin film prepared in Example 1 when square wave voltages of 30 s / step, 0 V and 30 s / step, 1.2 V are applied. Figure 5 The results in Example 1 show that the triphenylamine-based copper coordination polymer thin film has a faster current response speed.

[0077] Figure 6 The transmittance change graph of the triphenylamine-based copper coordination polymer thin film prepared in Example 1 under square wave voltages of 30 s / step, 0 V and 30 s / step, 1.2 V at a wavelength of 643 nm for 10 cycles. Figure 6 The results in Example 1 show that the triphenylamine-based copper coordination polymer thin film has a faster response speed and better cycle stability.

[0078] Figure 7 The coloring efficiency graph of the triphenylamine-based copper coordination polymer thin film prepared in Example 1 at a wavelength of 643 nm. Figure 7 The results in Example 1 show that the triphenylamine-based copper coordination polymer thin film has a coloring efficiency as high as 309.3 cm 2 / C, which means that it has a high charge utilization rate.

[0079] Figure 8 CIE chromaticity diagram of the triphenylamine-based copper coordination polymer thin film prepared in Example 1 at 0 V and 1.2 V. Figure 8 The results show that the triphenylamine-based copper coordination polymer thin film exhibits a yellow to green transition from 0 V to 1.2 V.

[0080] The above merely shows the preferred embodiments of the present application, but the protection scope of the present application is not limited thereto, and any person skilled in the art can easily think of changes or replacements within the technical scope disclosed by the present application, which should be covered within the protection scope of the present application.

Claims

1. A triphenylamine-based copper coordination polymer film, characterized in that, It was synthesized by electrochemical deposition using 4,4',4”,4”'-(1,4-phenylenebis(azatriyl))tetrabenzoic acid as a ligand and copper ions as the metal coordination center.

2. The triphenylamine-based copper coordination polymer film according to claim 1, characterized in that, The molar ratio of copper ions to 4,4',4”,4”'-(1,4-phenylenebis(azatriyl))tetrabenzoic acid is (2.5–4):

1.

3. A method for preparing a triphenylamine-based copper coordination polymer film as described in any one of claims 1-2, characterized in that, Includes the following steps: (1) Dissolve copper salt and potassium salt in an inorganic solvent to obtain a copper-containing electrolyte; (2) Using the copper-containing electrolyte obtained in step (1) as the electrolyte and the conductive glass as the working electrode, electrodeposition is performed to obtain a conductive glass with a copper nanoparticle film attached. (3) Dissolve 4,4',4”,4”'-(1,4-phenylenebis(azatriyl))tetrabenzoic acid and tetrabutylammonium perchlorate in a mixed solvent to obtain a coordination polymer organic-terminated electrolyte; (4) Using the organic end electrolyte of the coordination polymer obtained in step (3) as the electrolyte, and the conductive glass with copper nanoparticle film attached obtained in step (2) as the working electrode, electrodeposition is performed to obtain the triphenylamine copper coordination polymer film.

4. The method for preparing the triphenylamine-based copper coordination polymer film according to claim 3, characterized in that, In step (1), the copper salt is selected from at least one of copper nitrate, copper sulfate, copper chloride and copper acetate.

5. The method for preparing the triphenylamine-based copper coordination polymer film according to claim 3, characterized in that, In step (1), the potassium salt is potassium sulfate.

6. The method for preparing the triphenylamine-based copper coordination polymer film according to claim 3, characterized in that, In step (1), the concentration of copper salt in the copper-containing electrolyte is 5 mmol / L and the concentration of potassium salt is 0.1 mol / L.

7. The method for preparing the triphenylamine-based copper coordination polymer film according to claim 3, characterized in that, In step (2), the electrodeposition is performed under constant potential conditions, where the constant potential is -0.6 to -0.4V; and the electrodeposition time is 5 to 25 minutes.

8. The method for preparing the triphenylamine-based copper coordination polymer film according to claim 3, characterized in that, In step (3), the concentration of 4,4',4”,4”'-(1,4-phenylenebis(azatriyl))tetrabenzoic acid in the organic-terminated electrolyte of the coordination polymer is 1.25-1.87 mmol / L, and the concentration of tetrabutylammonium perchlorate is 5-7.5 mmol / L.

9. The method for preparing the triphenylamine-based copper coordination polymer film according to claim 3, characterized in that, In step (4), the electrodeposition is performed under constant potential conditions, where the constant potential is 1 to 1.2V; and the electrodeposition time is 5 to 25 minutes.

10. The use of a triphenylamine-based copper coordination polymer film as described in any one of claims 1-2 in the preparation of rigid or flexible devices with electrochromic functionality.

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