Preparation method and application of high-density one-dimensional wire film for salinity power generation

Abstract

The application provides a preparation method of a high-density one-dimensional wire film for salinity power generation, which comprises the following steps: synthesizing PTHLCAM-VI, configuring the PTHLCAM-VI into a solution, uniformly laying the configured solution on a mold, and evaporating and removing the solvent to obtain the high-density one-dimensional wire film for salinity power generation. The application also provides an application, and the film can prevent colony contamination when the salinity energy at the intersection of the ocean and the river is converted. The preparation method of the high-density one-dimensional wire film for salinity power generation is simple and easy to control, the obtained composite film has high ion transmission capacity, and the high and stable output can be realized when the film is applied to collect salinity energy. The energy density of the one-dimensional wire film provided by the application can reach 17.0-40.5 W / m 2 , which is much higher than that of a commercial ion exchange film under the same conditions.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of wire thin film, and particularly relates to a preparation method of a high-density one-dimensional wire thin film for salt difference power generation and application thereof. BACKGROUND

[0002] Salt difference energy is a renewable energy with huge energy, and its efficient capture depends on the key component ion-selective membrane in reverse electrodialysis technology. At present, the ion-selective mechanism mainly depends on electrostatic interaction. Generally, the charge groups in the membrane channel repel and attract counterions through electrostatic interaction to achieve selective anion-cation transport. However, it is still a challenge to simultaneously achieve high selectivity and high flux ion transport based on the membrane.

[0003] Polymer-based ion transport membranes have attracted much attention due to their excellent comprehensive performance. The inner surface of the nanochannel constructed based on the polymer membrane can expose active chemical groups under specific conditions, which is easy to realize further functionalization. The track etching technology based on the polymer substrate has the advantages of clear size and geometry, which can be used to prepare artificial nanochannels. The polymer porous membrane can be prepared based on non-solvent induced phase separation, which is simple and low in cost. The highly ordered and controllable nanochannels can be constructed based on the self-assembly of block copolymers, but the microphase separation results between different polymer segments are limited by the size and density, which restricts the improvement of ion transport performance.

[0004] Therefore, it is the key to realize the effective utilization of salt difference energy to improve the ion transport flux and selectivity by designing the polymer molecular structure, and to prepare a small-size, high-pore-density self-supporting porous thin film material. SUMMARY

[0005] The technical problem to be solved by the application is to provide a preparation method of a high-density one-dimensional wire thin film for salt difference power generation and application thereof to solve the problems of the prior art. The preparation method of the high-density one-dimensional wire thin film for salt difference power generation is simple and easy to control, and the obtained composite membrane has high ion transport flux and selectivity, and can realize high and stable output when applied to collect salt difference energy. The energy density of the one-dimensional wire thin film provided by the application can reach 17.0-40.5 W / m 2 , which is much higher than that of a commercial ion exchange membrane under the same conditions.

[0006] To solve the above technical problems, the technical scheme adopted by the application is as follows: a preparation method of a high-density one-dimensional wire thin film for salt difference power generation, which comprises the following steps:

[0007] S1, mixing tetrahydro linalool and chloroacetonitrile to obtain a mixture of tetrahydro linalool and chloroacetonitrile, then adding concentrated sulfuric acid dropwise under stirring at 0℃ in an ice bath until the mass fraction of the mixture of tetrahydro linalool and chloroacetonitrile in the system is 80%, removing the ice bath, reacting at 40℃ for 12h, then adding sodium hydroxide aqueous solution dropwise under stirring until the reaction system, dissolving the obtained crude product in dichloromethane (DCM), washing with saturated sodium chloride solution for 3 times, drying with anhydrous magnesium sulfate, then concentrating the organic layer, and drying under vacuum at room temperature for 24h to obtain substance A, named as THLCAM;

[0008] The ice bath condition in the embodiment can also be 5℃.

[0009] S2, adding THLCAM obtained in S1 and 1-vinylimidazole into N,N-dimethylformamide, and performing quaternary ammonium reaction at 80℃ for 12h to obtain a reaction mixture, then adding methyl tert-butyl ether (MTBE) to the reaction mixture under stirring, washing the precipitated substance for 2 times, and drying under vacuum at room temperature for 24h to obtain substance B, named as THLCAM-VI;

[0010] S3, dissolving azobisisobutyronitrile (AIBN) and THLCAM-VI obtained in S2 in DMF, passing nitrogen for 30min, then reacting at 65℃ in an oil bath for 24h, evaporating at 80℃, then adding methyl tert-butyl ether (MTBE), washing the precipitated substance for 2 times, and drying under vacuum at room temperature for 24h to obtain substance C, named as PTHLCAM-VI;

[0011] S4, dissolving PTHLCAM-VI obtained in S3 in ethanol to obtain an ethanol solution of PTHLCAM-VI;

[0012] S5, spreading the ethanol solution of PTHLCAM-VI obtained in S4 on a mold, and evaporating at 45℃ to obtain a high-density one-dimensional wire film for salt differential power generation.

[0013] Preferably, the concentration of the concentrated sulfuric acid in S1 is 1.84g / mL; and the ratio of the amount of sodium hydroxide to the amount of deionized water in the sodium hydroxide aqueous solution is 9.6g:200mL.

[0014] Preferably, the ratio of the amount of tetrahydro linalool to the amount of chloroacetonitrile in S1 is 15.8g:9.0g.

[0015] Preferably, the ratio of the amount of THLCAM to the amount of 1-vinylimidazole in S2 is 11.7g:7.05g.

[0016] Preferably, the ratio of the amount of the azobisisobutyronitrile and THLCAM-VI in S3 is 40 mg: 16.4 g.

[0017] Preferably, the concentration of the ethanol solution of the PTHLCAM-VI in S5 is 100 mg / mL.

[0018] Preferably, the high-density one-dimensional wire thin film energy density for salt differential power generation in S5 is 17.0 W / m 2 ~ 40.5 W / m 2 .

[0019] The application also provides the use of the high-density one-dimensional wire thin film for salt differential power generation prepared by the above preparation method, which is used to prevent bacterial colony contamination when the salt differential energy is converted in marine or / and river environment.

[0020] Compared with the prior art, the application has the following advantages:

[0021] The preparation method of the high-density one-dimensional wire thin film for salt differential power generation is simple and easy to control, and the obtained composite film has high ion transmission amount, and can realize high and stable output when applied to collect salt differential energy. The energy density of the one-dimensional wire thin film provided by the application can reach 17.0 ~ 40.5 W / m 2 , which is much higher than that of commercial ion exchange membranes under the same conditions.

[0022] The application will be further described in detail below in combination with the drawings and examples. BRIEF DESCRIPTION OF DRAWINGS

[0023] Figure 1 is the synthesis method of PTHLCAM-VI in Example 1 of the application and the actual optical picture of the high-density one-dimensional wire thin film for salt differential power generation prepared thereby.

[0024] Figure 2 is the nuclear magnetic resonance hydrogen spectrum spectrum of THLCAM in Example 1 of the application.

[0025] Figure 3 is the nuclear magnetic resonance hydrogen spectrum spectrum of PTHLCAM-VI in Example 1 of the application.

[0026] Figure 4 is the transmission electron microscope picture ( Figure 4 a) and the atomic force microscope picture ( Figure 4 b) of the high-density one-dimensional wire thin film for salt differential power generation prepared in Example 1 of the application.

[0027] Figure 5The ion conductivity of the high-density one-dimensional wire thin film for salinity power generation prepared in Example 1 of the present application in different concentrations of electrolyte solution.

[0028] Figure 6 The permeability curve of the high-density one-dimensional wire thin film for salinity power generation in Example 1 of the present application for cationic fluorescent dye rhodamine 6G and anionic fluorescent dye sodium fluorescein.

[0029] Figure 7 The schematic diagram of the salinity power conversion device of the high-density one-dimensional wire thin film for salinity power generation in Example 1 of the present application.

[0030] Figure 8 The change of the output power density measured under different concentration gradients in Example 1 of the present application.

[0031] Figure 9 The change of the output power density of the high-density one-dimensional wire thin film for salinity power generation prepared in Example 1 of the present application for 10 days.

[0032] Figure 10 The change of the output power density of the high-density one-dimensional wire thin film for salinity power generation prepared in Example 1 of the present application after experiencing ten times of reconstruction.

[0033] Figure 11 The antibacterial performance of the high-density one-dimensional wire prepared in Example 1 of the present application. DETAILED DESCRIPTION

[0034] Example 1

[0035] The preparation method of the high-density one-dimensional wire thin film for salinity power generation in the present example, which is as follows:

[0036] S1, 15.8 g (0.1 mol) of tetrahydro linalool and 9.0 g (0.12 mol) of chloroacetonitrile were mixed to obtain a mixture of tetrahydro linalool and chloroacetonitrile, then 11.76 g (0.12 mol) of 1.84 g / mL concentrated sulfuric acid was added dropwise under stirring at a temperature of 0-5°C, and the addition was stopped when the mass fraction of the mixture of tetrahydro linalool and chloroacetonitrile in the system was 80%, the ice bath was removed, and the reaction was carried out at a temperature of 40°C for 12 h; 9.6 g of sodium hydroxide was dissolved in 200 mL of deionized water to obtain a sodium hydroxide aqueous solution, which was then added dropwise to the reaction system under vigorous stirring; the obtained crude product was dissolved in 100 mL of dichloromethane (DCM), washed with saturated sodium chloride solution for 3 times, dried with anhydrous magnesium sulfate, and then the organic layer was concentrated and vacuum dried at room temperature for 24 h to obtain substance A, which was named as THLCAM;

[0037] S2, 11.7 g (0.05 mol) THLCAM obtained in S1 and 7.05 g (0.075 mol) 1-vinylimidazole were added to a 250 mL round bottom flask containing 50 mL N,N-dimethylformamide (DMF) and the quaternary ammonium reaction was carried out at a temperature of 80°C for 12 h to obtain a reaction mixture, then 150 mL methyl tert-butyl ether was added to the reaction mixture while stirring vigorously, the precipitated material was washed twice and dried under vacuum at room temperature for 24 h to obtain material B, named THLCAM-VI;

[0038] S3, 40 mg (0.25 mol) azobisisobutyronitrile (AIBN) and 16.4 g (0.05 mol) THLCAM-VI obtained in S2 were dissolved in 100 mL DMF, nitrogen was bubbled for 30 min to remove dissolved oxygen, then the reaction was carried out at a temperature of 65°C in an oil bath for 24 h, after the completion of the radical polymerization, evaporation was carried out at a temperature of 80°C, then methyl tert-butyl ether (MTBE) was added, the precipitated material was washed twice and dried under vacuum at room temperature for 24 h to obtain material C, named PTHLCAM-VI;

[0039] S4, PTHLCAM-VI obtained in S3 was dissolved in ethanol to obtain an ethanol solution of PTHLCAM-VI with a concentration of 100 mg / mL;

[0040] S5, 2 mL of the ethanol solution of PTHLCAM-VI obtained in S4 was spread on a mold made of polytetrafluoroethylene, and the solvent was removed by evaporation at a temperature of 45°C to obtain a high-density one-dimensional wire film for salt differential power generation.

[0041] From the perspective of molecular design, hydrophilic ionic segments and hydrophobic carbon chains can be introduced into the side groups of the same repeating unit of a homopolymer, and due to microphase separation, they can self-assemble to form nanostructures. The cable-type ion channels formed by the self-assembly of such short-chain molecules with hydrophilic segments as the core and hydrophobic segments as the shell will have higher channel density and smaller size, and can be regarded as ion wires. For ion transmission, high-density channels will have higher flux, and at the same time, due to the introduction of a large number of ionic groups, they will have higher selectivity to the channels.

[0042] This embodiment introduces hydrophilic ionic chains and hydrophobic carbon chains into the repeating units of a homopolymer through molecular design. Due to microphase separation, they can self-assemble to form high-density ion channels with hydrophilic segments as the core, hydrophobic segments as the shell, a size of less than 5 nm, and a density of up to 9.7 x 10 11 cm -2 .

[0043] Figure 1is the synthetic procedure of PTHLCAM-VI and the real optical picture of the one-dimensional wire thin film. It can be seen from the picture that the surface of the one-dimensional wire thin film is smooth and the underlying substrate can be seen through the thin film, which indicates that the thin film is very thin with a thickness of 96.2 μm.

[0044] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of THLCAM, which indicates the successful synthesis of THLCAM.

[0045] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of PTHLCAM-VI, which indicates the successful preparation of PTHLCAM-VI.

[0046] Figure 4 is the transmission electron microscope picture of the high-density one-dimensional wire thin film prepared in this example for salt difference power generation Figure 4 a) and the atomic force microscope picture Figure 4 b), from which it can be seen that the thin film has high-density pores, and the pore density is calculated to be 9.7 x 10 11 cm -2 .

[0047] Figure 5 is the ion conductivity of the high-density one-dimensional wire thin film prepared in this example for salt difference power generation in different concentrations of electrolyte solution. Equal volumes of salt solutions with the same concentration are added to both sides of the film, and the external circuit is linked by the self-made silver chloride electrode, and the I-V curve under different concentrations is obtained by the picoammeter, the conductivity value under different concentrations is calculated and compared, and it can be seen from the picture that the ion transport of the thin film is regulated by the surface charge of the ion channel (the red line is the actual test linear relationship, and the blue line is the bulk conductivity linear relationship).

[0048] Figure 6 The permeability curves of the cationic fluorescent dye rhodamine 6G and the anionic fluorescent dye sodium fluorescein through the thin film are shown. Equal volumes of fluorescent dyes (feed) and ultrapure water (permeate) are added to both sides of the film, and the permeate is sequentially taken according to the difference time and placed into the fluorescence spectrophotometer to test the intensity, which is converted into concentration to obtain the correlation curve of time and concentration. By comparing the penetration of cationic and anionic fluorescent dyes, it can be concluded that the thin film has good anion selectivity.

[0049] The schematic diagram of the salt difference energy conversion device of the thin film is shown in Figure 7 , the concentrated salt solution is the Yellow Sea seawater (Qingdao sea area), and the dilute salt solution is the city tap water (Qingdao). Specifically, the salt difference energy conversion device is composed of a pair of electrolytic cells, rubber O-rings and a polyimide sheet with holes. The thin film is placed between the polyimide sheet with holes and pressed tightly by the O-rings. The self-made silver / silver chloride electrodes are installed on both sides of the electrolytic cell and connected by a wire to a resistance meter picoammeter.

[0050] Figure 8 The output power density changes under different external resistance are recorded. Specifically, during the complete salinity gradient energy conversion device test, the output power density of the thin film is obtained by adjusting the resistance value of the resistor connected to the circuit. When the concentration gradient is 50 to 500 times, the output power density is calculated to be 17.0-40.5 W / m 2 .

[0051] Figure 9 The output power density changes of the thin film for 10 days are recorded, which shows that the one-dimensional wire thin film can maintain stable output. Specifically, the output power density of the same thin film sample is measured for consecutive days, and the corresponding linear relationship is obtained. The small fluctuation of the output power density within 10 days shows the stability of the thin film.

[0052] Figure 10 The output power density changes of the thin film for ten times of reconstruction are recorded, which shows that the high-density one-dimensional wire thin film prepared in this embodiment for salinity power generation has excellent recyclable performance. Specifically, the output power density of the thin film prepared by using the same thin film sample for consecutive cycles is measured, and the corresponding linear relationship is obtained. The small fluctuation of the output power density of the thin film for ten times of reconstruction shows the cycle stability of the thin film.

[0053] Figure 11 The antibacterial performance of the high-density one-dimensional ion wire. In order to test the antibacterial performance, the ground thin film is added to the E. coli culture medium. The polymer concentration is divided into four groups, which are 1 mg / mL, 2 mg / mL, 3 mg / mL and 4 mg / mL. The experimental group and the blank control group are added with the same amount of active E. coli solution. After 8 hours of culture, the same amount of bacteria solution of each group is transferred to the solid culture medium. After another 8 hours of continuous culture, the bacterial growth is observed. As Figure 11 shown, the comparison group shows a large number of bacteria. In contrast, when cultured with 1 mg / mL one-dimensional ion wire, the number of bacteria in the laboratory group is significantly reduced. Notably, at concentrations of 2 mg / mL, 3 mg / mL and 4 mg / mL, no obvious bacteria are detected. This excellent antibacterial effect is due to the inherent bactericidal properties of the imidazole salt group, which also enhances the hydrophilicity, thereby facilitating the contact and elimination of bacteria. Scanning electron microscopy observation shows that the morphology of the bacteria treated by adding the polymer is shriveled and deformed, and the morphology of the bacteria in the blank group is full, proving the inhibitory effect of the polymer on bacteria.

[0054] The high-density one-dimensional wire thin film prepared for salinity power generation in the present application is used to prevent bacterial contamination when converting salinity energy at the intersection of the ocean and the river.

[0055] The above merely describes preferred embodiments of the present application, and is not intended to limit the present application. Any simple modification, change and equivalent variation of the above embodiments according to the technical essence of the present application are still within the protection scope of the technical scheme of the present application.

Claims

1. A method for preparing a high-density one-dimensional conductor film for salinity difference power generation, characterized in that: The method is: S1. After tetrahydrolinalool and chloroacetonitrile are mixed to obtain a mixture of tetrahydrolinalool and chloroacetonitrile, concentrated sulfuric acid is added dropwise while stirring in an ice bath at a temperature of 0°C to 5°C, and diluted until the mass fraction of the mixture of tetrahydrolinalool and chloroacetonitrile in the system is 80%. The ice bath is removed, and the mixture is reacted at a temperature of 40°C for 12 hours. Then, an aqueous sodium hydroxide solution is added dropwise to the reaction system while stirring. The crude product is dissolved in dichloromethane, washed three times with a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. The organic layer is then concentrated and dried in vacuo at room temperature for 24 hours to obtain substance A, named THLCAM. S2. Add THLCAM and 1-vinylimidazole obtained in S1 to N,N-dimethylformamide, carry out quaternization reaction at 80° C. for 12 h to obtain a reaction mixture, then add methyl tert-butyl ether to the reaction mixture while stirring, wash the precipitate twice, and vacuum dry at room temperature for 24 h to obtain substance B, named THLCAM-VI; S3. Azobisisobutyronitrile and THLCAM-VI obtained in S2 were dissolved in N,N-dimethylformamide, nitrogen was introduced for 30 min, and then the mixture was reacted in an oil bath at 65°C for 24 h. After evaporation at 80°C, methyl tert-butyl ether was added. The precipitate was washed twice and dried in vacuo at room temperature for 24 h to obtain substance C, which was named PTHLCAM-VI. S4, dissolving the PTHLCAM-VI obtained in S3 in ethanol to obtain an ethanol solution of PTHLCAM-VI; S5. Spread the ethanol solution of PTHLCAM-VI obtained in S4 on a mold and evaporate it at a temperature of 45° C. to obtain a high-density one-dimensional conductor film for salt-difference power generation.

2. The method for preparing a high-density one-dimensional conductor film for salinity difference power generation according to claim 1, characterized in that: The concentration of the concentrated sulfuric acid in S1 is 1.84 g / mL; the usage ratio of sodium hydroxide to deionized water in the sodium hydroxide aqueous solution is 9.6 g:200 mL.

3. The method for preparing a high-density one-dimensional conductor film for salinity difference power generation according to claim 1, characterized in that: The usage ratio of tetrahydrolinalool and chloroacetonitrile in S1 is 15.8 g:9.0 g.

4. The method for preparing a high-density one-dimensional conductor film for salinity difference power generation according to claim 1, characterized in that: The usage ratio of THLCAM and 1-vinylimidazole in S2 is 11.7 g:7.05 g.

5. The method for preparing a high-density one-dimensional conductor film for salinity difference power generation according to claim 1, characterized in that: The usage ratio of azobisisobutyronitrile and THLCAM-VI in S3 is 40 mg:16.4 g.

6. The method for preparing a high-density one-dimensional conductor film for salinity difference power generation according to claim 1, characterized in that: The concentration of the PTHLCAM-VI ethanol solution in S5 is 100 mg / mL.

7. The method for preparing a high-density one-dimensional conductor film for salinity difference power generation according to claim 1, characterized in that: The energy density of the high-density one-dimensional conductor film for salt-difference power generation described in S5 is 17.0W / m 2 ~40.5W / m 2 .

8. An application of a high-density one-dimensional conductor film prepared by the preparation method according to any one of claims 1 to 7 for salt difference power generation, characterized in that: The high-density one-dimensional conductor film for salinity difference power generation is used to prevent bacterial colony contamination during salinity difference energy conversion at the confluence of oceans and rivers.

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