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

Abstract

The invention provides a preparation method of a high-density one-dimensional wire film for salinity gradient power generation. The method comprises the following steps: synthesizing PTHLCAM-VI, preparing PTHLCAM-VI into a solution, uniformly paving the prepared solution on a mold, and evaporating to remove a solvent, thereby obtaining the high-density one-dimensional wire film for salinity gradient power generation. The invention further provides application. The film can prevent bacterial colony pollution during salinity difference energy conversion at the junction of the ocean and the river. The preparation method of the high-density one-dimensional wire thin film for salinity gradient power generation is simple and easy to control, and the obtained composite film has high ion transmission quantity and can realize high and stable output when being applied to salinity gradient energy collection. The energy density of the one-dimensional lead film provided by the invention can reach 17.0-40.5 W / m < 2 >, which is far higher than that of a commercial ion exchange membrane under the same condition.

Description

Technical Field

[0001] The invention belongs to the technical field of conductor films, and in particular relates to a preparation method and application of a high-density one-dimensional conductor film for salt difference power generation. Background Art

[0002] Salt difference energy is a renewable energy source with huge energy. Its efficient capture depends on ion selective membrane, a key component in reverse electrodialysis technology. At present, the selectivity mechanism of ions mainly depends on electrostatic interactions. Generally, the charged groups in the membrane channels repel and attract counterions through electrostatic interactions to achieve selective anion-cation transport. However, it is still a challenge to achieve high selectivity and high flux ion transport based on membranes at the same time.

[0003] Polymer-based ion transport membranes have attracted much attention due to their excellent comprehensive performance. The inner surface of nanochannels constructed based on polymer membranes can expose active chemical groups under specific conditions, making it easy to achieve further functionalization. Track etching technology based on polymer substrates has the advantages of clear size and geometry, and can be used to prepare artificial nanochannels. Polymer porous membranes can be prepared based on non-solvent-induced phase separation, which is simple and low-cost. Highly ordered and controllable nanochannels can be constructed based on block copolymer self-assembly, but the microphase separation between different polymer segments results in insufficient size and density, which limits the improvement of ion transport performance.

[0004] Therefore, improving the ion transmission flux and selectivity by designing the polymer molecular structure and preparing a self-supporting porous film material with small size and high pore density are the key to achieving effective utilization of salt difference energy. Summary of the invention

[0005] The technical problem to be solved by the present invention is to provide a method for preparing a high-density one-dimensional conductor film for salt difference power generation and its application in view of the shortcomings of the above-mentioned prior art. The preparation method of the high-density one-dimensional conductor film for salt difference power generation prepared by the present invention is simple and easy to control. The obtained composite membrane has high ion transmission flux and selectivity, and can achieve high and stable output when used for collecting salt difference energy. The energy density of the one-dimensional conductor film provided by the present invention can reach 17.0-40.5W / m 2 , far exceeding the commercial ion exchange membrane under the same conditions.

[0006] In order to solve the above technical problems, the technical solution adopted by the present invention is: a method for preparing a high-density one-dimensional conductor film for salt difference power generation, the method comprising:

[0007] S1. After tetrahydrolinalool and chloroacetonitrile are mixed to obtain a mixture of tetrahydrolinalool and chloroacetonitrile, concentrated sulfuric acid is added dropwise while stirring under an ice bath at a temperature of 0° 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 for 12 h under a temperature of 40° C., and then an aqueous sodium hydroxide solution is added dropwise to the reaction system while stirring, and the obtained crude product is dissolved in dichloromethane (DCM), washed with a saturated sodium chloride solution for 3 times, and dried over anhydrous magnesium sulfate, and then the organic layer is concentrated and dried in vacuo at room temperature for 24 h to obtain substance A, named THLCAM;

[0008] The ice bath condition of this embodiment can also be 5°C;

[0009] S2, adding THLCAM and 1-vinylimidazole obtained in S1 to N,N-dimethylformamide, carrying out quaternization reaction at 80° C. for 12 h to obtain a reaction mixture, then adding methyl tert-butyl ether (MTBE) to the reaction mixture while stirring, washing the precipitate twice, and vacuum drying at room temperature for 24 h to obtain substance B, named THLCAM-VI;

[0010] S3, dissolving azobisisobutyronitrile (AIBN) and THLCAM-VI obtained in S2 in DMF, introducing nitrogen for 30 min, and then reacting in an oil bath at 65°C for 24 h. After evaporation at 80°C, adding methyl tert-butyl ether (MTBE), washing the precipitate twice, and vacuum drying at room temperature for 24 h to obtain substance C, named PTHLCAM-VI;

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

[0012] S5. Spread the ethanol solution of PTHLCAM-VI obtained in S4 on a mold, evaporate it at a temperature of 45° C., and obtain a high-density one-dimensional conductor film for salt difference power generation.

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

[0014] Preferably, the usage ratio of tetrahydrolinalool and chloroacetonitrile in S1 is 15.8 g:9.0 g.

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

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

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

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

[0019] The present invention also provides an application of a high-density one-dimensional conductor film for salinity difference power generation prepared by the above-mentioned preparation method, wherein the high-density one-dimensional conductor film for salinity difference power generation is used to prevent bacterial colony contamination during salinity difference energy conversion in marine and / or river environments.

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

[0021] The high-density one-dimensional conductor film for salt difference power generation prepared by the present invention is simple to prepare and easy to control. The obtained composite film has a high ion transmission capacity and can achieve high and stable output when used to collect salt difference energy. The energy density of the one-dimensional conductor film provided by the present invention can reach 17.0-40.5W / m 2 , far exceeding the commercial ion exchange membrane under the same conditions.

[0022] The present invention is further described in detail below with reference to the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1 This is a real optical picture of the synthesis method of PTHLCAM-VI in Example 1 of the present invention and the prepared high-density one-dimensional conductor film for salt difference power generation.

[0024] Figure 2 This is the H NMR spectrum of THLCAM in Example 1 of the present invention.

[0025] Figure 3 This is the H NMR spectrum of PTHLCAM-VI in Example 1 of the present invention.

[0026] Figure 4 Transmission electron microscope image of a high-density one-dimensional conductor film for salt difference power generation prepared in Example 1 of the present invention ( Figure 4 a) and atomic force microscopy images ( Figure 4 b).

[0027] Figure 5The ionic conductivity of the high-density one-dimensional conductor film for salt difference power generation prepared in Example 1 of the present invention in electrolyte solutions of different concentrations.

[0028] Figure 6 The transmittance curves of the cationic fluorescent dye Rhodamine 6G and the anionic fluorescent dye sodium fluorescein in Example 1 of the present invention through the high-density one-dimensional conductor film for salt difference power generation.

[0029] Figure 7 Schematic diagram of a salt difference energy conversion device of a high-density one-dimensional conductor film for salt difference power generation in Example 1 of the present invention.

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

[0031] Fig. 9 The output power density change of the high-density one-dimensional conductor film for salt difference power generation prepared in Example 1 of the present invention over a period of 10 days.

[0032] Fig.10 The output power density change of the high-density one-dimensional conductor film for salt difference power generation prepared in Example 1 of the present invention after ten reconstructions.

[0033] Fig.11 The antibacterial properties of the high-density one-dimensional wire prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0034] Example 1

[0035] The method for preparing a high-density one-dimensional conductor film for salt difference power generation in this embodiment is as follows:

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

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

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

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

[0040] S5. Spread 2 mL of the ethanol solution of PTHLCAM-VI obtained in S4 on a mold made of polytetrafluoroethylene, evaporate at a temperature of 45° C. to remove the solvent, and obtain a high-density one-dimensional conductor film for salt difference 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 the homopolymer, and due to microphase separation, they can self-assemble to form nanostructures. This short-chain molecule, with the hydrophilic segment as the core and the hydrophobic segment as the shell, self-assembles to form a cable-type ion channel with a higher channel density and a smaller size, and can be regarded as an ion conductor. For ion transport, high-density channels will have higher fluxes, and at the same time, due to the introduction of a large number of ionic groups, the channels will have higher selectivity.

[0042] In this embodiment, hydrophilic ionic chains and hydrophobic carbon chains are introduced into the homopolymer repeating unit through molecular design. Due to microphase separation, it can self-assemble with hydrophilic segments as core and hydrophobic segments as shell, with a size of less than 5nm and a density of up to 9.7×10 11 cm -2 High density of ion channels.

[0043] Figure 1The following are the steps of synthesizing PTHLCAM-VI and the actual optical picture of preparing the one-dimensional wire film. From the picture, we can see that the surface of the one-dimensional wire film is smooth, and the underlying substrate can be vaguely seen through the film, indicating that it is extremely thin, with a thickness of 96.2μm.

[0044] Figure 2 This is the H NMR spectrum of THLCAM, indicating the successful synthesis of THLCAM.

[0045] Figure 3 This is the H NMR spectrum of PTHLCAM-VI, indicating the successful preparation of PTHLCAM-VI.

[0046] Figure 4 This is a transmission electron microscope image of a high-density one-dimensional wire film for salt difference power generation prepared in this example ( Figure 4 a) and atomic force microscopy images ( Figure 4 b), the figure shows the high density of pores in the film. The pore density is calculated to be 9.7×10 11 cm -2 .

[0047] Figure 5 The ionic conductivity of the high-density one-dimensional wire film for salt difference power generation prepared in this embodiment in electrolyte solutions of different concentrations. An equal volume of salt solution of the same concentration was added to both sides of the membrane and connected to an external circuit through a homemade silver chloride electrode. The IV curves under different concentration environments were obtained using a picoammeter, and the conductivity values ​​under different concentration conditions were calculated and compared. It can be seen from the figure that the ion transport of the film is regulated by the surface charge of the ion channel (the red line is the linear relationship of the actual test, and the blue line is the linear relationship of the bulk conductivity).

[0048] Figure 6 The permeability curves of the cationic fluorescent dye Rhodamine 6G and the anionic fluorescent dye sodium fluorescein through the film are shown. Equal volumes of fluorescent dye (feed test) and ultrapure water (permeation test) are added to both sides of the membrane, and the permeation test is carried out in sequence at equal intervals. The intensity is tested by the fluorescence spectrophotometer and converted into concentration to obtain the correlation curve between time and concentration. By comparing the permeation of cationic and anionic fluorescent dyes, it can be concluded that the film has good anion selectivity.

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

[0050] Figure 8 The output power density changes under different external resistances were recorded. Specifically, when testing the complete salt difference energy conversion device, the variable resistor connected to the circuit was adjusted to adjust the resistance value, thereby obtaining the output power density of the film. When the concentration gradient was between 50 and 500 times, the calculated output power density reached 17.0 to 40.5 W / m 2 .

[0051] Fig. 9 The output power density of the film was recorded over a period of 10 days, indicating that the one-dimensional conductor film can maintain a stable output. Specifically, the output power density was measured on consecutive days using the same film sample and a corresponding linear relationship was obtained. The small fluctuation in the output power density over a period of 10 days indicates the stability of the film.

[0052] Fig.10 The output power density changes of the film after ten reconstructions were recorded, indicating that the high-density one-dimensional conductor film for salt difference power generation prepared in this embodiment has excellent recyclability. Specifically, the output power density of the film obtained by continuous recycling using the same film sample was obtained and the corresponding linear relationship was obtained. The small fluctuation of the output power density of the film after ten consecutive reconstructions indicates the cyclic stability of the film.

[0053] Fig.11 The antibacterial properties of high-density one-dimensional ion lines. In order to test the antibacterial properties, the ground film was added to the E. coli culture medium. The polymer concentration was divided into four groups, namely 1mg / mL, 2mg / mL, 3mg / mL and 4mg / mL. The experimental group and the blank control group were added with equal amounts of active E. coli solution. After 8 hours of culture, equal amounts of bacterial solution in each group were transferred to the solid culture medium. After another 8 hours of continuous culture, the bacterial growth was observed. Fig.11 As shown, the control group showed a large number of bacteria. In contrast, when cultured with 1 mg / mL one-dimensional ion line, the number of bacteria in the laboratory group was significantly reduced. It is worth noting that no obvious bacteria were detected at concentrations of 2 mg / mL, 3 mg / mL and 4 mg / mL. This excellent antibacterial effect is attributed to the inherent bactericidal properties of the imidazole salt base, which also enhances the hydrophilicity, thereby facilitating the contact and elimination of bacteria. Scanning electron microscopy observations showed that the morphology of the bacteria treated with the polymer was shriveled and deformed, while the bacteria in the blank group were plump, proving the inhibitory effect of the polymer on bacteria.

[0054] The high-density one-dimensional conductor film for salt difference power generation prepared by the present invention is used to prevent bacterial colony contamination during salt difference energy conversion at the junction of the ocean and the river.

[0055] The above are only the preferred embodiments of the present invention and do not impose any limitations on the present invention. Any simple modifications, changes, and equivalent variations made to the above embodiments based on the technical essence of the invention still fall within the protection scope of the technical solution of the present invention.

Claims

1. A method for preparing a high-density one-dimensional conductor film for salt 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 under an ice bath at a temperature of 0°C to 5°C to dilute the mixture until the mass fraction of the tetrahydrolinalool and chloroacetonitrile in the system is 80%, the ice bath is removed, the mixture is reacted at a temperature of 40°C for 12 hours, and then an aqueous sodium hydroxide solution is added dropwise to the reaction system while stirring, the obtained crude product is dissolved in dichloromethane, washed with a saturated sodium chloride solution for 3 times, and dried over anhydrous magnesium sulfate, and then the organic layer is concentrated and dried in vacuo at room temperature for 24 hours to obtain substance A, named THLCAM; S2, adding THLCAM and 1-vinylimidazole obtained in S1 to N,N-dimethylformamide, carrying out quaternization reaction at 80° C. for 12 h to obtain a reaction mixture, then adding methyl tert-butyl ether to the reaction mixture while stirring, washing the precipitate twice, and vacuum drying at room temperature for 24 h to obtain substance B, named THLCAM-VI; S3, dissolving azobisisobutyronitrile and THLCAM-VI obtained in S2 in DMF, introducing nitrogen for 30 min, and then reacting in an oil bath at 65° C. for 24 h. After evaporation at 80° C., adding methyl tert-butyl ether, washing the precipitate twice, and vacuum drying at room temperature for 24 h to obtain substance C, 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, evaporate it at a temperature of 45° C., and 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 salt 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 dosage 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 salt 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 salt 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 salt 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 salt 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 salt 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 salt difference power generation can be used to prevent bacterial colony contamination during salt difference energy conversion at the confluence of oceans and rivers.

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