Preparation of chiral polymer anion membrane and its application in hydrogen production by electrolysis of water

Abstract

The application discloses preparation of a chiral polymer anion membrane and application of the chiral polymer anion membrane in hydrogen production by electrolysis of water, and belongs to the field of high polymer functional materials. A polymer main chain is obtained through Friedel-Crafts hydroxyalkylation reaction catalyzed by super acid, a monomer with axial chiral structure is copolymerized with an achiral monomer, and a chiral helical structure is induced in the whole polymer molecular chain by means of a non-linear amplification effect of a chiral molecule, and then a microporous structure capable of efficiently transporting OH ‑ / H2O is constructed. On this basis, the polymer main chain is subjected to quaternary ammonium reaction, and a chiral polymer ionic membrane is obtained. The chiral polymer anion membrane prepared in the application has the advantages of good dimensional stability and excellent ion conduction capacity, and can be applied in the fields of fuel cells, hydrogen production by electrolysis of water, flow batteries, carbon dioxide reduction, acid separation, alkali separation and the like.

Description

Technical Field

[0001] This invention belongs to the field of functional polymer materials, specifically relating to the preparation of a chiral polymer anion exchange membrane and its application in hydrogen production by water electrolysis. Background Technology

[0002] Currently, the interconversion of chemical energy and electrical energy mainly relies on electrochemical reaction systems, with anion exchange membranes being the core component ensuring efficient reaction processes. However, commercially available anion exchange membranes currently suffer from numerous technical shortcomings, including cumbersome synthesis processes, high costs of reactant monomers, low ionic conductivity, insufficient stability of cationic groups, and poor membrane dimensional stability. These deficiencies severely restrict their electrochemical application efficiency and industrialization progress.

[0003] Conventional polymer anion exchange membranes lack an ordered induction mechanism in their molecular structure design. Their polymer molecular chains are mostly arranged randomly or linearly, and the resulting microporous channels mainly rely on the random stacking and free volume distribution between chain segments. This disordered molecular chain arrangement leads to discontinuous pore structures, tortuous, broken, or even mutually isolated transport paths, severely hindering the absorption of OH-. - While H2O can be transported continuously and efficiently within the membrane, it is difficult to balance high ionic conductivity with long-term operational stability, and overall, it still cannot meet the application requirements for industrialization and green development. Summary of the Invention

[0004] To address the problems existing in the prior art, this invention provides a method for preparing a chiral polymer anion exchange membrane and its application in water electrolysis for hydrogen production. The chiral polymer of this invention possesses a regular helical molecular chain structure, which is beneficial for further improving the OH content of the material. - / H2O transport capacity. This type of polymer membrane has the advantages of simple preparation method, good controllability, and easy large-area preparation, and can be used in many fields.

[0005] The present invention discloses a process for preparing a chiral polymer anion exchange membrane, wherein a chiral monomer and a non-chiral monomer are copolymerized by a superacid-catalyzed Friedel-Crafts hydroxyalkylation reaction, and the nonlinear amplification effect of chiral molecules is used to form a chiral helical structure in the polymer backbone to obtain polymer backbone A; then anion exchange groups are introduced into polymer backbone A by the Mensøe-Gold reaction to obtain quaternized polymer B; finally, the quaternized polymer B is prepared into a membrane solution, and a membrane is formed by casting to obtain a chiral polymer anion exchange membrane.

[0006] Specifically, the steps include the following:

[0007] Step 1: Thoroughly mix the chiral monomer Ar1 and the achiral monomer Ar2 in a solvent to obtain a mixture;

[0008] Step 2: Mix the mixed solution obtained in Step 1 with monomer T in a certain proportion until homogeneous;

[0009] Step 3: Trifluoroacetic acid and trifluoromethanesulfonic acid are introduced into the mixture obtained in Step 2, and polymer backbone A is obtained through superacid catalysis.

[0010] Step 4: Add the system obtained in Step 3 to the alkaline solution to quench the reaction, wash and dry the resulting solid to obtain a pure polymer solid, and dissolve it in a solvent to obtain a solution;

[0011] Step 5: The solution obtained in Step 4 is reacted with 1-haloalkane via the Mensoukin reaction to obtain a solution of quaternized polymer B;

[0012] Step 6: Precipitate the quaternized polymer B obtained in Step 5 and dry it, then dissolve it in a solvent to obtain a membrane solution;

[0013] Step 7: The membrane solution obtained in Step 6 is cast into a film by casting, the solvent is dried, and then the film is immersed in deionized water to obtain a chiral polymer ion membrane.

[0014] The chiral monomer Ar1 is selected from one of the monomers shown in the following structures:

[0015] .

[0016] Furthermore, the chiral monomer Ar1 is preferably (R)-2,2'-dimethoxy-1,1'-binaphthyl or (S)-2,2'-dimethoxy-1,1'-binaphthyl or 2,2'-dimethoxy-1,1'-binaphthyl.

[0017] The achiral monomer Ar2 is selected from one of the monomers with the following structures:

[0018] .

[0019] Furthermore, the achiral monomer Ar2 is preferably p-terphenyl or m-terphenyl.

[0020] The monomer T is selected from one of the monomers with the following structures:

[0021] .

[0022] Furthermore, the monomer T is preferably N-methyl-4-piperidinone.

[0023] further:

[0024] In step 1, the molar ratio of the chiral monomer Ar1 to the achiral monomer Ar2 is 1:19 to 2:8.

[0025] In step 1, the solvent is dichloromethane. The volume ratio of the solvent to the total mass of the chiral and achiral monomers is from 1 mL:1 g to 10 mL:1 g.

[0026] In step 2, the ratio of the molar amount of monomer T to the total molar amount of chiral and achiral monomers is 1.05:1 to 1.25:1.

[0027] In step 3, the molar ratio of trifluoromethanesulfonic acid to monomer T is 6:1 to 12:1; the molar ratio of trifluoroacetic acid to trifluoromethanesulfonic acid is 1:8 to 1:14. The superacid-catalyzed reaction temperature is -10℃ to 5℃, and the reaction time is 3-8 h.

[0028] In step 4, the alkaline solution is a 1-5 mol / L NaOH solution, the washing solution is a 1-5 mol / L NaOH solution, and the drying conditions are 30-100℃. After the polymer solid dissolves in the solvent, the concentration of the resulting solution is 0.05-0.2 g / mL.

[0029] In step 5, the alkane chain of the 1-haloalkane contains 1 to 12 carbon atoms, preferably iodomethane, and the molar ratio of the polymer solid to the 1-haloalkane is 1:1-1.2, preferably 1:1.2. The reaction temperature is 25-50℃, preferably 40℃.

[0030] In step 6, the reagent used for precipitation is ethyl acetate, and the drying conditions are 60-100℃. The concentration of the membrane solution is 0.05-0.2 g / mL.

[0031] In step 7, the film formation by casting specifically involves coating the film solution from step 6 onto a glass plate and drying it at 50-90°C.

[0032] The thickness of the chiral polymer anion exchange membrane prepared by this invention is 15 to 60 µm.

[0033] In this invention, the reaction route of polymer backbone A is shown below:

[0034] .

[0035] In this invention, the reaction route of the chiral polymer ion membrane is shown below:

[0036] .

[0037] Where n is an integer from 0 to 11, and R is I or Br.

[0038] The present invention relates to the application of chiral polymer anion exchange membranes in hydrogen production via water electrolysis.

[0039] The chiral polymer anion exchange membrane described above was assembled in a water electrolysis device to test its water electrolysis performance at 30-90℃. The results showed that the current density could reach 1.70-8.10 A cm⁻¹ under alkaline conditions with a reference voltage of 2 V. -2 .

[0040] The principle of this invention is as follows: By utilizing the nonlinear amplification effect of chiral molecules during polymerization, only a small number of chiral molecules are introduced to induce a uniform chiral helical configuration throughout the polymer molecular chain. This helical structure can effectively drive the formation of a stable, self-contained microporous framework within the polymer, thereby constructing a polymer for H2O / OH... - A high-efficiency transmission channel.

[0041] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0042] 1. The raw materials of the present invention are readily available, the monomers are highly selectable, and the process is simple. It only takes two steps to synthesize anion exchange membranes, which is easy to scale up for production, has high stability, and is conducive to promotion.

[0043] 2. This invention introduces chiral molecules through superacid-catalyzed copolymerization. Utilizing the nonlinear amplification effect of chiral molecules, the entire molecular chain is guided to possess a chiral helical structure, promoting the construction of micropores between molecular chains. This solves the problem that, due to the lack of an ordered induction mechanism in general polymer anion exchange membranes, the molecular chains are randomly or linearly arranged, and the micropore channels rely on random stacking and free volume distribution of chain segments, resulting in discontinuous channels, tortuous and broken transport paths, and severely hindering OH- transport. - The problem of continuous and efficient H2O transport has been addressed, demonstrating high performance in the field of hydrogen production through water electrolysis.

[0044] 3. The chiral polymer anion exchange membrane of the present invention can be formed using common industrial methods such as coating. The polymer membrane prepared has advantages such as large size, high mechanical strength, good stability and excellent ion conduction performance, and can be applied in fuel cells, water electrolysis for hydrogen production, carbon dioxide reduction, acid separation, alkali separation and other fields. Attached Figure Description

[0045] Figure 1 This is a digital photograph of the chiral polymer anion exchange membrane in Example 3.

[0046] Figure 2 This is a scanning electron microscope (SEM) image of the surface morphology of the chiral polymer anion exchange membrane in Example 3. From... Figure 2 As can be seen, the membrane surface is dense, the structure is complete and there are no obvious defects, indicating that it has good gas barrier properties.

[0047] Figure 3 This is a cross-sectional scanning electron microscope (SEM) image of the chiral polymer anion exchange membrane from Example 3. From... Figure 3As can be seen from the data, the membrane cross-section structure is dense, continuous, and free from defects such as delamination or pores, indicating that it has good gas barrier properties.

[0048] Figure 4 This is the 1H NMR spectrum of the chiral polymer anion exchange membrane from Example 3. From... Figure 4 As can be seen, the target chiral polymer was successfully prepared.

[0049] Figure 5 These are the circular dichroism spectra of the chiral polymer anion exchange membranes from Examples 3, 6, and 9. From... Figure 5 As can be seen, introducing chiral molecules with different optical rotations can give the polymers different optical rotations.

[0050] Figure 6 These are the carbon dioxide adsorption-desorption curves (a) and pore size distribution curves (b) of the chiral polymer anion exchange membranes from Examples 1, 2, and 3. From... Figure 6 As can be seen, the CO2 adsorption capacity of the polymer ion membrane increases with the increase of the proportion of chiral molecule copolymerization.

[0051] Figure 7 The figures show the swelling ratio (a), water absorption rate (b), and ionic conductivity (c) of the chiral polymer anion exchange membranes in Examples 1, 2, and 3 under pure water conditions. Figure 7 It can be seen that increasing the proportion of chiral molecules copolymerization is beneficial to enhancing the ion transport capacity of the membrane.

[0052] Figure 8 These are the voltage-current polarization curves of the chiral polymer anion exchange membrane in Example 3 under alkaline conditions of 30-90 °C and 1 M KOH. Figure 8 As can be seen, the current density of the chiral polymer ion exchange membrane increases continuously with the increase of the operating temperature, while the required electrolysis voltage is relatively low at the same current density, which confirms that the membrane has both high electrolysis efficiency and low energy consumption characteristics.

[0053] Figure 9 It is 0.5 A cm -2 Long-term stability graph of the chiral polymer anion exchange membrane in Example 3 under the conditions of 1 M KOH and 60 °C. From... Figure 9 As can be seen, the chiral polymer ion membrane exhibits excellent stability in long-term battery testing, with a degradation rate of only 77 μV h. -1 . Detailed Implementation

[0054] Unless otherwise defined, the technical terms used in the following embodiments have the same meanings as commonly understood by those skilled in the art. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0055] The present invention will be further described below with reference to specific embodiments, but the scope of protection of the present invention is not limited to the following embodiments.

[0056] Example 1:

[0057] 1. Dissolve 0.5 mmol and 9.5 mmol of (S)-2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0058] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0059] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer (S)-PTPMB-5 is obtained through superacid catalysis.

[0060] 4. The (S)-PTPMB-5 polymer obtained in step 3 was washed in 2 mol / L NaOH and dried to obtain pure (S)-PTPMB-5 polymer solid. The (S)-PTPMB-5 polymer solid was dissolved in DMSO to obtain a 0.1 g / mL solution.

[0061] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-(S)-PTPMB-5 through the Menxiujin reaction;

[0062] 6. Precipitate the Q-(S)-PTPMB-5 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-(S)-PTPMB-5 polymer solid in DMSO to obtain a Q-(S)-PTPMB-5 membrane solution with a concentration of 0.05 g / mL.

[0063] 7. The Q-(S)-PTPMB-5 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion membrane.

[0064] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-(S)-PTPMB-5 chiral polymer anion exchange membrane described above was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. The performance of water electrolysis at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.73-4.8 A cm⁻¹. -2 .

[0065] Example 2:

[0066] 1. Dissolve 1 mmol and 9 mmol of (S)-2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0067] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0068] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer (S)-PTPMB-10 is obtained by superacid catalysis.

[0069] 4. The (S)-PTPMB-10 polymer obtained in step 3 was washed and dried in 2 mol / L NaOH to obtain pure (S)-PTPMB-10 polymer solid. The (S)-PTPMB-10 polymer solid was dissolved in DMSO to obtain a 0.1 g / mL solution.

[0070] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-(S)-PTPMB-10 through the Menxiujin reaction;

[0071] 6. Precipitate the Q-(S)-PTPMB-10 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-(S)-PTPMB-10 polymer solid in DMSO to obtain a Q-(S)-PTPMB-10 membrane solution with a concentration of 0.05 g / mL.

[0072] 7. The Q-(S)-PTPMB-10 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion membrane.

[0073] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-(S)-PTPMB-10 chiral polymer anion exchange membrane was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.85-6.78 A cm⁻¹. -2 .

[0074] Example 3:

[0075] 1. Dissolve 1.5 mmol and 8.5 mmol of (S)-2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0076] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0077] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer (S)-PTPMB-15 is obtained by superacid catalysis.

[0078] 4. The (S)-PTPMB-15 polymer obtained in step 3 was washed and dried in 2 mol / L NaOH to obtain pure (S)-PTPMB-15 polymer solid. The (S)-PTPMB-15 polymer solid was dissolved in DMSO to obtain a 0.1 g / mL solution.

[0079] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-(S)-PTPMB-15 through the Menxiujin reaction;

[0080] 6. Precipitate the Q-(S)-PTPMB-15 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-(S)-PTPMB-15 polymer solid in DMSO to obtain a Q-(S)-PTPMB-15 membrane solution with a concentration of 0.05 g / mL.

[0081] 7. The Q-(S)-PTPMB-15 membrane solution obtained in step 6 is coated onto a glass plate using a casting method. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain the chiral polymer ion exchange membrane. A macroscopic photograph of the membrane is shown below. Figure 1 As shown;

[0082] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The above-mentioned Q-(S)-PTPMB-15 chiral polymer anion exchange membrane was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.96-8 A cm⁻¹. -2 .

[0083] Example 4:

[0084] 1. Dissolve 0.5 mmol and 9.5 mmol of (R)-2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0085] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0086] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer (R)-PTPMB-5 is obtained by superacid catalysis.

[0087] 4. The (R)-PTPMB-5 polymer obtained in step 3 was washed in 2 mol / L NaOH and dried to obtain pure (R)-PTPMB-5 polymer solid. The (R)-PTPMB-5 polymer solid was dissolved in DMSO to obtain a 0.1 g / mL solution.

[0088] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-(R)-PTPMB-5 through the Menxiujin reaction;

[0089] 6. Precipitate the Q-(R)-PTPMB-5 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-(R)-PTPMB-5 polymer solid in DMSO to obtain a Q-(R)-PTPMB-5 membrane solution with a concentration of 0.05 g / mL.

[0090] 7. The Q-(R)-PTPMB-5 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion membrane.

[0091] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-(R)-PTPMB-5 chiral polymer anion exchange membrane described above was used as a diaphragm in a water electrolysis device to test its water electrolysis performance at 30-90 °C. The results showed that under alkaline conditions of 1 M KOH and a reference voltage of 2 V, with the anode being NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435) and the cathode being Pt / C, the density could reach 1.69-4.6 A cm⁻¹ using 1 M KOH solution as the electrolyte. -2 .

[0092] Example 5:

[0093] 1. Dissolve 1 mmol and 9 mmol of (R)-2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0094] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0095] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer (R)-PTPMB-10 is obtained through superacid catalysis.

[0096] 4. The (R)-PTPMB-10 polymer obtained in step 3 was washed and dried in 2 mol / L NaOH to obtain pure (R)-PTPMB-10 polymer solid. The (R)-PTPMB-10 polymer solid was dissolved in DMSO to obtain a 0.1 g / mL solution.

[0097] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-(R)-PTPMB-10 through the Menxiujin reaction;

[0098] 6. Precipitate the Q-(R)-PTPMB-10 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-(R)-PTPMB-10 polymer solid in DMSO to obtain a Q-(R)-PTPMB-10 membrane solution with a concentration of 0.05 g / mL.

[0099] 7. The Q-(R)-PTPMB-10 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion membrane.

[0100] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-(R)-PTPMB-10 chiral polymer anion exchange membrane described above was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.69-6.54 A cm⁻¹. -2 .

[0101] Example 6:

[0102] 1. Dissolve 1.5 mmol and 8.5 mmol of (R)-2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0103] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0104] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer (R)-PTPMB-15 is obtained by superacid catalysis.

[0105] 4. The (R)-PTPMB-15 polymer obtained in step 3 was washed and dried in 2 mol / L NaOH to obtain pure (R)-PTPMB-15 polymer solid. The (R)-PTPMB-15 polymer solid was dissolved in DMSO to obtain a 0.1 g / mL solution.

[0106] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-(R)-PTPMB-15 through the Menxiujin reaction;

[0107] 6. Precipitate the Q-(R)-PTPMB-15 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-(R)-PTPMB-15 polymer solid in DMSO to obtain a Q-(R)-PTPMB-15 membrane solution with a concentration of 0.05 g / mL.

[0108] 7. The Q-(R)-PTPMB-15 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion exchange membrane.

[0109] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-(R)-PTPMB-15 chiral polymer anion exchange membrane was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.91-7.80 A cm⁻¹. -2 .

[0110] Example 7:

[0111] 1. Dissolve 0.5 mmol and 9.5 mmol of 2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0112] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0113] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer PTPMB-5 is obtained through superacid catalysis.

[0114] 4. Wash the PTPMB-5 polymer obtained in step 3 in 2 mol / L NaOH and dry it to obtain pure PTPMB-5 polymer solid. Dissolve the PTPMB-5 polymer solid in DMSO to obtain a 0.1 g / mL solution.

[0115] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-PTPMB-5 through the Menxiujin reaction;

[0116] 6. Precipitate the Q-PTPMB-5 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-PTPMB-5 polymer solid in DMSO to obtain a Q-PTPMB-5 membrane solution with a concentration of 0.05 g / mL.

[0117] 7. The Q-PTPMB-5 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion exchange membrane.

[0118] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-PTPMB-5 chiral polymer anion exchange membrane described above was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.43-3.86 A cm⁻¹. -2 .

[0119] Example 8:

[0120] 1. Dissolve 1 mmol and 9 mmol of 2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0121] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0122] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer PTPMB-10 is obtained through superacid catalysis.

[0123] 4. Wash the PTPMB-10 polymer obtained in step 3 in 2 mol / L NaOH and dry it to obtain pure PTPMB-10 polymer solid. Dissolve the PTPMB-10 polymer solid in DMSO to obtain a 0.1 g / mL solution.

[0124] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-PTPMB-10 through the Menxiujin reaction;

[0125] 6. Precipitate the Q-PTPMB-10 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-PTPMB-10 polymer solid in DMSO to obtain a Q-PTPMB-10 membrane solution with a concentration of 0.05 g / mL.

[0126] 7. The Q-PTPMB-10 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion exchange membrane.

[0127] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The above-mentioned Q-PTPMB-10 chiral polymer ion exchange membrane was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density could reach 1.55-6.08 A cm⁻¹ under alkaline conditions with a reference voltage of 2 V. -2 .

[0128] Example 9:

[0129] 1. Dissolve 1.5 mmol and 8.5 mmol of 2,2'-dimethoxy-1,1'-binaphthylene and p-terphenyl in 5 mL of dichloromethane to obtain a mixed solution of the monomers;

[0130] 2. Mix the mixed solution obtained in step 1 with 12 mmol of N-methyl-4-piperidinone and stir for about 10 min to obtain a homogeneous mixture;

[0131] 3. The mixture obtained in step 2 is introduced into 1 mL of trifluoroacetic acid and 10 mL of trifluoromethanesulfonic acid, and polymer PTPMB-15 is obtained through superacid catalysis.

[0132] 4. Wash the PTPMB-15 polymer obtained in step 3 in 2 mol / L NaOH and dry it to obtain pure PTPMB-15 polymer solid. Dissolve the PTPMB-15 polymer solid in DMSO to obtain a 0.1 g / mL solution.

[0133] 5. The membrane solution obtained in step 4 is reacted with iodomethane at a molar ratio of 1:1.2 to obtain the quaternized polymer solution Q-PTPMB-15 through the Menxiujin reaction;

[0134] 6. Precipitate the Q-PTPMB-15 polymer solution obtained in step 5 and dry it to obtain a pure polymer solid. Dissolve the obtained Q-PTPMB-15 polymer solid in DMSO to obtain a Q-PTPMB-15 membrane solution with a concentration of 0.05 g / mL.

[0135] 7. The Q-PTPMB-15 membrane solution obtained in step 6 is coated onto a glass plate by casting. The solvent is dried at 80°C, and then the membrane is immersed in deionized water to obtain a chiral polymer ion exchange membrane.

[0136] 8. Application of the chiral polymer anion exchange membrane in water electrolysis in this embodiment: The Q-PTPMB-15 chiral polymer anion exchange membrane described above was assembled as a diaphragm in a water electrolysis device. The anode was NiFeCo (preparation method reference: Angew. Chem. Int. Ed. 2025, 64, e202418435), and the cathode was Pt / C. Its water electrolysis performance at 30-90 °C was tested using 1 M KOH solution as the electrolyte. The results showed that the current density under 1 M KOH alkaline conditions and a 2 V reference voltage could reach 1.65-7.05 A cm⁻¹. -2 .

[0137] Examples 1-3, 4-6, and 7-9 investigate the effect of varying chiral molecule copolymerization ratios on membrane performance. Electrolysis performance tests under identical conditions show that increasing the copolymerization ratio of the same chiral molecules significantly improves the membrane's water electrolysis performance.

Claims

1. A method for preparing a chiral polymer anion exchange membrane, characterized in that: Chiral monomer Ar1 and achiral monomer Ar2 were copolymerized via a superacid-catalyzed Friedel-Crafts hydroxyalkylation reaction. The nonlinear amplification effect of chiral molecules enabled the polymer backbone to form a chiral helical structure, resulting in polymer backbone A. Anion exchange groups were then introduced onto polymer backbone A using the Mensoukin reaction to obtain quaternized polymer B. Finally, quaternized polymer B was prepared into a membrane solution, which was then cast into a membrane using a casting method to obtain a chiral polymer ion exchange membrane. The chiral monomer Ar1 is selected from one of the monomers shown in the following structures: ； The achiral monomer Ar2 is selected from one of the monomers shown in the following structures: 。 2. The preparation method according to claim 1, characterized in that... Includes the following steps: Step 1: Thoroughly mix the chiral monomer Ar1 and the achiral monomer Ar2 in a solvent to obtain a mixed solution; Step 2: Mix the mixed solution obtained in Step 1 with monomer T until homogeneous; Step 3: Trifluoroacetic acid and trifluoromethanesulfonic acid are introduced into the mixture obtained in Step 2, and polymer backbone A is obtained through superacid catalysis. Step 4: Add the system obtained in Step 3 to the alkaline solution to quench the reaction, wash and dry the resulting solid to obtain a pure polymer solid, and dissolve it in a solvent to obtain a solution; Step 5: The solution obtained in Step 4 is reacted with 1-haloalkane via the Mensoukin reaction to obtain a solution of quaternized polymer B; Step 6: Precipitate the quaternized polymer B obtained in Step 5 and dry it, then dissolve it in a solvent to obtain a membrane solution; Step 7: The membrane solution obtained in Step 6 is cast into a film by casting, the solvent is dried, and then the film is immersed in deionized water to obtain a chiral polymer ion membrane.

3. The preparation method according to claim 2, characterized in that... The monomer T is selected from one of the monomers with the following structures: 。 4. The preparation method according to claim 2, characterized in that: In step 1, the molar ratio of the chiral monomer Ar1 to the achiral monomer Ar2 is 1:19 to 2:

8.

5. The preparation method according to claim 2, 3 or 4, characterized in that: In step 2, the ratio of the molar amount of monomer T to the total molar amount of chiral and achiral monomers is 1.05:1 to 1.25:

1.

6. The preparation method according to claim 2, characterized in that: In step 3, the reaction temperature for superacid catalysis is -10℃ to 5℃, and the reaction time is 3-8h.

7. The preparation method according to claim 2, characterized in that: The 1-haloalkane contains 1 to 12 carbon atoms in its alkane chain; the molar ratio of the polymer solid to the 1-haloalkane is 1:1-1.

2.

8. A chiral polymer anion exchange membrane, prepared by the preparation method according to any one of claims 1-7.

9. The application of the chiral polymer anion exchange membrane according to claim 8 in hydrogen production by water electrolysis.

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