Hydrogen bond organic framework proton conductor based on rigid-flexible assembly, preparation method and application

Abstract

The invention relates to a hydrogen bond organic framework proton conductor based on a rigid-flexible assembly, a preparation method and application, and the method comprises the steps: S1, selecting a first compound, and dissolving the first compound in a first solvent to obtain a first solution, the first compound being a linear alkyl sulfonic acid compound; s2, selecting a second compound, and dissolving the second compound in a second solvent to obtain a second solution, the second compound being an amino aromatic compound; and S3, mixing the first solution with the second solution, standing, volatilizing and crystallizing to obtain the hydrogen bond organic framework proton conductor. According to the technical scheme, the first compound representing the flexible material building unit and the second compound representing the rigid material building unit are self-assembled through the charge-assisted hydrogen bond, so that the hydrogen bond organic framework proton crystal constructed by the scheme has higher purity and better performance of various parameters; and particularly, the conductivity of the conductor is better.

Description

Technical Field

[0001] This invention belongs to the field of hydrogen-bonded organic framework materials technology, specifically designing hydrogen-bonded organic framework materials and their preparation methods. Background Technology

[0002] As a highly efficient and clean energy conversion device, the performance of the proton exchange membrane (PEM) as its core component directly determines the efficiency and stability of the fuel cell. An ideal PEM needs to simultaneously possess high proton conductivity, excellent chemical and dimensional stability, and low fuel permeability.

[0003] Currently, while commercially available perfluorosulfonic acid membranes exhibit high proton conductivity under humid conditions, their conduction mechanism heavily relies on water molecules. This leads to a sharp drop in proton conductivity at high temperatures (>80°C) or low humidity, resulting in demanding operating conditions. Furthermore, their high methanol permeability limits their application in direct methanol fuel cells. Some existing technologies rely on inorganic materials for preparing hydrogen-bonded frameworks. The bottleneck of this technology lies in the limited plasticity of inorganic materials, which restricts the selection and construction of hydrogen-bonded organic frameworks. Summary of the Invention

[0004] Therefore, a novel method for preparing hydrogen-bonded organic framework proton conductors is needed.

[0005] To achieve the above objectives, the inventors provide a method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component, comprising the following steps:

[0006] S1. Select a first compound, dissolve the first compound in a first solvent to obtain a first solution, wherein the first compound is a linear alkyl sulfonic acid compound;

[0007] S2. Select a second compound, dissolve the second compound in a second solvent to obtain a second solution, wherein the second compound is an amino aromatic compound;

[0008] S3. Mix the first solution with the second solution, then allow it to stand and evaporate to crystallize, to obtain a hydrogen-bonded organic framework proton conductor.

[0009] In some embodiments of this application, the mixing ratio of the first solution to the second solution is between 1:0.2 and 1:5 by volume.

[0010] In some embodiments of this application, the first solvent is water, hydrochloric acid, or a water-methanol mixture.

[0011] In some embodiments of this application, the second solvent is one of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and dioxane.

[0012] In some embodiments of this application, the linear alkyl sulfonic acid compound is one of various isomers of methane disulfonic acid, ethane disulfonic acid, or propane disulfonic acid.

[0013] In some embodiments of this application, the amino aromatic compound includes one of various isomers of phenylenediamine, dimethyl-p-phenylenediamine, tetramethylphenylenediamine, naphthylenediamine, 4,4'-(4-aminopyridine-2,6-diyl)diphenylamine, tetraaminotetraphenylene, and 1,2,4,5-tetra(aminophenyl)benzene.

[0014] In some embodiments of this application, the amino aromatic compound is APyDAn, p-ETTA, or p-TAnB.

[0015] Another aspect of this application is the design of a hydrogen-bonded organic framework proton conductor, which is prepared by the method described above.

[0016] Another aspect of this application is the design of a proton exchange membrane comprising a hydrogen-bonded organic framework proton conductor as described above.

[0017] Another aspect of this application is the design of a proton exchange membrane fuel cell, comprising the proton exchange membrane described above.

[0018] Unlike existing technologies, the above-mentioned technical solution enables the self-assembly of a first compound representing a flexible building block and a second compound representing a rigid building block through charge-assisted hydrogen bonding. The second compound can be selected in various ways to provide a highly symmetrical rigid framework and dense protonation sites (–NH3⁺). The flexible building block is a linear organic alkyl sulfonic acid compound, which acts as a functional hinge, providing sulfonate groups (–SO3⁻) and conformationally tunable alkyl chains. Ultimately, this method results in a hydrogen-bonded organic framework proton crystal with higher purity and better performance across various parameters, especially improved conductivity.

[0019] The above description of the invention is merely an overview of the technical solution of this application. In order to enable those skilled in the art to better understand the technical solution of this application and to implement it based on the description and drawings, and to make the above-mentioned objectives and other objectives, features and advantages of this application easier to understand, the following description is provided in conjunction with the specific embodiments and drawings of this application. Attached Figure Description

[0020] The accompanying drawings are only used to illustrate the principles, implementation methods, applications, features, and effects of specific embodiments of this application and other related content, and should not be considered as limitations on this application.

[0021] In the accompanying drawings of the instruction manual:

[0022] Figure 1 This is a flowchart illustrating the method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component, as described in the specific implementation.

[0023] Figure 2 Molecular structure diagrams of the first and second compounds for specific embodiments;

[0024] Figure 3 This is a schematic diagram of the crystal structure of Example 1, a specific implementation method.

[0025] Figure 4 X-ray diffraction comparison of crystal powder and its single crystal structure as a specific embodiment of Example 1;

[0026] Figure 5 The Nyquist plot of the crystal in Example 1 of the specific implementation method;

[0027] Figure 6 This is a schematic diagram of the crystal structure of Example 2, a specific implementation method.

[0028] Figure 7 Example 2, a specific implementation method, shows a comparison of X-ray diffraction patterns of crystal powder and its single crystal structure.

[0029] Figure 8 The Nyquist plot of the crystal in Example 2 of the specific implementation method;

[0030] Figure 9 This is a schematic diagram of the crystal structure of Example 3, a specific implementation method.

[0031] Figure 10 X-ray diffraction comparison pattern of crystal powder and its single crystal structure as a specific embodiment of Example 3;

[0032] Figure 11 The Nyquist plot of the crystal in Example 3 of the specific implementation method;

[0033] Figure 12 This is a schematic diagram of the crystal structure of Example 4, a specific implementation method.

[0034] Figure 13 Example 4, a specific implementation method, shows a comparison of X-ray diffraction patterns of crystal powder and its single crystal structure.

[0035] Figure 14 The Nyquist plot of the crystal in Example 4 of the specific implementation method;

[0036] Figure 15 This is a schematic diagram of the crystal structure of Example 5, a specific implementation method.

[0037] Figure 16 This is a schematic diagram of the crystal structure of Example 6, a specific implementation method.

[0038] Figure 17 This is a schematic diagram of the crystal structure of Example 7, a specific implementation method.

[0039] Figure 18 This is a schematic diagram of the crystal structure of Example 8, a specific implementation method.

[0040] Figure 19 This is a schematic diagram of the crystal structure of Example 9, a specific implementation method.

[0041] Figure 20 This is a schematic diagram of the crystal structure of Example 10, which is a specific implementation method. Detailed Implementation

[0042] To illustrate the possible application scenarios, technical principles, implementable specific solutions, and achievable objectives and effects of this application in detail, the following description, in conjunction with the listed specific embodiments and accompanying drawings, provides a detailed explanation. The embodiments described herein are merely illustrative of the technical solutions of this application and are therefore intended to limit the scope of protection of this application.

[0043] In this document, the term "embodiment" means that a specific feature, structure, or characteristic described in connection with an embodiment may be included in at least one embodiment of this application. The term "embodiment" appearing in various places throughout the specification does not necessarily refer to the same embodiment, nor does it specifically limit its independence or connection with other embodiments. In principle, in this application, as long as there are no technical contradictions or conflicts, the technical features mentioned in each embodiment can be combined in any way to form corresponding implementable technical solutions.

[0044] Unless otherwise defined, the technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains; the use of related terms herein is merely for the purpose of describing particular embodiments and is not intended to limit this application.

[0045] In the description of this application, the term "and / or" is used to describe the logical relationship between objects, indicating that three relationships can exist. For example, A and / or B means: A exists, B exists, and A and B exist simultaneously. Additionally, the character " / " in this document generally indicates that the preceding and following objects have an "or" logical relationship.

[0046] In this application, terms such as “first” and “second” are used only to distinguish one entity or operation from another, and do not necessarily require or imply any actual quantity, hierarchy or order relationship between these entities or operations.

[0047] Unless otherwise specified, the use of terms such as “comprising,” “including,” “having,” or other similar expressions in this application is intended to cover non-exclusive inclusion, which does not exclude the presence of additional elements in a process, method, or product that includes the stated elements, such that a process, method, or product that includes a list of elements may include not only those defined elements but also other elements not expressly listed, or elements inherent to such a process, method, or product.

[0048] As understood in the Examination Guidelines, in this application, expressions such as "greater than," "less than," and "exceeding" are understood to exclude the stated number; expressions such as "above," "below," and "within" are understood to include the stated number. Furthermore, in the description of the embodiments in this application, "multiple" means two or more (including two), and similar expressions related to "multiple" are also understood in this way, such as "multiple groups" and "multiple times," unless otherwise explicitly specified.

[0049] In the description of the embodiments of this application, the space-related expressions used, such as "center," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "vertical," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," and "circumferential," indicate the orientation or positional relationship based on the orientation or positional relationship shown in the specific embodiments or drawings. They are only for the purpose of describing the specific embodiments of this application or for the reader's understanding, and do not indicate or imply that the device or component referred to must have a specific position, a specific orientation, or be constructed or operated in a specific orientation. Therefore, they should not be construed as limitations on the embodiments of this application.

[0050] Unless otherwise expressly specified or limited, the terms "installation," "connection," "linking," "fixing," and "setting," as used in the description of the embodiments of this application, should be interpreted broadly. For example, "connection" can be a fixed connection, a detachable connection, or an integral setting; it can be a mechanical connection, an electrical connection, or a communication connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be the internal connection of two components or the interaction between two components. For those skilled in the art to which this application pertains, the specific meaning of the above terms in the embodiments of this application can be understood according to the specific circumstances.

[0051] Please see Figure 1 This embodiment provides a method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component, comprising the following steps:

[0052] S1. Select a first compound, dissolve the first compound in a first solvent to obtain a first solution, wherein the first compound is a linear alkyl sulfonic acid compound;

[0053] S2. Select a second compound, dissolve the second compound in a second solvent to obtain a second solution, wherein the second compound is an amino aromatic compound;

[0054] S3. Mix the first solution with the second solution, then allow it to stand and evaporate to crystallize, to obtain a hydrogen-bonded organic framework proton conductor.

[0055] The above design scheme can simultaneously achieve high structural stability and long-range order of proton transport networks through simplified molecular design and synthesis pathways.

[0056] The material described in this invention is formed by the self-assembly of rigid and flexible building units through charge-assisted hydrogen bonding. The rigid building units are polyamino aromatic compounds, which act as structural pillars providing a highly symmetrical rigid framework and dense protonation sites (–NH3⁺). The flexible building units are linear organic alkyl sulfonic acid compounds, which act as functional hinges providing sulfonate groups (–SO3⁻) and conformationally tunable alkyl chains. The two are connected by strong charge-assisted hydrogen bonds (N–H⁺⋯⁻O–S), forming a crystal framework with a highly ordered hydrogen bond network. Unlike the fully ionized NH4⁺ exhibited in aqueous solutions in existing inorganic ammonium salt solutions, the organic aromatic amine solution has a more complete rigid framework, resulting in a more ordered and complete crystal structure.

[0057] In some embodiments of this application, the mixing ratio of the first solution to the second solution is between 1:0.2 and 1:5 by volume. After mixing, the solution can be allowed to stand for 18-32 hours to allow for sufficient reaction, resulting in the final crystals, which can be used for...

[0058] In some embodiments of this application, the first solvent is water, hydrochloric acid, or a water-methanol mixture. The solvent provides a suitable reaction environment, allowing the reaction of the hydrogen-bonded organic conductor material to proceed more smoothly.

[0059] In some embodiments of this application, the second solvent is one of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and dioxane. The solvent provides a reaction environment that facilitates the reaction of the hydrogen-bonded organic conductor material.

[0060] In some embodiments of this application, the linear alkyl sulfonic acid compound is one of various isomers of methane disulfonic acid, ethane disulfonic acid, or propane disulfonic acid. In some specific application examples, (1) methane disulfonic acid (molecular formula CH4O6S2, labeled as H2MDS); (2) ethane disulfonic acid (molecular formula C2H6O6S2, with two isomers, 1,1-ethane disulfonic acid labeled as 1,1-H2EDS, 1,2-ethane disulfonic acid labeled as 1,2-H2EDS); (3) propane disulfonic acid (molecular formula C3H8O6S2, with four isomers, 1,1-propane disulfonic acid labeled as 1,1-H2PDS, 1,2-propane disulfonic acid labeled as 1,2-H2PDS, 1,3-propane disulfonic acid labeled as 1,3-H2PDS, 2,2-propane disulfonic acid labeled as 2,2-H2PDS).

[0061] In some preferred embodiments, please refer to Figure 2 H2MDS is preferred due to its easy availability and low cost. 1,2-H2EDS is also preferred, as it offers a better balance between cost and structural flexibility.

[0062] In some embodiments of this application, the amino aromatic compound includes one of various isomers of phenylenediamine, dimethyl-p-phenylenediamine, tetramethylphenylenediamine, naphthylenediamine, 4,4'-(4-aminopyridine-2,6-diyl)diphenylamine, tetraaminotetraphenylene, and 1,2,4,5-tetra(aminophenyl)benzene.

[0063] Specifically, the following materials can be selected: (1) Phenylenediamine (molecular formula C6H6N2, with three isomers: o-phenylenediamine is denoted as o-BDA, m-phenylenediamine as m-BDA, and p-phenylenediamine as p-BDA).

[0064] (2) Dimethyl-p-phenylenediamine (molecular formula C8H) 12 N2 has three isomers: 2,3-dimethyl-1,4-phenylenediamine (denoted as o-DMBDA), 2,5-dimethyl-1,4-phenylenediamine (denoted as p-DMBDA), and 2,6-dimethyl-1,4-phenylenediamine (denoted as m-DMBDA).

[0065] (3) Tetramethylphenylenediamine (molecular formula C) 10 H 16 N2 has three isomers: tetramethyl-o-phenylenediamine (o-TMBDA), tetramethyl-m-phenylenediamine (m-TMBDA), and tetramethyl-p-phenylenediamine (p-TMBDA).

[0066] (4) Naphthyldiamine (molecular formula C 10 H 10N2, in this case there are five isomers: 1,4-naphthyldiamine (denoted as 1,4-NpDA), 1,5-naphthyldiamine (denoted as 1,5-NpDA), 1,8-naphthyldiamine (denoted as 1,8-NpDA), 2,6-naphthyldiamine (denoted as 2,6-NpDA), and 2,7-naphthyldiamine (denoted as 2,7-NpDA).

[0067] (5) 4,4'-(4-aminopyridine-2,6-diyl)diphenylamine (molecular formula C) 17 H 16 N4, denoted as APyDAn);

[0068] (6) Tetraaminotetraphenylene (molecular formula C) 26 H 24 N4 has three isomers: tetra(o-amino)tetraphenylene (o-ETTA), tetra(m-amino)tetraphenylene (m-ETTA), and tetra(p-amino)tetraphenylene (p-ETTA).

[0069] (7) 1,2,4,5-Tetra(aminophenyl)benzene (molecular formula C 30 H 26 N4 has three isomers: 1,2,4,5-tetra(o-aminophenyl)benzene (o-TAnB), 1,2,4,5-tetra(m-aminophenyl)benzene (m-TAnB), and 1,2,4,5-tetra(p-aminophenyl)benzene (p-TAnB).

[0070] The preferred materials are p-BDA, p-DMBDA, p-TMBDA, 1,5-NpDA, APyDAn, p-ETTA, and p-TAnB.

[0071] For some preferred embodiments, please refer to Figure 2 The preferred compounds used in these applications are: p-BDA, p-DMBDA, p-TMBDA, 1,5-NpDA, APyDAn, p-ETTA, and p-TAnB. These compounds exhibit greater crystal stability and better performance characteristics compared to their corresponding isomers.

[0072] Example 1: The alkyl sulfonic acid compound chosen was H2MDS, solvent A was water, the polyamino aromatic compound chosen was 1,5-NpDA, and solvent B was methanol. 2 mL of a 0.025 mol / L aqueous solution of H2MDS was thoroughly mixed with 2 mL of a 0.01 mol / L methanol solution of 1,5-NpDA. After standing at room temperature for 24 h, crystalline MDS_1,5-H2NpDA_H2O was obtained, with the molecular formula C2. 11 H 16 N₂O₇S₂. Please refer to [link / reference]. Figure 3This is a schematic diagram of the crystal structure of MDS_1,5-H2NpDA_H2O. It belongs to the monoclinic crystal system, space group P21 / n. The cell parameters are a = 14.12 Å, b = 5.33 Å, c = 18.60 Å, α = γ = 90°, β = 92.7°, V = 712.6 Å. 3 . Figure 4 A comparison of the X-ray diffraction pattern of crystalline MDS_1,5-H2NpDA_H2O powder with the pattern simulated by its single-crystal structure is also shown. Please refer to [link / reference]. Figure 5 Proton conduction tests were conducted using a single MDS crystal of 1,5-H2NpDA_H2O with dimensions of 0.4×0.1×0.04 mm³. The maximum conductivity of 1.57×10⁻⁴ was achieved at 80℃ and 98%RH. -2 S / cm. Where RH is relative humidity.

[0073] Example 2: The alkyl sulfonic acid compound chosen was H2MDS, solvent A was water, the polyamino aromatic compound chosen was p-ETTA, and solvent B was methanol. 2 mL of a 0.025 mol / L aqueous solution of H2MDS was thoroughly mixed with 4 mL of a 0.005 mol / L methanol solution of p-ETTA. After standing at room temperature for 30 h, pale purple transparent crystals 2(MDS)_p-H4ETTA_0.5(H2O) were obtained, with the molecular formula C. 28 H 33 N4O 12.5 S4. Please refer to its spatial structure diagram. Figure 6 Crystal 2 (MDS)_p-H4ETTA_0.5(H2O) belongs to the monoclinic crystal system, space group P21. The cell parameters are a = 12.96 Å, b = 10.33 Å, c = 15.43 Å, α = γ = 90°, β = 113.6°, V = 1891.6 Å. 3 . Figure 7 This is a comparison between the powder X-ray diffraction pattern and the pattern simulated by its single-crystal structure. Please refer to [link / reference]. Figure 8 Proton conductivity tests were conducted using a 0.22×0.1×0.03 mm³ 2(MDS)_p-H4ETTA_0.5(H2O) single crystal, achieving a maximum conductivity of 1.22×10⁻⁶ at 70℃ and 98%RH. -2 S / cm. Where RH is relative humidity.

[0074] Example 3: The alkyl sulfonic acid compound chosen was 1,2-H2EDS, solvent A was water, the polyamino aromatic compound chosen was p-ETTA, and solvent B was methanol. 2 mL of a 0.025 mol / L aqueous solution of 1,2-H2EDS was thoroughly mixed with 4 mL of a 0.005 mol / L methanol solution of p-ETTA. After standing at room temperature for 32 h, pale green transparent crystals 2(1,2-EDS)_p-H4ETTA_4(H2O) were obtained, with the molecular formula C2. 15 H 22 N₂O₈S₂. Please refer to the schematic diagram of its spatial structure. Figure 9 Crystal 2(1,2-EDS)_p-H4ETTA_4(H2O) belongs to the triclinic crystal system, space group P-1. Its unit cell parameters are a = 10.51 Å, b = 12.74 Å, c = 14.39 Å, α = 88.1°, β = 89.4°, γ = 79.1°, and V = 1890.4 Å. 3 . Figure 10 This is a comparison between the powder X-ray diffraction pattern and the pattern simulated by its single-crystal structure. Please refer to [link / reference]. Figure 11 Proton conduction tests were performed using a 0.37×0.04×0.01 mm³ 2(1,2-EDS)_p-H4ETTA_4(H2O) single crystal, achieving a maximum conductivity of 1.12×10⁻⁶ at 70℃ and 98%RH. -3 S / cm. Where RH is relative humidity.

[0075] Example 4: The alkyl sulfonic acid compound was selected as H2MDS, solvent A was water, and the polyamino aromatic compound was selected as p-TAnB, solvent B was methanol. 2 mL of an aqueous solution of 0.025 mol / L H2MDS was thoroughly mixed with 4 mL of a methanol solution of 0.005 mol / L p-TAnB. After standing at room temperature for 16 h, crystal 2(MDS)_p-H4TAnB_6.5(H2O) was obtained, with the molecular formula C. 32 H 47 N4O 18.5 S4. Please refer to its spatial structure diagram. Figure 12 Crystal 2 (MDS)_p-H4TAnB_6.5(H2O) belongs to the monoclinic crystal system with space group C2 / c. Its unit cell parameters are a = 28.89 Å, b = 16.99 Å, c = 10.08 Å, α = γ = 90°, β = 98.1°, and V = 4898.2 Å. 3 . Figure 13 This is a comparison between the powder X-ray diffraction pattern and the pattern simulated by its single-crystal structure. Please refer to [link / reference]. Figure 14Proton conductivity tests were conducted using a 0.53×0.1×0.03 mm³ 2(MDS)_p-H4TAnB_6.5(H2O) single crystal. The maximum conductivity of 1.55×10⁻⁶ was achieved at 70℃ and 98%RH. -2 S / cm. Where RH is relative humidity.

[0076] Example 5: The alkyl sulfonic acid compound chosen was H2MDS, solvent A was water, the polyamino aromatic compound chosen was p-BDA, and solvent B was methanol. 2 mL of an aqueous solution of 0.025 mol / L H2MDS was thoroughly mixed with 1 mL of a methanol solution of 0.01 mol / L p-BDA. After standing at room temperature for 24 h, crystalline MDS_p-H2BDA was obtained with the molecular formula C4H7NO3S. For the crystal structure, please refer to [link to crystal structure]. Figure 15 It belongs to the monoclinic crystal system, space group P21 / c. The cell parameters are a = 12.06 Å, b = 7.20 Å, c = 7.28 Å, α = γ = 90°, β = 91.355°, V = 631.7 Å. 3 .

[0077] Example 6: The alkyl sulfonic acid compound selected was 1,2-H₂EDS, solvent A was water, the polyamino aromatic compound selected was p-DMBDA, and solvent B was methanol. 5 mL of a 0.025 mol / L aqueous solution of 1,2-H₂EDS was thoroughly mixed with 1 mL of a 0.01 mol / L methanol solution of p-DMBDA. After standing at room temperature for 20 h, crystalline 1,2-EDS_p-H₂DMBDA with the molecular formula C₅H₹NO₃S was obtained. For the crystal structure, please refer to [link to crystal structure description]. Figure 16 It belongs to the triclinic crystal system, space group P-1. The unit cell parameters are a = 5.95 Å, b = 6.07 Å, c = 10.11 Å, α = 86.6°, β = 87.4°, γ = 75.9°, V = 353.6 Å. 3 .

[0078] Example 7: The alkyl sulfonic acid compound chosen was H2MDS, solvent A was water, the polyamino aromatic compound chosen was p-TMBDA, and solvent B was methanol. 2 mL of a 0.025 mol / L aqueous solution of H2MDS was thoroughly mixed with 10 mL of a 0.01 mol / L methanol solution of p-TMBDA. After standing at room temperature for 24 h, crystal 2(MDS)_p-H4DMBDA_H2O was obtained, with the molecular formula C2. 11 H 24 For the crystal structure of N2O8S2, please refer to [link / reference]. Figure 17It belongs to the triclinic crystal system, space group P-1. The unit cell parameters are a = 9.24 Å, b = 9.36 Å, c = 11.05 Å, α = 101.1°, β = 93.5°, γ = 113.8°, V = 848.6 Å. 3 .

[0079] Example 8: The alkyl sulfonic acid compound selected was 1,2-H2EDS, solvent A was water, the polyamino aromatic compound selected was p-TMBDA, and solvent B was methanol. 2 mL of a 0.025 mol / L aqueous solution of 1,2-H2EDS was thoroughly mixed with 8 mL of a 0.01 mol / L methanol solution of p-TMBDA. After standing at room temperature for 24 h, crystals 2(1,2-EDS)_p-H4DMBDA_H2O were obtained, with the molecular formula C2. 12 H 24 For the crystal structure of N2O7S2, please refer to [link / reference]. Figure 18 It belongs to the monoclinic crystal system, with space group C2 / c. The cell parameters are a = 14.28 Å, b = 7.26 Å, c = 16.96 Å, α = γ = 90°, β = 111.805(3)°, V = 848.6 Å. 3 .

[0080] Example 9: The alkyl sulfonic acid compound selected was 1,2-H₂EDS, solvent A was water, the polyamino aromatic compound selected was 1,5-NpDA, and solvent B was methanol. 2 mL of an aqueous solution of 0.025 mol / L 1,2-H₂EDS was thoroughly mixed with 0.4 mL of a methanol solution of 0.01 mol / L 1,5-NpDA. After standing at room temperature for 16 h, crystalline 1,2-EDS_1,5-NpDA was obtained, with the molecular formula C. 12 H 16 For the crystal structure of N2O6S2, please refer to [link / reference]. Figure 19 It belongs to the triclinic crystal system, space group P-1. The unit cell parameters are a = 7.33 Å, b = 9.18 Å, c = 11.18 Å, α = 72.3°, β = 88.9°, γ = 83.6°, V = 712.6 Å. 3 .

[0081] Example 10: The alkyl sulfonic acid compound chosen was H2MDS, solvent A was water, the polyamino aromatic compound chosen was APyDAn, and solvent B was methanol. 4 mL of a 0.025 mol / L aqueous solution of APyDAn was thoroughly mixed with 0.8 mL of a 0.01 mol / L methanol solution of p-TMBDA. After standing at room temperature for 32 h, crystals 3(MDS)_2(H3APyDAn)_5H2O were obtained, with the molecular formula C2. 37 H 54 N8O 23 S6, crystal structure please refer to Figure 20 It belongs to the monoclinic crystal system, space group P21 / c. The cell parameters are a = 32.28 Å, b = 7.22 Å, c = 21.34 Å, α = γ = 90°, β = 105.2°, V = 4801.6 Å. 3 .

[0082] Another aspect of this application involves the design of a hydrogen-bonded organic framework proton conductor, which is prepared using the method described above. The hydrogen-bonded organic framework proton crystal constructed using this method exhibits higher purity and better performance across various parameters, particularly superior conductor conductivity.

[0083] Another aspect of this application involves the design of a proton exchange membrane comprising a hydrogen-bonded organic framework proton conductor as described above. The proton exchange membrane constructed using this method exhibits superior performance across various parameters, particularly enhanced stability and conductivity.

[0084] Another aspect of this application involves the design of a proton exchange membrane fuel cell, comprising the aforementioned proton exchange membrane. The proton exchange membrane fuel cell constructed using this method exhibits better performance across various parameters, particularly superior stability and conductivity.

[0085] It should be noted that although the above embodiments have been described herein, this does not limit the scope of patent protection of the present invention. Therefore, any changes and modifications made to the embodiments described herein based on the innovative concept of the present invention, or equivalent structural or procedural transformations made using the content of the present invention's specification and drawings, directly or indirectly applying the above technical solutions to other related technical fields, are all included within the scope of patent protection of the present invention.

[0086] Although the above embodiments have been described, those skilled in the art, once they understand the basic inventive concept, can make other changes and modifications to these embodiments. Therefore, the above descriptions are merely embodiments of the present invention and do not limit the scope of patent protection of the present invention. Any equivalent structural or procedural transformations made using the content of the present invention's specification and drawings, or direct or indirect applications in other related technical fields, are similarly included within the scope of patent protection of the present invention.

Claims

1. A method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component, characterized in that, Includes the following steps: A first compound is selected, and the first compound is dissolved in a first solvent to obtain a first solution. The first compound is a linear alkyl sulfonic acid compound. A second compound is selected, and the second compound is dissolved in a second solvent to obtain a second solution. The second compound is an amino aromatic compound. The first solution was mixed with the second solution, and then allowed to stand and evaporate to crystallize, resulting in a hydrogen-bonded organic framework proton conductor.

2. The method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component according to claim 1, characterized in that, The mixing ratio of the first solution to the second solution is between 1:0.2 and 1:5 by volume.

3. The method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component according to claim 1, characterized in that, The first solvent is water, hydrochloric acid, or a water-methanol mixture.

4. The method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component according to claim 1, characterized in that, The second solvent is one of methanol, ethanol, acetone, tetrahydrofuran, acetonitrile, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and dioxane.

5. The method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component according to claim 1, characterized in that, The linear alkyl sulfonic acid compound is one of the various isomers of methane disulfonic acid, ethane disulfonic acid, or propane disulfonic acid.

6. The method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component according to claim 1, characterized in that, The amino aromatic compound includes one of the various isomers of phenylenediamine, dimethyl-p-phenylenediamine, tetramethylphenylenediamine, naphthylenediamine, 4,4'-(4-aminopyridine-2,6-diyl)diphenylamine, tetraaminotetraphenylene, and 1,2,4,5-tetra(aminophenyl)benzene.

7. The method for preparing a hydrogen-bonded organic framework proton conductor based on a rigid-flexible component according to claim 6, characterized in that, The amino aromatic compound is APyDAn, p-ETTA, or p-TAnB.

8. A hydrogen-bonded organic framework proton conductor, characterized in that, Prepared by the method of any one of claims 1-7.

9. A proton exchange membrane, characterized in that, Including the hydrogen-bonded organic framework proton conductor as described in claim 8.

10. A proton exchange membrane fuel cell, characterized in that, Includes the proton exchange membrane as described in claim 9.

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