A polyacid-organic supermolecular framework material and a preparation method and application thereof

Abstract

This invention discloses a polyacid-organic supramolecular framework material, its preparation method, and its applications. The molecular formula of the polyacid-organic supramolecular framework material is H3(HIm). 11 [Sb2W 19 O 67 (H₂O)]·solvent, where Im=imidazole; the polyacid-organic supramolecular framework material has hexagonal channels, and the structural characteristics of the polyacid-organic supramolecular framework are: six [Sb₂W] 19 O 67 [H2O] The polyanionic building block is located at the six corners of a hexagon, and is formed by 30 protonated imidazole countercations linked by multiple hydrogen bonds to form a hexagonal supramolecular cluster. The molecular formula of the cluster is {[Sb2W] 19 O 67 (H2O)]6(Him) 30 Adjacent clusters form a one-dimensional nanotube structure through supramolecular interactions of imidazole counter cations, and the nanotubes are then connected by imidazole counter cations to form a three-dimensional supramolecular framework; the polyacid-organic supramolecular framework material is used as a proton conduction material in the field of fuel cells.

Description

Technical Field

[0001] This invention belongs to the field of new materials technology, specifically relating to a polyacid-organic supramolecular framework material, its preparation method, and its application. Background Technology

[0002] Proton exchange membrane fuel cells (PEMFCs) are very promising alternatives to traditional fuel cells due to their high power density and ultra-low emissions. The proton exchange membrane (PEM), a crucial component of the PEMFC, plays a key role in proton transport and migration; its material properties directly affect the fuel cell's performance and lifespan (see working principle diagram). Figure 1 (As shown). The proton-conducting materials used in PEMs should meet the following basic conditions: (1) good proton conductivity; (2) high material stability; (3) low preparation cost and reasonable price; (4) simple preparation process and high yield. Although various crystalline porous proton-conducting materials, such as MOFs, porous coordination polymers (PCPs) and COFs, have been reported, their application in PEMFCs is limited by narrow operating temperatures (20-80℃) and high humidity dependence. For example, the widely used Nafion membrane exhibits the highest proton conductivity at 80℃, while the conductivity decreases significantly above 80℃, which severely limits their operating conditions and may lead to poisoning of noble metal catalysts. Therefore, it is extremely important and challenging to develop proton-conducting materials that can operate efficiently under high temperature and anhydrous conditions.

[0003] Polyoxometalates (POMs), often shortened to polyoxometalates, are typically inorganic oxometalates of high-valence transition metals such as V, Nb, Ta, Mo, and W that undergo condensation and dehydration to form polynuclear metal cluster structures. They exhibit a rich variety of structural types, with modifiable and tunable size and charge, strong electron and proton transfer / storage capabilities, and good stability. Furthermore, POMs can serve as flexible building blocks for constructing various nanostructures, including POM-based cage, framework, cup, macrocyclic, and composite nanostructures. In contrast, the construction of POM-organic hybrid supramolecular framework materials has not been extensively studied. These hybrid supramolecular framework materials, due to their unique composition and structural characteristics, such as the unique hydrogen bonding interactions between POM and organic components and nanoscale proton transport channels, possess excellent stability and proton conductivity. Therefore, in recent years, the exploration of POM-organic hybrid supramolecular framework proton conduction materials has attracted the attention of many scientific researchers, who hope to synthesize multi-acid proton conduction materials with high proton conductivity, good stability, and simple and low cost of preparation. Summary of the Invention

[0004] To address the above problems, this invention provides a polyacid-organic supramolecular framework material, its preparation method, and its applications.

[0005] The present invention adopts the following technical solution:

[0006] A polyacid-organic supramolecular framework material, wherein the molecular formula of the polyacid-organic supramolecular framework material is H3(HIm). 11 [Sb2W 19 O 67 (H₂O)]·solvent, where Im=imidazole; the polyacid-organic supramolecular framework material has hexagonal channels, and the structural characteristics of the polyacid-organic supramolecular framework are: six [Sb₂W ... 19 O 67 [H2O] The polyanionic building block is located at the six corners of a hexagon, and is formed by 30 protonated imidazole countercations linked by multiple hydrogen bonds to form a hexagonal supramolecular cluster. The molecular formula of the cluster is {[Sb2W] 19 O 67 (H2O)]6(Him) 30 Adjacent clusters form one-dimensional nanotube structures through supramolecular interactions of imidazole counter cations, and the nanotubes are then connected to each other through imidazole counter cations to form a three-dimensional supramolecular framework.

[0007] The polyacid-organic supramolecular framework material belongs to the hexagonal crystal system, with space group P6 / mcc and corresponding space group number 192.

[0008] The unit cell parameters of the polyacid-organic supramolecular framework material are: α = β = 90°, γ = 120°.

[0009] A method for preparing a polyacid-organic supramolecular framework material includes the following steps:

[0010] S1, Tri-vacant antimony tungstate precursor Na9[B-α-SbW9O] 33 Synthesis of 19.5H₂O: S11, Prepare an aqueous solution of sodium tungstate at 80℃ and a concentration of 1.5-2.0 mol / L; S12, Prepare a concentrated antimony hydrochloric acid solution, wherein the antimony raw material is antimony trioxide, and the molar ratio of antimony trioxide to hydrochloric acid is 1:18; S13, Add the concentrated antimony hydrochloric acid solution dropwise to the sodium tungstate solution, and reflux at 80-110℃ for 1-2 hours. Then concentrate the reaction solution to 2 / 3 of its volume, cool to room temperature, and obtain white crystals. After filtration, wash with ethanol, and air dry to obtain white granular crystals, i.e., Na₂[B-α-SbW₉O] 33 19.5H2O;

[0011] S2. Synthesis of acetate-sodium acetate buffer: S21. Prepare an aqueous solution of sodium acetate with a concentration of 0.2-0.35 mol / L and an aqueous solution of acetic acid with a concentration of 0.3-0.45 mol / L; S22. Mix the aqueous solutions of sodium acetate and acetic acid of the above concentrations to obtain the acetate-sodium acetate buffer.

[0012] S3. Sequentially weigh the Na9[B-α-SbW9O] prepared in step S1. 33 19.5H2O and imidazole were added to a polytetrafluoroethylene (PTFE) reactor, followed by the acetate-sodium acetate buffer solution prepared in step S2. The mixture was stirred at room temperature for 0.5-2 hours to ensure homogeneity. The PTFE reactor was then placed in a constant temperature oven for hydrothermal reaction. After the reaction cooled to room temperature, the crystals were extracted and vacuum dried to obtain 0.5-2.0 mm hexagonal colorless plate-like crystals, thus obtaining the polyacid-organic supramolecular framework material. Na9[B-α-SbW9O] 33 The concentration ratio of 19.5H2O to imidazole is 1:11; the hydrothermal reaction temperature is 100-160℃, and the hydrothermal reaction time is 1-6 days.

[0013] An application of a polyacid-organic supramolecular framework material, wherein the polyacid-organic supramolecular framework material is used as a proton conduction material in the field of fuel cells.

[0014] By adopting the above technical solution, the present invention has the following advantages compared with the prior art:

[0015] 1) The hexagonal pore multi-acid-organic supramolecular framework material prepared by this invention has a water-resistant and heat-resistant one-dimensional hydrogen bond network channel, which provides an effective proton conduction channel and proton transport site, providing an important guarantee for exploring the proton conduction performance under high temperature and anhydrous conditions.

[0016] 2) The hexagonal pore multi-acid-organic supramolecular framework material prepared by this invention can conduct protons under high-temperature and anhydrous conditions, and its anhydrous proton conductivity at 150℃ is 5.83 × 10⁻⁶. -5 S cm -1 .

[0017] 3) This invention employs a simple hydrothermal treatment process to synthesize a multi-acid-organic supramolecular framework material with hexagonal channels in a "one-pot" method. The synthesis process is simple, with good crystallinity and high yield. This multi-acid-organic supramolecular framework material can be used as a proton conduction material in the field of fuel cells. Attached Figure Description

[0018] Figure 1 This is a schematic diagram illustrating the working principle of a fuel cell.

[0019] Figure 2 Here is a physical image of the polyacid-organic supramolecular framework crystal material prepared in this invention;

[0020] Figure 3 The crystal structure diagram of the polyacid-organic supramolecular framework material of the present invention is shown in Figure a: where Figure a is [Sb2W 19 O 67 (H2O)] polyanion clusters; Figure b shows protonated imidazole cations; Figure c shows a cluster based on 6 [SbW 19 O 67 (H2O)] clusters and a supramolecular macrocycle {[SbW 19 O 67 (H2O)]6(HIm) 30 Figure d is a top view based on 6 [SbW] 19 O 67 (H2O)] clusters and a supramolecular macrocycle {[SbW 19 O 67 (H2O)]6(HIm) 30 Figure e is a side view of a one-dimensional nanotube based on a supramolecular macrocycle; Figure f is a side view of a one-dimensional nanotube based on a supramolecular macrocycle.

[0021] Figure 4 A three-dimensional supramolecular framework structure diagram of the polyacid-organic supramolecular framework material prepared in this invention;

[0022] Figure 5 This is a powder diffraction pattern of the polyacid-organic supramolecular framework material prepared in this invention;

[0023] Figure 6 Thermogravimetric analysis diagram of the polyacid-organic supramolecular framework material prepared in this invention;

[0024] Figure 7 Temperature-dependent powder diffraction pattern of the polyacid-organic supramolecular framework material prepared in this invention;

[0025] Figure 8 Powder diffraction patterns of the polyacid-organic supramolecular framework material prepared in this invention under different pH solutions;

[0026] Figure 9 Powder diffraction patterns of the polyacid-organic supramolecular framework material prepared in this invention under different organic solvents;

[0027] Figure 10 Anhydrous proton conductivity tests of the polyacid-organic supramolecular framework materials prepared in this invention: Figures ab and b show the Nyquist plots of their AC impedance data under anhydrous conditions at temperatures of 25-150℃; Figure c shows their proton conductivity under anhydrous conditions at temperatures of 25-150℃; Figure d shows the Arrhenius plot under anhydrous conditions.

[0028] Figure 11 The powder diffraction pattern of the polyacid-organic supramolecular framework material prepared in this invention after high-temperature anhydrous proton conduction testing. Detailed Implementation

[0029] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0030] Example 1: Polyacid-Organic Supramolecular Framework Material H3(HIm) 11 [Sb2W 19 O 67 Preparation of (H2O)·solvent

[0031] (1) Tri-vacancy antimony tungstate precursor Na9[B-α-SbW9O] 33 Synthesis of 19.5H2O:

[0032] 40g of sodium tungstate dihydrate was dissolved in 80mL of deionized water at 80℃ to obtain a sodium tungstate solution. Then, 1.96g of antimony trioxide was dissolved in 10mL of concentrated hydrochloric acid to obtain a mixed solution. The mixed solution was added dropwise to the sodium tungstate solution and refluxed at 95℃ for 1 hour. The reaction solution was then concentrated to 2 / 3 of its volume, cooled to room temperature, and white crystals were obtained. After filtration, the crystals were washed with ethanol and naturally dried to obtain white granular crystals, i.e., Na₂[B-α-SbW₉O₂]. 33 19.5H2O;

[0033] (2) Synthesis of acetate-sodium acetate buffer:

[0034] Weigh 10.25g of sodium acetate and measure 6.25mL of glacial acetic acid. Dilute with deionized water to a volumetric flask containing 250mL to obtain an acetate-sodium acetate buffer solution with a pH of 4.80.

[0035] (3) Compound H3(HIm) 11 [Sb2W 19 O 67 Preparation of (H2O)·solvent:

[0036] Weigh out the Na9[B-α-SbW9O] obtained in step S1 sequentially. 33 Add 19.5H₂O (5.00g, 1.75mmol) and imidazole (1.30g, 19.10mmol) to a 100mL polytetrafluoroethylene (PTFE) reactor, then add 50mL of acetate-sodium acetate buffer solution (pH 4.80) prepared in step S2, and stir at room temperature for 1 hour to ensure homogeneity. The PTFE reactor is then placed in a constant temperature oven for hydrothermal reaction at 140℃ for 1 day. After cooling to room temperature, the crystals are extracted, vacuum dried, and 0.5-2.0mm hexagonal colorless plate-like crystals are obtained, thus yielding the polyacid-organic supramolecular framework material.

[0037] (4) Basic characterization of the hexagonal pore multi-acid-organic supramolecular framework material prepared in this embodiment:

[0038] 1) Crystal structure determination

[0039] Select a single crystal of suitable size, regular shape, and transparency under a microscope. Then, using a Bruker APEX II CCD diffractometer, monochromate the Mo-Kα rays at 175(2)K using a graphite monochromator. The crystal was used as an incident light source to collect diffraction data. In the structural analysis, the Shelextl-2018 program was used to directly analyze and refine the crystal structure. Simultaneously, non-hydrogen atoms and their anisotropic treatment parameters were corrected using the full-matrix least squares method. All hydrogen atoms were obtained through theoretical hydrogenation. The resulting crystal structure is shown below. Figure 3 and Figure 4 As shown, some crystallographic data and refinement parameters are shown in Table 1.

[0040] Table 1: Crystal parameters of the compounds

[0041]

[0042] 2) Powder diffraction characterization:

[0043] Take an appropriate amount of the polyacid-organic supramolecular framework material crystals prepared by the above method, grind them thoroughly into powder, and analyze the powder diffraction pattern measured at room temperature (e.g., ...). Figure 5 As shown in the figure, the experimental results are in good agreement with the results of the Mercury software fitting, indicating that the compound is a pure phase. The anisotropy of the crystal causes some differences in the peak intensity of some diffraction peaks.

[0044] 3) Stability test:

[0045] Thermogravimetric analysis and temperature-dependent powder diffraction tests showed that (e.g.) Figure 6-7 As shown in the figure, the hexagonal pore multi-acid-organic supramolecular framework material remains stable at 180℃, indicating its high thermal stability. Furthermore, after immersion in aqueous solutions with pH values ​​ranging from 2 to 13 and in various organic solvents for 24 hours, its powder diffraction pattern matches the fitted PXRD pattern well (e.g., ...). Figure 8-9 As shown in the figure, its good acid-base stability and chemical stability are further revealed.

[0046] Example 2: Polyacid-Organic Supramolecular Framework Material H3(HIm) 11 [Sb2W 19 O 67 Preparation of (H2O)·solvent

[0047] (1) Tri-vacancy antimony tungstate precursor Na9[B-α-SbW9O] 33 Synthesis of 19.5H2O:

[0048] 45g of sodium tungstate dihydrate was dissolved in 90mL of deionized water at 80℃ to obtain a sodium tungstate solution. Then, 2.12g of antimony trioxide was dissolved in 15mL of concentrated hydrochloric acid to obtain a mixed solution. The mixed solution was added dropwise to the sodium tungstate solution and refluxed at 90℃ for 1.5 hours. The reaction solution was then concentrated to 2 / 3 of its volume, cooled to room temperature, and white crystals were obtained. After filtration, the crystals were washed with ethanol and naturally dried to obtain white granular crystals, i.e., Na₂[B-α-SbW₉O₂]. 33 19.5H2O;

[0049] (2) Synthesis of acetate-sodium acetate buffer:

[0050] Weigh 12.3g of sodium acetate and measure 8.25mL of glacial acetic acid. Dilute with deionized water to a volumetric flask containing 250mL to obtain an acetate-sodium acetate buffer solution with a pH of 5.0.

[0051] (3) Compound H3(HIm) 11 [Sb2W 19 O 67 Preparation of (H2O)·solvent:

[0052] Weigh out the Na9[B-α-SbW9O] obtained in step S1 sequentially. 33 19.5H₂O (6.00g, 2.10mmol) and imidazole (1.5g, 22.06mmol) were added to a 100mL polytetrafluoroethylene (PTFE) reactor. Then, 60mL of acetate-sodium acetate buffer solution (pH 5.0) prepared in step S2 was added, and the mixture was stirred at room temperature for 1.5 hours to ensure homogeneity. The PTFE reactor was then placed in a constant temperature oven for hydrothermal reaction at 160℃ for 1.5 days. After cooling to room temperature, the crystals were extracted, vacuum dried, and 0.5-2.0mm hexagonal colorless plate-like crystals were obtained, thus yielding the polyacid-organic supramolecular framework material.

[0053] Example 3: Polyacid-Organic Supramolecular Framework Material H3(HIm) 11 [Sb2W 19 O 67 Preparation of (H2O)·solvent

[0054] (1) Tri-vacancy antimony tungstate precursor Na9[B-α-SbW9O] 33 Synthesis of 19.5H2O:

[0055] 50g of sodium tungstate dihydrate was dissolved in 100mL of deionized water at 80℃ to obtain a sodium tungstate solution. Then, 2.5g of antimony trioxide was dissolved in 10mL of concentrated hydrochloric acid to obtain a mixed solution. The mixed solution was added dropwise to the sodium tungstate solution and refluxed at 90℃ for 2 hours. The reaction solution was then concentrated to 2 / 3 of its volume, cooled to room temperature, and white crystals were obtained. After filtration, the crystals were washed with ethanol and naturally dried to obtain white granular crystals, i.e., Na₂[B-α-SbW₉O₂]. 33 19.5H2O;

[0056] (2) Synthesis of acetate-sodium acetate buffer:

[0057] Weigh 15g of sodium acetate and measure 10mL of glacial acetic acid. Dilute with deionized water to a volumetric flask containing 250mL to obtain an acetate-sodium acetate buffer solution with a pH of 4.5.

[0058] (3) Compound H3(HIm) 11 [Sb2W 19 O 67 Preparation of (H2O)·solvent:

[0059] Weigh out the Na9[B-α-SbW9O] obtained in step S1 sequentially. 33 19.5H₂O (8.00g, 2.8mmol) and imidazole (2.0g, 29.41mmol) were added to a 100mL polytetrafluoroethylene (PTFE) reactor. Then, 80mL of acetate-sodium acetate buffer solution (pH 4.50) prepared in step S2 was added, and the mixture was stirred at room temperature for 1 hour to ensure homogeneity. The PTFE reactor was then placed in a constant temperature oven for hydrothermal reaction at 150℃ for 2 days. After cooling to room temperature, the crystals were extracted, vacuum dried, and 0.5-2.0mm hexagonal colorless plate-like crystals were obtained, thus yielding the polyacid-organic supramolecular framework material.

[0060] Example 4: Polyacid-Organic Supramolecular Framework Material H3(HIm) 11 [Sb2W 19 O 67 Applications of (H2O)·solvent in fuel cells

[0061] (1) Sample preparation method: First, the obtained crystal powder was thoroughly ground and dried. An appropriate amount of the ground crystal powder and two 70mg portions of carbon powder were weighed. Then, a tablet press was used to press the central sample powder and the carbon powder at both ends into a three-layer cylindrical sheet with a diameter of φ5mm × 1.5mm and a central sample and carbon powder at both ends. Test method: The cylindrical sheet was placed in a STIKCorp CIHI-150BS3 constant temperature and humidity chamber, and a silver electrode was connected. The resistance was tested using an SI 1260IMPEDANCE / GAINPHASE impedance analyzer. The test voltage was 50mV, and the test range was 0.1Hz-5 MHz. The test results were obtained by fitting the Nyquist curve using ZSimpWin software to obtain the impedance value R. The conductivity was then obtained by substituting the obtained impedance value into the formula σ=L / RS.

[0062] (2) Proton conductivity performance test: Proton conductivity was tested under high-temperature, anhydrous conditions (e.g., Figure 10 As shown in ab), the conductivity of the proton-conducting material prepared according to this embodiment as a function of temperature was obtained. From Figure 10 c shows that the proton conductivity at 25℃ is 9.59 × 10⁻⁶. -8 S cm -1 This value is higher than the conductivity of pure imidazole (1.00 × 10⁻⁶). -8 Scm -1 This is an order of magnitude higher. As temperature increases, the proton conductivity rapidly reaches 1.03 × 10⁻⁶ at 85 °C. -5 S cm -1 It then increases slowly and reaches a maximum value of 5.83 × 10 at 150℃. -5 S cm -1 This conductivity is superior to most polyacid-based anhydrous proton-conducting materials. The graph shows that increasing temperature significantly improves the material's proton conductivity. This is because the thermal motion of the carrier molecules increases with temperature, thereby enhancing proton conductivity.

[0063] (3) Investigation of proton conduction mechanism: In order to reveal the proton conduction mechanism in this supramolecular framework material, the conductivity at different temperatures was linearly fitted, and the Arrhenius formula Σt=σ0exp(-E) was used. a / k b T), with ln(σT) / (S·cm) -1 ·K) for 1000 / T(K -1 )Draw a diagram, such as Figure 10As shown in Figure d, the Arrhenius diagram in the 25-150℃ range can be divided into two parts. In the 25-85℃ range, the activation energy is 0.75 eV, and the transport mechanism can be attributed to the vehicle mechanism, indicating that proton transport in this supramolecular framework material is dominated by diffusion. However, in the 85-150℃ range, the activation energy of this supramolecular framework material is 0.36 eV, which is much lower than the activation energy in the low-temperature region. Its proton transport mechanism follows the Grotthuss mechanism, indicating that at this temperature, protons in the supramolecular framework material are transported via the HIm... + The hydrogen bond network between cations and POM clusters shifts and transfers. This may be due to the loss of water of crystallization molecules at high temperatures, leading to a reduction in the number of proton carriers, thus changing proton motion from diffusion to hopping. This can be seen by comparing the powder diffraction pattern of the sample after testing with the powder diffraction pattern before testing (e.g., Figure 11 As shown in the figure, the diffraction peaks did not change and showed good agreement, indicating that the crystal framework structure of the sample remained intact after the test.

[0064] The above description is merely a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A polyacid-organic supramolecular framework material, characterized in that: The molecular formula of the polyacid-organic supramolecular framework material is H3(HIm). 11 [Sb2W 19 O 67 [(H2O)]·nH2O, where Im is imidazole; n is the number of water molecules of crystallization; the polyacid-organic supramolecular framework material has hexagonal channels, and the structural characteristics of the polyacid-organic supramolecular framework are: six [Sb2W 19 O 67 [H2O] The polyanionic building block is located at the six corners of a hexagon, and is formed by 30 protonated imidazole countercations linked by multiple hydrogen bonds to form a hexagonal supramolecular cluster. The molecular formula of the cluster is {[Sb2W] 19 O 67 (H2O)]6(HIm) 30 Adjacent clusters form one-dimensional nanotube structures through supramolecular interactions of imidazole counter cations, and the nanotubes are then connected to each other through imidazole counter cations to form a three-dimensional supramolecular framework.

2. The polyacid-organic supramolecular framework material as described in claim 1, characterized in that: The crystal structure of the polyacid-organic supramolecular framework material belongs to the hexagonal crystal system, with space group [space group missing]. P 6 / mcc The corresponding spatial group number is 192.

3. The polyacid-organic supramolecular framework material as described in claim 2, characterized in that: The unit cell parameters of the polyacid-organic supramolecular framework material are: a = 33.9033(7) (Å), b = 33.9033(7) (Å), c = 38.4911(17)(Å), α = β = 90°, γ = 120°.

4. A method for preparing a polyacid-organic supramolecular framework material as described in any one of claims 1-3, characterized in that, Includes the following steps: S1, Tri-vacant antimony tungstate precursor Na9[ B - α -SbW9O 33 Synthesis of 19.5H2O: S11, Prepare an aqueous solution of sodium tungstate at 80℃ and a concentration of 1.5-2.0 mol / L; S12, Prepare a concentrated hydrochloric acid solution of antimony, wherein the antimony raw material is antimony trioxide, and the molar ratio of antimony trioxide to hydrochloric acid is 1:18; S13, Add the concentrated hydrochloric acid solution of antimony dropwise to the sodium tungstate solution, reflux at 80-110℃ for 1-2 hours, then concentrate the reaction solution to 2 / 3 volume, cool to room temperature to obtain white crystals, filter, wash with ethanol, and air dry to obtain white granular crystals, i.e., Na9[ B - α -SbW9O 33 19.5H2O; S2. Synthesis of acetate-sodium acetate buffer: S21. Prepare an aqueous solution of sodium acetate with a concentration of 0.2-0.35 mol / L and an aqueous solution of acetic acid with a concentration of 0.3-0.45 mol / L; S22. Mix the aqueous solutions of sodium acetate and acetic acid of the above concentrations to obtain the acetate-sodium acetate buffer. S3. Sequentially weigh the Na9[ obtained in step S1] B - α -SbW9O 33 19.5 H2O and imidazole were added to a polytetrafluoroethylene reactor, followed by the acetate-sodium acetate buffer solution prepared in step S2. The mixture was stirred at room temperature for 0.5-2 hours to ensure uniform mixing of the raw materials. The polytetrafluoroethylene reactor was then placed in a constant temperature oven for hydrothermal reaction. After the reaction cooled to room temperature, the crystals were extracted and vacuum dried to obtain 0.5-2.0 mm hexagonal colorless plate-like crystals, which is the polyacid-organic supramolecular framework material. Among them, Na9[ B - α -SbW9O 33 The molar ratio of 19.5H2O to imidazole is 1:11; the hydrothermal reaction temperature is 100-160 ℃, and the hydrothermal reaction time is 1-6 days.

5. An application of the polyacid-organic supramolecular framework material as described in claim 1, characterized in that: The aforementioned polyacid-organic supramolecular framework material is used as a proton conduction material in the field of fuel cells.

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