Platinum nanoparticle-loaded covalent organic framework material and method for preparing the same

Abstract

The application belongs to the technical field of hydrogen production catalysts for water electrolysis, and particularly relates to a two-dimensional covalent organic framework material loaded with Pt nanoparticles and a preparation method thereof. The two-dimensional covalent organic framework material loaded with Pt nanoparticles has a two-dimensional covalent organic framework containing hexaazatriphenylene (HATN) and Pt loaded on the two-dimensional covalent organic framework in the form of nanoparticles by complexing sites on the nitrogen atoms in HATN. The application successfully constructs the two-dimensional covalent organic framework material loaded with Pt nanoparticles by means of the complexing ability of the HATN structure to metals, and finds that the material can be used as a high-efficiency hydrogen production catalyst for water electrolysis. The material preparation process of the application is simple, and the process does not involve high temperature, and the material has the characteristics of green environmental protection, low preparation cost and large-scale promotion.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of catalysts for hydrogen production by water electrolysis, and particularly relates to a platinum nanoparticle-loaded covalent organic framework material and a preparation method thereof. BACKGROUND

[0002] Water electrolysis for hydrogen production as an important green energy production method has attracted more and more attention in recent years. Catalysts play a crucial role in the process of water electrolysis for hydrogen production, and the optimization design of catalysts is of great significance in improving reaction efficiency, reducing energy consumption and improving the stability of catalysts. Noble metals such as platinum (Pt) are widely used in water electrolysis catalytic reactions due to their excellent catalytic performance, but their cost is high and resources are limited. Therefore, how to design a low-cost, efficient and stable Pt catalyst for water electrolysis for hydrogen production has become a research hotspot. Covalent organic framework (COFs) materials have become an ideal choice for catalyst carriers due to their adjustable structure, high porosity and excellent stability. However, the traditional high-temperature reduction loading method will destroy the structure of COFs, and high temperature will also cause the agglomeration of metal nanoparticles loaded on COFs to intensify.

[0003] Therefore, how to uniformly load noble metal nanoparticles on COFs at room temperature, effectively inhibit their agglomeration and protect the structure of COFs from being destroyed so that they can exert the best performance in water electrolysis catalytic reactions has always been a technical problem. SUMMARY

[0004] To solve the above problems, the application provides a platinum nanoparticle-loaded covalent organic framework material and a preparation method thereof, and the application is realized by the following technical scheme.

[0005] A platinum nanoparticle-loaded covalent organic framework material, the two-dimensional platinum nanoparticle-loaded covalent organic framework material has a two-dimensional covalent organic framework containing HATN and metal Pt loaded on the two-dimensional covalent organic framework in the form of nanoparticles by complexing sites in HATN with nitrogen atoms, the HATN is hexaazatriphenylene, and the metal Pt is platinum.

[0006] The metal Pt is first complexed in the form of ions at the HATN position, and after reduction by a reducing agent, it becomes nanoparticles and grows in situ in the pores of the two-dimensional covalent organic framework.

[0007] Further, the platinum nanoparticle-loaded covalent organic framework material is prepared by forming an intermediate HATN from cyclohexanehexone and o-phenylenediamine and complexing Pt ions, and then forming a two-dimensional covalent organic framework by dynamic exchange of o-phenylenediamine in HATN with tetraamino-p-benzoquinone monomers.

[0008] Further, the reducing agent is NaBH4 aqueous solution, and the concentration is 2-8 mol / L.

[0009] A preparation method of a platinum nanoparticle loaded covalent organic framework material, comprising the following steps:

[0010] S1, first, HKH, OPD and H2PtCl6·xH2O are added into a reaction tube, the reaction tube is provided with ethanol and trimethylbenzene, and the mixture is prepared by mixing and stirring for 15 min, the HKH is cyclohexanone octahydrate, the OPD is o-phenylenediamine, and the H2PtCl6·xH2O is chloroplatinic acid solution;

[0011] S2, acetic acid is added to the obtained mixture, and the mixture is stirred for 15 min, and then the mixture is transferred to blue light LED light with a wavelength of 460 nm for irradiation, and the mixture is reacted for 4 h, so that the Pt3-HATN precursor is formed;

[0012] S3, TABQ and acetic acid are added into the reaction tube in which the Pt3-HATN precursor is formed, and then the mixture is irradiated for 12 h, so that the skeleton crystallization process is completed, and the π conjugated COFs with high crystallinity and ordered pores are obtained, and the TABQ is tetraamino-p-quinone monomer;

[0013] S4, the obtained product is washed with ethanol and then washed with water, and then the product is dried at 80 DEG C under vacuum for 12 h after water washing, so that the Pt / COF is obtained;

[0014] S5, 40 mg of the Pt / COF is dissolved in 5 ml of water, and then the mixture is ultrasonically treated for 30 min to obtain a suspension;

[0015] S6, then, the newly configured NaBH4 aqueous solution is quickly injected into the obtained suspension, and the mixture is stirred for 15 s, and then the mixture is left to stand for 24 h to obtain a mixture;

[0016] S7, the obtained mixture is filtered, and then the filtered mixture is washed with water, and then the washed mixture is dried at 80 DEG C under vacuum for 12 h, so that the Pt / COF-R is obtained.

[0017] Further, in the step S1, the HKH is 62.4 mg, the OPD is 64.8 mg, the H2PtCl6·xH2O is chloroplatinic acid aqueous solution (the content is 8 wt.%in H2O), the ethanol is 2 ml, and the trimethylbenzene is 2 ml.

[0018] Further, in the step S2, the acetic acid is 1 ml, and the concentration is 36%.

[0019] Further, in the step S3, the TABQ is 50.4 mg, and the acetic acid is 1 ml with a concentration of 36%.

[0020] Further, in the step S6, the NaBH4 aqueous solution is 5 ml.

[0021] The material successfully constructs a two-dimensional covalent organic framework loaded with Pt nanoparticles by using the complexing ability of the hexaazatriphenylene structure to metals, and the material has excellent performance in the hydrogen production catalysis of water electrolysis. BRIEF DESCRIPTION OF DRAWINGS

[0022] In order to more clearly illustrate the technical solutions of the present application, the following will briefly introduce the drawings needed in the specific implementation manner. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0023] Figure 1 The material synthesis and characterization of the covalent organic framework material loaded with platinum nanoparticles and the preparation method thereof according to the present application;

[0024] Figure 2 The catalyst morphology and microstructure analysis according to the present application;

[0025] Figure 3 The electronic structure analysis of the catalyst according to the present application;

[0026] Figure 4 The electrochemical performance characterization of the catalyst according to the present application. DETAILED DESCRIPTION

[0027] The technical solutions in the embodiments of the present application will be described clearly and completely in combination with the drawings in the embodiments of the present application. Obviously, the described embodiments are only some embodiments of the present application, not all. Based on the embodiments in the present application, all other embodiments obtained by those skilled in the art without creative labor are within the scope of protection of the present application.

[0028] As shown in the following specific embodiments, the present application has the following specific embodiments. Figures 1-4

[0029] Embodiment:

[0030] ​A kind of platinum nanoparticle loaded covalent organic framework material, the two-dimensional covalent organic framework material loaded with Pt nanoparticles has two-dimensional covalent organic framework comprising HATN and metal Pt loaded on two-dimensional covalent organic framework in the form of nanoparticles by complexing site in HATN nitrogen atom, wherein HATN is hexaazatriphenylene, and metal Pt is platinum;

[0031] Metal Pt is first complexed in ion form at HATN position, and becomes nanoparticles after reduction by reducing agent to grow in-situ in the channel of two-dimensional covalent organic framework.

[0032] Further, the platinum nanoparticle loaded covalent organic framework material is prepared by the intermediate HATN formed by cyclohexanhexone and o-phenylenediamine and complexing Pt ions, and then forming two-dimensional covalent organic framework by dynamic exchange of o-phenylenediamine in HATN by tetraamino-p-benzoquinone monomer.

[0033] Further, the reducing agent is NaBH4 aqueous solution, and the concentration is 2-8 mol / L.

[0034] A preparation method of a platinum nanoparticle loaded covalent organic framework material, comprising the following steps:

[0035] S1, first, HKH, OPD and H2PtCl6·xH2O are added to a reaction tube, and ethanol and trimethylbenzene are provided in the reaction tube, so that they are mixed and stirred for 15 min to obtain a mixture, HKH is cyclohexanhexone octahydrate, OPD is o-phenylenediamine, and H2PtCl6·xH2O is chloroplatinic acid solution;

[0036] S2, acetic acid is added to the obtained mixture, and it is stirred for 15 min, and then it is transferred to blue light LED light of 460 nm wavelength for irradiation, so that it is reacted for 4 h, thereby forming Pt3-HATN precursor;

[0037] S3, TABQ and acetic acid are added to the reaction tube in which Pt3-HATN precursor is formed, and then it is irradiated for 12 h, thereby completing the skeleton crystallization process, obtaining π conjugated COFs with high crystallinity and ordered pores, and TABQ is tetraamino-p-benzoquinone monomer;

[0038] S4, the obtained product is first washed with ethanol, and then washed with water, and after water washing, it is dried at 80℃ under vacuum for 12 h, thereby obtaining Pt / COF;

[0039] S5, 40 mg of the above Pt / COF is dissolved in 5 ml of water, and then ultrasonic treatment is carried out for 30 min to obtain a suspension;

[0040] S6, then the newly configured NaBH4 aqueous solution is quickly injected into the obtained suspension, and the mixture is stirred for 15 s, and then is left to stand for 24 h to obtain a mixture;

[0041] S7, the mixture obtained above is filtered, and then is washed with water, and then is dried at 80 °C under vacuum for 12 h to obtain Pt / COF-R.

[0042] Specifically, in step S1, HKH is 62.4 mg, OPD is 64.8 mg, H2PtCl6 x H2O is an aqueous solution of chloroplatinic acid (the content is 8 wt.% in H2O), ethanol is 2 ml, and mesitylene is 2 ml.

[0043] Specifically, in step S2, acetic acid is 1 ml, and the concentration is 36%.

[0044] Specifically, in step S3, TABQ is 50.4 mg, acetic acid is 1 ml, and the concentration is 36%.

[0045] Specifically, in step S6, the aqueous solution of NaBH4 is 5 ml.

[0046] In the synthesis of Pt / COF and Pt / COF-R:

[0047] ① Synthesis of Pt / COF: 62.4 mg of HKH, 64.8 mg of OPD and a certain amount of H2PtCl6 x H2O are added to a reaction tube containing 2 mL of ethanol and 2 mL of mesitylene, and the mixed solvent is stirred for 15 min. Then 1 ml of 36% acetic acid is added to the above mixture, and after stirring for 15 min, the reaction is transferred to a blue light LED light with a wavelength of 460 nm for irradiation, and the reaction is carried out for 4 h to form a Pt3-HATN precursor. Subsequently, 50.4 mg of TABQ and another 1 ml of 36% acetic acid are added to the above reaction tube. Then, blue light irradiation is used for 12 h to complete the skeleton crystallization process, and a π-conjugated COF with high crystallinity and ordered pores is obtained. The obtained powder precipitate is washed with ethanol and water respectively, and then dried at 80 °C under vacuum for 12 h to obtain Pt / COF. According to the different amounts of H2PtCl6 x H2O (25, 50, 100, 200 μL), four samples of Pt / COF-1, Pt / COF-2, Pt / COF-3, Pt / COF-4 are obtained. In order to compare, we also synthesized COFs without adding Pt (named: pure COF).

[0048] According to the different amounts of H2PtCl6 x H2O added, five samples can be synthesized:

[0049]

[0050] ii. Synthesis of Pt / COF-R: 40 mg of Pt / COF was dispersed in 5 ml of water and sonicated for 30 min. Then, 5 ml of freshly prepared NaBH4 aqueous solution was quickly injected into the suspension above, stirred for 15 s, and left to stand for 24 h. The mixture was filtered and washed with water, and dried at 80 °C under vacuum for 12 h to obtain Pt / COF-R (i.e., Pt / COF-R1, Pt / COF-R2, Pt / COF-R3 and Pt / COF-R4);

[0051] As shown in Figure 1 , the synthesis and characterization of materials:

[0052] Figure 1 a is a schematic diagram of the synthesis of pure COF, Pt / COF and Pt / COF-R, wherein the pure COF is synthesized by condensation reaction (i.e., assisted dynamic imine exchange reaction) between HKH and TABQ under blue light illumination, having a porous structure with π conjugation. In the above condensation reaction, we focus on the intermediate of the process: hexaazatriphenylene (HATN, as shown in the shaded area of Figure 1 a), which is an electron-deficient conjugated planar system that can coordinate with various metal ions to form M3-HATN. Given the above characteristics, HATN is used as a dynamic precursor to construct Pt / COF. After NaBH4 induced reduction, Pt 4+ is converted into Pt nanowires to obtain Pt / COF-R( Figure 1 a). Therefore, we can establish a hydrogen overflow channel by assembling Pt nanowires on porous nitrogen-rich COFs with crystalline structure, which is conducive to hydrogen overflow and improves the performance of HER ( Figure 1 b). In order to find the best HER electrocatalyst, we synthesized a series of Pt / COF-R with different Pt contents, i.e., Pt / COF-R1, Pt / COF-R2, Pt / COF-R3 and Pt / COF-R4, and determined their chemical composition, bonding configuration and structural characteristics by Fourier transform infrared spectroscopy (FTIR, Figure 1 c), X-ray diffraction analysis (XRD, Figure 1 d and e). As shown in Figure 1 c, the peaks at ~1620 cm -1 and ~1240 cm -1 belong to -C=C- and -C=N-, which indicates that a π conjugated network has been formed. Interestingly, for Pt / COF-3 and Pt / COF-R3, no structural damage occurred after the introduction of Pt ions and NaBH4 reduction. The above results prove that the COFs we synthesized have strong metal ion coordination ability, and their structure is not damaged in this process. Figure 1The XRD patterns of d show that the crystal structure of Pt / COF-x (x = 1, 2, 3, and 4) is in good agreement with that of the original COF. The strong diffraction peaks at ~16° and ~28° are attributed to the (101) and (002) crystal planes of the AB stacking structure of COFs. After reduction, Pt / COF-Rx (x = 1, 2, 3, and 4) exhibit similar diffraction peaks, while the diffraction peaks at ~40° and ~46° indicate the presence of Pt nanowires (PDF#87-0640). Figure 1 e) Furthermore, the diffraction peaks of the platinum nanowires gradually increased with increasing initial Pt content. XRD analysis showed that after Pt was grown on COFs, the COF structure was not destroyed and its characteristics were preserved, which is beneficial for retaining hydrogen overflow channels and thus facilitates the HER process.

[0053] like Figure 2 The image shows the catalyst morphology and microstructure analysis:

[0054] Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) further revealed the morphology and distribution of Pt / COF-R3, in which COFs existed in a nanotube morphology. Figure 2 a, b). Pt nanowires were observed to be uniformly distributed on COF nanotubes in dark-field (DF)-TEM images. Figure 2 c). High-resolution transmission electron microscopy of Pt / COF-R3 ( Figure 2 As shown in d and e), the repeating distance of the parallel lines is approximately 0.97 nm (3d), which is formed by the interplanar spacing of ~0.32 nm (π-packing distance) (consistent with the peak at ~28° in the XRD pattern). Figure 1 e). Figure 2 The selected area electron diffraction (SAED) pattern in f shows results consistent with the characteristic diffraction rings of Pt. High-resolution TEM images further reveal the lattice fringes of the Pt nanowires with interplanar spacings of 0.19 nm and 0.23 nm, corresponding to Pt(200) and Pt(111), respectively. Figure 2 g, h). Energy-dispersive X-ray spectroscopy (EDS) further confirmed that the Pt nanowires were uniformly dispersed on a nitrogen-doped COF matrix. Figure 2 i). The above results demonstrate the successful synthesis of nitrogen-rich COFs with clear pores and good crystallinity; more importantly, the COFs structure remains intact after being successfully mounted with Pt nanowires.

[0055] like Figure 3 The image shows the electronic structure analysis of the catalyst: X-ray photoelectron spectroscopy.

[0056] X-ray photoelectron spectroscopy (XPS) revealed the chemical valence state and electronic structure of Pt / COF and Pt / COF-R. Figure 3 ).likeFigure 3 a, b show typical C, N, O and Pt characteristic binding energies, where the Pt content of Pt / COF-R1, Pt / COF-R2, Pt / COF-R3 and Pt / COF-R4 is 1.11 wt%, 2.34 wt%, 3.58 wt% and 7.32 wt%, respectively, indicating that the Pt content gradually increases with the increase of the initial addition of chloroplatinic acid solution. The C 1s high-resolution XPS spectra of Pt / COF-Rx (x = 1, 2, 3 and 4) show that the peaks located at 284.4, 284.8, 285.7, 286.7, 287.9 and 290.4 eV are attributed to C=C, C-C, C-N, C=N, C=O bonds and π-π satellite peaks, respectively Figure 3 c) As shown in Figure 3 d, the XPS spectrum of N 1s can be divided into two peaks: 399.0 eV and 400.6 eV, which correspond to pyrazine-N and “pyrazine-N coordinated with metal”, respectively. Interestingly, in terms of peak area, the proportion of “pyrazine-N coordinated with metal” in Pt / COF-R1 is 22.67%, which is lower than that of Pt / COF-R2 (23.02%), Pt / COF-R3 (25.50%) and Pt / COF-R4 (28.08%); that is, with the increase of Pt content, the proportion of “pyrazine-N coordinated with metal” gradually increases, indicating that the N atom in COF is the anchoring site of Pt. In Figure 1 a, we mentioned: “Pt / COF was constructed by using HATN as a dynamic precursor”, which is consistent with the above analysis results. In addition, the Pt 4f spectrum of Pt / COF-R1 exhibits two valence states of Pt 0 (71.1 eV and 74.5 eV) and Pt 4+ (73.0 eV and 76.3 eV) Figure 3 e); while in Pt / COF-R2, Pt / COF-R3 and Pt / COF-R4 samples, these peaks of Pt 0 and Pt 4+ slightly move to the side of higher binding energy, indicating that there is a strong electronic interaction between atomic Pt and the COF matrix.

[0057] As shown in Figure 4 is the electrochemical performance characterization of the catalyst:

[0058] In order to evaluate the HER electrocatalytic activity of the prepared catalyst, the samples were tested in 0.5 M H2SO4 electrolyte, and the electrochemical hydrogen evolution performance of Pt / COF-Rx (x = 1, 2, 3 and 4) and 20 wt% commercial Pt / C was evaluated on a glassy carbon disc electrode Figure 4 ). Figure 4The HER polarization curves in a show that Pt / COF-R1 reaches 10 mA cm⁻¹ –2 An overpotential of 63mV (i.e., η) is required at the current density. 10 The η of Pt / COF-R2 (47mV), Pt / COF-R3 (11mV), and Pt / COF-R4 (6mV) is 63mV. 10 The value gradually decreases with increasing Pt content. Figure 4 The Tafel slopes in b and c yield consistent results, with Pt / COF-R4 showing the smallest Tafel slope (17.6 mV dec). –1 ), lower than Pt / COF-R1 (70.8mV dec –1 ), Pt / COF-R2 (58.6mV dec) –1 ), Pt / COF-R3 (19.5mV dec) –1 ) and 20% Pt / C (18.3mV dec –1 The reaction kinetics are studied by calculating the exchange current density (j0), such as... Figure 4 As shown in d, the exchange current density (j0) of Pt / COF-R4 is 4.40 mA cm⁻¹. –2 The value is much higher than that of Pt / COF-R1 (1.28 mA cm⁻¹). –2 Pt / COF-R2 (1.63 mA cm) –2 Pt / COF-R3 (2.74 mA cm) –2 ) and 20% Pt / C (0.49 mAcm) –2 This indicates that the reaction kinetics of Pt / COF-R4 are the highest. However, considering the utilization rate of Pt, combined with the electron transfer resistance (R... ct , Figure 4 e) Quality activity ( Figure 4 f, g) and turnover frequency (TOF, Figure 4 Among the catalysts prepared, Pt / COF-R3 exhibited the best HER activity (h) and other indicators; in particular, the mass activity of Pt / COF-R3 at an overpotential of 100 mV was 125 Amg. –1 The TOF value is 49.0 H2 s. -1 (per Pt atom), which is 20 times and 16 times that of 20% wt% Pt / C, respectively. Considering that Pt / COF-R3 has the highest overall HER activity, we measured its cycling stability ( Figure 4 i). At a constant current density of 10 mA cm⁻¹ –2 When running for 80,000 s, the overpotential only increased by ~47 mV, indicating its good electrochemical stability.

[0059] In conclusion, the application provides a platinum nanoparticle loaded covalent organic framework material and a preparation method thereof, the preparation process does not involve high temperature, the process flow is simple, it is a high-activity water electrolysis hydrogen production catalyst with great potential, and has wide application prospect.

[0060] The preferred embodiments disclosed above are only used to help explain the application. The preferred embodiments do not describe all the details and limit the application to the specific embodiments. Obviously, many modifications and variations can be made according to the content of the specification. The specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the application, so that those skilled in the art can well understand and utilize the application. The application is limited only by the claims and their full scope and equivalents.

Claims

1. A platinum nanoparticle-loaded covalent organic framework material, characterized in that, The Pt nanoparticle-loaded two-dimensional covalent organic framework material has a two-dimensional covalent organic framework containing HATN, which is hexaazatriphenylene, and metal Pt, which is platinum, loaded on the two-dimensional covalent organic framework in the form of nanoparticles by complexing the sites with nitrogen atoms in HATN; The metal Pt is first complexed in the form of ions at the HATN sites, and after reduction by a reducing agent, becomes nanoparticles and grows in situ in the channels of the two-dimensional covalent organic framework.

2. The platinum nanoparticle-loaded covalent organic framework material of claim 1, wherein: The Pt nanoparticle-loaded covalent organic framework material is prepared by an intermediate HATN formed by cyclohexanhexone and o-phenylenediamine and complexing Pt ions, and then a two-dimensional covalent organic framework formed by dynamic exchange of o-phenylenediamine in HATN with tetraamino-p-benzoquinone monomers.

3. The platinum nanoparticle-loaded covalent organic framework material of claim 1, wherein: The reducing agent is an aqueous NaBH4 solution with a concentration of 2-8 mol / L.

4. A method for preparing a platinum nanoparticle-loaded covalent organic framework material according to any one of claims 1 to 3, characterized in that, The method comprises the following steps: S1, first, HKH, OPD and H2PtCl6·xH2O are added to a reaction tube provided with ethanol and trimethylbenzene, and mixed and stirred for 15 min to obtain a mixture, the HKH is cyclohexanhexone octahydrate, the OPD is o-phenylenediamine, and the H2PtCl6·xH2O is chloroplatinic acid solution; S2, acetic acid is added to the obtained mixture, and stirred for 15 min, and then transferred to blue light LED light with a wavelength of 460 nm for irradiation, and reacted for 4 h to form a Pt3-HATN precursor; S3, TABQ and acetic acid are added to the reaction tube in which the Pt3-HATN precursor is formed, and then irradiated for 12 h to complete the skeleton crystallization process, and obtain a π-conjugated two-dimensional covalent organic framework with high crystallinity and ordered pores, the TABQ is tetraamino-p-benzoquinone monomer; S4, the obtained product is first washed with ethanol and then with water, and then dried at 80°C under vacuum for 12 h to obtain Pt / COF; S5, 40 mg of the Pt / COF is dissolved in 5 ml of water, and then treated with ultrasonic waves for 30 min to obtain a suspension; S6, then, a freshly prepared aqueous NaBH4 solution is quickly injected into the obtained suspension, and stirred for 15 s, and then left to stand for 24 h to obtain a mixture; S7, the obtained mixture is filtered, and then washed with water, and then dried at 80°C under vacuum for 12 h to obtain Pt / COF-R.

5. The method for preparing a covalent organic framework material loaded with platinum nanoparticles according to claim 4, characterized in that, In the step S1, the HKH is 62.4 mg, the OPD is 64.8 mg, the H2PtCl6·xH2O is an aqueous chloroplatinic acid solution with a content of 8 wt.%, the ethanol is 2 ml, and the trimethylbenzene is 2 ml.

6. The method of claim 4, wherein the platinum nanoparticle-loaded covalent organic framework material is prepared by the following steps: (a) synthesizing a covalent organic framework material; (b) synthesizing platinum nanoparticles; (c) mixing the covalent organic framework material and the platinum nanoparticles; and (d) drying the mixture. In the step S2, the acetic acid is 1 ml with a concentration of 36%.

7. The method for preparing a covalent organic framework material loaded with platinum nanoparticles according to claim 4, characterized in that, In the step S3, the TABQ is 50.4 mg, and the acetic acid is 1 ml with a concentration of 36%.

8. The method for preparing a covalent organic framework material loaded with platinum nanoparticles according to claim 4, characterized in that, In the step S6, the aqueous NaBH4 solution is 5 ml.

9. The platinum nanoparticle-loaded covalent organic framework material of any one of claims 1 to 3, characterized in that, The covalent organic framework material is applied as a catalyst in the hydrogen evolution reaction of water electrolysis.

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