MOF (Metal Organic Framework) capable of being used for glycerin oxidation assisted hydrogen production and preparation method thereof
By growing a vertical nanorod array structure of MOF catalyst on a conductive metal foam substrate, the problems of insufficient conductivity and binding strength of MOF materials in glycerol oxidation-assisted hydrogen production were solved, achieving high loading capacity and long-term stability, and significantly reducing hydrogen production energy consumption.
Patent Information
- Application Number
- CN202512010116.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-29
- Publication Date
- 2026-02-10
AI Technical Summary
In the prior art, MOF materials in powder form have poor electrical conductivity, low utilization of active sites, and insufficient mechanical stability. Furthermore, the traditional hydrothermal method results in low MOF loading and insufficient bonding strength on the surface of conductive metal foam substrates, which limits its application in glycerol oxidation-assisted hydrogen production.
The surface of a conductive metal foam substrate was modified by hydrogen peroxide oxidation, and the ratio of water to N,N-dimethylformamide was optimized. A MOF catalyst with a vertical nanorod array structure was grown on the conductive metal foam substrate by in-situ synthesis, achieving high loading and strong bonding.
A high loading of MOF of up to 1.2 mg/cm2 and strong bonding were achieved on a conductive metal foam substrate, which significantly reduced the overpotential of the anodic reaction and improved the efficiency of electrocatalytic hydrogen production. The material exhibited excellent GOR activity and long-term stability.
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Figure CN121496438A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the fields of materials chemistry and catalysis technology, specifically relating to a MOF that can be used for glycerol oxidation-assisted hydrogen production and its preparation method. Background Technology
[0002] Hydrogen (H2) is a key energy carrier, and water electrolysis for hydrogen production is one of the most important technological pathways currently available. However, the core challenge of this technology lies in the kinetic sluggishness of the oxygen evolution reaction (OER) at the anolyte, requiring a high overpotential, which directly leads to high energy consumption throughout the electrolysis process. Using glycerol (GOR) to replace the traditional OER is an effective solution. Glycerol, as a major byproduct in biodiesel production, not only has the advantages of abundant reserves and low price, but its theoretical oxidation potential is only 0.003 V (relative to the standard hydrogen electrode RHE), significantly lower than the 1.23 V required for OER. More importantly, this reaction can simultaneously generate a variety of high-value-added chemical products, such as formic acid and dihydroxyacetone, compounds with significant industrial value. In the field of electrocatalysts, MOF materials are widely recognized as promising electrocatalytic materials due to their unique advantages, including high specific surface area, abundant pore structure, densely distributed metal active sites, and tunable functional ligands. However, these catalysts have significant drawbacks when existing in powder form: they need to be fixed to the electrode surface through coating, leading to poor conductivity, low utilization of active sites, and insufficient mechanical stability, which severely restricts their industrial application. In-situ growth of MOF materials on conductive substrates is an effective technical approach to solve these problems. Copper foam (CF) is an ideal MOF growth substrate due to its low cost, excellent conductivity, and three-dimensional porous structure that facilitates mass transfer. However, existing technologies have two main bottlenecks: the MOF loading on the CF substrate surface using traditional hydrothermal methods is generally below 0.5 mg / cm³. 2 This significantly limits the number of active sites. Furthermore, conventional acid washing pretreatment processes struggle to form a uniform hydrophilic layer on the substrate surface, resulting in insufficient bonding strength between the MOF and the CF substrate. To address these issues, this invention employs a hydrogen peroxide oxidation process to modify the surface of the conductive metal foam substrate and systematically optimizes the mixed solvent ratio of water and N,N-dimethylformamide (DMF). This technical solution offers dual advantages: firstly, it achieves a high concentration of 1.2 mg / cm³. 2 The method achieves excellent MOF material loading; on the other hand, the in-situ synthesis method ensures a strong chemical bond between the MOF and the conductive metal foam substrate. More importantly, the obtained material can be directly used as a self-supporting electrode in the electrolysis system of GOR-assisted hydrogen production, significantly reducing the energy consumption of hydrogen production. Summary of the Invention
[0003] The purpose of this invention is to provide a method for preparing an in-situ supported MOF catalyst on a conductive metal substrate, achieved through synergistic optimization of a hydrogen peroxide oxidation process and a water / DMF mixed solvent ratio. This method features a simple process flow, mild and controllable reaction conditions, and environmental friendliness. It not only enables uniform and high-loading growth of MOFs on the conductive metal foam substrate but also ensures a strong chemical bond between the catalyst and the substrate, further inducing the formation of a vertically aligned nanorod array structure. Another objective of this invention is to provide the application of the catalyst prepared by the above method in the field of electrocatalytic glycerol oxidation-assisted hydrogen production. This catalyst exhibits excellent GOR activity and long-term stability, effectively reducing the anodic overpotential and thus improving the overall electrocatalytic hydrogen production efficiency.
[0004] This invention provides a MOF (Metal-Oxide-Factory) for glycerol oxidation-assisted hydrogen production. The MOF is a nanorod array structure vertically grown on a conductive metal substrate; the MOF nanorod array is a solid structure; the nanorods have a diameter of 25-30 nm and a length of 250-300 nm; and the MOF loading is 1.0-1.2 mg / cm³. 2 The density of the solid nanorod array on the conductive metal substrate is 1.6 × 10⁻⁶. 10 ~ 2 × 10 10 root / cm 2 .
[0005] This invention provides a method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production, comprising the following steps:
[0006] Step 1: Pre-treat the conductive metal substrate, and then oxidize the pre-treated conductive metal substrate again.
[0007] Step 2: Dissolve the MOF organic ligand, and after vigorous shaking and sonication, obtain a uniform dark brown solution;
[0008] Step 3: Tilt the oxidized conductive metal substrate and place it in the dark brown solution obtained in Step 2 for hydrothermal treatment;
[0009] Step 4: After the reaction is complete, the substrate is naturally cooled to room temperature. The conductive metal substrate loaded with the dark product is removed, washed, and dried to obtain the MOF catalyst loaded on the conductive metal substrate.
[0010] Further, in step 1, the conductive metal substrate is a copper-containing substrate, an iron-containing substrate, a cobalt-containing substrate, or a nickel-containing substrate; the conductive metal substrate is in the form of a foamed metal substrate.
[0011] Further, in step 1, the pretreatment involves sequentially ultrasonic treatment with 3M hydrochloric acid aqueous solution, anhydrous ethanol, and deionized water; the ultrasonic treatment time for the 3M hydrochloric acid aqueous solution is 5 min; the ultrasonic treatment time for the anhydrous ethanol and deionized water is 10 min; and the ultrasonic frequency is 33~40 kHz.
[0012] Further, in step 1, the oxidation treatment is to oxidize the pretreated conductive metal substrate with hydrogen peroxide; the mass concentration of the hydrogen peroxide is 25%~35%, and the ultrasonic time is 8~15 min.
[0013] Further, in step 2, the MOF organic ligand is a multidentate ligand; the solvent is deionized water and DMF in a volume ratio of 3~5:1; and the concentration of the MOF organic ligand is 1~2 mg / mL.
[0014] Furthermore, in step 2, the violent shaking time is 1-5 minutes, and the frequency is 280-300 times / min; the ultrasound time is 1-3 minutes.
[0015] Further, in step 3, the hydrothermal treatment involves placing a dark brown solution containing a conductive metal substrate into a reaction vessel and heating it at 5~7℃ / min to 80~90℃ for 1~12 hours.
[0016] Further, in step 4, the conductive metal substrate is thoroughly washed with DMF and ethanol in sequence; the drying is performed under vacuum at 50~60℃ for 12~16h.
[0017] This invention also provides an application of a MOF for glycerol oxidation-assisted hydrogen production, wherein in a standard three-electrode system, the counter electrode is a graphite rod, the reference electrode is a calomel electrode, and the working electrode is a MOF; in an alkaline glycerol electrolyte, 10 mA cm⁻¹ -2 Under current density, after 100 hours of stable operation, the hydrogen evolution efficiency remains above 99.5%.
[0018] The beneficial effects of this invention are as follows:
[0019] The method of this invention features a simple and highly controllable process flow, employing a one-step solvothermal synthesis method. The operation is simple and easy to implement, with mild reaction conditions that facilitate large-scale production. It exhibits excellent environmental friendliness, primarily using deionized water as the solvent, with only a small amount of DMF. Residual organic solvents can be effectively recovered and removed through post-treatment processes, significantly reducing the amount of organic solvent used and the risk of environmental pollution. It achieves outstanding material loading performance. By employing a unique hydrogen peroxide oxidation treatment technology on the substrate, combined with a carefully optimized water / DMF mixed solvent ratio, uniform and dense growth of MOFs on conductive metal substrates was successfully achieved, with a loading capacity as high as approximately 1.2 mg / cm³. 2 This value is significantly superior to many similar preparation methods. A strong bond exists between the material and the substrate; a strong interaction forms between the MOF crystal and the conductive metal substrate, resulting in a tight bond that is not easily detached, effectively ensuring the mechanical stability and long-term performance of the electrode material. It can be used directly as a self-supporting electrode, exhibiting high catalytic activity and good stability in GOR, effectively replacing OER, reducing overpotential, and significantly improving the overall efficiency of hydrogen production through water electrolysis. Attached Figure Description
[0020] Figure 1 This is a scan of a MOF used for glycerol oxidation-assisted hydrogen production according to Example 1 of the present invention.
[0021] Figure 2 This is the XRD pattern of a MOF used for glycerol oxidation-assisted hydrogen production according to Example 1 of the present invention.
[0022] Figure 3 The graph shows the performance of GOR and OER of a MOF used for glycerol oxidation-assisted hydrogen production according to Example 1 of the present invention.
[0023] Figure 4 This is a GOR stability diagram of a MOF used for glycerol oxidation-assisted hydrogen production according to Example 1 of the present invention.
[0024] Figure 5 This is a full electrolyzer performance diagram of a MOF used for glycerol oxidation-assisted hydrogen production according to Embodiment 1 of the present invention. Detailed Implementation
[0025] The present invention will now be further described with reference to the accompanying drawings.
[0026] A novel metal-organic fiber (MOF) for glycerol oxidation-assisted hydrogen production is disclosed. The MOF is a solid nanorod array structure vertically grown on a conductive metal substrate; the nanorods have a diameter of 25-30 nm and a length of 250-300 nm; the MOF loading is 1.0-1.2 mg / cm³. 2The density of the solid nanorod array on the conductive metal substrate is 1.6 × 10⁻⁶. 10 ~ 2 × 10 10 root / cm 2 .
[0027] The technical solution adopted in this invention includes the following steps:
[0028] Step 1: Pretreatment of the conductive metal substrate: A conductive metal substrate, preferably a CF substrate, was used. The CF substrate was sequentially subjected to ultrasonic treatment in 3M hydrochloric acid (HCl) aqueous solution, anhydrous ethanol, and deionized water to remove surface oxides and organic contaminants, resulting in a clean CF substrate.
[0029] Step 2: Oxidation treatment of conductive metal substrate: Immerse the CF substrate obtained in Step 1 into a hydrogen peroxide solution with a mass concentration of 25%~35%. After ultrasonic oxidation treatment of the hydrogen peroxide for 8~15 minutes, dry it to form an active surface on the conductive metal substrate.
[0030] Step 3: Preparation of reaction solution: Dissolve the MOF organic ligand in a mixed solvent composed of deionized water and N,N-dimethylformamide (DMF), and after vigorous shaking and brief sonication, obtain a homogeneous dark brown solution; wherein, the volume ratio of deionized water to DMF in the mixed solvent is (3~5):1 (preferably 3:1); the concentration of MOF organic ligand is 1~2 mg / mL;
[0031] Step 4: Solvothermal reaction: Immerse the CF substrate obtained in step 2 after hydrogen peroxide oxidation into the reaction solution prepared in step 3, place it in a reaction vessel, and heat it in an oven at 80~90 ℃ (preferably 85 ℃) for 1~12 hours (preferably 4 hours).
[0032] Step 5: Post-processing: After the reaction is complete, allow it to cool naturally to room temperature. Remove the conductive metal substrate loaded with the dark product and wash it thoroughly with DMF and ethanol to remove residual unreacted ligands and solvent molecules. After drying, the MOF catalyst supported on the CF substrate is obtained. The catalyst loading on the CF substrate is approximately 1.2 ± 0.2 mg / cm³. 2 .
[0033] In the above steps, the ultrasonic frequency is 33~40kHz.
[0034] In step 1 above, the CF substrate is cut to the required size before use, such as 1×3 cm. 2 .
[0035] In step 1 above, the treatment time in 3M HCl is 5 minutes, and the treatment in ethanol and water includes ultrasonic cleaning and soaking, with a treatment time of 10 minutes.
[0036] In step 3 above, the MOF organic ligand is a multidentate ligand; preferably a polyhydroxy aromatic ligand.
[0037] In step 3 above, the duration of the violent shaking is 1 to 5 minutes, and the frequency of the violent shaking is 280 to 300 times / min; the duration of the ultrasonic treatment is 1 to 3 minutes.
[0038] In step 5 above, the drying is either natural drying at room temperature or vacuum drying at low temperature (<60 ℃) for 12~16 hours.
[0039] Example 1
[0040] (1) Take a conductive CF substrate with a size of 1 cm × 3 cm and perform the following treatments in sequence: Immerse it in a 3 M hydrochloric acid (HCl) aqueous solution and sonicate for 5 minutes. Rinse it thoroughly with plenty of deionized water, immerse it in anhydrous ethanol and sonicate for 10 minutes, then rinse it with anhydrous ethanol. Immerse it in deionized water and sonicate for 10 minutes, then rinse it thoroughly with deionized water; dry the treated conductive metal substrate for later use.
[0041] (2) The clean conductive CF substrate obtained in step 1 was immersed in hydrogen peroxide solution, ultrasonically treated for 10 minutes and then dried to obtain the CF substrate after hydrogen peroxide oxidation treatment.
[0042] (3) Accurately weigh 15 mg of MOF ligand and place it in a glass sample vial. Add 10 mL of a mixed solvent of deionized water and DMF in a volume ratio of 3:1 to the vial. Tightly seal the vial, place it on a shaker and shake vigorously for 3 minutes, then sonicate for 2 minutes to obtain a uniform dark brown solution.
[0043] (4) Immerse the conductive CF substrate obtained in step 2 after hydrogen peroxide oxidation into the reaction solution prepared in step 3, ensuring that the conductive CF substrate is completely submerged. Tightly seal the glass bottle, place it in the reaction vessel, and put it in an oven at 85 °C for 4 hours.
[0044] (5) After the reaction is complete, remove the reactor from the oven and allow it to cool naturally to room temperature (approximately 25 °C). Carefully remove the conductive CF substrate loaded with the dark product. Wash the CF substrate thoroughly with DMF (approximately 10 mL, soak and shake several times) and anhydrous ethanol (approximately 10 mL, soak and shake several times) to completely remove residual MOF ligands and solvent molecules. Finally, dry the washed MOF catalyst in a vacuum drying oven at 60 °C for 12 h before removing it.
[0045] (6) The mass (m1) of the pretreated clean conductive metal substrate and the mass (m2) of the dried MOF-loaded substrate were accurately weighed using a balance. Catalyst loading = (m2 - m1) / area of conductive metal substrate. The calculated loading is approximately 1.2 mg / cm². 2 .
[0046] The morphology characterization results of the Cu-MOF prepared in the examples are as follows: Figure 1 As shown in the image, the scanning electron microscope (SEM) image reveals a hexagonal rod-shaped array structure with a diameter of approximately 30 nanometers. The nanorods have a diameter of 25–30 nm and a length of 250–300 nm.
[0047] Figure 2 The XRD pattern of the Cu-MOF prepared in this embodiment shows that the characteristic diffraction peaks at 4.6°, 9.5°, 12.6° and 27.0° correspond to the (100), (200), (210) and (001) crystal planes of the Cu-MOF material, respectively.
[0048] Example 2 and Example 3
[0049] The difference from Example 1 is that different MOF ligand concentrations are used; the amount of MOF ligand used in step (3) is changed, and 10 mg and 20 mg of MOF ligand are weighed respectively.
[0050] Examples 4 and 5
[0051] The difference from Example 1 is that different deionized water / DMF ratios are used; the volume ratio of deionized water to DMF in step (3) is changed to 4:1 and 5:1 respectively, and the total volume of the mixed solvent is 10 mL.
[0052] Examples 6, 7 and 8
[0053] The difference from Example 1 is that different temperatures and times are used; the thermal reaction temperature and reaction time in step (4) are changed; the thermal reaction temperature and time are 1 hour at 80°C, 8 hours at 85°C, and 12 hours at 90°C.
[0054] Comparative Example 1
[0055] The difference from Example 1 is that the oxidation treatment time of the CF substrate is different; the ultrasonic time of immersion in hydrogen peroxide solution in step (2) is changed to 40 min. The CF substrate is severely oxidized by hydrogen peroxide, and the MOF growth length on the substrate is too long, which affects the interface effect between the MOF and the substrate.
[0056] Comparative Example 2
[0057] The difference from Example 1 is that the oxidation treatment time of the CF substrate is different; the ultrasonic time of immersing the clean conductive CF substrate in hydrogen peroxide solution in step (2) is changed to 1 min. The CF substrate was not completely oxidized by hydrogen peroxide, resulting in the failure of MOF growth in some areas of the substrate.
[0058] Comparative Example 3
[0059] The difference from Example 1 is that a different deionized water / DMF ratio was used; the volume ratio of deionized water to DMF in step (3) was changed to 2:1, and the total volume of the mixed solvent was 10 mL. MOF nanorods were sparsely grown on the CF substrate, with a loading of 0.3~0.5 mg / cm³. 2 .
[0060] Comparative Example 4
[0061] The difference from Example 1 is that a different deionized water / DMF ratio was used; the volume ratio of deionized water to DMF in step (3) was changed, and only deionized water was used, with a total volume of 10 mL. The MOF on the CF substrate did not grow in the form of solid nanorods, and its morphology changed.
[0062] Comparative Example 5
[0063] The difference from Example 1 is that a different thermal reaction temperature was used; the reaction temperature in step (4) was changed, the glass bottle was tightly sealed, placed in a reaction vessel, and put into an oven at 120 °C for 4 hours. The MOF nanorods grown on the CF substrate were approximately 350 nm in length. If the temperature is too high, the nanorods will be too long, affecting the interface effect between the substrate and the MOF.
[0064] Comparative Example 6
[0065] The difference from Example 1 is that different thermal reaction conditions were used; the reaction temperature in step (4) was changed, the glass bottle was tightly sealed, placed in a reaction vessel, and put into an oven at 50°C for 4 hours. The length of the MOF nanorods grown on the CF substrate was approximately 50~100 nm. If the temperature is too low, the length of the nanorods will be too short, affecting the interface effect between the substrate and the MOF.
[0066] Comparative Example 7
[0067] The difference from Example 1 is that different thermal reaction conditions were used; step (4) was changed, the glass bottle was tightly sealed and placed directly into an oven at 85 °C for 4 hours. In this comparative example, the sample was not placed in a reaction vessel, no pressure was applied to the thermal reaction conditions, and the MOF nanorods grown on the CF substrate were sparse.
[0068] Comparative Example 8
[0069] The difference from Example 1 is that a different drying temperature is used; the vacuum drying temperature of the washed MOF catalyst in step (5) is changed; the washed MOF catalyst is dried in a vacuum drying oven at 80°C and then taken out, resulting in excessive oxidation of the MOF catalyst and rough deformation of the catalyst surface.
[0070] Test Example 1: Electrochemical Performance Test
[0071] (1) Electrode preparation: The Cu-MOF prepared in Example 1 was used directly as the working electrode, a graphite rod was used as the counter electrode, and a calomel electrode was used as the reference electrode.
[0072] (2) Electrochemical testing:
[0073] Linear sweep voltammetry (LSV): In a standard three-electrode system, the scan range is typically 0–0.8 V vs. RHE, with a scan rate of 5 mV / s. The current versus potential curve (GOR activity) in a 1.0 M KOH electrolyte containing 0.5 M glycerol is recorded. For comparison, the OER activity of the same electrode is tested in a 1.0 M KOH electrolyte (without glycerol).
[0074] (3) Chronoamperometry (CA): At a fixed current density (e.g., 10 mA / cm²), 2 Under these conditions, the catalyst is operated for an extended period (e.g., 100 hours) and the change in current over time is recorded to evaluate the GOR stability of the catalyst.
[0075] (4) Full electrolysis cell test (glycerol-assisted hydrogen production):
[0076] Using Cu-MOF as the anode and cathode (area matched), the overpotentials at the same current density were compared in 1.0 M KOH electrolyte with and without glycerol.
[0077] Figure 3 This is a performance comparison chart of GOR and OER for the Cu-MOF prepared in Example 1. It exhibits a much higher current density and onset potential than OER in a glycerol-containing electrolyte, indicating its high activity for GOR. Figure 4 The GOR stability of the Cu-MOF prepared in Example 1 was measured at 10 mA cm⁻¹. -2 At current density, it can operate stably for 100 hours, maintaining a hydrogen evolution efficiency of 99.5% and a glycerol oxidation efficiency of 96.13%, demonstrating excellent stability. Figure 5 The image shows the full electrolyzer performance of Cu-MOF prepared in Example 1. In the presence of glycerol, the potential required to achieve the same current density is significantly lower than that required for conventional water electrolysis, demonstrating that replacing OER with GOR can effectively reduce hydrogen production energy consumption. Simultaneously, hydrogen can be collected at the cathode, and glycerol oxidation products can be collected at the anode.
[0078] In summary, the catalyst material prepared by the method of this invention forms a robust bonding interface with the substrate, effectively ensuring the mechanical stability and long-term performance of the electrode material. When this material is used as a self-supporting electrode in the glycerol oxidation reaction (GOR), it exhibits excellent catalytic activity and superior structural stability. In the all-electrolyte system, the reaction potential required to achieve the same current density is significantly lower than that required in the traditional water electrolysis process, demonstrating that using GOR to replace OER can effectively reduce hydrogen production energy consumption, while simultaneously allowing hydrogen to be collected at the cathode and glycerol oxidation products to be collected at the anode.
[0079] The above description is merely a preferred embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.
Claims
1. A MOF that can be used for glycerol oxidation-assisted hydrogen production, characterized in that, The MOF is a vertically grown nanorod array structure on a conductive metal substrate; the MOF nanorod array is a solid structure; the diameter of the nanorods is 25-30 nm, and the length is 250-300 nm; the MOF loading is 1.0-1.2 mg / cm³. 2 The nanorod array density of the conductive metal substrate is 1.6 × 10⁻⁶. 10 ~ 2 × 10 10 root / cm 2 .
2. A method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production, characterized in that, Includes the following steps: Step 1: Pre-treat the conductive metal substrate, and then oxidize the pre-treated conductive metal substrate again. Step 2: Dissolve the MOF organic ligand, and after vigorous shaking and sonication, obtain a uniform dark brown solution; Step 3: Tilt the oxidized conductive metal substrate and place it in the dark brown solution obtained in Step 2 for hydrothermal treatment; Step 4: After the reaction is complete, the substrate is naturally cooled to room temperature. The conductive metal substrate loaded with the dark product is removed, washed, and dried to obtain the MOF catalyst loaded on the conductive metal substrate.
3. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 1, the conductive metal substrate is a copper-containing substrate, an iron-containing substrate, a cobalt-containing substrate, or a nickel-containing substrate; the conductive metal substrate is in the form of a foamed metal substrate.
4. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 1, the pretreatment involves sequentially ultrasonic treatment with 3M hydrochloric acid aqueous solution, anhydrous ethanol, and deionized water; the ultrasonic treatment time for the 3M hydrochloric acid aqueous solution is 5 min; the ultrasonic treatment time for the anhydrous ethanol and deionized water is 10 min; and the ultrasonic frequency is 33~40 kHz.
5. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 1, the oxidation treatment involves oxidizing the pretreated conductive metal substrate with hydrogen peroxide; the mass concentration of the hydrogen peroxide is 25%~35%, and the ultrasonic time is 8~15 min.
6. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 2, the MOF organic ligand is a multidentate ligand; the solvent is deionized water and DMF in a volume ratio of 3~5:1; and the concentration of the MOF organic ligand is 1~2 mg / mL.
7. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 2, the violent shaking time is 1-5 minutes and the frequency is 280-300 times / min; the ultrasound time is 1-3 minutes.
8. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 3, the hydrothermal treatment involves placing a dark brown solution containing a conductive metal substrate into a reaction vessel and heating it at 5~7℃ / min to 80~90℃ for 1~12 hours.
9. The method for preparing MOFs that can be used for glycerol oxidation-assisted hydrogen production according to claim 2, characterized in that, In step 4, the conductive metal substrate is thoroughly washed with DMF and ethanol in sequence; the drying is carried out under vacuum at 50~60℃ for 12~16h.
10. An application of the MOF for glycerol oxidation-assisted hydrogen production as described in claim 1, characterized in that, In the standard three-electrode system, the counter electrode is a graphite rod, the reference electrode is a calomel electrode, and the working electrode is a MOF; in an alkaline glycerol electrolyte, 10 mA cm⁻¹ -2 Under current density, after 100 hours of stable operation, the hydrogen evolution efficiency remains above 99.5%.