A MOFs-based wood-derived membrane, and a preparation method and application thereof

Abstract

The application discloses a MOFs-based wood-derived membrane and a preparation method and application thereof. The derived membrane comprises a carrier part and a catalytic part, and MOFs are synthesized in situ on wood. The MOFs-based wood-derived membrane is derived without using an adhesive and keeps material stability. The increase of the graphitization degree after derivation accelerates the transmission of electrons in the material, accelerates the rate of generating OH by metal active sites, improves the electrocatalytic performance of the material, and has more than 90% removal rate on antibiotics in water. The MOFs-based wood-derived membrane can be self-cleaned, prolongs the service life, is conducive to the reuse of the membrane, and effectively removes new pollutants in water through an external electric field. The MOFs-based wood-derived membrane is easy to prepare, raw materials are easy to obtain, and the MOFs-based material overcomes the defects of poor conductivity, instability and easy agglomeration, and has an excellent application prospect in water treatment.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrocatalysis and water treatment, in particular to a MOFs-based wood-derived membrane and a preparation method and application thereof. BACKGROUND

[0002] At present, antibiotics as a kind of antibacterial drugs are widely used, but the bioavailability of antibiotics is very low, which means that a large amount of antibiotics will be discharged into the environment after use, causing bacterial drug resistance. Due to its small molecular weight, the existing separation technology cannot effectively separate it in water, and catalytic means is needed to remove antibiotics in water. Electro-catalysis is an effective method for degrading antibiotics, which can gradually degrade antibiotics through oxidation-reduction process to achieve the effect of removal.

[0003] MOFs have the advantages of large specific surface area, active site dispersion, high porosity, etc., and have wide application prospects in the fields of adsorption, catalysis, separation, etc. However, MOFs have the disadvantages of poor stability and poor conductivity, etc. At the same time, MOFs often exist in the form of powder, which makes MOFs have many limitations in practical application. Therefore, it is necessary to load MOFs on a suitable carrier to take advantage of MOFs, maintain the crystal structure of MOFs itself, and avoid agglomeration.

[0004] Wood-based biomass materials have a large reserve on the earth, are easy to obtain, and have a unique layered and porous structure, which is conducive to the transmission of matter and electrons. Moreover, wood is mainly composed of cellulose and hemicellulose, and the rich oxygen-containing functional groups are very conducive to the dispersion and growth of MOFs. Wood has the potential to combine with MOFs, and the vertical and interconnected pipeline structure of wood is very conducive to the full contact of fluid with MOFs materials inside. On this basis, the MOFs-loaded wood membrane is carbonized, which effectively preserves the framework structure of MOFs and makes the connection between metal and carrier more stable. The derived metal oxide has strong chemical stability, and the surface is rich in oxygen vacancies and acid sites, which is a good electro-catalytic membrane material. In summary, the MOFs-based wood-derived membrane is expected to efficiently remove antibiotic new pollutants in wastewater. SUMMARY

[0005] Technical problems solved:

[0006] The technical problem to be solved by the present application is the poor stability and poor conductivity of MOFs, the many limitations of MOFs in practical application, etc. A MOFs-based wood-derived membrane and a preparation method and application thereof are provided, which in-situ synthesizes and derives MOFs on the wood membrane through a two-step hydrothermal method without adding adhesive, and effectively electro-catalytically degrades antibiotic new pollutants in water.

[0007] Technical scheme:

[0008] A preparation method of MOFs-based wood-derived membrane, and the specific process conditions are:

[0009] First step: activate the wood membrane with 20% NaOH solution to expose more oxygen-containing functional groups and form more channel structures;

[0010] Second step, two-step synthesis of MOFs in situ in wood membrane: load metal ions on the surface of wood membrane and the inner wall of the pipe; use the metal ions loaded on the wood membrane to synthesize MOFs in situ on the wood membrane without adhesive, and obtain a wood membrane loaded with MOFs;

[0011] Third step: derive the obtained wood membrane loaded with MOFs in a tube furnace to obtain a MOFs-based wood-derived membrane.

[0012] Further, the specific steps of the first step are: soaking the wood membrane in 20% NaOH solution for 2h for activation, repeatedly washing with deionized water until the washing liquid pH is 8-9, and then freeze-drying at-60℃ for 12h to remove part of the lignin in the wood membrane, expose more oxygen-containing functional groups, and obtain a rough wood membrane surface, while forming more channel structures in the wood membrane, which is conducive to the interaction of metal elements and ligands with the wood membrane, and obtain M1.

[0013] As a preferred technical solution of the present application: the specific steps of the second step are: first, dissolve 0.5-1 parts of ZrCl4 in 40-100 parts of DMF solution, ultrasonic for 5min to form solution one;

[0014] Soak M1 in solution one, put it in a reaction kettle at 100-140℃, 0.18-0.22MPa, and react for 2h to obtain M2;

[0015] Dissolve 0.5-1 parts of ZrCl4 in 40-100 parts of DMF solution, ultrasonic for 5min to form solution one; dissolve 5-8 parts of terephthalic acid in 40-100 parts of DMF solution, ultrasonic for 5min to form solution two; mix 1 part of solution one with 1-3 parts of solution two uniformly on a magnetic stirrer, then put it into M2, and put the obtained mixed solution soaked with M2 into a reaction kettle at 100-140℃, 0.18-0.22MPa, and react for 48h to obtain a wood membrane loaded with MOFs M3, and then wash and dry the obtained M3.

[0016] As a preferred technical solution of the present application: carbonize the wood membrane loaded with MOFs M3 in a tube furnace at 400-800℃ for 2h to derive a MOFs-based wood-derived membrane.

[0017] As a preferred technical solution of the present application: the reaction temperature for obtaining M2 is 120 DEG C, and the reaction time is 2h; the temperature for obtaining the wood film loaded with MOFs M3 is 120 DEG C, and the reaction time is 48h.

[0018] As a preferred technical solution of the present application: the wood film loaded with MOFs M3 is first soaked in DMF solution for 12h for cleaning, and the DMF solution is replaced constantly during the soaking process until the DMF solution is clear, and then M3 is soaked in anhydrous ethanol for 12h, and the solution is replaced every 3h, and then vacuum drying is carried out at 60 DEG C, and then calcination is carried out in a tube furnace.

[0019] As a preferred technical solution of the present application: the wood film loaded with MOFs M3 is heated in a tube furnace under N2 atmosphere at a heating rate of 5 DEG C / min, and carbonization is carried out at 400-800 DEG C for 2h.

[0020] The present application also discloses a MOFs-based wood-derived film prepared by the above preparation method, which comprises a carrier part and a catalytic part closely combined with the carrier part, the carrier part is a wood-based derived material; the catalytic part is a MOFs derived material; the wood-based derived material is a charcoal carrier carbonized after activation treatment; and the MOFs derived material is a metal oxide with a reserved MOFs framework.

[0021] Application of a MOFs-based wood-derived film in electrocatalytic oxidation removal of difficult-to-degrade new pollutants in water.

[0022] As a preferred technical solution of the present application: the wood film is obtained by cutting softwood or hardwood, and the softwood or hardwood is natural linden wood, poplar wood, pine wood or balsa wood, and the cutting mode is perpendicular to the growth direction of the wood.

[0023] The technical principle of the present application is that the MOFs-based wood-derived film provided by the present application generates MOFs in situ on the wood film, and then carbonization is carried out. In the activation process, part of the lignin in the wood film is removed under the action of NaOH, which makes the inner wall of the smooth inner wall of the pipeline structure of the wood film more rough, facilitating the fixation of MOFs. At the same time, due to the removal of lignin, more cellulose and hemicellulose are exposed, which means that more oxygen-containing functional groups are exposed, and the partial removal of lignin means that more pores are formed on the inner wall of the pipeline structure, which is beneficial to the increase of specific surface area and the full contact of pollutants with the catalytic material. The metal ions are coordinated with the hydroxyl groups, and the metal-oxygen bond is formed on the pipeline structure of the wood film, and then the ligand is coordinated with the metal ions loaded on the wood film as the core to generate MOFs in situ on the wood film without adhesive. Since the MOFs are formed with the metal ions coordinated with the hydroxyl groups on the wood film as the core, the agglomeration of the MOFs can be effectively avoided, so that the MOFs are uniformly dispersed on the wood film, and the active sites are effectively exposed.

[0024] Advantages:

[0025] The MOFs-based wood-derived membrane, the preparation method and the application thereof have the following technical effects compared with the prior art by adopting the above technical scheme:

[0026] 1. The wood membrane loaded with MOFs is carbonized to form the MOFs-based wood-derived membrane, the MOFs are carbonized to form metal oxides, and meanwhile the framework structure of the MOFs is preserved, so that the metal oxides are uniformly dispersed on the wood membrane;

[0027] 2. After the current is applied, the charcoal itself is a good channel for transmitting electrons, and the electrons are efficiently transmitted to the dispersed active sites of the metal oxides, so that a large number of hydroxyl radicals and superoxide radicals are generated, the radicals attack the antibiotic pollutants, and the antibiotic pollutants are efficiently degraded;

[0028] 3. The MOFs-based wood-derived membrane has good electrocatalytic effect on antibiotic small molecule new pollutants; the removal effect of common processes such as activated sludge process, adsorption-biodegradation process, anaerobic and aerobic process on antibiotics is not ideal, and is between 20% and 70%, and most of the antibiotics cannot be effectively removed, the MOFs-based wood-derived membrane has more than 90% removal rate on tetracycline and norfloxacin antibiotic pollutants, and has excellent self-cleaning performance.

[0029] 4. The MOFs-based wood-derived membrane has a removal rate of more than 90% on tetracycline and norfloxacin small molecule antibiotic pollutants. DETAILED DESCRIPTION

[0030] Figure 1 Figure 1 is a SEM image of M1, M3 and the MOFs-based wood-derived membrane of the present application, wherein a is a scanning electron microscope image of the section of M1, b is a local magnified scanning electron microscope image of the section of M1, c is a scanning electron microscope image of the section of M3, d is a local magnified scanning electron microscope image of the section of M3, e is a scanning electron microscope image of the MOFs-based wood-derived membrane, and f is a local magnified scanning electron microscope image of the MOFs-based wood-derived membrane;

[0031] Figure 2 Figure 2 is an XRD pattern of M3 synthesized by using pine wood as a wood membrane, M3 and M1 synthesized by using basswood as a wood membrane, wherein a is an XRD pattern of M3 synthesized by using pine wood as a wood membrane, b is an XRD pattern of M3 synthesized by using basswood as a wood membrane, and c is an XRD pattern of M1;

[0032] Figure 3 Figure 3 is a removal effect diagram of the MOFs-based wood-derived membrane for electrocatalytic removal of tetracycline and norfloxacin;

[0033] Figure 4EPR signal spectrum of MOFs-based wood-derived membrane before and after electrification

[0034] Figure 5 Removal effect diagram of MOFs-based wood-derived membrane synthesized from solution with different metal concentrations for electrocatalytic removal of tetracycline

[0035] Figure 6 MOFs-based wood-derived membrane long-term self-cleaning effect diagram DETAILED DESCRIPTION

[0036] The application will be explained in more detail below with reference to specific embodiments, it should be noted that the listed embodiments are not all the embodiments, but only a part of them. The parts not explained in detail in the detailed description of the specification are common knowledge to those skilled in the art.

[0037] Example 1:

[0038] A preparation method of a MOFs-based wood-derived membrane, the specific process conditions are:

[0039] (1) Soak the wood membrane in 20% NaOH solution for 2h for activation, to remove part of the lignin in the wood membrane, expose more oxygen-containing functional groups and obtain a rough wood membrane surface, at the same time, form more channel structures in the wood membrane, which is conducive to the interaction between metal elements and ligands and the wood membrane, repeatedly rinse with deionized water until the pH of the rinse is 8-9, and then freeze-dry at-60℃ for 12h to obtain M1;

[0040] (2) Dissolve 0.85g ZrCl4 in 80mL DMF, ultrasonic for 5min to form solution one; soak the dried M1 in solution one, transfer to the reaction kettle, react at 120℃ under 0.18-0.22MPa for 2h to obtain M2;

[0041] (3) Dissolve 0.85g ZrCl4 in 80mL DMF, ultrasonic for 5min to form solution one; dissolve 6.54g terephthalic acid in 80mL DMF, ultrasonic for 5min to form solution two; mix 1 part of solution one and 2 parts of solution two, mix them uniformly on a magnetic stirrer, and then transfer them to the reaction kettle together with M2; react at 120℃ under 0.18-0.22MPa for 48h; after reaction, wash and dry the obtained wood membrane to obtain MOFs-loaded wood membrane M3;

[0042] (4) Place the MOFs-loaded wood membrane M3 in a tube furnace, heat to 500℃ at a rate of 5℃ / min under N2 atmosphere, and keep for 2h, and obtain MOFs-based wood-derived membrane after cooling.

[0043] Preferably, the selected wood membrane is made of natural linden wood, and the cutting method is to cut it perpendicular to the growth direction of the wood, which ensures the integrity of the tubular structure of the wood membrane itself.

[0044] Preferably, in step (3), the wood film M3 loaded with MOFs is first soaked and cleaned in DMF solution for 12 hours, and the DMF solution is changed continuously during the soaking process until the DMF solution is clear. Then, M3 is soaked in anhydrous ethanol for 12 hours, and the solution is changed continuously during the process. Finally, it is vacuum dried at 60°C.

[0045] Figure 1 These are scanning electron microscope images of the wood film obtained in steps (1), (3), and (4), where... Figure 1 (a) is a scanning electron microscope image of section M1; Figure 1 (b) is Figure 1 (a) is a magnified portion of the image; Figure 1 (c) is a scanning electron microscope image of the M3 section; Figure 1 (d) is Figure 1 (c) is a magnified portion of the image; Figure 1 (e) is a scanning electron microscope image of a MOF-based wood-derived membrane; Figure 1 (f) is Figure 1 (e) shows a magnified portion of the image.

[0046] Depend on Figure 1 (a) The pipe structure of M1 is clearly visible; upon magnification, it can be seen that... Figure 1 (b) Wrinkled patterns formed after activation can be seen on the surface of the pipe structure. These patterns provide a favorable environment for the growth of MOFs, which is conducive to the combination of metal ions and hydroxyl groups and their fixation on the surface of the pipe structure. Figure 1 (c) and Figure 1 (a) Compared to, it is obvious that Figure 1 (c) The pipe structure of M3 is loaded with a large number of MOFs, and many new pore structures appear on the pipe wall. This is because under the high temperature and high pressure conditions in the reactor, the pore structures that were not fully formed during the activation process on the wood membrane pipe wall are further enlarged. The formation of such pore structures is conducive to the exchange of fluid between pipes in the wood membrane, extending the path of the fluid through the wood membrane, increasing the contact area between the active sites and the pollutants, and thus facilitating the removal of pollutants. Figure 1 As shown in (d), MOFs are generated in situ on the wood membrane and extensively cover the surface of the wood membrane pipe structure. Figure 1 (e) shows the microstructure of MOF-based wood-derived membranes. Figure 2As can be seen from (f), calcination at 500℃ does not cause the original structure of the MOFs to collapse, which enables the pore structure of the MOFs to be retained, making the flow path of water in the membrane more complex, prolonging the reaction time, and thus being conducive to the degradation of the antibiotic pollutants.

[0047] Example 2

[0048] A preparation method of a MOFs-based wood-derived membrane, taking pine wood as the wood membrane, and the synthesis steps are the same as those in Example 1.

[0049] The M1 obtained in Example 1 and M3 and the MOFs-based wood-derived membrane taking pine wood as the wood membrane obtained in the present example were subjected to XRD characterization, and the results are shown in Figure 2 , wherein 2(a) is the XRD image of M3 synthesized by taking pine wood as the wood membrane; Figure 2 (b) is the XRD image of M3 synthesized by taking basswood as the wood membrane; Figure 2 (c) is the XRD image of M1.

[0050] Figure 2 (a), Figure 2 (b) and Figure 2 (c), the diffraction peak at 22.17° is a characteristic peak of cellulose in the wood membrane. Figure 2 (a) and Figure 2 (b), 7.26°, 17.24°, 25.06° and 27.78° are the crystal peaks of MOFs, Figure 3 (a) and Figure 4 The appearance of the crystal peaks of MOFs in (a) and (b) indicates that the in-situ synthesis of MOFs on the surface of the wood membrane is successful, and at the same time, it indicates that the synthesis method of the MOFs-based wood-derived membrane provided by the present application has a certain universality for natural wood.

[0051] Example 3

[0052] In the present example, tetracycline and norfloxacin were selected as model pollutants. Tetracycline and norfloxacin were added to deionized water to prepare a 0.00125 mM tetracycline aqueous solution and a norfloxacin aqueous solution. The prepared wastewater was subjected to degradation at an electric current density of 13.3 mA / cm -2 The samples were taken at 0, 5, 10, 20, 30, 60, 90 and 120 min, and the concentrations of tetracycline and norfloxacin in the water samples were detected by high performance liquid chromatography. In the high performance liquid chromatography, the mobile phase for tetracycline was acetonitrile: 0.05% H3PO4 aqueous solution = 20:80, and the mobile phase for norfloxacin was methanol: 0.2% formic acid aqueous solution = 45:55.

[0053] The experimental results are shown in Figure 4It can be seen that the removal rates of MOFs-based wood-derived membranes for tetracycline and norfloxacin can both reach more than 90%. Figure 4 For EPR characterization of MOFs-based wood-derived membranes, obvious ·OH free radical signals can be detected after power-on. Combined with the results of FTIR and XRD, it can be inferred that the MOFs-based wood-derived membranes have good catalytic activity for the degradation of antibiotics. Figure 6 It is speculated that wood becomes a good conductive material after carbonization, and under the action of an external current, a large number of ·OH active oxygen species are generated at the active sites of metal oxides, and the attack of ·OH radicals on antibiotic pollutants effectively catalyzes their degradation.

[0054] Example 4

[0055] To explore the influence of metal ion concentration on the separation performance of MOFs-based wood membranes for antibiotics during preparation, the following modifications were made during preparation:

[0056] In step (2), 0.70 g of ZrCl4 was dissolved in 80 mL of DMF and ultrasonicated for 5 min to form solution one. The dried M1 was immersed in solution one and transferred to a reaction kettle, and reacted at 120°C for 2 h to obtain M2. In step (3), 0.70 g of ZrCl4 was dissolved in 40 mL of DMF and ultrasonicated for 5 min to form solution one. 6.54 g of terephthalic acid was dissolved in 40 mL of DMF and ultrasonicated for 5 min to form solution two. Solution one and solution two were mixed, and after being mixed uniformly on a magnetic stirrer, they were transferred to the reaction kettle together with M2. The reaction was carried out at 120°C for 48 h. After the reaction, the obtained wood membrane was washed and dried to obtain M3. M3 was placed in a tube furnace, heated to 500°C at a heating rate of 5°C / min under N2 atmosphere, and kept for 2 h. After cooling, MOFs-based wood-derived membrane (a) was obtained.

[0057] In step (2), 1.00 g of ZrCl4 was dissolved in 80 mL of DMF and ultrasonicated for 5 min to form solution one. The dried M1 was immersed in solution one and transferred to a reaction kettle, and reacted at 120°C for 2 h to obtain M2. In step (3), 1.00 g of ZrCl4 was dissolved in 40 mL of DMF and ultrasonicated for 5 min to form solution one. 6.54 g of terephthalic acid was dissolved in 40 mL of DMF and ultrasonicated for 5 min to form solution two. Solution one and solution two were mixed, and after being mixed uniformly on a magnetic stirrer, they were transferred to the reaction kettle together with M2, and the reaction was carried out at 120°C for 48 h. After the reaction, the obtained wood membrane was washed and dried to obtain M3. M3 was placed in a tube furnace, heated to 500°C at a heating rate of 5°C / min under N2 atmosphere, and kept for 2 h. After cooling, MOFs-based wood-derived membrane (b) was obtained.

[0058] The MOFs-based wood membrane, the MOFs wood-derived membrane (a), the MOFs-based wood-derived membrane (b) were used for catalytic degradation of tetracycline according to the sewage preparation method and separation experiment method in Example 3, ​ The results show that the MOFs-based wood-derived membrane mentioned in the present application has the best electrocatalytic effect on tetracycline in the experiment, and the catalytic performance of the MOFs-based wood membrane (a) and the MOFs-based wood membrane (b) on tetracycline decreases to different degrees compared with the MOFs-based wood-derived membrane. For the MOFs-based wood-derived membrane (a), the decrease in catalytic performance can be attributed to the decrease in metal ion concentration during synthesis, which leads to the fact that the synthesized MOFs-based wood-derived membrane (a) does not grow uniformly and densely on the pipeline structure of the wood membrane, i.e., the MOFs loaded on the wood membrane is less, which leads to the decrease in the content of metal oxides after derivation, resulting in the decrease in catalytic performance. For the MOFs-based wood membrane (b), the decrease in catalytic performance can be attributed to the fact that too much metal ion is added during synthesis, which leads to the fact that too much MOFs is loaded on the wood membrane, and the excess MOFs agglomerates on the pipeline structure of the wood membrane, resulting in the agglomeration of active sites of metal oxides after derivation, which ultimately leads to the decrease in catalytic performance.

[0059] Example 5

[0060] The MOFs-based wood-derived membrane not only has excellent removal performance on antibiotic pollutants, but also can be self-cleaning. The MOFs-based wood-derived membrane described in Example 1 was used for long-term self-cleaning experiments. The macromolecular pollutant simulation sewage formula: bovine serum albumin (BSA) and anhydrous sodium sulfate were added to deionized water to prepare a pollutant solution containing 20 mg / L BSA and 1 M anhydrous sodium sulfate. The sewage was subjected to MOFs-based wood-derived membrane self-cleaning at a current density of 13.3 mA / cm -2 The results are shown in Figure 6. After 1100 min of continuous operation, the flux of the membrane still maintained at about 95%, which indicates that the MOFs-based wood-derived membrane has excellent self-cleaning performance. ​ ​

Claims

1. A method for preparing a MOFs-based wood-derived membrane, characterized in that, The specific process conditions are as follows: The first step is to activate the wood membrane with 20% NaOH solution to expose more oxygen-containing functional groups and form more porous structures: the wood membrane is soaked in 20% NaOH solution for 2 hours for activation, rinsed repeatedly with deionized water until the pH of the rinsing solution is 8-9, and then freeze-dried at -60℃ for 12 hours to remove some lignin from the wood membrane, expose more oxygen-containing functional groups and obtain a rough wood membrane surface, and at the same time form more porous structures in the wood membrane, which is conducive to the interaction between metal elements and ligands and the wood membrane, thus obtaining M1; The second step involves a two-step in-situ synthesis of MOFs from a wood membrane: metal ions are loaded onto the surface of the wood membrane and the inner walls of its channels; using the metal ions loaded on the wood membrane, MOFs are synthesized in situ on the wood membrane without adhesives, yielding a wood membrane loaded with MOFs. Step 3: Carbonize the obtained MOF-loaded wood film in a tube furnace at 400~800℃ for 2 h to derivatize and obtain MOF-based wood-derived film. The second step is as follows: First, dissolve 0.5-1 parts of ZrCl4 in 40-100 parts of DMF solution according to the mass ratio, and sonicate for 5 min to form solution one; immerse M1 in solution one, place it in a reaction vessel at 100-140℃, 0.18-0.22MPa for 2 h to obtain M2; dissolve 0.5-1 parts of ZrCl4 in 40-100 parts of DMF solution, and sonicate for 5 min to form solution one; dissolve 5-8 parts of terephthalic acid in 40-100 parts of DMF solution, and sonicate for 5 min to form solution two; Mix 1 part of solution one and 1-3 parts of solution two evenly on a magnetic stirrer according to the mass ratio, and then put them into M2. Place the resulting mixed solution impregnated with M2 in a reaction vessel and react at 100-140℃, 0.18-0.22 MPa for 48 h to obtain a wood film M3 loaded with MOFs. The obtained M3 is then washed and dried.

2. The method for preparing a MOFs-based wood-derived membrane according to claim 1, characterized in that: The reaction temperature for obtaining M2 was 120℃ and the reaction time was 2 h; the reaction temperature for obtaining the MOF-loaded wood film M3 was 120℃ and the reaction time was 48 h.

3. The method for preparing MOFs-based wood-derived membranes according to claim 1, characterized in that: The MOF-loaded wood film M3 was first soaked in DMF solution for 12 h to clean it, and the DMF solution was changed continuously during the soaking process until the DMF solution became clear. Then, M3 was soaked in anhydrous ethanol for 12 h, and the solution was changed every 3 h. After that, it was vacuum dried at 60 °C and then calcined in a tube furnace.

4. The method for preparing MOFs-based wood-derived membranes according to claim 3, characterized in that: The MOF-loaded wood film M3 was heated in a tube furnace under N2 atmosphere at a heating rate of 5 °C / min and carbonized at 400~800 °C for 2 h.

5. The method for preparing a MOFs-based wood-derived membrane according to claim 1, characterized in that: The wood membrane is obtained by cutting softwood or hardwood, which can be natural linden, poplar, pine or balsa wood, and the cutting method is to cut perpendicular to the growth direction of the wood.

6. A MOF-based wood-derived membrane prepared by any one of the preparation methods of claims 1-4, characterized in that: The device includes a support portion and a catalytic portion tightly bonded to the support portion. The support portion is a wood-based derived material; the catalytic portion is a MOFs-derived material; the wood-based derived material is a carbonized charcoal support after activation treatment; and the MOFs-derived material is a metal oxide that retains the MOFs framework.

7. The application of the MOFs-based wood-derived membrane of claim 6 in the electrocatalytic oxidation removal of recalcitrant new pollutants in water.

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