CN116371371A - Polymer-COFs-biomass composite membrane and preparation method and application thereof - Google Patents
Polymer-COFs-biomass composite membrane and preparation method and application thereof Download PDFInfo
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- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 9
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- 238000000034 method Methods 0.000 claims description 7
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Abstract
The invention discloses a polymer-COFs-biomass composite membrane and a preparation method and application thereof, and the preparation method comprises the following steps: preparation of a COFS material, synthesis of a polymer-COFS material, preparation of a bacterial cellulose dry film, synthesis of a polymer-COFs-biomass composite film and activation of the polymer-COFs-biomass composite film. The polymer-COFs-biomass composite membrane has good adsorption effect, good application range and good mechanical property. The catalyst has good adsorption effect on metal ions such as Fe3+, cu2+, cd2+ and the like, and has reusable performance.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a polymer-COFs-biomass composite membrane, and a preparation method and application thereof.
Background
Polymer (Polymer) films are excellent in chemical stability, and are one of the most widely used film materials at present; the Polymer film for water treatment has the advantages of high toughness, high permeability to liquid, high resistance to most chemicals, solvents, good weather resistance and the like. However, the Polymer membrane has some problems in the use process, such as easy pollution caused by strong hydrophobicity, great reduction of the flux of the membrane, and the mechanical strength to be improved. In order to overcome the above problems, modification of Polymer films has become a research hotspot, and common modification methods include raw material modification, surface modification, blending modification, and the like. These modification methods are mainly aimed at improving hydrophilicity of Polymer membranes, increasing water flux and reducing contamination rate.
Modification of polymers with COF materials is also one of the ways to modify Polymer films. First preparing one monomer from a COF ligand and a linear hydrophilic Polymer, and then copolymerizing with the other monomer to form a Polymer covalent organic framework (Polymer-COF); the Polymer covalent bond and the COFs realize chemical combination, and the structural stability is improved. And the pore diameter of the composite membrane is reduced, the porosity is increased, and the sieving property is improved. However, the stability and mechanical strength of the synthesized Polyer-COF still need to be further improved due to the existence of the linear Polymer, which is unfavorable for recycling the composite film.
Bacterial Cellulose (BC) is an ideal ion-adsorbing material due to its strong self-hydrophilicity, biodegradability, and the characteristic of containing a large amount of hydroxyl functions. However, the application of the bacterial cellulose in the field of adsorption materials is limited due to the influence of the structure-activity relationship of the bacterial cellulose.
Disclosure of Invention
In order to solve the technical problems, the invention adopts the following technical scheme: the preparation method of the polymer-COFs-biomass composite membrane comprises the following steps:
step one, preparing a COFs material: mixing a certain amount of 2,4, 6-tris (4-aminophenyl) 1.3,5-triazine with a certain amount of 2,3,5, 6-tetrafluoroterephthalaldehyde, adding a certain amount of 1, 2-dichlorobenzene and a certain amount of n-butanol, performing ultrasonic treatment on the mixed solution, and adding a certain amount of acetic acid aqueous solution to obtain a uniformly dispersed yellow solution;
the yellow solution is treated for a plurality of times by nitrogen, freezing and degassing, oxygen in the yellow solution is removed, then the yellow solution is dried and heated in a drying box for a period of time, finally the product is respectively centrifugally cleaned by tetrahydrofuran, acetone and methanol, then the product is filtered by normal hexane and is placed in a vacuum drying box for drying, and orange solid powder is obtained, namely the required COFs material;
step two, synthesizing a polymer-COFS material: weighing a certain amount of COFs material, dispersing the COFs material into a certain amount of N, N-dimethylformamide, adding a certain amount of anhydrous potassium carbonate and a certain amount of DMF solution dissolved with dopamine hydrochloride, heating at constant temperature for a period of time after ultrasonic treatment, centrifugally cleaning a reaction product by using acetone, water and methanol respectively, and vacuum drying the reaction product to obtain brown solid powder, namely the required polymer-COFS material;
step three, preparing a bacterial cellulose dry film: transferring the bacterial cellulose nutrient solution inoculated with the acetobacter xylinum bacterial solution into a biological incubator in a constant temperature state, culturing and growing in a static state, taking out the grown bacterial cellulose, and cleaning the bacterial cellulose with deionized water to remove impurities on the surface of the bacterial cellulose; preparing NaOH solution, putting the cleaned bacterial cellulose into the NaOH solution, heating in a water bath heating pot, taking out the bacterial cellulose after the treatment, repeatedly flushing with deionized water, and then heating in the water bath heating pot together with ionized water until the pH value of the bacterial cellulose is neutral; finally, putting the bacterial cellulose into a freeze dryer for freeze-drying to obtain a bacterial cellulose dry film;
step four, synthesizing a polymer-COFs-biomass composite membrane: dissolving the polymer-COFS material prepared in the second step in acetic acid solution, stirring and carrying out ultrasonic treatment; putting the bacterial cellulose dry film into a high-pressure reaction kettle, and then adding an acetic acid solution dissolved with a polymer-COFS material into the high-pressure reaction kettle to submerge the bacterial cellulose dry film; reacting for a period of time at high temperature in a high-pressure reaction kettle to obtain a UiO-66-NH2/BC composite nanofiber membrane; washing the prepared UiO-66-NH2/BC composite nanofiber membrane with DMF and methanol for multiple times respectively, freeze-drying, and vacuum drying to obtain a polymer-COFs-biomass composite membrane;
step five, activating a polymer-COFs-biomass composite membrane: soaking the polymer-COFs-biomass composite membrane in methanol, wrapping the membrane with filter paper, drying the sample by using a supercritical carbon dioxide dry-burning instrument, and finally drying and solidifying the polymer-COFs-biomass composite membrane in an oven.
As the optimization of the technical scheme, in the first step, 108.6mg of 2,4, 6-tris (4-aminophenyl) 1.3,5-triazine and 105mg of 2,3,5, 6-tetrafluoroterephthalaldehyde are mixed in a glass tube, then 2mL of 1, 2-dichlorobenzene and 4mL of n-butanol are added, the mixed solution is treated by ultrasonic for 20min, and then 1mL of acetic acid aqueous solution with the concentration of 6M is added to obtain a uniformly dispersed yellow solution;
and (3) carrying out nitrogen-freezing-degassing treatment on the yellow solution for 5 times to remove oxygen in the yellow solution, drying the yellow solution in a drying oven at 120 ℃ for 3 days, centrifugally cleaning the product by tetrahydrofuran, acetone and methanol respectively, filtering the product by n-hexane, and vacuum-drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain orange solid powder which is the required COFs material.
As the optimization of the technical scheme, in the second step, 20mg of the COFS material is weighed into 3.0mL of N, N-dimethylformamide, ultrasonic dispersion is carried out for 60min, 40mg of anhydrous potassium carbonate and 0.5mL of DMF solution dissolved with dopamine hydrochloride are added, the concentration of the dopamine hydrochloride is 80mg/mL, after ultrasonic treatment is carried out for 3h, the mixture is heated at the constant temperature of 100 ℃ for 1 day, finally, the reaction product is respectively centrifugally washed by acetone, water and methanol, and the reaction product is dried in vacuum at 60 ℃ for 12h, thus obtaining brown solid powder, namely the required polymer-COFS material.
As the optimization of the technical scheme, in the third step, the bacterial cellulose nutrient solution inoculated with the acetobacter xylinum solution is transferred into a biological incubator in a constant temperature state, cultured and grown for 5 days in a static state, the grown bacterial cellulose is taken out, and the bacterial cellulose is cleaned by deionized water to remove impurities on the surface of the bacterial cellulose; preparing a 1mol/L NaOH solution, putting the cleaned bacterial cellulose into the NaOH solution, heating the bacterial cellulose in a water bath heating pot at 80 ℃ for 12 hours, taking out the bacterial cellulose after the treatment, repeatedly flushing the bacterial cellulose with deionized water, and heating the bacterial cellulose in the water bath heating pot at 80 ℃ for 12 hours together with ionized water until the PH value of the bacterial cellulose is neutral; and finally, putting the bacterial cellulose into a freeze dryer for freeze-drying for 36 hours to obtain a bacterial cellulose dry film.
As a preferable mode of the above technical scheme, in the fourth step, the polymer-COFS material prepared in the second step is dissolved in acetic acid solution, the molar ratio of the polymer-COFS material to acetic acid is 200:1, and after stirring for 2 hours, the mixture is subjected to ultrasonic treatment for 1 hour; putting the bacterial cellulose dry film into a high-pressure reaction kettle, and then adding an acetic acid solution dissolved with a polymer-COFS material into the high-pressure reaction kettle to submerge the bacterial cellulose dry film; reacting for 24 hours at 120 ℃ in a high-pressure reaction kettle to obtain a UiO-66-NH2/BC composite nanofiber membrane; and cleaning the prepared UiO-66-NH2/BC composite nanofiber membrane with DMF and methanol for multiple times respectively, freeze-drying for 24 hours, and continuously performing vacuum drying treatment at 80 ℃ for 8 hours to obtain the polymer-COFs-biomass composite membrane.
As a preferable mode of the technical scheme, in the fifth step, the polymer-COFs-biomass composite film is finally put into an oven to be dried and cured for 12 hours.
Polymer-COFs-biomass composite membranes are prepared by the preparation method.
Application of Polymer-COFs-Biomass composite membrane Polymer-COFs-biomass composite membrane is used for metal ion adsorption.
Preferably, the metal ions include Fe 3+ 、Cu 2+ 、Cd 2+ 、Fe 3+ 、Cu 2+ 、Cd 2+ 、Hg 2+ 、Co 2+ 、Ni 2+ 、U 4+、 Cr 2+ One or more of the following.
The ion has the beneficial effects that: the polymer-COFs-biomass composite membrane has good adsorption effect, good application range and good mechanical property. For Fe 3+ 、Cu 2+ 、Cd 2+ 、Hg 2+ 、Co 2+ 、Ni 2+ 、U 4+ 、Cr 2+ The equivalent weight metal has good adsorption effect and reusability.
Drawings
FIG. 1 is an SEM image of a polymer-COFs-biomass composite film;
fig. 2 is an SEM image of the intermediate COF film.
Detailed Description
The following description of the embodiments of the present invention will be made apparent and fully in view of the accompanying drawings, in which some, but not all embodiments of the invention are shown. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the description of the present invention, it should be noted that, unless explicitly specified and limited otherwise, the terms "mounted," "connected," and "connected" are to be construed broadly, and may be either fixedly connected, detachably connected, or integrally connected, for example; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium, and can be communication between two elements. The specific meaning of the above terms in the present invention will be understood in specific cases by those of ordinary skill in the art.
And (3) weighing a certain amount of the COFS material, dispersing the COFS material into a certain amount of N, N-dimethylformamide, adding a certain amount of anhydrous potassium carbonate and a certain amount of DMF solution dissolved with dopamine hydrochloride, heating at constant temperature for a period of time after ultrasonic treatment, centrifugally cleaning a reaction product by using acetone, water and methanol respectively, and vacuum drying the reaction product to obtain brown solid powder, namely the required polymer-COFS material.
And (3) carrying out nitrogen-freezing-degassing treatment on the yellow solution for 5 times to remove oxygen in the yellow solution, drying the yellow solution in a drying oven at 120 ℃ for 3 days, centrifugally cleaning the product by tetrahydrofuran, acetone and methanol respectively, filtering the product by n-hexane, and vacuum-drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain orange solid powder which is the required COFs material.
Weighing 20mg of the COFS material into 3.0mL of N, N-dimethylformamide, performing ultrasonic dispersion for 60min, adding 40mg of anhydrous potassium carbonate and 0.5mL of DMF solution dissolved with dopamine hydrochloride, wherein the concentration of the dopamine hydrochloride is 80mg/mL, performing ultrasonic treatment for 3h, heating at a constant temperature of 100 ℃ for 1 day, and finally centrifugally cleaning a reaction product by using acetone, water and methanol respectively, and performing vacuum drying on the reaction product at 60 ℃ for 12h to obtain brown solid powder, namely the required polymer-COFS material.
Transferring the bacterial cellulose nutrient solution inoculated with the acetobacter xylinum bacterial solution into a biological incubator in a constant temperature state, culturing and growing for 5 days in a static state, taking out the grown bacterial cellulose, and cleaning the bacterial cellulose with deionized water to remove impurities on the surface of the bacterial cellulose; preparing a 1mol/L NaOH solution, putting the cleaned bacterial cellulose into the NaOH solution, heating the bacterial cellulose in a water bath heating pot at 80 ℃ for 12 hours, taking out the bacterial cellulose after the treatment, repeatedly flushing the bacterial cellulose with deionized water, and heating the bacterial cellulose in the water bath heating pot at 80 ℃ for 12 hours together with ionized water until the PH value of the bacterial cellulose is neutral; and finally, putting the bacterial cellulose into a freeze dryer for freeze-drying for 36 hours to obtain a bacterial cellulose dry film.
Dissolving a polymer-COFS material in an acetic acid solution, wherein the molar ratio of the polymer-COFS material to acetic acid is 200:1, stirring for 2 hours, and then carrying out ultrasonic treatment for 1 hour; putting the bacterial cellulose dry film into a high-pressure reaction kettle, and then adding an acetic acid solution dissolved with a polymer-COFS material into the high-pressure reaction kettle to submerge the bacterial cellulose dry film; reacting for 24 hours at 120 ℃ in a high-pressure reaction kettle to obtain a UiO-66-NH2/BC composite nanofiber membrane; and cleaning the prepared UiO-66-NH2/BC composite nanofiber membrane with DMF and methanol for multiple times respectively, freeze-drying for 24 hours, and continuously performing vacuum drying treatment at 80 ℃ for 8 hours to obtain the polymer-COFs-biomass composite membrane.
Soaking the polymer-COFs-biomass composite membrane in methanol, wrapping the membrane with filter paper, drying the sample by using a supercritical carbon dioxide dry-burning instrument, and finally drying and solidifying the polymer-COFs-biomass composite membrane in an oven for 12 hours.
The activated polymer-COFs-biomass composite membrane is observed by using a scanning electron microscope, an SEM image is shown in figure 1, and the SEM image shows that the ploymer-COFs biomass composite membrane extends the three-dimensional porous structure of the COFs membrane, aggregation and adhesion do not occur due to the addition of PDA and BC, and compared with a pure COF membrane ploymer-COFs biomass composite membrane, the ploymer-COFs biomass composite membrane has smaller pore diameter and more adsorption sites, so that the ploymer-COFs biomass composite material has more excellent adsorption performance.
SEM images of intermediate COF films are shown in fig. 2.
The physical properties of the activated polymer-COFs-biomass composite film were tested, and the test results are shown in the following table. From the test results, the mechanical properties of the COFs film are poor, and the mechanical properties of the polymer-COFs-biomass composite film are obviously improved, but slightly reduced compared with the pure BC film.
The physical properties of the activated polymer-COFs-biomass composite film were tested, and the contents of ions in the solutions before and after adsorption were measured by Inductively Coupled Plasma (ICP) spectrometer, respectively, and the test results are shown in the following table.
Compared with the intermediate COFs, the polymer-COFs-biomass composite membrane prepared by the method has obviously improved adsorption capacity for metal ions.
It should be noted that technical features such as a vacuum drying oven and the like related to the present application should be considered as the prior art, and specific structures, working principles, and control modes and spatial arrangement modes possibly related to the technical features should be selected conventionally in the art, and should not be considered as the invention point of the present application, and the present application is not further specifically developed in detail.
While the preferred embodiments of the present invention have been described in detail, it should be appreciated that numerous modifications and variations may be made in accordance with the principles of the present invention by those skilled in the art without undue burden, and thus, all technical solutions which may be obtained by logic analysis, reasoning or limited experimentation based on the principles of the present invention as defined by the claims are within the scope of protection as defined by the present invention.
Claims (9)
- The preparation method of the polymer-COFs-biomass composite membrane is characterized by comprising the following steps of:step one, preparing a COFs material: mixing a certain amount of 2,4, 6-tris (4-aminophenyl) 1.3,5-triazine with a certain amount of 2,3,5, 6-tetrafluoroterephthalaldehyde, adding a certain amount of 1, 2-dichlorobenzene and a certain amount of n-butanol, performing ultrasonic treatment on the mixed solution, and adding a certain amount of acetic acid aqueous solution to obtain a uniformly dispersed yellow solution;the yellow solution is treated for a plurality of times by nitrogen, freezing and degassing, oxygen in the yellow solution is removed, then the yellow solution is dried and heated in a drying box for a period of time, finally the product is respectively centrifugally cleaned by tetrahydrofuran, acetone and methanol, then the product is filtered by normal hexane and is placed in a vacuum drying box for drying, and orange solid powder is obtained, namely the required COFs material;step two, synthesizing a polymer-COFS material: weighing a certain amount of COFs material, dispersing the COFs material into a certain amount of N, N-dimethylformamide, adding a certain amount of anhydrous potassium carbonate and a certain amount of DMF solution dissolved with dopamine hydrochloride, heating at constant temperature for a period of time after ultrasonic treatment, centrifugally cleaning a reaction product by using acetone, water and methanol respectively, and vacuum drying the reaction product to obtain brown solid powder, namely the required polymer-COFS material;step three, preparing a bacterial cellulose dry film: transferring the bacterial cellulose nutrient solution inoculated with the acetobacter xylinum bacterial solution into a biological incubator in a constant temperature state, culturing and growing in a static state, taking out the grown bacterial cellulose, and cleaning the bacterial cellulose with deionized water to remove impurities on the surface of the bacterial cellulose; preparing NaOH solution, putting the cleaned bacterial cellulose into the NaOH solution, heating in a water bath heating pot, taking out the bacterial cellulose after the treatment, repeatedly flushing with deionized water, and then heating in the water bath heating pot together with ionized water until the pH value of the bacterial cellulose is neutral; finally, putting the bacterial cellulose into a freeze dryer for freeze-drying to obtain a bacterial cellulose dry film;step four, synthesizing a polymer-COFs-biomass composite membrane: dissolving the polymer-COFS material prepared in the second step in acetic acid solution, stirring and carrying out ultrasonic treatment; putting the bacterial cellulose dry film into a high-pressure reaction kettle, and then adding an acetic acid solution dissolved with a polymer-COFS material into the high-pressure reaction kettle to submerge the bacterial cellulose dry film; reacting for a period of time at high temperature in a high-pressure reaction kettle to obtain a UiO-66-NH2/BC composite nanofiber membrane; washing the prepared UiO-66-NH2/BC composite nanofiber membrane with DMF and methanol for multiple times respectively, freeze-drying, and vacuum drying to obtain a polymer-COFs-biomass composite membrane;step five, activating a polymer-COFs-biomass composite membrane: soaking the polymer-COFs-biomass composite membrane in methanol, wrapping the membrane with filter paper, drying the sample by using a supercritical carbon dioxide dry-burning instrument, and finally drying and solidifying the polymer-COFs-biomass composite membrane in an oven.
- 2. The method for preparing the polymer-COFs-biomass composite membrane according to claim 1, wherein in the first step, 108.6mg of 2,4, 6-tris (4-aminophenyl) 1.3,5-triazine and 105mg of 2,3,5, 6-tetrafluoroterephthalaldehyde are mixed in a glass tube, 2mL of 1, 2-dichlorobenzene and 4mL of n-butanol are added, and after the mixed solution is sonicated for 20min, 1mL of an aqueous solution of acetic acid having a concentration of 6M is added to obtain a uniformly dispersed yellow solution;and (3) carrying out nitrogen-freezing-degassing treatment on the yellow solution for 5 times to remove oxygen in the yellow solution, drying the yellow solution in a drying oven at 120 ℃ for 3 days, centrifugally cleaning the product by tetrahydrofuran, acetone and methanol respectively, filtering the product by n-hexane, and vacuum-drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain orange solid powder which is the required COFs material.
- 3. The method for preparing the polymer-COFs-biomass composite membrane according to claim 2, wherein in the second step, 20mg of the COFs material is weighed into 3.0mL of N, N-dimethylformamide, the mixture is subjected to ultrasonic dispersion for 60min, 40mg of anhydrous potassium carbonate and 0.5mL of DMF solution dissolved with dopamine hydrochloride are added, the concentration of the dopamine hydrochloride is 80mg/mL, the mixture is subjected to ultrasonic treatment for 3h and then heated at a constant temperature of 100 ℃ for 1 day, finally the reaction product is respectively centrifugally washed by acetone, water and methanol, and the reaction product is dried in vacuum at 60 ℃ for 12h, so that brown solid powder which is the required polymer-COFs material is obtained.
- 4. The method for preparing polymer-COFs-biomass composite membrane according to claim 3, wherein in the third step, the bacterial cellulose nutrient solution inoculated with acetobacter xylinum solution is transferred into a biological incubator in a constant temperature state, cultured and grown for 5 days in a static state, the grown bacterial cellulose is taken out, and the bacterial cellulose is cleaned by deionized water to remove impurities on the surface of the bacterial cellulose; preparing a 1mol/L NaOH solution, putting the cleaned bacterial cellulose into the NaOH solution, heating the bacterial cellulose in a water bath heating pot at 80 ℃ for 12 hours, taking out the bacterial cellulose after the treatment, repeatedly flushing the bacterial cellulose with deionized water, and heating the bacterial cellulose in the water bath heating pot at 80 ℃ for 12 hours together with ionized water until the PH value of the bacterial cellulose is neutral; and finally, putting the bacterial cellulose into a freeze dryer for freeze-drying for 36 hours to obtain a bacterial cellulose dry film.
- 5. The method for preparing a polymer-COFs-biomass composite membrane according to claim 4, wherein in the fourth step, the polymer-COFs material prepared in the second step is dissolved in an acetic acid solution, the molar ratio of the polymer-COFs material to acetic acid is 200:1, and the solution is stirred for 2 hours and then subjected to ultrasonic treatment for 1 hour; putting the bacterial cellulose dry film into a high-pressure reaction kettle, and then adding an acetic acid solution dissolved with a polymer-COFS material into the high-pressure reaction kettle to submerge the bacterial cellulose dry film; reacting for 24 hours at 120 ℃ in a high-pressure reaction kettle to obtain a UiO-66-NH2/BC composite nanofiber membrane; and cleaning the prepared UiO-66-NH2/BC composite nanofiber membrane with DMF and methanol for multiple times respectively, freeze-drying for 24 hours, and continuously performing vacuum drying treatment at 80 ℃ for 8 hours to obtain the polymer-COFs-biomass composite membrane.
- 6. The method for preparing the polymer-COFs-biomass composite membrane according to claim 5, wherein in the fifth step, the polymer-COFs-biomass composite membrane is finally dried and cured in an oven for 12 hours.
- Polymer-COFs-biomass composite membrane, characterized in that it is produced by the preparation method according to any one of claims 1 to 6.
- 8. The use of a polymer-COFs-biomass composite membrane according to claim 7, wherein the polymer-COFs-biomass composite membrane is used for metal ion adsorption.
- 9. The use of polymer-COFs-biomass composite membrane according to claim 8, wherein the metal ions comprise Fe 3+ 、Cu 2+ 、Cd 2+ 、Fe 3+ 、Cu 2+ 、Cd 2+ 、Hg 2+ 、Co 2+ 、Ni 2+ 、U 4+、 Cr 2+ One or more of the following.
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