CN114917887A - Wood-based/MOF composite aerogel film and preparation method thereof - Google Patents
Wood-based/MOF composite aerogel film and preparation method thereof Download PDFInfo
- Publication number
- CN114917887A CN114917887A CN202210628974.9A CN202210628974A CN114917887A CN 114917887 A CN114917887 A CN 114917887A CN 202210628974 A CN202210628974 A CN 202210628974A CN 114917887 A CN114917887 A CN 114917887A
- Authority
- CN
- China
- Prior art keywords
- wood
- solution
- mof composite
- composite aerogel
- aerogel film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
-
- 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
- B01J20/26—Synthetic macromolecular compounds
-
- 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
-
- 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
- B01J20/28047—Gels
-
- 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
- B01J20/28054—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 surface properties or porosity
-
- 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
-
- 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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
- B01J2220/4825—Polysaccharides or cellulose materials, e.g. starch, chitin, sawdust, wood, straw, cotton
-
- 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
-
- 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
- C02F2101/30—Organic compounds
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a wood-based/MOF composite aerogel membrane and a preparation method thereof in the technical field of material synthesis, and aims to solve the problems of high cost, poor effect and the like of traditional materials used for sewage treatment in the prior art. The invention constructs a preparation route from the traditional wood to a new sewage treatment material, creatively introduces the bimetallic MOFs, endows the green material with enough treatment capacity for different types of sewage, and constructs the wood-based composite aerogel material with toughness, integration, multiple functions and adjustable performance.
Description
Technical Field
The invention relates to a wood-based/MOF composite aerogel membrane and a preparation method thereof, belonging to the technical field of material synthesis.
Background
Although China has made great progress and remarkable results in the aspects of resource and environmental protection, the water body pollution in China is still an urgent problem to be solved. Many lakes and reservoirs have developed serious eutrophication problems due to excessive nitrogen and phosphorus concentrations, and toxic substances have a negative effect on water organisms. Heavy metal and organic contamination has become a major water quality problem.
Adsorption is currently a simple, easy to operate and inexpensive method of wastewater treatment, and recently, research has focused on screening relatively low cost adsorbents such as montmorillonite, kaolin, tridymite and mineral silicates. However, for any adsorbent, adsorption performance is still the most critical specification. Especially for low-concentration pollutant wastewater, it is important to find a high-efficiency adsorbent with excellent adsorption performance and strong adsorption specificity. Therefore, there is a need to prepare a new adsorbent with large adsorption capacity, large specific surface area, abundant pore structure, abundant sources, low cost, good stability, and easy recovery and regeneration.
Aerogel is an emerging porous material with many advantages not available with other materials. For example, (1) the density is low, with the lightest aerogels being only 0.16mg per cubic centimeter, slightly less dense than air; (2) the porosity is high, the porosity of the aerogel can reach 99.9%, the size of the pores is mostly below 50 mm, and a large amount of other ions with catalytic function can be carried; (3) the specific surface area is large, and the specific surface area of the aerogel is as high as 600m/g-1000m 2 The water-soluble organic solvent has obvious advantages in the aspect of adsorbing pollutants; (4) the compression modulus is wide, the compression modulus of the aerogel can be changed within the range of 6 orders of magnitude, the density adjustability is strong, and the aerogel can adapt to the use environments with different sizes and shapes; (5) the heat conductivity coefficient is low; (6) can be repeatedly used. Therefore, the development of environmentally friendly aerogels is the current development direction to solve the water quality problem.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a wood-based/MOF composite aerogel membrane and a preparation method thereof, and the MOF808 with double metal ions is introduced, so that the degradation of tetracycline and the adsorption performance of heavy metals of the wood-based aerogel membrane are obviously improved, and the wood-based/MOF composite aerogel membrane can be applied to actual sewage treatment.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
according to a first aspect of the invention, a method of making a wood-based/MOF composite aerogel film, comprises the steps of,
s1, adding a certain amount of trimesic acid and N, N-dimethylformamide into a formic acid solution, and performing ultrasonic treatment to completely dissolve the trimesic acid;
dissolving a certain amount of ammonium ceric nitrate and hafnium oxychloride hydrate in deionized water, adding the obtained solution into the solution, and carrying out reflux reaction;
centrifuging the solution obtained after the reaction is finished, collecting a crude product, and washing and drying the crude product to obtain MOF808(Ce/Hf) powder;
s2, dispersing the MOF808(Ce/Hf) powder obtained in the step S1 in the balsawood cell wall solution, adding a certain amount of polyvinyl alcohol, and stirring until the polyvinyl alcohol is completely dissolved;
s3, carrying out vacuum filtration on the solution obtained in the step S2, and carrying out freeze drying on the wood-based/MOF composite wet membrane obtained on the filter membrane to obtain the wood-based/MOF composite aerogel membrane.
Further, the preparation method of the balsawood cell wall solution comprises the following steps:
cutting the balsa wood slices into wood strips;
sequentially adding a sodium acetate buffer solution and a sodium chlorite aqueous solution, heating in an oil bath and stirring;
taking out the balsawood after the reaction is finished, washing the balsawood, putting the balsawood into a sodium hydroxide aqueous solution, heating and refluxing the balsawood, and adding a hydrogen peroxide aqueous solution to continue the reaction;
filtering the obtained solution, taking a filtrate, sequentially adding a phosphoric acid buffer solution, a sodium hypochlorite solution and a chlorous acid solution into the filtrate, heating and stirring, adding 2,2,6, 6-tetramethyl piperidine oxide, and continuously heating and stirring;
stopping heating, adding ethanol, cooling the obtained solid-liquid mixture, cleaning, performing ultrasonic treatment, collecting supernatant, performing ultrasonic treatment again, and repeating for multiple times to obtain wood-based cell wall solution.
Furthermore, the concentration of the sodium chlorite solution is 4-6 wt%, the concentration of the sodium hypochlorite solution is 3-5 wt%, and the concentration of the chlorous acid solution is 6-8 wt%.
Further, the concentration of the wood-based cell wall solution is controlled by concentrating water.
Further, in step S1, the molar ratio of the ammonium ceric nitrate to the hafnia dichloride hydrate is 1.0 to 4.0.
Furthermore, the dosage of the polyvinyl alcohol in the step S2 is 0.5-2 times of the mass of the wood-based cell wall solution.
Further, the freeze-drying time of the wood-based/MOF composite wet film in the step S3 is 12-48 h.
According to a second aspect of the invention, there is also provided a wood-based/MOF composite aerogel film produced by the method of any one of the above.
According to a third aspect of the invention, the application of the wood-based/MOF composite aerogel film in photocatalytic tetracycline degradation and heavy metal ion adsorption is further provided.
Compared with the prior art, the invention has the following beneficial effects:
according to the wood-based/MOF composite aerogel membrane and the preparation method thereof, MOF808(Ce/Hf) of bimetallic ions is prepared, the photocatalytic performance of MOF materials can be obviously improved, the wood cell wall of a porous two-dimensional lamellar layer is also prepared, and the high-added-value utilization of wood can be effectively realized;
the wood-based/MOF composite aerogel membrane compounded by MOF808(Ce/Hf) and a wood cell wall solution shows excellent performance in the adsorption of water quality pollutant tetracycline and heavy metal ions under an illumination condition, and has wide application prospect in the aspect of water treatment.
Drawings
FIG. 1 is an XRD schematic of the bimetallic ion MOF808(Ce/Hf) in an embodiment of the present invention;
FIG. 2 is an electron micrograph of an embodiment of the present invention; (a) the method comprises the following steps of (a) taking a transmission electron microscope picture of a wood-based cell wall, (b) taking a surface electron microscope picture of a wood-based/MOF composite aerogel thin film, and (c) taking a section electron microscope picture of the wood-based/MOF composite aerogel thin film.
FIG. 3 is a graphical representation of the photodegradation rate of wood-based/MOF composite aerogel films for tetracycline in an example of the present invention;
fig. 4 is a graph showing a Cu (ii) adsorption amount curve of the wood-based/MOF composite aerogel film and a change in conductivity of the solution after adsorption in an embodiment of the present invention.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For numerical ranges, each new numerical range or ranges can be obtained by combining the values between the endpoints of each range, between the endpoints of each range and the individual values, and between the individual values with each other, and these numerical ranges should be construed as specifically disclosed herein.
For the purposes of the present specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and appended claims, are to be understood as being modified in all instances by the term "about". Moreover, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
Example 1:
(1) preparation of bimetallic MOF808(Ce/Hf)
0.05mmol of trimesic acid, 10mL of N, N-Dimethylformamide (DMF) and an equal volume of formic acid solution are added into a single-neck flask and sonicated for 10min to dissolve all the trimesic acid.
0.07mmol of ammonium ceric nitrate and 0.08mmol of hafnium dichloride octahydrate are dissolved in a small amount of deionized water, added into the single-neck flask, and subjected to reflux reaction at 100 ℃ for 48 hours.
And after the reaction is finished, centrifuging and collecting a crude product, washing the crude product for 3 times by using DMF and methanol, and drying for 12h under the vacuum condition of 70 ℃ to obtain bimetallic MOF808(Ce/Hf) powder.
(2) Preparation of a Wood-based cell wall solution
Cutting 2g of balsa wood slices into small wood strips, putting the small wood strips into a beaker, adding 100mL of sodium acetate buffer solution with the pH value of 4.6, adding 100mL of sodium chlorite aqueous solution, finally pouring the solution in the beaker and the wood strips into a three-neck flask, and heating and stirring the three-neck flask in an oil bath at 90 ℃ for 12 hours.
And after the reaction is finished, pouring out the solution, washing the small wood strips twice by using water, continuously adding 100mL of sodium hydroxide aqueous solution, heating and refluxing for 12h at 90 ℃, and then adding 100mL of 30% hydrogen peroxide solution to continuously react for 12 h.
And after the reaction is finished, filtering the solution, taking the filtrate, putting the filtrate into a 1L beaker, adding 500 mL of phosphate buffer solution with the pH value of 6.8-7, adding 200mL of sodium hypochlorite solution and 200mL of chlorous acid solution, heating and stirring for 4h at the temperature of 30 ℃, adding 0.1g of 2,2,6, 6-tetramethylpiperidine oxide, continuing stirring for 2h, stopping heating, adding a small amount of ethanol, and cleaning after the solid-liquid mixture is cooled.
And (3) putting the solid-liquid mixture into an ultrasonic machine for ultrasonic treatment for 1h, taking the supernatant, performing ultrasonic treatment again, and repeating the ultrasonic treatment for five times to obtain a clear and transparent wood-based cell wall solution.
(3) Preparation of wood-based/MOF composite aerogel film
Concentrating the wood-based cell wall solution to 3mg/mL, dispersing 3mg of MOF808 in 30mL of cell wall solution, continuously adding 30mg of polyvinyl alcohol (PVA) solid, stirring at room temperature for 3h until the PVA is completely dissolved, carrying out vacuum filtration on the mixed solution on a filter membrane, and after a wet membrane is formed, carrying out freeze drying on the wet membrane to obtain the wood-based/MOF composite aerogel.
Example 2:
(1) preparation of bimetallic MOF808(Ce/Hf)
0.05mmol of trimesic acid 10mL of N, N-Dimethylformamide (DMF) and an equal volume of formic acid solution were added to a single-neck flask and sonicated for 10min to allow the trimesic acid to dissolve completely.
0.10mmol of ammonium ceric nitrate and 0.05mmol of hafnium dichloride octahydrate are dissolved in a small amount of deionized water, added into the single-neck flask, and subjected to reflux reaction at 100 ℃ for 48 hours.
And after the reaction is finished, centrifuging and collecting a crude product, washing the crude product for 3 times by using DMF (dimethyl formamide) and methanol, and drying for 12 hours at 70 ℃ under a vacuum condition to obtain bimetal MOF808(Ce/Hf) powder.
(2) Preparation of a Wood-based cell wall solution
The wood-based cell wall solution was prepared in the same manner as in example 1.
(3) Preparation of wood-based/MOF composite aerogel film
Concentrating the wood-based cell wall solution to 3mg/mL, dispersing 6mg of MOF808 in 30mL of cell wall solution, continuously adding 30mg of PVA solid, stirring at room temperature for 3h until PVA is completely dissolved, carrying out vacuum filtration on the mixed solution on a filter membrane, and after a wet membrane is formed, carrying out freeze drying on the mixed solution to obtain the wood-based/MOF composite aerogel.
Example 3:
(2) preparation of bimetallic MOF808(Ce/Hf)
0.05mmol of trimesic acid 10mL of N, N-Dimethylformamide (DMF) and an equal volume of formic acid solution were added to a single-neck flask and sonicated for 10min to allow the trimesic acid to dissolve completely.
0.05mmol of ammonium ceric nitrate and 0.10mmol of hafnium dichloride octahydrate are dissolved in a small amount of deionized water, added into the single-neck flask and subjected to reflux reaction at 100 ℃ for 48 hours.
And after the reaction is finished, centrifuging and collecting a crude product, washing the crude product for 3 times by using DMF and methanol, and drying for 12h under the vacuum condition of 70 ℃ to obtain bimetallic MOF808(Ce/Hf) powder.
(2) Preparation of a Wood-based cell wall solution
The wood-based cell wall solution was prepared in the same manner as in example 1.
(3) Preparation of wood-based/MOF composite aerogel film
Concentrating the wood-based cell wall solution to 3mg/mL, dispersing 9mg of MOF808 in 30mL of cell wall solution, continuously adding 30mg of PVA solid, stirring at room temperature for 3h until PVA is completely dissolved, carrying out vacuum filtration on the mixed solution on a filter membrane, and after a wet membrane is formed, carrying out freeze drying on the mixed solution to obtain the wood-based/MOF composite aerogel.
Example 4:
(1) preparation of a Wood-based cell wall solution
The wood-based cell wall solution was prepared in the same manner as in example 1.
(2) Preparation of pure wood-based aerogel film
Concentrating the wood-based cell wall solution to 3mg/mL, taking 30mL of the cell wall solution, adding 30mg of PVA solid into the solution, stirring at room temperature for 3h until the PVA is completely dissolved, carrying out vacuum filtration on the mixed solution on a filter membrane, and after a wet membrane is formed, carrying out freeze drying on the mixed solution to obtain the pure wood-based aerogel membrane.
The properties of the wood-based/MOF composite aerogel film obtained by the embodiment of the present invention will be analyzed with reference to the accompanying drawings.
As shown in FIG. 1, from an XRD data diagram, the crystal form of the prepared bimetallic MOF808(Ce/Hf) powder is sharp, and the peak position has good matching with the simulated peak of a standard MOF material, which indicates that the bimetallic MOF808(Ce/Hf) is successfully prepared.
From FIG. 2a, it can be seen from the transmission electron micrograph of the wood-based cell wall that the prepared wood-based cell wall is a two-dimensional porous lamellar structure. From the surface electron microscope image of fig. 2b and the cross-sectional electron microscope image of fig. 2c, it can be seen that the aerogel film is formed by vacuum self-assembly stacking of cell wall sheets, and MOF808(Ce/Hf) is uniformly dispersed among the cell wall sheets.
With reference to fig. 3, fig. 3 is a graph illustrating the degradation rate of the wood-based/MOF composite aerogel film to tetracycline within 180 min under the illumination condition. The pure wood-based aerogel film has low photocatalytic degradation efficiency on tetracycline, and the degradation efficiency is only 2.63% in 180 min. The degradation rate of tetracycline in 180 minutes of the wood-based aerogel film added with 10% of MOF808 (example 1) reaches 23.43%, the degradation rate of the wood-based aerogel film added with 20% of MOF808 (example 2) reaches 28.62%, and the degradation rate of the wood-based aerogel film added with 30% of MOF (example 3) is higher than 37.17%, which shows that the wood-based aerogel film can be subjected to photocatalytic degradation of tetracycline by adding MOF808(Ce/Hf), and shows that the higher the concentration of the added MOF808(Ce/Hf), the higher the degradation rate of tetracycline by the wood-based/MOF composite aerogel film.
As shown in fig. 4, fig. 4 is a graph of Cu (ii) adsorption amount curve of the wood-based/MOF composite aerogel film and conductivity change of the solution after adsorption. As can be seen from the figure, the adsorption of the four aerogel films to Cu (II) ions is increased along with the increase of time, and a large amount of Cu (II) ions are rapidly absorbed in the first 60 minutes and all of the Cu (II) ions basically reach the equilibrium adsorption amount of the Cu (II) ions finally. But for the aerogel film added with MOF808, more Cu (II) ions can be adsorbed in a shorter time, and the final equilibrium adsorption amount is larger.
And the conductivity of the solutions treated by the four aerogel films is reduced, which shows that the concentration of ionic Cu (II) in the solutions is reduced, and further proves that the ionic Cu (II) in the solutions is adsorbed by the aerogel films.
By comparing examples 1 to 3, wherein example 1 is an aerogel film added with 10% of MOF808(Ce/Hf), example 1 is an aerogel film added with 20% of MOF808(Ce/Hf), and example 3 is an aerogel film added with 30% of MOF808(Ce/Hf), it can be seen that the higher the concentration of MOF808(Ce/Hf) contained in the aerogel film is, the better the adsorption effect of the aerogel film on heavy metal ions is.
The invention constructs a preparation route from the traditional wood to a new sewage treatment material, creatively adds the bimetallic MOFs into the preparation route, endows the green material with enough treatment capacity for different types of sewage, and constructs a wood-based composite aerogel material with toughness, integration, multiple functions and adjustable performance.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and those improvements and modifications should be considered as the protection scope of the present invention.
Claims (9)
1. A preparation method of a wood-based/MOF composite aerogel film is characterized by comprising the following steps: comprises the following steps of (a) preparing a solution,
s1, adding a certain amount of trimesic acid and N, N-dimethylformamide into a formic acid solution, and performing ultrasonic treatment to completely dissolve the trimesic acid;
dissolving a certain amount of ammonium ceric nitrate and hafnium oxychloride hydrate in deionized water, adding the obtained solution into the solution, and carrying out reflux reaction;
centrifuging the solution obtained after the reaction is finished, collecting a crude product, and washing and drying the crude product to obtain MOF808(Ce/Hf) powder;
s2, dispersing the MOF808(Ce/Hf) powder obtained in the step S1 in a wood-based cell wall solution, adding a certain amount of polyvinyl alcohol, and stirring until the polyvinyl alcohol is completely dissolved;
and S3, carrying out vacuum filtration on the solution obtained in the step S2, and carrying out freeze drying on the wood-based/MOF composite wet membrane obtained on the filter membrane to obtain the wood-based/MOF composite aerogel membrane.
2. The method of preparing a wood-based/MOF composite aerogel film according to claim 1, wherein: the preparation method of the wood-based cell wall solution comprises the following steps:
cutting the balsa wood slices into wood strips;
sequentially adding a sodium acetate buffer solution and a sodium chlorite aqueous solution, heating in an oil bath and stirring;
taking out the balsawood after the reaction is finished, washing the balsawood, putting the balsawood into a sodium hydroxide aqueous solution, heating and refluxing the balsawood, and then adding a hydrogen peroxide aqueous solution to continue the reaction;
filtering the obtained solution, taking a filtrate, sequentially adding a phosphoric acid buffer solution, a sodium hypochlorite solution and a chlorous acid solution into the filtrate, heating and stirring, adding 2,2,6, 6-tetramethyl piperidine oxide, and continuously heating and stirring;
stopping heating, adding ethanol, cooling the obtained solid-liquid mixture, cleaning, performing ultrasonic treatment, collecting supernatant, performing ultrasonic treatment again, and repeating for multiple times to obtain wood-based cell wall solution.
3. The method for preparing the wood-based/MOF composite aerogel film according to claim 2, wherein the method comprises the following steps: the concentration of the sodium chlorite solution is 4-6 wt%, the concentration of the sodium hypochlorite solution is 3-5 wt%, and the concentration of the chlorous acid solution is 6-8 wt%.
4. The method for preparing the wood-based/MOF composite aerogel film according to claim 2, wherein the method comprises the following steps: the concentration of the wood-based cell wall solution is regulated by concentrating the water.
5. The method for preparing the wood-based/MOF composite aerogel film according to claim 1, wherein the method comprises the following steps: in step S1, the molar ratio of the ammonium ceric nitrate to the hafnium oxychloride hydrate is 1.0-4.0.
6. The method of preparing a wood-based/MOF composite aerogel film according to claim 1, wherein: in the step S2, the dosage of the polyvinyl alcohol is 0.5-2 times of the mass of the wood-based cell wall solution.
7. The method of preparing a wood-based/MOF composite aerogel film according to claim 1, wherein: in the step S3, the freeze-drying time of the wood-based/MOF composite wet film is 12-48 h.
8. A wood-based/MOF composite aerogel film, characterized in that: prepared by the preparation method of any one of claims 1 to 7.
9. Use of the wood-based/MOF composite aerogel film of claim 8 in photocatalytic degradation of tetracycline and adsorption of heavy metal ions.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210628974.9A CN114917887B (en) | 2022-06-06 | 2022-06-06 | Wood-based/MOF composite aerogel film and preparation method thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202210628974.9A CN114917887B (en) | 2022-06-06 | 2022-06-06 | Wood-based/MOF composite aerogel film and preparation method thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN114917887A true CN114917887A (en) | 2022-08-19 |
CN114917887B CN114917887B (en) | 2023-08-18 |
Family
ID=82812972
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202210628974.9A Active CN114917887B (en) | 2022-06-06 | 2022-06-06 | Wood-based/MOF composite aerogel film and preparation method thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN114917887B (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116330420A (en) * | 2023-05-15 | 2023-06-27 | 西安交通大学 | Hexagonal boron nitride/wood composite aerogel and preparation method thereof |
Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018046925A1 (en) * | 2016-09-08 | 2018-03-15 | Universitetet I Oslo | Process for preparing a cerium-zirconium mof and materials so obtained |
CN109608685A (en) * | 2018-12-14 | 2019-04-12 | 中国林业科学研究院木材工业研究所 | A kind of anisotropy wood based nano-fiber aeroge and preparation method thereof |
CN109999757A (en) * | 2019-04-16 | 2019-07-12 | 浙江农林大学 | A kind of Cr-MOF/ wood composite aeroge and preparation method and application capturing heavy metal ion |
CN110252257A (en) * | 2019-07-03 | 2019-09-20 | 江南大学 | A kind of carbon nanotube metal organic frame composite material and preparation method |
CN110358505A (en) * | 2019-07-04 | 2019-10-22 | 北京林业大学 | A kind of preparation method of functional form photo-thermal composite phase-change heat-storage material |
CN111073026A (en) * | 2019-12-30 | 2020-04-28 | 国际竹藤中心 | Bamboo cellulose aerogel thermal insulation material and preparation method and application thereof |
CN111804346A (en) * | 2020-07-17 | 2020-10-23 | 中国人民解放军国防科技大学 | Method for rapidly preparing metal organic layer material and application |
CN113686838A (en) * | 2021-08-19 | 2021-11-23 | 中国热带农业科学院分析测试中心 | Preparation of superfine mixed-valence Ce-MOF nanowire and application of superfine mixed-valence Ce-MOF nanowire in electrochemiluminescence sensing |
CN114210275A (en) * | 2021-10-21 | 2022-03-22 | 西南林业大学 | Method for preparing MOF/wood aerogel composite material |
-
2022
- 2022-06-06 CN CN202210628974.9A patent/CN114917887B/en active Active
Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018046925A1 (en) * | 2016-09-08 | 2018-03-15 | Universitetet I Oslo | Process for preparing a cerium-zirconium mof and materials so obtained |
CN109608685A (en) * | 2018-12-14 | 2019-04-12 | 中国林业科学研究院木材工业研究所 | A kind of anisotropy wood based nano-fiber aeroge and preparation method thereof |
CN109999757A (en) * | 2019-04-16 | 2019-07-12 | 浙江农林大学 | A kind of Cr-MOF/ wood composite aeroge and preparation method and application capturing heavy metal ion |
CN110252257A (en) * | 2019-07-03 | 2019-09-20 | 江南大学 | A kind of carbon nanotube metal organic frame composite material and preparation method |
CN110358505A (en) * | 2019-07-04 | 2019-10-22 | 北京林业大学 | A kind of preparation method of functional form photo-thermal composite phase-change heat-storage material |
CN111073026A (en) * | 2019-12-30 | 2020-04-28 | 国际竹藤中心 | Bamboo cellulose aerogel thermal insulation material and preparation method and application thereof |
CN111804346A (en) * | 2020-07-17 | 2020-10-23 | 中国人民解放军国防科技大学 | Method for rapidly preparing metal organic layer material and application |
CN113686838A (en) * | 2021-08-19 | 2021-11-23 | 中国热带农业科学院分析测试中心 | Preparation of superfine mixed-valence Ce-MOF nanowire and application of superfine mixed-valence Ce-MOF nanowire in electrochemiluminescence sensing |
CN114210275A (en) * | 2021-10-21 | 2022-03-22 | 西南林业大学 | Method for preparing MOF/wood aerogel composite material |
Non-Patent Citations (3)
Title |
---|
BENJAMIN BOHIGUES等: "Coordinatively Unsaturated Hf-MOF-808 Prepared via Hydrothermal Synthesis as a Bifunctional Catalyst for the Tandem N‑Alkylation of Amines with Benzyl Alcohol", 《ACS SUSTAINABLE CHEMISTRY & ENGINEERING》, vol. 9, pages 15793 * |
M. LAMMERT等: "Tuning the stability of bimetallic Ce(IV)/Zr(IV)-based MOFs with UiO-66 and MOF-808 structures", 《DALTON TRANSACTIONS》, vol. 46, pages 2425 * |
高景然等: "木材细胞壁的超微构造与气凝胶型木材的制备原理", 《东北林业大学学报》, vol. 36, no. 11, pages 98 - 100 * |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN116330420A (en) * | 2023-05-15 | 2023-06-27 | 西安交通大学 | Hexagonal boron nitride/wood composite aerogel and preparation method thereof |
CN116330420B (en) * | 2023-05-15 | 2024-04-12 | 西安交通大学 | Hexagonal boron nitride/wood composite aerogel and preparation method thereof |
Also Published As
Publication number | Publication date |
---|---|
CN114917887B (en) | 2023-08-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104437344B (en) | A kind of Copper-cladding Aluminum Bar composite magnetic nano material and preparation thereof and application | |
CN106699817B (en) | A kind of preparation method and applications of metal-organic framework material | |
CN109261141B (en) | ZIF-8 nanocrystal and preparation method and application thereof | |
CN111001388B (en) | Preparation method and application of bamboo-based biochar phosphorus removal adsorbent | |
CN102515145A (en) | Preparation process for high specific surface porous carbon material | |
CN105903439A (en) | Three-dimensional layered graphite-phase nitrogen carbide/MOF composite material and preparation method thereof | |
Gao et al. | Adsorptive separation performance of 1-butanol onto typical hydrophobic zeolitic imidazolate frameworks (ZIFs) | |
CN106000319B (en) | Remove the sorbing material of trace arsenic and its minimizing technology to trace arsenic in water body in water body | |
CN114917887A (en) | Wood-based/MOF composite aerogel film and preparation method thereof | |
CN115475604B (en) | Manufacturing method of composite multifunctional adsorbent based on cork activated carbon and amino carbon quantum dots | |
CN110627065A (en) | Preparation method and application of jute-based nitrogen-containing porous carbon | |
Chen et al. | ZnO@ ZIF-8 core–shell heterostructures with improved photocatalytic activity | |
US11369942B2 (en) | Method for assembling and synthesizing Cu2O particle-supported porous CuBTC | |
CN112642406A (en) | Wood fiber based composite sponge and preparation method thereof | |
CN113683089A (en) | Layered porous biochar and preparation method and application thereof | |
CN112958061A (en) | Oxygen vacancy promoted direct Z mechanism mesoporous Cu2O/TiO2Photocatalyst and preparation method thereof | |
CN106076260A (en) | A kind of room temperature fast preparation method of metallic organic framework oxidized graphite composite material | |
CN109467073B (en) | Preparation method and application of porous carbon | |
CN102580690B (en) | Nano-aperture granular adsorbent and preparation and application thereof | |
CN115646454B (en) | Hierarchical pore ZIFs material and low-temperature plasma preparation method and application thereof | |
CN114288866B (en) | Method for preparing two-dimensional vertical heterojunction separation membrane | |
CN110559983B (en) | Preparation method of cobalt-doped porous ZnO for pollutant adsorption | |
CN114644334A (en) | Preparation method of multilayer nitrogen-doped carbon material for efficiently removing heavy metal pollutants | |
KR100553179B1 (en) | Production Method and Regeneration Method of Mesoporous Alumina for Arsenic Adsorbents | |
CN116003815B (en) | Microporous MOFs material ZnAtzCO constructed by carbonate 3 Is used for preparing and application in carbon dioxide/nitrogen separation |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant |