CN110102267B - Aluminum-based MOFs/chitosan composite microsphere and preparation method and application thereof - Google Patents
Aluminum-based MOFs/chitosan composite microsphere and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the field of environmental science and engineering, discloses an aluminum-based MOFs/chitosan composite microsphere and a preparation method and application thereof, and solves the problem that the adsorption capacity is reduced after the conventional MOFs is molded. The invention takes an aluminum-based MOFs material MIL-68(Al) as a matrix, obtains the composite microsphere with the surface coated with chitosan under the joint crosslinking action of sodium alginate and chitosan, has the particle size of about 2mm, and is easy to separate and recycle from water. The method has the advantages of simple operation process, lower requirements on equipment conditions and easy implementation, and the aluminum-based MOFs/chitosan composite microspheres can achieve the removal efficiency equivalent to that of the powder MOFs, can efficiently adsorb and remove the bisphenol A in the water body, and can quickly separate and recover the adsorbing material from the water body.
Description
Technical Field
The invention belongs to the field of environmental science and engineering, and particularly relates to an aluminum-based MOFs/chitosan composite microsphere as well as a preparation method and application thereof.
Background
With the development of social industry and the improvement of the living standard of people, environmental problems are increasingly prominent, wherein the problem of water pollution becomes an important restriction factor for the sustainable development of human economy. Environmental Endocrine Disrupting Substances (EEDs) have the characteristics of high toxicity, difficult degradation and the like, are the focus of current environmental problems, and have great influence on both ecological environment and human health. Bisphenol A is a typical environmental endocrine interfering substance existing in water, the concentration in the environment is increased year by year, the bisphenol A can enter water environment through various ways and cause pollution, even at low concentration, the bisphenol A can interfere the reproductive system of wild animals and human, and has the hazards of neurocytotoxicity, immunotoxicity, carcinogenesis, teratogenesis and mutagenesis and the like. Therefore, the novel efficient treatment material is developed to effectively remove the bisphenol A in the water body, which has important scientific and practical significance for solving the national water environment safety problem.
Due to the hydrophobicity, low volatility and difficult degradability of bisphenol A, the traditional wastewater treatment method is difficult to effectively remove the bisphenol A and even brings secondary pollution. Compared with other methods, the adsorption method for removing bisphenol A has the advantages of simple operation, high removal efficiency, low cost and no generation of toxic by-products, and is widely researched. The key to the adsorption process is the development and use of adsorbents with desirable properties. The adsorbents currently used for treating bisphenol a mainly include mineral adsorbents (such as zeolite, montmorillonite, kaolinite and the like), carbonaceous adsorbents (biochar, graphene, carbon nanotubes and the like), high-molecular adsorbents (polyethersulfone, resin, nanofibers, chitosan, polyaniline and the like), domestic and industrial and agricultural waste derivative adsorbents, magnetic material adsorbents and molecularly imprinted polymer adsorbents. However, the conventional adsorbents for treating bisphenol A in water have some defects, such as poor selectivity, low adsorption efficiency, high preparation cost and complex process.
In recent years, due to the characteristics of the MOFs materials such as high specific surface area, high porosity and pore volume, adjustable function and the like, more and more researchers are attracted to treat pollutants in water by using MOFs as an adsorbent, but the following problems still exist when the prepared MOFs materials are applied to water: (1) the MOFs generally exist in a form of nanoparticles, so that the MOFs are not easy to separate and recover in liquid phase adsorption; (2) although the MOFs can be more easily recovered and separated by molding and then using the molded MOFs for liquid phase adsorption, the adsorption performance of the MOFs is reduced. Therefore, it is necessary to develop a novel adsorption material which can efficiently remove bisphenol a in water and can be rapidly separated and recovered from water.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention mainly aims to provide the aluminum-based MOFs/chitosan composite microsphere.
The invention also aims to provide a preparation method of the aluminum-based MOFs/chitosan composite microsphere.
The invention further aims to provide application of the aluminum-based MOFs/chitosan composite microspheres.
The purpose of the invention is realized by the following technical scheme:
a preparation method of an aluminum-based MOFs/chitosan composite microsphere is characterized by comprising the following steps:
(1) preparation of monomer aluminum-based MOFs material
Adding soluble aluminum salt and terephthalic acid into N, N-dimethylformamide, fully stirring to completely dissolve the soluble aluminum salt and the terephthalic acid to obtain a reaction mixed solution, heating the reaction mixed solution at 130-150 ℃ for reaction for 8-16 h, cooling after the reaction is finished, and filtering, washing and drying the obtained product to obtain the monomer aluminum-based MOFs material;
(2) preparation of the Mixed solution
Dispersing the monomer aluminum-based MOFs material obtained in the step (1) in deionized water, uniformly stirring, heating, slowly adding a cross-linking agent sodium alginate in the heating process, and cooling after completely dissolving to obtain an aluminum-based MOFs-sodium alginate mixed solution;
adding chitosan into acetic acid aqueous solution, fully dissolving, adding anhydrous calcium chloride, and uniformly stirring to obtain a chitosan-calcium chloride mixed solution;
(3) preparation of aluminum-based MOFs/chitosan composite microspheres
And (3) dropwise adding the aluminum-based MOFs-sodium alginate mixed solution in the step (2) into the chitosan-calcium chloride mixed solution to react to form balls, standing, filtering, and freeze-drying to obtain the aluminum-based MOFs/chitosan composite microspheres.
Preferably, the mass ratio of the aluminum-based MOFs, the deionized water and the cross-linking agent in the step (2) is 1: (15-20): (0.1 to 0.3); the mass ratio of the chitosan to the anhydrous calcium chloride is 1: (1-3).
Preferably, the mass ratio of the cross-linking agent to the chitosan in the step (3) is (0.5-1): (1-2).
Preferably, the mass ratio of the chitosan to the anhydrous calcium chloride in the step (2) is 1: (1-2); the mass ratio of the cross-linking agent to the chitosan in the step (3) is 0.8: (1-2).
Preferably, the mass ratio of the aluminum-based MOFs, the deionized water and the cross-linking agent in the step (2) is 1: (15-19): (0.15 to 0.2); the mass ratio of the chitosan to the anhydrous calcium chloride is 1: (1.3-2); the mass ratio of the cross-linking agent to the chitosan in the step (3) is 0.8: (1-1.5).
Preferably, the mass ratio of the soluble aluminum salt to the terephthalic acid in the step (1) is (1-5): 1; the concentration of the soluble aluminum salt in the reaction mixed liquid in the step (1) is 0.01-0.03 g/mL.
Preferably, the washing in step (1) is washing with N, N-dimethylformamide for 3 times, and then washing with methanol for 3 times; the drying in the step (1) is drying for 8-12 hours at the temperature of 60-120 ℃.
Preferably, the mass fraction of acetic acid in the acetic acid aqueous solution in the step (2) is 0.5-2%; the heating temperature in the step (2) is 40-90 ℃; and (4) dropwise adding the mixed solution in the step (3) at a speed of 6-30 mL/min.
The aluminum-based MOFs/chitosan composite microsphere is applied to adsorbing bisphenol A in water.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the MOFs material used in the invention has good water stability and large specific surface area, can provide enough adsorption sites, and has the advantages of simple preparation process, lower requirements on equipment conditions and low cost.
(2) The particle size of the composite microspheres prepared by the method is about 2mm, and the composite microspheres are easy to separate and recover from water, so that the defects that the particle size of MOFs materials is small and the MOFs materials are difficult to separate from water after liquid phase adsorption are overcome.
(3) According to the invention, the cross-linking agent sodium alginate and chitosan can form a polyelectrolyte membrane through the attraction of positive and negative charges, so that the adsorbent can be better embedded, the synergistic adsorption effect can be exerted, the adsorption effect of the MOFs material after molding can be basically maintained, the removal efficiency equivalent to that of powder MOFs can be achieved, and thus the bisphenol A in the water body can be efficiently adsorbed and removed, and the adsorbing material can be rapidly separated and recovered from the water body.
(4) The invention uses natural macromolecule cross-linking agent sodium alginate to replace glutaraldehyde for cross-linking, and is more nontoxic and pollution-free.
Drawings
FIG. 1 is a comparison of XRD spectra of the monomeric aluminum-based MOFs material MIL-68(Al) prepared in comparative example 1, the aluminum-based MOFs microsphere prepared in comparative example 2, and the aluminum-based MOFs/chitosan composite microsphere prepared in examples 1-3.
FIG. 2 is an SEM photograph of MIL-68(Al) obtained in comparative example 1.
FIG. 3 is an SEM image of the aluminum-based MOFs microspheres obtained in comparative example 2.
FIG. 4 is an SEM image of the aluminum-based MOFs/chitosan composite microspheres prepared in example 2.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Comparative example 1:
preparation of monomer aluminum-based MOFs material MIL-68(Al)
3.00g of aluminum chloride and 3.00g of terephthalic acid are dissolved in 150mL of N, N-dimethylformamide, fully stirred to be completely dissolved, uniformly mixed, stirred and reacted for 16 hours at the constant temperature of 130 ℃, and naturally cooled to room temperature. And washing the obtained product for 3 times by using N, N-dimethylformamide after suction filtration and separation, then washing the product for 3 times by using methanol, and finally drying and activating the product for 12 hours at 105 ℃ under a vacuum condition to obtain the monomer aluminum-based MOFs material MIL-68 (Al).
Comparative example 2:
preparation of aluminum-based MOFs microspheres
Dispersing 5.00g of monomer aluminum-based MOFs in 95.00g of deionized water, uniformly stirring, heating, slowly adding 0.8g of cross-linking agent sodium alginate in the heating process, and cooling to room temperature after completely dissolving to obtain a mixed solution. Then the mixed solution is dropwise added into CaCl-containing solution2And standing the formed solution with the mass fraction of 2% for 12 hours, filtering, washing, and freeze-drying to obtain the aluminum-based MOFs microspheres.
Example 1:
preparation of aluminum-based MOFs/chitosan composite microspheres
Dispersing 5.00g of monomer aluminum-based MOFs in 95.00g of deionized water, uniformly stirring, heating, slowly adding 0.8g of cross-linking agent sodium alginate in the heating process, and cooling to room temperature after completely dissolving to obtain a mixed solution. Then 1.0g of chitosan and 2.0g of anhydrous CaCl2Dissolving the mixture in 1 wt% acetic acid water solution to obtain a chitosan-calcium chloride mixed solution, finally, dropwise adding the aluminum-based MOFs-sodium alginate mixed water solution into the chitosan-calcium chloride mixed solution at the flow rate of 10mL/min to react to form balls, standing for 12h, filtering, washing with deionized water, and freeze-drying to obtain the aluminum-based MOFs/chitosan composite microspheres.
Example 2:
preparation of aluminum-based MOFs/chitosan composite microspheres
Dispersing 5.00g of monomer aluminum-based MOFs in 95.00g of deionized water, uniformly stirring, heating, slowly adding 0.8g of cross-linking agent sodium alginate in the heating process, and cooling to room temperature after completely dissolving to obtain a mixed solution. Then 1.5g of chitosan and 2.0g of anhydrous CaCl2Dissolving in 1 wt% acetic acid water solution to obtain chitosan-calcium chloride mixed solution, and adding the aluminum-based MOFs-sodium alginate mixed water solution into the chitosan-calcium chloride mixed solution dropwise at the flow rate of 10mL/min to react to form spheresStanding for 12h, filtering, washing with deionized water, and freeze-drying to obtain the aluminum-based MOFs/chitosan composite microsphere.
Example 3:
preparation of aluminum-based MOFs/chitosan composite microspheres
Dispersing 5.00g of monomer aluminum-based MOFs in 95.00g of deionized water, uniformly stirring, heating, slowly adding 0.8g of cross-linking agent sodium alginate in the heating process, and cooling to room temperature after completely dissolving to obtain a mixed solution. Then 2.0g of chitosan and 2.0g of anhydrous CaCl2Dissolving the mixture in 1 wt% acetic acid water solution to obtain a chitosan-calcium chloride mixed solution, finally, dropwise adding the aluminum-based MOFs-sodium alginate mixed water solution into the chitosan-calcium chloride mixed solution at the flow rate of 10mL/min to react to form balls, standing for 12h, filtering, washing with deionized water, and freeze-drying to obtain the aluminum-based MOFs/chitosan composite microspheres.
The characterization results and the bisphenol A adsorption performance of the aluminum-based MOFs/chitosan composite microspheres prepared in the comparative example 1, the comparative example 2 and the examples 1-3 are as follows:
(1) XRD Crystal Structure analysis
The crystal structure of the aluminum-based MOFs/chitosan composite microspheres prepared in comparative example 1, comparative example 2 and examples 1-3 of the invention is characterized by adopting an Empyrean sharp-shadow X-ray diffractometer produced by Pynaudiaceae, the Netherlands, the results are shown in figure 1, and the operation conditions are as follows: the radiation source being a Cu Ka ray
40KV and 40mA of copper target, the scanning step length is 0.0131 degrees, the scanning speed is 9.664 seconds per step, and the scanning range 2 theta is 3-50 degrees. The material samples were dried under vacuum at 110 ℃ and ground to a fine powder in a quartz mortar before testing.
As can be seen from FIG. 1, the diffraction peaks of the aluminum-based MOFs/chitosan composite microspheres prepared in examples 1 to 3 are substantially consistent with the XRD diffraction patterns of the aluminum-based MOFs material MIL-68(Al) prepared in comparative example 1 and the aluminum-based MOFs microspheres prepared in comparative example 2, and the main peak positions appear at 5 degrees, 10 degrees and 15 degrees, which indicates that the aluminum-based MOFs/chitosan composite microspheres prepared in examples 1 to 3 retain the crystal structure of the monomer MIL-68(Al) and have good crystal forms, but the peak strength after molding is weakened, which may be the reason that the relative content of the aluminum-based MOFs material MIL-68(Al) is reduced after the molding agent is added.
(2) SEM characterization
The surface topography of the samples was characterized using a Merlin-type field emission scanning electron microscope from Zeiss, Germany. FIG. 2 is an SEM photograph of MIL-68(Al) prepared in comparative example 1, and it can be seen from FIG. 2 that MIL-68(Al) prepared in comparative example 1 has a rod-like or rod-like crystal structure, has a smooth surface and is stacked on each other, and has a crystal length of 200nm to 1 um. FIG. 3 is an SEM image of the aluminum-based MOFs microspheres obtained in comparative example 2, and it can be seen from FIG. 3 that a large number of rod-like crystals are randomly aggregated due to the crosslinking agent. FIG. 4 is an SEM image of the aluminum-based MOFs/chitosan composite microspheres prepared in example 2, and as can be seen from FIG. 4, the surface morphology of the aluminum-based MOFs/chitosan composite microspheres is similar to that of the aluminum-based MOFs microspheres, but less rod-like crystals can be clearly observed, and most of the crystals are stacked into blocks.
(3) Analysis of adsorption Performance results
A constant-temperature oscillating table is utilized to provide a temperature-controllable environment, a bisphenol A aqueous solution with a certain concentration and a proper amount of adsorbent material to be detected are added into a conical flask, and adsorption reaction is carried out after uniform dispersion. And (3) testing and analyzing the change of the bisphenol A concentration in the adsorption process by using Waters High Performance Liquid Chromatography (HPLC), wherein the testing conditions are as follows: the mobile phase was methanol/water in a 70:30(V/V) ratio, a flow rate of 1.0mL/min, and a test temperature of 30 ℃. The column was a Sunfire C18 column (250 mm. times.4.6 mm), the detector was a PDA detector, the detection wavelength was 270nm, and the sample injection volume was 15. mu.L. Table 1 shows the adsorption removal effect data of the aluminum-based MOFs/chitosan composite microspheres prepared in examples 1 to 3, the monomeric aluminum-based MOFs material MIL-68(Al) prepared in comparative example 1 and the aluminum-based MOFs microspheres prepared in comparative example 2 on bisphenol A. As can be seen from Table 1, under the same experimental conditions (bisphenol A concentration: 50 mg/L; adsorbent dosage: 0.2 g/L; adsorption time: 18h), the removal effect (close to that of powder MIL-68 (Al)) of the aluminum-based MOFs/chitosan composite microspheres prepared in examples 1-3 on the bisphenol A in the water body is far better than that of the aluminum-based MOFs microspheres prepared in comparative example 2, wherein the adsorption removal efficiency of example 2 on the bisphenol A is as high as 92.5%, and the removal efficiency of comparative example 2 (the removal efficiency is only 58.5%) is sufficiently improved by 58.1%. Therefore, the aluminum-based MOFs/chitosan composite microspheres prepared by the technical method can ensure that the adsorption material is easy to separate and recover, and simultaneously keep higher adsorption capacity, so that the adsorption performance of the material is better.
TABLE 1 adsorption Effect summary of bisphenol A
| Adsorbent and process for producing the same | Comparative example 1 | Comparative example 2 | Example 1 | Example 2 | Example 3 |
| Removal efficiency/%) | 90.2 | 58.5 | 90.4 | 92.5 | 89.7 |
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of an aluminum-based MOFs/chitosan composite microsphere is characterized by comprising the following steps:
(1) preparation of monomer aluminum-based MOFs material
Adding soluble aluminum salt and terephthalic acid into N, N-dimethylformamide, fully stirring to completely dissolve the soluble aluminum salt and the terephthalic acid to obtain a reaction mixed solution, heating the reaction mixed solution at 130-150 ℃ for reaction for 8-16 h, cooling after the reaction is finished, and filtering, washing and drying the obtained product to obtain the monomer aluminum-based MOFs material;
(2) preparation of the Mixed solution
Dispersing the monomer aluminum-based MOFs material obtained in the step (1) in deionized water, uniformly stirring, heating, slowly adding a cross-linking agent sodium alginate in the heating process, and cooling after completely dissolving to obtain an aluminum-based MOFs-sodium alginate mixed solution;
adding chitosan into acetic acid aqueous solution, fully dissolving, adding anhydrous calcium chloride, and uniformly stirring to obtain a chitosan-calcium chloride mixed solution;
(3) preparation of aluminum-based MOFs/chitosan composite microspheres
And (3) dropwise adding the aluminum-based MOFs-sodium alginate mixed solution in the step (2) into the chitosan-calcium chloride mixed solution to react to form balls, standing, filtering, and freeze-drying to obtain the aluminum-based MOFs/chitosan composite microspheres.
2. The preparation method according to claim 1, wherein the mass ratio of the aluminum-based MOFs, the deionized water and the crosslinking agent in the step (2) is 1: (15-20): (0.1 to 0.3); the mass ratio of the chitosan to the anhydrous calcium chloride is 1: (1-3).
3. The preparation method according to claim 2, wherein the mass ratio of the cross-linking agent to the chitosan in the step (3) is (0.5-1): (1-2).
4. The method according to claim 3, wherein the mass ratio of the chitosan to the anhydrous calcium chloride in the step (2) is 1: (1-2); the mass ratio of the cross-linking agent to the chitosan in the step (3) is 0.8: (1-2).
5. The preparation method according to claim 4, wherein the mass ratio of the aluminum-based MOFs, the deionized water and the cross-linking agent in the step (2) is 1: (15-19): (0.15 to 0.2); the mass ratio of the chitosan to the anhydrous calcium chloride is 1: (1.3-2); the mass ratio of the cross-linking agent to the chitosan in the step (3) is 0.8: (1-1.5).
6. The method according to any one of claims 1 to 4, wherein the mass ratio of the soluble aluminum salt to terephthalic acid in step (1) is (1 to 5): 1; the concentration of the soluble aluminum salt in the reaction mixed liquid in the step (1) is 0.01-0.03 g/mL.
7. The method according to any one of claims 1 to 4, wherein the washing in step (1) is performed by washing with N, N-dimethylformamide 3 times and then with methanol 3 times; the drying in the step (1) is drying for 8-12 hours at the temperature of 60-120 ℃.
8. The method according to any one of claims 1 to 4, wherein the mass fraction of acetic acid in the aqueous acetic acid solution in the step (2) is 0.5 to 2%; the heating temperature in the step (2) is 40-90 ℃; and (4) dropwise adding the mixed solution in the step (3) at a speed of 6-30 mL/min.
9. The aluminum-based MOFs/chitosan composite microspheres prepared by the method of any one of claims 1 to 8.
10. The use of the aluminum-based MOFs/chitosan composite microspheres of claim 9 for adsorbing bisphenol a in a body of water.
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