CN116273183A - Tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles and preparation method thereof - Google Patents
Tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles and preparation method thereof Download PDFInfo
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- CN116273183A CN116273183A CN202310134218.5A CN202310134218A CN116273183A CN 116273183 A CN116273183 A CN 116273183A CN 202310134218 A CN202310134218 A CN 202310134218A CN 116273183 A CN116273183 A CN 116273183A
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- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 title claims abstract description 202
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 title claims abstract description 202
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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 title claims abstract 44
- 239000002105 nanoparticle Substances 0.000 claims abstract description 98
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 88
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- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 20
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- 235000010413 sodium alginate Nutrition 0.000 claims description 20
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 12
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 6
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims description 5
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- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallyl group Chemical group C1(=C(C(=CC=C1)O)O)O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 claims description 2
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- LRBQNJMCXXYXIU-QWKBTXIPSA-N gallotannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@H]2[C@@H]([C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-QWKBTXIPSA-N 0.000 description 112
- 239000000523 sample Substances 0.000 description 75
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 49
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- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
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- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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Abstract
The invention provides tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles and a preparation method thereof, wherein the composite porous structure photocatalytic particles consist of gel particles containing tannic acid modified metal organic framework nano materials and tannic acid deposited on the surfaces of the gel particles and distributed in a high polymer three-dimensional network structure of the gel particles; the gel particles containing the tannic acid modified metal organic framework nano material consist of gel matrix high polymer materials and tannic acid modified metal organic framework nano materials distributed in the gel matrix high polymer materials; the tannic acid modified metal organic framework nano material is tannic acid modified ZIF-8 nano particles. The composite porous structure photocatalytic particles provided by the invention can be effectively coupled and cooperatively strengthen the adsorption characteristic and catalytic characteristic of the composite porous structure, so that the composite porous structure photocatalytic particles have the characteristics of convenient recycling, difficult secondary pollution and the like, and simultaneously realize the efficient treatment of organic pollutants in water.
Description
Technical Field
The invention belongs to the field of functional hydrogels, and relates to tannic acid modified MOF/hydrogel composite photocatalytic particles and a preparation method thereof.
Background
With the rapid development of industry in recent years, the problem of water pollution caused by organic dyes (such as methylene blue and other cationic organic dyes) is increasingly serious, so that the realization of effective removal of organic dye pollutants in water is of great significance for sustainable development of ecological environment. Adsorption separation and catalytic degradation play an important role in the field of water purification. The adsorption separation can realize enrichment and separation of organic pollutants through an adsorbent, but usually requires post-treatment of the enriched organic pollutants and is easy to cause secondary pollution. In contrast, catalytic degradation can convert organic pollutants into low-toxic, even non-toxic compounds, thereby enabling more effective water purification. The functional particles with porous structures and active catalytic sites have wide application in the aspects of adsorption separation and catalytic degradation of water pollutants. By combining nano-scale porous functional particles with larger-sized micron-sized and millimeter-sized porous functional particles, the advantages of the nano-scale porous functional particles and the millimeter-sized porous functional particles, such as high specific surface area of the nano-particles, rich catalytic sites, and operational flexibility and recovery convenience of the large-sized particles, can be coupled, so that the treatment of organic pollutants in the water body is realized.
Currently, researchers have constructed particles of various composite structures for adsorption separation and catalytic degradation of contaminants in water bodies by incorporating organometallic framework nanoparticles, metal oxide nanoparticles, metal nanoparticles, biological enzymes, and the like into micron-sized, millimeter-sized porous polymer particles. In the field, how to cooperatively couple the adsorption characteristic and the catalytic characteristic of the composite structure has important significance for realizing the efficient purification of organic pollutants in water bodies, but challenges still exist.
Disclosure of Invention
Aiming at the problems, the invention provides tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles and a preparation method thereof, so as to effectively and cooperatively couple the adsorption characteristic and catalytic characteristic of the composite porous structure, and realize the efficient treatment of organic pollutants in water while having the characteristics of convenient recycling, difficult secondary pollution and the like.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a tannic acid modified MOF/hydrogel composite porous structure photocatalysis particle is composed of gel particles containing tannic acid modified metal organic framework nano materials and tannic acid deposited on the surfaces of the gel particles and distributed in a high molecular three-dimensional network structure of the gel particles; the gel particles containing the tannic acid modified metal organic framework nano material consist of gel matrix polymer materials and hydrogel particles which are distributed in the tannic acid modified metal organic framework nano material in the gel matrix polymer materials; the tannic acid modified metal organic framework nano material is tannic acid modified ZIF-8 nano particles.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, in the tannic acid modified metal organic framework nano material-containing gel particles, the mass ratio of the gel matrix polymer material to the tannic acid modified metal organic framework nano material is (0.1-0.5) to (0.1-1).
Further, in the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, in the tannic acid modified ZIF-8 nanoparticles, the pyrogallol group of TA is coupled with the organic ligand dimethyl imidazole in the ZIF-8 nanoparticles to form a covalent bond, and meanwhile, H released in tannic acid + Can destroy part of Zn 2+ Coordination bond Zn-N between the tannic acid and the dimethylimidazole, and then phenolic hydroxyl group of tannic acid and Zn in ZIF-8 nano particles 2+ Dynamically bonding to form Zn-O bond.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, zn in ZIF-8 nano particles 2+ The molar ratio of the modified ZIF-8 nano particles to the organic ligand dimethyl imidazole is 1:4, tannic acid is adopted to modify the ZIF-8 nano particles, the pore structure of the ZIF-8 nano particles can be regulated and controlled, and a multi-layer pore structure is built in the ZIF-8 nano particles, so that mass transfer of pollutants to the porous structure in the tannic acid modified ZIF-8 nano particles can be promoted. Tannic acid can also reduce the band gap of ZIF-8 nano particles, so that the ZIF-8 nano particles have better photocatalytic performance.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, the composite porous structure photocatalytic particles are formed by modifying gel particles containing tannic acid modified metal organic framework nano materials with tannic acid, and after the tannic acid is modified, tannic acid is deposited on the surfaces of the gel particles containing the tannic acid modified metal organic framework nano materials to form a tannic acid layer, and the tannic acid enters and is combined in a high polymer three-dimensional network structure of the gel particles.
Further, in the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, the tannic acid modification means that gel particles containing tannic acid modified metal organic framework nano materials are immersed in tannic acid aqueous solution for 5-30 min.
Further, in the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, the mass ratio of tannic acid to water in the tannic acid aqueous solution is (0.005-0.05): 1.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, after tannic acid modification, a tannic acid layer formed by tannic acid deposited on the surface of gel particles containing tannic acid modified metal organic framework nano materials is a discontinuous tannic acid layer, and the tannic acid layer is discretely distributed on the surface of the gel particles containing tannic acid modified metal organic framework nano materials.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, the gel matrix polymer material comprises any one of calcium alginate, crosslinked chitosan, cellulose or crosslinked polyvinyl alcohol.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, tannic acid in tannic acid modified ZIF-8 nano particles and tannic acid which is modified by tannic acid and is combined on the surfaces of gel particles containing tannic acid modified metal organic framework nano materials and distributed in a high polymer three-dimensional network structure are combined into a whole through intermolecular force. More specifically, tannic acid contains a large amount of phenolic hydroxyl groups, and the gel-based polymer material also contains hydroxyl groups, carboxyl groups and other groups, which can generate intermolecular hydrogen bonds, electrostatic interactions and other interaction forces. Therefore, the binding force between the ZIF-8 nano particles and the gel polymer three-dimensional network structure can be enhanced by introducing tannic acid soaking modification and tannic acid modification of the ZIF-8 nano particles.
In the technical scheme of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, the particle size of the composite porous structure photocatalytic particles is determined according to practical application requirements, and the particle size of the composite porous structure photocatalytic particles is usually in a range from micron level to millimeter level.
The invention also provides a preparation method of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, which comprises the following steps:
(1) Preparation of gel particles
Dripping aqueous phase fluid into the collecting liquid through a microfluidic device, and crosslinking monomers of gel-based polymer materials in the aqueous phase fluid drops to form gel particles containing tannic acid modified metal organic framework nano materials;
the aqueous phase fluid contains a monomer of a gel matrix polymer material, a water-soluble surfactant and a metal organic framework nanomaterial modified by tannic acid, and the collecting liquid contains a cross-linking agent; or the aqueous phase fluid contains a monomer of a gel matrix polymer material, a water-soluble surfactant, a cross-linking agent and a tannic acid modified metal organic framework nano material, and the collecting liquid or a reagent providing conditions for the cross-linking of the monomer of the gel matrix material and the cross-linking agent;
(2) Tannic acid modification
Separating gel particles of the tannic acid modified metal organic framework nano material prepared in the step (1) from the collecting liquid, immersing the gel particles in the modifying liquid for 5-30 min, and then washing the collecting liquid and the modifying liquid with water to remove the collecting liquid and the modifying liquid to obtain the tannic acid modified metal organic framework nano material; the modified liquid is tannic acid aqueous solution, and the mass ratio of deionized water to tannic acid in the modified liquid is 1 (0.005-0.05).
In the technical scheme of the preparation method of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, when the monomer of the gel matrix polymer material is sodium alginate, the crosslinking agent can be calcium ions; when the monomer of the gel matrix polymer material is polyvinyl alcohol, the crosslinking agent can be boric acid, and the boric acid needs to be crosslinked with the polyvinyl alcohol under alkaline conditions.
In the technical scheme of the preparation method of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, when the gel matrix polymer material is calcium alginate, the preparation method of the aqueous phase fluid and the collection liquid is as follows:
preparing an aqueous phase fluid: dissolving sodium alginate and a water-soluble surfactant in deionized water, and then fully dispersing a tannic acid modified metal organic framework nanomaterial in the obtained solution to obtain an aqueous phase fluid; in the aqueous phase fluid, the mass ratio of sodium alginate, water-soluble surfactant and tannic acid-modified metal organic framework nano material to water is (0.01-0.05): 0.01-0.03): 0.01-0.1): 1;
preparing a collection liquid: adding calcium chloride into deionized water, and uniformly mixing to obtain a collection liquid, wherein the mass ratio of the deionized water to the calcium chloride in the collection liquid is 1 (0.05-0.5).
According to the technical scheme of the preparation method of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, aqueous phase fluid is dripped into a collection liquid at a constant flow rate (for example, a constant flow rate in 200-500 mu L/min) through an injection needle of a microfluidic device, gel particles containing tannic acid modified metal organic framework nano materials with uniform sizes can be obtained after crosslinking, and the particle size of the gel particles containing tannic acid modified metal organic framework nano materials can be adjusted through adjusting the size of the injection needle of the microfluidic device and the flow rate of the aqueous phase fluid.
The invention mainly utilizes the double modification of tannic acid, effectively improves the pollutant removal capability of the existing ZIF-8 nano material, and prepares the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles. On one hand, the tannic acid is utilized to modify the ZIF-8 nano particles, so that the pore structure of the ZIF-8 nano particles is improved, the band gap of the ZIF-8 nano particles can be reduced, and the photocatalytic performance of the ZIF-8 nano particles is enhanced. On the other hand, after the gel particles containing the tannic acid modified metal organic framework nano material are prepared, the gel particles are soaked and modified by tannic acid, tannic acid is deposited on the surfaces of the gel particles and in a high polymer three-dimensional network structure, and the adsorption capacity of the material on organic molecules is enhanced by using phenolic hydroxyl groups rich in tannic acid, so that the organic molecules are rapidly adsorbed and enriched in the gel particles to promote photocatalytic degradation of the material, and meanwhile, the binding force between ZIF-8 nano particles and the gel matrix high polymer material is enhanced, and the recycling performance of the material is enhanced.
Experiments prove that the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle provided by the invention has good adsorption capacity on organic molecules, and meanwhile, under ultraviolet irradiation, the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle also has photocatalytic degradation capacity, wherein ZIF-8 nano particles serve as catalysts, and can effectively catalyze and degrade the organic molecules. Namely, the tannic acid modified MOF/hydrogel composite porous structure-based photocatalytic particles effectively enrich organic molecules in water through adsorption and further degrade the organic molecules through photocatalysis. Under the ultraviolet irradiation condition, 99.37% of methylene blue in the methylene blue aqueous solution (40 mg/L) can be effectively removed by the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles provided by the invention, meanwhile, the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles provided by the invention have good recycling performance, the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles are recycled for 4 times, and the removal rate of the methylene blue in the methylene blue aqueous solution (40 mg/L) is still kept above 85%.
Compared with the prior art, the technical scheme provided by the invention has the following beneficial technical effects:
1. the invention provides tannic acid modified MOF/hydrogel composite porous structure photocatalysis particles, which consist of gel particles containing tannic acid modified metal organic framework nano materials and tannic acid deposited on the surfaces of the gel particles and distributed in a high molecular three-dimensional network structure of the gel particles; the gel particles containing the tannic acid modified metal organic framework nano material consist of gel matrix polymer materials and tannic acid modified metal organic framework nano materials distributed in the gel matrix polymer materials; the tannic acid modified metal organic framework nano material is tannic acid modified ZIF-8 nano particles. The invention prepares the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles through double modification of tannic acid. On one hand, the tannic acid is utilized to modify the ZIF-8 nano particles, so that the pore structure of the ZIF-8 nano particles is improved, the band gap of the ZIF-8 nano particles is reduced, and the photocatalytic performance of the ZIF-8 nano particles is enhanced. On the other hand, tannic acid is adopted to soak and modify gel particles containing tannic acid modified metal organic framework nano materials, tannic acid is deposited on the surfaces of the gel particles and in a high polymer three-dimensional network structure, and phenolic hydroxyl groups rich in tannic acid are utilized to enhance the adsorption capacity of the materials on organic molecules so as to rapidly adsorb and enrich the organic molecules in the gel particles and promote photocatalytic degradation of the organic molecules, and meanwhile, the binding force between ZIF-8 nano particles and gel matrix high polymer materials is enhanced, and the recycling performance of the materials is enhanced. The invention effectively couples the adsorption characteristic and the catalytic characteristic of the particle composite structure, and cooperatively strengthens the adsorption and photocatalytic degradation capability of the material on pollutants.
2. Experiments prove that the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle provided by the invention has good adsorption capacity on organic molecules, and meanwhile, under ultraviolet irradiation, the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle also has photocatalytic degradation capacity, wherein ZIF-8 nano particles serve as catalysts, and can effectively catalyze and degrade the organic molecules. Under the condition of ultraviolet irradiation, 99.37% of methylene blue in a methylene blue aqueous solution (40 mg/L) can be effectively removed by the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles provided by the invention, meanwhile, the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles have good recycling performance, the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles are recycled for 4 times, and the removal rate of the methylene blue in the methylene blue aqueous solution (40 mg/L) is still maintained to be more than 85%. The characteristics are beneficial to popularization and application of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles in water treatment.
3. The invention also provides the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles, and the method is simple in process and low in process cost, and is beneficial to large-scale production of the tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles.
Drawings
FIG. 1 is a scanning electron micrograph and a transmission electron micrograph of ZIF-8 nanoparticles and ZIF-8@TA nanoparticles prepared in example 1.
Fig. 2 is a schematic structural view of the microfluidic device employed in the examples and comparative examples.
FIG. 3 is a photograph showing the morphology characterization of the calcium alginate hydrogel particles prepared in comparative example 1.
FIG. 4 is a graph showing the particle diameter distribution of calcium alginate hydrogel particles prepared in comparative example 1.
Fig. 5 is a scanning electron micrograph of sample No. 1 and sample No. 2.
Fig. 6 is a scanning electron micrograph of sample No. 3 and sample No. 4.
Fig. 7 is a scanning electron micrograph of sample No. 5 and sample No. 6.
FIG. 8 is the results of the adsorption performance test of the calcium alginate hydrogel particles prepared in comparative example 1 and the 1# sample and the 2# sample against methylene blue.
FIG. 9 is the results of photocatalytic degradation performance test of comparative example 1 for methylene blue for calcium alginate hydrogel particles, sample # 4, sample # 5, and sample # 6.
FIG. 10 is the results of the reusability test of sample No. 6.
Detailed Description
The tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles and the preparation method thereof are further described in the following by means of examples. It is noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many insubstantial modifications and variations of the present invention will be apparent to those skilled in the art in light of the foregoing disclosure, and are still within the scope of the invention.
In the following examples and comparative examples, pluronic F127, which is a block polyether F127, is an addition polymer of polypropylene glycol and ethylene oxide, pluronic F127 is a trade name thereof, available from Sigma company.
Example 1
In this example, ZIF-8 nanoparticles and ZIF-8@TA nanoparticles were prepared as follows:
ZIF-8 nanoparticles were prepared according to the hydrothermal method reported in literature (Simple and Continuous Fabrication of Self-Propelled Micromotors with Photocatalytic Metal-Organic Frameworks for Enhanced Synergistic Environmental Remediation), specifically as follows:
10mL of aqueous solution containing 0.922g of zinc nitrate hexahydrate and 100mL of aqueous solution containing 10.262g of dimethyl imidazole are mixed, stirred at room temperature for reaction for 10min, centrifuged at 10000r/min for 3min, the supernatant is removed, the washing is carried out by deionized water, centrifugal washing is repeated for 3 times, and the obtained product is dried at 70 ℃ to obtain ZIF-8 nano particles.
ZIF-8@TA nanoparticles were prepared according to the method reported in literature (Hierarchically Porous and Water-Tolerant Metal-Organic Frameworks for Enzyme Encapsulation), as follows:
adding 0.5g of ZIF-8 nano particles into 50mL of aqueous solution containing 0.25g of tannic acid, etching for 5min, centrifugally washing for 3 times by using deionized water, and drying the obtained product at 70 ℃ to obtain the ZIF-8@TA nano particles.
FIG. 1 (a) and FIG. 1 (b) are respectively a scanning electron microscope image of ZIF-8 nanoparticles and ZIF-8@TA nanoparticles prepared in this example, and FIG. 1 (c) and FIG. 1 (d) are respectively a transmission electron microscope image of ZIF-8 nanoparticles and ZIF-8@TA nanoparticles prepared in this example.
Comparative example 1
In the comparative example, calcium alginate hydrogel particles were prepared as follows:
(1) Preparing aqueous fluid and collecting liquid
Preparing an aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate to the Pluronic F127 to deionized water is 0.01:0.01:1.
Preparing a collection liquid: dissolving anhydrous calcium chloride in deionized water to obtain a collecting liquid, wherein the mass ratio of the deionized water to the anhydrous calcium chloride in the collecting liquid is 1:0.1.
(2) Preparation of calcium alginate hydrogel particles
The preparation is carried out by adopting a micro-fluidic device with the structure shown in figure 2, which is specifically a disposable syringe, and the inner diameter of the needle head is 330 mu m, and the outer diameter is 630 mu m.
Dropping aqueous phase fluid into a container containing a collecting liquid at a flow rate of 200 mu L/min through a microfluidic device, performing a crosslinking reaction on the aqueous phase fluid drops and calcium ions in the collecting liquid to form calcium alginate hydrogel particles, separating the calcium alginate hydrogel particles from the collecting liquid, washing the collecting liquid for multiple times by using deionized water to remove the collecting liquid on the surfaces of the calcium alginate hydrogel particles, and storing the washed calcium alginate hydrogel particles in the deionized water for standby.
The morphology characterization photo of the calcium alginate hydrogel particles prepared in the comparative example is shown in fig. 3, wherein (a) is an overall optical image, and (b) and (c) are scanning electron microscope photos of the outer surface and the cross section respectively, and as can be seen from fig. 3, the outer surface of the calcium alginate hydrogel particles prepared in the comparative example is smooth, and the cross section has no three-dimensional network structure and pore structure.
FIG. 4 is a graph showing the particle size distribution of the calcium alginate hydrogel particles prepared in this comparative example, wherein the particle size distribution of the calcium alginate hydrogel particles prepared in this comparative example is 1 to 1.5mm, and the particle size distribution is mainly concentrated at about 1.3mm, as can be seen from FIG. 4.
Comparative example 2
In this comparative example, calcium alginate hydrogel particles containing ZIF-8 nanoparticles were prepared as follows:
(1) Preparing aqueous fluid and collecting liquid
Preparing a No. 1 aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature, and ZIF-8 nanoparticles prepared in example 1 are fully dispersed in the obtained solution to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate, the Pluronic F127 and the ZIF-8 nanoparticles to the deionized water is 0.01:0.01:0.01:1.
Preparing a No. 2 aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature, and ZIF-8 nanoparticles prepared in example 1 are fully dispersed in the obtained solution to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate, the Pluronic F127 and the ZIF-8 nanoparticles to deionized water in the aqueous phase fluid is 0.01:0.01:0.03:1.
Preparing a collection liquid: and adding anhydrous calcium chloride into deionized water, and uniformly mixing to obtain a collection liquid, wherein the mass ratio of the deionized water to the anhydrous calcium chloride in the collection liquid is 1:0.1.
(2) Preparation of calcium alginate hydrogel particles containing ZIF-8 nanoparticles
The preparation is carried out by adopting a micro-fluidic device with the structure shown in figure 2, which is specifically a disposable syringe, and the inner diameter of the needle head is 330 mu m, and the outer diameter is 630 mu m.
And (3) dripping the No. 1 aqueous phase fluid into a container containing the collecting liquid at a flow rate of 200 mu L/min through a microfluidic device, and performing a crosslinking reaction on the aqueous phase fluid drops and calcium ions in the collecting liquid to form the calcium alginate hydrogel particles containing ZIF-8 nano particles. Separating the calcium alginate hydrogel particles containing the ZIF-8 nano particles from the collecting liquid, washing the collecting liquid with deionized water for multiple times to remove the collecting liquid on the surfaces of the calcium alginate hydrogel particles containing the ZIF-8 nano particles, marking the washed calcium alginate hydrogel particles containing the ZIF-8 nano particles as a No. 1 sample, and storing the No. 1 sample in deionized water for later use.
And (3) dripping the 2# aqueous phase fluid into a container containing the collecting liquid at a flow rate of 200 mu L/min through a microfluidic device, and performing a crosslinking reaction on the aqueous phase fluid drops and calcium ions in the collecting liquid to form the calcium alginate hydrogel particles containing ZIF-8 nano particles. Separating the calcium alginate hydrogel particles containing the ZIF-8 nano particles from the collecting liquid, washing the collecting liquid with deionized water for multiple times to remove the collecting liquid on the surfaces of the calcium alginate hydrogel particles containing the ZIF-8 nano particles, marking the washed calcium alginate hydrogel particles containing the ZIF-8 nano particles as a No. 2 sample, and storing the No. 2 sample in deionized water for later use.
The scanning electron micrographs of the sample 1 and the sample 2 are shown in fig. 5, wherein a 1), a 2) and a 3) are the whole optical view, the outer surface and the cross-section scanning electron micrograph of the sample 1, and b 1), b 2) and b 3) are the whole optical view, the outer surface and the cross-section scanning electron micrograph of the sample 2. As can be seen from FIG. 5, the external surfaces of the sample # 1 and the sample # 2 are opaque and milky, and the ZIF-8 nano particles with uniform distribution are arranged on the external surfaces and the cross sections of the sample # 1 and the sample # 2, and have a pore structure. This is because the aqueous fluid contains ZIF-8 nanoparticles during the preparation of the sample # 1 and the sample # 2, and the sodium alginate has interstitial spaces due to the presence of the ZIF-8 nanoparticles during the crosslinking, thereby resulting in the generation of a pore structure.
Comparative example 3
In this comparative example, calcium alginate hydrogel particles containing ZIF-8@ta nanoparticles were prepared as follows:
(1) Preparing aqueous fluid and collecting liquid
Preparing a 3# aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature, and ZIF-8@TA nanoparticles prepared in example 1 are fully dispersed in the obtained solution to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate, the Pluronic F127 and the ZIF-8@TA nanoparticles to deionized water is 0.01:0.01:0.01:1.
Preparing a No. 4 aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature, and ZIF-8@TA nanoparticles prepared in example 1 are fully dispersed in the obtained solution to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate, the Pluronic F127 and the ZIF-8@TA nanoparticles to deionized water is 0.01:0.01:0.03 1.
Preparing a collection liquid: and adding anhydrous calcium chloride into deionized water, and uniformly mixing to obtain a collection liquid, wherein the mass ratio of the deionized water to the anhydrous calcium chloride in the collection liquid is 1:0.1.
(2) Preparation of calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles
The preparation is carried out by adopting a micro-fluidic device with the structure shown in figure 2, which is specifically a disposable syringe, and the inner diameter of the needle head is 330 mu m, and the outer diameter is 630 mu m.
And (3) dripping the 3# aqueous phase fluid into a container containing the collecting liquid at a flow rate of 200 mu L/min through a microfluidic device, and performing a crosslinking reaction on the aqueous phase fluid drops and calcium ions in the collecting liquid to form calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles. Separating calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles from the collecting liquid, washing the collecting liquid with deionized water for multiple times to remove the collecting liquid on the surfaces of the calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles, marking the washed calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles as a 3# sample, and storing the 3# sample in deionized water for later use.
And dripping the 4# aqueous phase fluid into a container containing the collecting liquid at a flow rate of 200 mu L/min through a microfluidic device, and performing a crosslinking reaction on the aqueous phase fluid drops and calcium ions in the collecting liquid to form calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles. Separating calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles from the collecting liquid, washing the collecting liquid with deionized water for multiple times to remove the collecting liquid on the surfaces of the calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles, marking the washed calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles as a 4# sample, and storing the 4# sample in deionized water for later use.
The scanning electron micrographs of the sample 3 and the sample 4 are shown in fig. 6, wherein a 1), a 2) and a 3) are the whole optical view, the outer surface and the cross-section scanning electron micrograph of the sample 3, and b 1), b 2) and b 3) are the whole optical view, the outer surface and the cross-section scanning electron micrograph of the sample 4. As can be seen from FIG. 6, the outer surfaces of the sample # 3 and the sample # 4 are both in opaque yellowish color, the outer surfaces and the cross sections of the sample # 3 and the sample # 4 are uniformly distributed ZIF-8@TA nanoparticles, and the cross sections of the sample # 3 and the sample # 4 are in an obvious three-dimensional network structure.
Example 2
In this example, tannic acid modified calcium alginate hydrogel particles containing ZIF-8@ta nanoparticles were prepared as follows:
(1) Preparing aqueous phase fluid, collecting liquid and modifying liquid
Preparing a No. 5 aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature, and ZIF-8@TA nanoparticles prepared in example 1 are fully dispersed in the obtained solution to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate, the Pluronic F127 and the ZIF-8@TA nanoparticles to deionized water is 0.01:0.01:0.01:1.
Preparing a No. 6 aqueous phase fluid: sodium alginate and a surfactant Pluronic F127 are dissolved in deionized water at room temperature, and ZIF-8@TA nanoparticles prepared in example 1 are fully dispersed in the obtained solution to obtain an aqueous phase fluid, wherein the mass ratio of the sodium alginate, the Pluronic F127 and the ZIF-8@TA nanoparticles to deionized water is 0.01:0.01:0.03:1.
Preparing a collection liquid: and adding anhydrous calcium chloride into deionized water, and uniformly mixing to obtain a collection liquid, wherein the mass ratio of the deionized water to the anhydrous calcium chloride in the collection liquid is 1:0.1.
Preparing a modified liquid: and (3) dissolving Tannic Acid (TA) in deionized water to obtain a modified liquid, wherein the mass ratio of the deionized water to the tannic acid in the modified liquid is 1:0.005.
(2) Preparation of calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles
The preparation is carried out by adopting a micro-fluidic device with the structure shown in figure 2, which is specifically a disposable syringe, and the inner diameter of the needle head is 330 mu m, and the outer diameter is 630 mu m.
And dripping the No. 5 aqueous phase fluid into a container containing the collecting liquid at a flow rate of 200 mu L/min by a microfluidic device, and performing a crosslinking reaction on the aqueous phase fluid drops and calcium ions in the collecting liquid to form calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles.
And dripping the No. 6 aqueous phase fluid into a container containing the collecting liquid at a flow rate of 200 mu L/min through a microfluidic device, and performing a crosslinking reaction on the aqueous phase fluid liquid drops and calcium ions in the collecting liquid to form calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles.
(3) Tannic acid modification
Separating the calcium alginate hydrogel particles containing the ZIF-8@TA nanoparticles prepared in the step (2) from the collecting liquid, immersing the calcium alginate hydrogel particles in the modifying liquid for 5min, and obtaining the TA modified calcium alginate hydrogel particles containing the ZIF-8@TA nanoparticles.
Washing the obtained TA modified calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles with deionized water for multiple times to remove the collection liquid and the modification liquid on the surfaces of the TA modified calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles, and storing the collection liquid and the modification liquid in deionized water for later use. TA modified calcium alginate hydrogel particles containing ZIF-8@TA nanoparticles prepared on the basis of No. 5 and No. 6 aqueous phase fluids are respectively marked as No. 5 samples and No. 6 samples.
The scanning electron micrographs of the sample No. 5 and the sample No. 6 are shown in FIG. 7, wherein a 1), a 2) and a 3) are the whole optical image, the outer surface and the cross-section scanning electron micrograph of the sample No. 5, and b 1), b 2) and b 3) are the whole optical image, the outer surface and the cross-section scanning electron micrograph of the sample No. 6. As can be seen from FIG. 7, the outer surfaces of the sample # 5 and the sample # 6 are opaque yellow, the cross sections of the sample # 5 and the sample # 6 are uniformly distributed ZIF-8@TA nanoparticles, and the cross sections are in an obvious three-dimensional network structure. The outer surfaces of the sample # 5 and sample # 6 have a TA layer attached thereto, and the outer surfaces of the sample # 5 and sample # 6 are rougher relative to the surfaces of the samples # 1-4.
Example 3
In this example, the calcium alginate hydrogel particles prepared in comparative example 1, and the adsorption properties of methylene blue of sample # 1 and sample # 2 prepared in comparative example 2 were examined.
330 calcium alginate hydrogel particles prepared in comparative example 1 (bulk volume: about 3 mL) were taken, respectively, and the sample # 1 and sample # 2 prepared in comparative example 2 were put into a container filled with a concentration of 12mL (C 0 ) The solution is placed in a test tube of 10mg/L methylene blue solution, then placed on a solution mixer to shake at uniform speed, 2mL of methylene blue solution is taken every 2h and placed in a cuvette, and the absorbance is measured by an ultraviolet spectrophotometer and then poured into the test tube. The concentration Ct of methylene blue was calculated from the measured absorbance by the removal rate formula: r= (C 0 -C t )/C 0 * The removal rate of methylene blue was calculated to be 100%.
The test results of this example are shown in fig. 8. As can be seen from FIG. 8, the calcium alginate hydrogel particles prepared in comparative example 1 reached adsorption equilibrium to 10mg/L of methylene blue solution at about 120min, at which time the removal rate of methylene blue was about 50%; the sample # 2 reached adsorption equilibrium for 10mg/L methylene blue solution at about 480min, at which time the methylene blue removal was about 88%; sample # 1 had not reached adsorption equilibrium for 10mg/L of methylene blue solution at about 720 minutes, at which point the methylene blue removal was about 80%. From the above experimental results, it is known that the adsorption performance of the ZIF-8 nanoparticles to methylene blue is improved after the ZIF-8 nanoparticles are introduced into the calcium alginate hydrogel particles, which is caused by the fact that a large number of pore structures are formed in the gel particles after the ZIF-8 nanoparticles are introduced into the calcium alginate hydrogel particles.
Example 4
In this example, the photocatalytic degradation properties of methylene blue were examined for the calcium alginate hydrogel particles prepared in comparative example 1, the sample # 4 prepared in comparative example 3, and the sample # 5 and sample # 6 prepared in example 2.
200 calcium alginate hydrogel particles prepared in comparative example 1 (bulk volume of about 2 mL), sample # 4 prepared in comparative example 3, and sample # 5 and sample # 6 prepared in example 2 were separately taken and placed in a container having a concentration of 50mL (C 0 ) In a beaker of 40mg/L methylene blue solution, stirring magnetically at a constant speed under the condition of UV illumination, and controlling the height of a UV light source from the methylene blue liquid level to be 22cm. Sampling is performed at intervals of 1min from 0 to 10min, at intervals of 2min from 10 to 20min, at intervals of 5min from 20 to 30min, and at intervals of 40 min. 500. Mu.L of each sample was diluted with 1500. Mu.L of pure water and placed in a cuvette, and the absorbance was measured by an ultraviolet spectrophotometer. The concentration Ct of methylene blue was calculated from the measured absorbance by the removal rate formula: r= (C 0 -C t )/C 0 * The removal rate of methylene blue was calculated to be 100%.
As shown in FIG. 9, the results of the test in this example show that, after UV irradiation, the 5# sample and the 6# sample can remove more than 95% of the methylene blue in 40mg/L of the methylene blue solution within 40min, while the removal rate of the 4# sample to the methylene blue in 40mg/L of the methylene blue solution is about 75% under the same conditions. This means that after the tannic acid solution is soaked and modified, the removal capability of the material to methylene blue can be improved, which is probably due to the fact that phenolic hydroxyl groups which are deposited on the surface of gel particles and in tannic acid in a high-molecular three-dimensional network structure are abundant after the tannic acid solution is soaked and modified, the adsorption capability of the material to organic molecules (methylene blue) can be enhanced, and then organic molecules in water can be more effectively enriched, and on the basis, the methylene blue can be more effectively degraded by utilizing the photocatalysis.
Example 5
In this example, the reusability of sample # 6 prepared in example 2 was examined.
(1) 200 samples of sample # 6 prepared in example 2 (bulk volume of about 2 mL) were taken and placed in a container containing 50mL (C) 0 ) In a beaker of 40mg/L methylene blue solution, stirring at constant speed under UV illumination for 40min, and controlling the height of a UV light source from the methylene blue liquid level to be 22cm.
(2) Transferring 200 # 6 samples after the use of step (1) to a fresh 50mL concentration (C 0 ) In 40mg/L methylene blue solution, uniformly magnetically stirring for 40min under the condition of UV illumination, and controlling the height of a UV light source from the surface of the methylene blue solution to be 22cm.
(3) Transferring 200 # 6 samples after the use of step (2) to a fresh 50mL concentration (C 0 ) In 40mg/L methylene blue solution, uniformly magnetically stirring for 40min under the condition of UV illumination, and controlling the height of a UV light source from the surface of the methylene blue solution to be 22cm.
(4) Transferring 200 # 6 samples after the use of step (3) to a fresh 50mL concentration (C 0 ) In 40mg/L methylene blue solution, uniformly magnetically stirring for 40min under the condition of UV illumination, and controlling the height of a UV light source from the surface of the methylene blue solution to be 22cm.
And (3) immediately sampling 500 mu L of the sample after uniformly magnetically stirring the sample for 40min under UV illumination in each of the steps (1) - (4), diluting the sample with 1500 mu L of pure water, and then placing the diluted sample into a cuvette, and measuring the absorbance of the cuvette by using an ultraviolet spectrophotometer. The concentration Ct of methylene blue was calculated from the measured absorbance by the removal rate formula: r= (C 0 -C t )/C 0 * The removal rate of methylene blue was calculated to be 100%. As shown in FIG. 10, it is clear from FIG. 10 that the removal rate of methylene blue in the 40mg/L methylene blue solution is as high as 99.37% in the first use of sample No. 6, and the sample was reused for 4 times to 40mg/L methylene blue solutionThe removal rate of the methylene blue in the process is still kept above 85 percent, and the process has excellent reusability.
Claims (10)
1. The tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle is characterized by comprising gel particles containing tannic acid modified metal organic framework nano materials and tannic acid deposited on the surfaces of the gel particles and distributed in a high polymer three-dimensional network structure of the gel particles; the gel particles containing the tannic acid modified metal organic framework nano material consist of gel matrix polymer materials and tannic acid modified metal organic framework nano materials distributed in the gel matrix polymer materials; the tannic acid modified metal organic framework nano material is tannic acid modified ZIF-8 nano particles.
2. The tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle of claim 1, wherein the mass ratio of the gel matrix polymer material to the tannic acid modified metal organic framework nanomaterial in the tannic acid modified metal organic framework nanomaterial-containing gel particle is (0.1-0.5): 0.1-1.
3. The tannic acid modified MOF/hydrogel composite porous structured photocatalytic particle of claim 2, wherein in the tannic acid modified ZIF-8 nanoparticle, the pyrogallol group of TA is coupled to the organic ligand dimethyl imidazole in the ZIF-8 nanoparticle to form a covalent bond, while the phenolic hydroxyl group of tannic acid is coupled to Zn in the ZIF-8 nanoparticle 2+ Dynamically bonding to form Zn-O bond.
4. The tannic acid modified MOF/hydrogel composite porous structure photocatalytic particle of claim 1, wherein the composite porous structure photocatalytic particle is formed by modifying a tannic acid-containing gel particle of a tannic acid-modified metal organic framework nanomaterial, wherein tannic acid is deposited on the surface of the tannic acid-containing gel particle of the tannic acid-modified metal organic framework nanomaterial to form a tannic acid layer, and wherein the tannic acid is incorporated into a polymeric three-dimensional network structure of the gel particle.
5. The tannic acid modified MOF/hydrogel composite porous structured photocatalytic particle of claim 4, wherein the tannic acid modification is to submerge the gel particles comprising tannic acid modified metal organic framework nanomaterial in an aqueous tannic acid solution for 5-30 minutes.
6. The tannic acid modified MOF/hydrogel composite porous structured photocatalytic particle of claim 5, wherein the tannic acid aqueous solution has a tannic acid to water mass ratio of (0.005 to 0.05): 1.
7. The tannic acid modified MOF/hydrogel composite porous structured photocatalytic particle of any one of claims 1 to 6, wherein the gel-based polymeric material comprises any one of calcium alginate, crosslinked chitosan, cellulose, or crosslinked polyvinyl alcohol.
8. The tannic acid modified MOF/hydrogel composite porous structured photocatalytic particle of any of claims 1 to 6, wherein the composite porous structured photocatalytic particle has a particle size of between microns and millimeters.
9. The method for preparing tannic acid modified MOF/hydrogel composite porous structure photocatalytic particles of claim 1, comprising the steps of:
(1) Preparation of gel particles
Dripping aqueous phase fluid into the collecting liquid through a microfluidic device, and crosslinking monomers of gel-based polymer materials in the aqueous phase fluid drops to form gel particles containing tannic acid modified metal organic framework nano materials;
the aqueous phase fluid contains a monomer of a gel matrix polymer material, a water-soluble surfactant and a metal organic framework nanomaterial modified by tannic acid, and the collecting liquid contains a cross-linking agent; or the aqueous phase fluid contains a monomer of a gel matrix polymer material, a water-soluble surfactant, a cross-linking agent and a tannic acid modified metal organic framework nano material, and the collecting liquid or a reagent providing conditions for the cross-linking of the monomer of the gel matrix material and the cross-linking agent;
(2) Tannic acid modification
Separating gel particles of the tannic acid modified metal organic framework nano material prepared in the step (1) from the collecting liquid, immersing the gel particles in the modifying liquid for 5-30 min, and then washing the collecting liquid and the modifying liquid with water to remove the collecting liquid and the modifying liquid to obtain the tannic acid modified metal organic framework nano material; the modified liquid is tannic acid aqueous solution, and the mass ratio of deionized water to tannic acid in the modified liquid is 1 (0.005-0.05).
10. The method for preparing tannic acid modified MOF/hydrogel composite porous structured photocatalytic particles according to claim 9, wherein when the gel matrix polymer material is calcium alginate, the preparation method of the aqueous fluid and the collection liquid is as follows:
preparing an aqueous phase fluid: dissolving sodium alginate and a water-soluble surfactant in deionized water, and then fully dispersing a tannic acid modified metal organic framework nanomaterial in the obtained solution to obtain an aqueous phase fluid; in the aqueous phase fluid, the mass ratio of sodium alginate, water-soluble surfactant and tannic acid-modified metal organic framework nano material to water is (0.01-0.05): 0.01-0.03): 0.01-0.1): 1;
preparing a collection liquid: adding calcium chloride into deionized water, and uniformly mixing to obtain a collection liquid, wherein the mass ratio of the deionized water to the calcium chloride in the collection liquid is 1 (0.05-0.5).
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