A method for preparing a bifunctional In-MOG / BC adsorption-photocatalysis membrane and its application

Abstract

A method for preparing a bifunctional In-MOG / BC adsorption-photocatalytic membrane includes the following steps: In(NO3)3·xH2O is weighed and dissolved in water, and sonicated until fully dissolved. 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine is weighed and added to water, along with TEA to promote its dissolution. The two solutions are mixed in a 1:1 volume ratio, resulting in the instantaneous formation of In-MOG at room temperature, which is evaluated using a tube inversion test. The prepared In-MOG is collected by centrifugation and washed several times with water, followed by freeze-drying to obtain In-MOG powder. The In-MOG powder is weighed and uniformly mixed with 0.85% w / w bacterial cellulose hydrogel, and the mixed gel is poured into a mold and freeze-dried to obtain the In-MOG / BC adsorption-photocatalytic membrane. This invention offers advantages such as simple preparation method, high plasticity, large swelling capacity, environmental friendliness, and easy separation and regeneration. It can effectively remove CTC and TTC from aqueous solutions through adsorption-photocatalysis synergistic removal.

Description

Technical Field

[0001] This invention belongs to the field of nanomaterials and environmental materials preparation, and specifically relates to a method for preparing and applying a bifunctional In-MOG / BC adsorption-photocatalytic membrane.

[0002] In-MOG is an indium-based organogel; BC is bacterial cellulose; the Chinese name for In-MOG / BC is indium-based organogel / bacterial cellulose composite gel. Background Technology

[0003] Aureomycin and tetracycline, as representatives of tetracycline antibiotics, are widely used in the prevention and treatment of bacterial infections and other diseases due to their broad antibacterial spectrum, strong antibacterial activity, and high cost-effectiveness. However, they are highly soluble in water, and a large portion cannot be absorbed and metabolized by organisms, resulting in 30-90% of the ingested amount being excreted into the aquatic environment. Their non-biodegradable nature and potential carcinogenicity pose a serious threat to the ecological environment and human health, while traditional wastewater treatment plants achieve a removal rate of approximately 14.3% for tetracycline antibiotics. Therefore, there is an urgent need for efficient, energy-saving, and pollution-free treatment methods to remove tetracycline antibiotics from water bodies.

[0004] Adsorption and photocatalysis are two well-studied water treatment technologies with outstanding advantages such as simplicity, high efficiency, and strong adaptability. However, both technologies have certain drawbacks and limitations. Adsorption is prone to saturation, has high regeneration costs, and may cause secondary pollution. Photocatalysis, on the other hand, presents dispersed pollutants that are less effective against reactive oxygen species during photocatalysis, while pollutants enriched on the catalyst surface are more conducive to in-situ photodegradation. To overcome these drawbacks, a synergistic adsorption-photocatalysis method has been proposed in recent years, which can simultaneously achieve material regeneration and efficient pollutant removal. Therefore, fabricating a novel bifunctional material with strong adsorption and photocatalytic capabilities is key to achieving both pollutant enrichment and degradation.

[0005] Metal-organic gels (MOGs) are hybrid soft materials with hierarchical porous structures, abundant active sites, and stable physicochemical properties, constructed from metal ions and organic ligands through non-covalent interactions. Furthermore, the diversity of ligands and metals can endow MOGs with various superior properties. Currently, most MOG materials exhibit framework instability in aqueous environments, while In... 3+With high charge density and polarizability, it can form strong coordination interactions with organic ligands, resulting in MOGs with strong thermal and chemical stability. 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine, containing triazine components, can be used as an organic ligand to improve the electronic delocalization of the synthesized materials. Combining these two would be an ideal choice. Furthermore, bacterial cellulose (BC), as a natural, biocompatible, and non-toxic polysaccharide, possesses high porosity, nanostructure, good hydrophilicity, good photoconductivity, and excellent water retention, making it an ideal flexible matrix for use as a carrier. Combining powdered In-MOGs with BC can expand its practical applications. Summary of the Invention

[0006] The purpose of this invention is to provide a method for preparing and applying a bifunctional In-MOG / BC adsorption-photocatalytic membrane for more effective removal of tetracycline antibiotics from wastewater.

[0007] TEA stands for triethylamine; CTC stands for chlortetracycline hydrochloride; TTC stands for chlortetracycline hydrochloride.

[0008] A method for preparing a bifunctional In-MOG / BC adsorption-photocatalytic membrane, characterized by comprising the following steps:

[0009] Step 1: Weigh 0.3008 g of (In(NO3)3·xH2O) and dissolve it in 10 mL of water. Sonicate the solution until it is fully dissolved. Name the resulting solution A.

[0010] Step 2: Weigh 0.4414 g of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine and add it to 10 mL of water. Add 0.5 mL of TEA to promote its dissolution in water. The resulting solution is named solution B.

[0011] Step 3: Mix solutions A and B in a 1:1 volume ratio. In-MOG forms instantaneously at room temperature and is evaluated using a tube inversion test.

[0012] Step 4: The In-MOG obtained in Step 3 is collected by centrifugation and washed several times with water to remove uncoordinated metal ions and ligands, and then freeze-dried to obtain In-MOG powder.

[0013] Step 5: Weigh 0.17 g In-MOG powder and 40.00 g of 0.85% w / w bacterial cellulose hydrogel.

[0014] The gel was uniformly mixed, and then the mixed gel was poured into a mold and freeze-dried to obtain an In-MOG / BC adsorption-photocatalytic membrane.

[0015] The bifunctional In-MOG / BC adsorption-photocatalytic membrane synthesized in this invention can simultaneously remove CTC from aqueous solution.

[0016] In the application of TTC, the dosage of the In-MOG / BC adsorption-photocatalytic membrane is such that the effective component In-MOG in the aqueous solution is 0.5 g / L, and the light source for photocatalysis is visible light with a wavelength greater than 420 nm.

[0017] The beneficial effects of this invention are:

[0018] The In-MOG / BC adsorption-photocatalytic membrane preparation method provided by this invention is simple, highly flexible, portable, environmentally friendly, and easy to separate and regenerate. This material can effectively remove CTC and TTC from water, providing a reasonable solution for converting powdered In-MOG into macroscopic materials through design.

[0019] from Figure 1 , Figure 2 , Figure 3 , Figure 4 and Figure 5 It can be concluded that the In-MOG / BC adsorption-photocatalytic membrane prepared by this invention has the following advantages:

[0020] 1. Unique porous structure and strong stability;

[0021] 2. Abundant functional groups can serve as active sites;

[0022] 3. It has swelling properties, which facilitates the access of external antibiotic molecules to the internal active site;

[0023] 4. The adsorption-photocatalytic synergistic removal rates of CTC and TTC can reach 90.12% and 91.95%, respectively.

[0024] The case results show that the In-MOG / BC adsorption-photocatalytic membrane of the present invention has the advantages of simple preparation method, strong plasticity, large swelling capacity, environmental friendliness and easy separation and regeneration, and can effectively adsorb and photocatalyze synergistic removal of CTC and TTC in aqueous solution. Attached Figure Description

[0025] Figure 1 The N2 adsorption-desorption curves and pore size distribution of the In-MOG / BC adsorption-photocatalytic membrane prepared in this invention are shown.

[0026] Figure 2 The infrared spectrum of the In-MOG / BC adsorption-photocatalytic membrane prepared in this invention is shown.

[0027] Figure 3Thermogravimetric curve of the In-MOG / BC adsorption-photocatalytic membrane prepared in this invention.

[0028] Figure 4 The swelling behavior of the In-MOG / BC adsorption-photocatalytic membrane prepared in this invention in different water samples is shown.

[0029] Figure 5 The image shows the removal effect of the In-MOG / BC adsorption-photocatalytic membrane prepared in this invention on CTC.

[0030] Figure 6 The image shows the TTC removal effect of the In-MOG / BC adsorption-photocatalytic membrane prepared in this invention. Detailed Implementation

[0031] Example

[0032] A method for preparing a bifunctional In-MOG / BC adsorption-photocatalysis membrane, comprising the following steps:

[0033] Step 1: Weigh 0.3008 g of (In(NO3)3·xH2O) and dissolve it in 10 mL of water. Under sonication conditions, the solution is completely dissolved and named Solution A.

[0034] Step 2: Weigh 0.4414 g of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine and add it to 10 mL of water. Use 0.5 mL of TEA to promote its dissolution in water and sonicate it until fully dissolved. Name it solution B.

[0035] Step 3: Mix solutions A and B in a 1:1 volume ratio. In-MOG forms instantaneously at room temperature and is evaluated using a tube inversion test.

[0036] Step 4: The In-MOG obtained in Step 3 is collected by centrifugation and washed several times with water to remove uncoordinated metal ions and ligands. Then, it is freeze-dried under vacuum to obtain In-MOG powder.

[0037] Step 5: Weigh 0.17 g In-MOG powder and mix it evenly with 40.00 g bacterial cellulose hydrogel (0.85% w / w). Then pour the mixed gel into a mold and freeze-dry it under vacuum to obtain the In-MOG / BC adsorption-photocatalytic membrane. Example

[0038] Application of In-MOG / BC for the synergistic removal of CTCs and TTCs from water via adsorption-photocatalysis. Removal performance was tested using the following method: all adsorption and photocatalysis studies were conducted by dispersing the In-MOG / BC containing 0.5 g / L of the active ingredient In-MOG provided in this invention into 10.00 mg / L of CTCs and TTCs. The difference lies in that the adsorption experiments were conducted under light-protected conditions, while the adsorption-photocatalysis synergistic experiments were conducted under visible light conditions provided by a 300W xenon lamp equipped with a filter (λ < 420 nm). The In-MOG / BC adsorption-photocatalysis membrane prepared in this invention achieved adsorption-photocatalysis synergistic removal rates of 90.12% and 91.95% for CTCs and TTCs, respectively.

Claims

1. A method for preparing a bifunctional In-MOG / BC adsorption-photocatalytic membrane, characterized in that: Includes the following steps: Step 1: Weigh 0.3008 g of In(NO3)3·xH2O and dissolve it in 10 mL of water. Sonicate the solution until it is fully dissolved. Name the resulting solution A. Step 2: Weigh 0.4414 g of 2,4,6-tris(4-carboxyphenyl)-1,3,5-triazine and add it to 10 mL of water. Add 0.5 mL of triethylamine to promote its dissolution in water. Name the resulting solution B. Step 3: Mix solutions A and B in a 1:1 volume ratio. In-MOG forms instantaneously at room temperature and is evaluated using a tube inversion test. Step 4: The In-MOG obtained in Step 3 is collected by centrifugation and washed several times with water to remove uncoordinated metal ions and ligands, and then freeze-dried to obtain In-MOG powder. Step 5: Weigh 0.17 g of In-MOG powder and mix it evenly with 40.00 g of 0.85% w / w bacterial cellulose hydrogel. Then pour the mixed gel into a mold and freeze-dry it to obtain the In-MOG / BC adsorption-photocatalytic membrane.

2. The application of a bifunctional In-MOG / BC adsorption-photocatalytic membrane prepared according to claim 1 in the simultaneous removal of CTC and TTC from aqueous solution.

3. The application of the bifunctional In-MOG / BC adsorption-photocatalysis membrane according to claim 2, characterized in that: The dosage of the In-MOG / BC adsorption-photocatalytic membrane ensures that the effective component In-MOG in the aqueous solution is 0.5 g / L, and the light source for photocatalysis is visible light with a wavelength greater than 420 nm.

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