CN-122006813-A - MIL-88B (Fe)/alpha-Fe2O3Preparation method of/PBC composite material and application of PBC composite material in photocatalytic degradation of meloxicam

Abstract

The invention relates to a preparation method of an MIL-88B (Fe)/alpha-Fe 2 O 3 /PBC composite material and application thereof in photocatalytic degradation of meloxicam. Soaking pine cone powder in acid solution, centrifuging, filtering, drying, carbonizing, and drying to obtain PBC. And magnetically stirring the PBC and FeCl 3 ‧6H 2 O in mixed water, and calcining to obtain the alpha-Fe 2 O 3 /PBC. And (3) placing the alpha-Fe 2 O 3 /PBC、FeCl 3 ‧6H 2 O and terephthalic acid in DMF, stirring and mixing, heating for reaction, washing and drying in vacuum to obtain the MIL-88B (Fe)/alpha-Fe 2 O 3 /PBC composite material. The 4-MFPBC composite material synthesized by the method of the invention has excellent photocatalytic performance. Within 60 min, the removal rate of MLX reaches 99.93%.

Inventors

• LIU YANGCHENG
• SUN DI
• WANG YANG
• WANG XIN
• XIANG ZHENG

Assignees

• 辽宁大学

Dates

Publication Date

20260512

Application Date

20260128

Claims (9)

1. 1. A MIL-88B (Fe)/alpha-Fe 2 O 3 /PBC composite material is characterized in that the preparation method is as follows, Step 1, synthesizing PBC, soaking pine cone powder in phosphoric acid solution, centrifugally filtering, drying, carbonizing, drying to obtain PBC, Step 2, PBC and FeCl 3 ‧6H 2 O are stirred in water, then stirred in a 70 ℃ water bath for 3 h, calcined under the protection of nitrogen to obtain alpha-Fe 2 O 3 /PBC, And 3, putting the alpha-Fe 2 O 3 /PBC and FeCl ‧ H 2 O into a DMF solution, stirring, adding terephthalic acid, continuously stirring, reacting, washing and drying to obtain MIL-88B (Fe)/alpha-Fe 2 O 3 /PBC.
2. 2. The MILs-88B (Fe)/α -Fe 2 O 3 /PBC composite according to claim 1, wherein the carbonization in step 1 is 2h carbonization in a tube furnace at 600 ℃ under nitrogen atmosphere.
3. 3. The MILs-88B (Fe)/α -Fe 2 O 3 /PBC composite of claim 1, wherein in step 2 the mass ratio of PBC to FeCl 3 ‧6H 2 O is 2:1.
4. 4. The MILs-88B (Fe)/α -Fe 2 O 3 /PBC composite according to claim 1 wherein in step 2 the calcination is in a tube furnace at 550 ℃ calcination 2 h.
5. 5. The MIL-88B (Fe)/alpha-Fe 2 O 3 /PBC composite according to claim 1, wherein in the step 3, alpha-Fe 2 O 3 /PBC：FeCl‧6H 2 O is (2-10): 9 in mass ratio.
6. 6. The MILs-88B (Fe)/α -Fe 2 O 3 /PBC composite according to claim 1 wherein in step 3 the reaction is 18h at 110 ℃.
7. 7. Use of MILs-88B (Fe)/α -Fe 2 O 3 /PBC composite according to any one of claims 1-6 in photocatalytic degradation of meloxicam in wastewater.
8. 8. The use according to claim 7, characterized in that the photocatalytic degradation is carried out by adding the MILs-88B (Fe)/α -Fe 2 O 3 /PBC composite material according to any one of claims 1 to 7 to a wastewater containing meloxicam.
9. 9. The use according to claim 8, wherein the meloxicam concentration is 60 mg L -1 -160 mg L -1 ,MIL-88B(Fe)/α-Fe 2 O 3 /PBC composite and the concentration is 0.2 g L -1 -1.0 g L -1 .

Description

Preparation method of MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material and application of MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material in photocatalytic degradation of meloxicam Technical Field The invention relates to the technical field of wastewater treatment, in particular to a preparation method of an MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material and application thereof in photocatalytic degradation of meloxicam. Background Currently, in the treatment of disease, non-steroidal anti-inflammatory drugs are widely used. Among them, meloxicam (MLX) has remarkable analgesic effect and is a common clinical medicine. However, the environmental hosting of pharmaceutically active ingredients and their potential ecological hazards have raised great attention. The complex structure and limited biodegradability of pharmaceutical compounds makes them difficult to remove from waste water, and long-term exposure poses a significant threat to human and animal health. Therefore, there is a need to develop a viable strategy to clear MLX from a body of water. The photocatalysis technology provides a new solution for the bottleneck of the traditional wastewater treatment. Among them, the degradation of organic pollutants using semiconductor materials is one of the more efficient approaches. However, the semiconductor generally has the problems of limited light absorption range, rapid photo-generated carrier recombination and the like, and severely restricts the practical application of the technology. Therefore, developing a photocatalyst with high degradation capability and broad spectrum absorption performance under visible light becomes a key problem for promoting the development of photocatalysis technology. MIL-88B (Fe) is considered to be a very valuable photocatalyst. MILs-88B (Fe) has great potential in the field of heterogeneous photocatalysts due to its highly ordered structure, non-toxic nature and ability to absorb visible light. At the same time, it is also widely used for persulfate activation. However, fe-MOFs generally suffer from limited light absorption and poor charge separation. Therefore, the invention improves the photocatalysis performance of MIL-88B (Fe) by compounding alpha-Fe 2O3/PBC to generate photocatalysis activated persulfate, and applies the composite material in the aspect of photocatalytic degradation MLX. Disclosure of Invention The technical proposal of the invention is that the MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material is prepared by the following method, Step 1, synthesizing PBC, soaking pine cone powder in phosphoric acid solution, centrifugally filtering, drying, carbonizing, drying to obtain PBC, Step 2, PBC and FeCl 3‧6H2 O are stirred in water, then stirred in a 70 ℃ water bath for 3 h, calcined under the protection of nitrogen to obtain alpha-Fe 2O3/PBC, And 3, putting the alpha-Fe 2O3/PBC and FeCl ‧ H 2 O into a DMF solution, stirring, adding terephthalic acid, continuously stirring, reacting, washing and drying to obtain MIL-88B (Fe)/alpha-Fe 2O3/PBC. In step 1, the carbonization is performed in a tubular furnace at 600 ℃ under nitrogen atmosphere for 2h of the MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material. In the MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material, in the step 2, the mass ratio of PBC to FeCl 3‧6H2 O is 2:1. In step 2, the MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material is calcined in a tube furnace at 550 ℃ for 2 h. In the MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material, in the step 3, according to the mass ratio, alpha-Fe 2O3/PBC：FeCl‧6H2 O is (2-10): 9. In step 3, a MIL-88B (Fe)/α -Fe 2O3/PBC composite as described above, the reaction is carried out at 110℃with 18: 18 h. The MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material is applied to photocatalytic degradation of meloxicam in wastewater. The application method is that the MIL-88B (Fe)/alpha-Fe 2O3/PBC composite material is added into the wastewater containing meloxicam to carry out photocatalysis degradation. For the above application, the meloxicam concentration is 60 mg L -1-160 mg L-1,MIL-88B(Fe)/α-Fe2O3/PBC composite and the meloxicam concentration is 0.2 g L -1-1.0 g L-1. The invention has the beneficial effects that The heterojunction constructed in the MIL-88B (Fe)/alpha-Fe 2O3/PBC system reduces the recombination rate of the photo-generated carriers, solves the problem of rapid recombination of the photo-generated carriers, and simultaneously, the persulfate is added to construct a photo-catalytic persulfate activation degradation system so as to generate more ROS, thereby realizing the efficient removal of meloxicam under the irradiation of visible light. Drawings XRD patterns of FIGS. 1 MIL-88B (Fe), α -Fe 2O3,α-Fe2O3/PBC and MIL-88B (Fe)/α -Fe 2O3/PBC. FIG. 2 (a) SEM of α -Fe 2O3、(b) PBC、(c) α-Fe2O3/PBC, (d) MIL-88B (Fe) and (e) of 4-MFPBC, and (d) EDS of 4-MFPBC. FIG. 3 (a) XPS spectra of 4-MFPBC composite, (B) C1 s, (C) O1 s, (d) Fe 2P and (e) P2P, high resolution XPS spectr