CN-121991368-A - Ln-BMOF-based fluorescence sensor and preparation method and application thereof

Abstract

The invention belongs to the technical field of fluorescence sensing detection, and particularly relates to a fluorescence sensor based on Ln-BMOF, and a preparation method and application thereof. According to the invention, tb (NO 3 ) 3 ·5H 2 O、Eu(NO 3 ) 3 ·5H 2 O, 2-amino terephthalic acid and O-fluorobenzoic acid) is mixed and dissolved in a DMF/H 2 O mixed solvent, and then the mixed solvent is heated and cooled to room temperature, and is filtered and dried in vacuum to obtain the sensor Eu 0.01 Tb 0.99 -BDC-NH 2 .

Inventors

• WANG SIYUAN
• Luo Yanpei
• YANG XIAONING
• WANG KAI
• LEI SIYUAN
• WANG LELE
• HE CHUAN
• YANG YUHANG
• LIU JIAN
• BAO QIANG
• MA YUNLONG
• YAO YAN

Assignees

• 苏州西热节能环保技术有限公司
• 西安热工研究院有限公司

Dates

Publication Date

20260508

Application Date

20260105

Claims (8)

1. 1. The preparation method of the fluorescence sensor based on Ln-BMOF is characterized by adopting a solvothermal method for synthesis, and comprises the following specific steps: (1) Pretreatment, namely dissolving Tb (NO 3 ) 3 ·5H 2 O、Eu (NO 3 ) 3 ·5H 2 O, 2-amino terephthalic acid and O-fluorobenzoic acid in a mixed solvent of DMF/H 2 O according to the mol ratio of 0.99:0.01:1:20, and stirring at room temperature to obtain a mixed solution; (2) Solvothermal reaction, namely placing the mixed solution into an oven for heating; (3) After the post-treatment, after cooling to room temperature, filtering the product, washing 3 times by DMF and ethanol respectively, and drying in vacuum for 8-12h to obtain the fluorescence sensor Eu 0.01 Tb 0.99 -BDC-NH 2 based on Ln-BMOF.
2. 2. The method according to claim 1, wherein in the step (1), the volume ratio of DMF/H 2 O is 1:0.8-1.2.
3. 3. The method according to claim 1, wherein in the step (1), the stirring is performed at room temperature for 30 to 40 minutes.
4. 4. The method according to claim 1, wherein the heating temperature in the step (2) is 120 ℃.
5. 5. The method according to claim 1, wherein the heating time in the step (2) is 36 to 40 hours.
6. 6. The method according to claim 1, wherein the vacuum drying time in the step (3) is 8 to 12 hours.
7. 7. A fluorescent sensor Eu 0.01 Tb 0.99 -BDC-NH 2 obtained by the production method according to any one of claims 1 to 6.
8. 8. Use of Eu 0.01 Tb 0.99 -BDC-NH 2 according to claim 7 for the detection of picric acid and Fe 3+ in aqueous solutions.

Description

Ln-BMOF-based fluorescence sensor and preparation method and application thereof Technical Field The invention belongs to the technical field of fluorescence sensing detection, and particularly relates to a fluorescence sensor based on Ln-BMOF, and a preparation method and application thereof. Background Picric Acid (PA) is widely used as an important chemical raw material in the fields of dyes, explosives and the like, but the high water solubility and the environment accumulation of the Picric Acid (PA) can endanger ecological environment and human health (such as carcinogenesis, skin irritation and the like). Fe 3+ is a key ion in biological and environmental systems, and the unbalance of the content of the Fe 3+ can cause various diseases such as anemia, renal failure and the like. Therefore, the efficient and sensitive detection of PA and Fe 3+ has important practical significance. The prior detection method has the limitations that the traditional detection method (such as capillary electrophoresis, high performance liquid chromatography, gas chromatography-mass spectrometry and the like) relies on expensive equipment, the pretreatment of a sample is complex, and the on-site rapid detection is difficult to realize. The fluorescence detection method has advantages due to simple operation and rapid response, but needs to develop a fluorescence sensing material with high selectivity and high stability. The lanthanide Metal Organic Frameworks (MOFs) have the advantages of porous structure and controllability and have great potential in fluorescence sensing. The application of the bimetal organic framework (Ln-BMOFs) in the sensing field has not been fully developed due to the characteristics of sharp emission peak, long luminescence lifetime, large Stokes shift and the like of lanthanoids (such as Eu and Tb), and has unique advantages. Disclosure of Invention Aiming at the problems existing in the prior art, the invention provides a fluorescence sensor based on Ln-BMOF, and a preparation method and application thereof. The research synthesizes a lanthanide bimetallic organic framework material Eu 0.01Tb0.99-BDC-NH2 by a solvothermal method, takes Eu 3+、Tb3+ as a metal node, takes 2-amino terephthalic acid (H 2BDC-NH2) as an organic ligand, and is used for fluorescence sensing detection of PA and Fe 3+ in aqueous solution. The technical scheme of the invention is as follows: the preparation method of the fluorescence sensor based on Ln-BMOF adopts solvothermal synthesis, and comprises the following specific steps: (1) Pretreatment, namely dissolving Tb (NO 3)3·5H2O、Eu (NO3)3·5H2 O, 2-amino terephthalic acid and O-fluorobenzoic acid in a mixed solvent with the volume ratio of DMF/H 2 O=1:0.8-1.2 according to the molar ratio of 0.99:0.01:1:20, and stirring for 30-40 minutes at room temperature to fully dissolve the mixture to obtain a mixed solution; (2) Solvothermal reaction, namely placing the mixed solution into an oven preheated to 120 ℃ for heating for 36-40 hours; (3) After the post-treatment, after cooling to room temperature, the product is filtered, washed 3 times with DMF and ethanol respectively, and dried in vacuum overnight to obtain a fluorescence sensor Eu 0.01Tb0.99-BDC-NH2. The invention also provides application of the Eu 0.01Tb0.99-BDC-NH2 material in detection of Picric Acid (PA) and Fe 3+ in aqueous solution. Compared with the prior art, the invention has the following beneficial effects: (1) The invention uses the unique luminescent characteristic of lanthanide and the porous structure of MOFs, firstly uses lanthanide bimetal organic frameworks (Eu0.01Tb0.99-BDC-NH 2) for synchronous detection of PA and Fe 3+, fills the blank of Ln-BMOFs application in the field, and enhances the fluorescence performance through the bimetal synergistic effect at the same time, thereby realizing high-selectivity identification of the target. (2) The Eu0.01Tb0.99-BDC-NH 2 sensor generates strong fluorescence emission at 430nm under 344nm excitation, and PA and Fe 3+ can be detected through fluorescence quenching effect, and has the characteristics of quick response, response time to PA and Fe 3+ of only 10 seconds, wide application range, good durability, and stable performance after repeated cyclic use in a wide pH range. (3) The Eu 0.01Tb0.99-BDC-NH2 obtained by the method can be directly detected in the aqueous solution, is suitable for actual water sample analysis, can be reused, meets the sample analysis requirement of an actual environment, and provides a novel platform for on-site rapid screening of PA and Fe 3+ in the environment. (4) Experiments prove that fluorescence quenching is derived from energy competitive absorption of a target object and a sensor, but not structural collapse or ion exchange, and a mechanism reference is provided for the design of the similar sensor. Drawings FIG. 1 is a photograph of Eu 0.01Tb0.99-BDC-NH2 under natural light and ultraviolet light; FIG. 2 is a scanning el