CN-121991362-A - Bimetallic organic framework luminescent material and preparation method and application thereof

Abstract

The invention belongs to the technical field of metal organic framework materials, and particularly relates to a bimetallic organic framework luminescent material. The preparation method of the material has a chemical formula of [Tb 6 Pr 4 (DBA) 6 (OH) 4 (H 2 O) 5 ·(H 3 O) 4 ] n ;, and comprises the steps of 1, uniformly mixing Tb (NO 3 ) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 O、H 5 DBA, 4-bipyridine, H 2 O, DMF and HNO 3 , placing the mixture into a reaction kettle, 2, heating the mixture to 160 ℃ in an electric heating oven, keeping the temperature for 72 hours, cooling the mixture to room temperature at a speed of 4 ℃ per hour, 3, filtering the synthesized product, washing the product with ultrapure water and ethanol for multiple times, and naturally drying the product in air to obtain green block Tb/Pr-MOF crystals.

Inventors

• CHAI HONGMEI
• ZHANG YUZHE
• LI YE
• SUN XUEHUA
• BAI WANQIAO

Assignees

• 延安大学

Dates

Publication Date

20260508

Application Date

20240315

Claims (4)

1. 1. A bimetallic organic framework luminescent material is characterized in that the molecular formula is as follows: [Tb 6 Pr 4 (DBA) 6 (OH) 4 (H 2 O) 5 ·(H 3 O) 4 ] n , Abbreviated as Tb/Pr-MOF.
2. 2. The method for preparing a bimetallic organic framework luminescent material as claimed in claim 1, comprising Step 1, evenly mixing Tb (NO 3 ) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 O、H 5 DBA, 4-bipyridine, H 2 O, DMF and HNO 3 , stirring for 20 minutes, and putting into a reaction kettle; step 2, heating to 160 ℃ in an electric heating oven, keeping the temperature for 72 hours at constant temperature, and cooling to room temperature at a speed of 4 ℃ per hour; And 3, filtering the product synthesized in the step 2, washing the product with ultrapure water and ethanol for a plurality of times, and naturally drying the product in air to obtain green blocky [Tb 6 Pr 4 (DBA) 6 (OH) 4 (H 2 O) 5 ·(H 3 O) 4 ] n crystals.
3. 3. The method for preparing a luminescent material with a bimetal organic framework as claimed in claim 2, wherein the molar ratio of Tb (NO 3 ) 3 ·6H 2 O、Pr(NO 3 ) 3 ·6H 2 O、H 5 DBA, 4-bipyridine) is 3:3:6:5.
4. 4. Use of the bimetallic organic framework luminescent material prepared by the method of any one of claims 2-3 in the inspection of Fe 3+ or MnO 4 - .

Description

Bimetallic organic framework luminescent material and preparation method and application thereof Technical Field The invention belongs to the technical field of metal organic framework materials, and particularly relates to a bimetal organic framework luminescent material, a preparation method and application thereof. Background With the development of modern society and industry, toxic chemical substances such as harmful organic compounds, heavy metals and anions are increasingly released from industrial facilities and other artificial activities, so it is very important to explore a pollutant sensor with strong anti-interference performance and universal applicability. Polynuclear lanthanide complexes are paid attention to due to their attractive topology, diverse properties and potential applications as functional solid materials in luminescence, catalysis, magnetism, etc., and because of their good optical properties, the construction of binuclear complexes is expected to be a new functional material. For luminescent lanthanide complexes, they are widely recognized as having particular value in sensors and display devices. For example, tb (III) and Eu (III) complexes emit strongly in the visible region, and are used in important fields such as luminescent materials and sensors, and their long luminescence lifetime and sharp linear emission make detection easier. The structure and properties of some mononuclear complexes have been successfully designed and studied at present, but the assembly of heteronuclear coordination polymer extended structures remains an area of interest to researchers. To date, only a few reported efforts have involved coordination polymers containing heteronuclear lanthanides. The detection of permanganate ions (MnO 4-) is reported relatively rarely. However, they are known to be toxic in aqueous solutions and have been used in the past as disinfectants for disinfecting drinking water, permanganate ions are a strong oxidizing agent and are used in analytical experiments, water treatment, medicine, aquaculture and other various applications. At present, potassium permanganate is widely used in the production stage of aquatic products for pond culture to treat various fish diseases, however, the potassium permanganate aqueous solution is not an ideal aquaculture therapeutic agent, and when the concentration is too high, the potassium permanganate aqueous solution has side effects, and only the low-concentration potassium permanganate solution has excellent disinfection treatment effect on the potassium permanganate aqueous solution, so that the potassium permanganate aqueous solution causes ecological risks in water. If the potassium permanganate solution is taken, the gastrointestinal tract spasm is caused, and the large-dose intake can cause the necrosis of esophagus, stomach or liver and even the respiratory arrest after the hemorrhage. Therefore, analytical techniques and strategies for detection, monitoring and removal of environmental pollutants are highly desirable to reduce the risk of contamination. The prior art "ACS Omega,2020,5,33039-33046 (Tb-MOF) and Inorganic Chemistry,2022,61,7286-7295 (Pr-MOF)" discloses Pr-MOF and Tb-MOF materials, as well as the structural and partial properties of the materials. Tb-MOF is also used for sensing Fe 3+ and MnO 4-, but has poor selectivity (large interference), and Pr-MOF has poor fluorescence performance, so that the existing detection requirements are difficult to meet. Disclosure of Invention In order to comprehensively solve the problems, the invention aims to establish a simple and feasible synthetic route to obtain a novel bimetal lanthanide framework complex, 3, 5-bis (2 ',4' -dicarboxyphenyl) benzoic acid (H 5 DBA) is selected as a ligand and Tb (NO 3)3·6H2O、Pr(NO3)3·6H2 O two lanthanide metal salts), and the heteronuclear bimetal organic framework [Tb6Pr4(DBA)6(OH)4(H2O)5·(H3O)4]n(5), is prepared by utilizing a solvothermal method, so that the material can specifically identify Fe 3+、MnO4- by researching the luminous property of the complex, and has the advantages of high analysis speed, high selectivity and the like. In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: A bimetallic organic skeleton luminescent material has a molecular formula ：[Tb6Pr4(DBA)6(OH)4(H2O)5·(H3O)4]n, abbreviated as Tb/Pr-MOF. A method for preparing a bimetallic organic framework luminescent material comprises Step 1, evenly mixing Tb (NO 3)3·6H2O、Pr(NO3)3·6H2O、H5 DBA, 4-bipyridine, H 2 O, DMF and HNO 3, stirring for 20 minutes, and putting into a reaction kettle; step 2, heating to 160 ℃ in an electric heating oven, keeping the temperature for 72 hours at constant temperature, and cooling to room temperature at a speed of 4 ℃ per hour; And 3, filtering the product synthesized in the step 2, washing the product with ultrapure water and ethanol for a plurality of times, and naturally drying the produc