CN-121991373-A - Lanthanide metal organic framework material, fluorescence sensor, preparation methods of lanthanide metal organic framework material and fluorescence sensor, and application of fluorescence sensor in pesticide detection

Abstract

The invention belongs to the technical field of metal-organic frame materials, and relates to a lanthanide metal-organic frame material, a fluorescence sensor, a preparation method thereof and application thereof in pesticide detection. The preparation method of the lanthanide metal organic framework material comprises the following steps of taking lanthanide metal salt and organic ligand as raw materials, and then adopting a solvothermal method to obtain the lanthanide metal organic framework material, wherein the organic ligand is 1, 4-naphthalene dicarboxylic acid or 2, 6-naphthalene dicarboxylic acid. The invention adopts the organic ligand with isomer and lanthanide metal salt to prepare lanthanide metal organic frame material by solvothermal method, effectively sensitizes lanthanide metal ions to emit light by antenna effect, improves fluorescence quantum yield and luminous intensity, further improves signal to noise ratio of lanthanide metal organic frame material, and has high sensitivity and accuracy for detecting 2, 6-dichloro-4-nitroaniline.

Inventors

• FAN YAN
• WANG LEI
• SUN XUEQIN

Assignees

• 青海师范大学

Dates

Publication Date

20260508

Application Date

20260209

Claims (9)

1. 1. The preparation method of the lanthanide metal organic framework material is characterized by comprising the following steps of: The lanthanide metal organic frame material is prepared by using lanthanide metal salt and organic ligand as raw materials and adopting a solvothermal method, wherein the organic ligand is 1, 4-naphthalene dicarboxylic acid or 2, 6-naphthalene dicarboxylic acid.
2. 2. The method for preparing a lanthanide metal-organic framework material according to claim 1, wherein the molar ratio of the lanthanide metal salt to the organic ligand is 2 (1-5).
3. 3. The method for preparing a lanthanide-series metal-organic framework material according to claim 1, wherein in the lanthanide-series metal salt, the lanthanide-series metal is lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium or lutetium.
4. 4. The preparation method of the lanthanide metal organic framework material according to claim 1, wherein the lanthanide metal organic framework material is obtained by dissolving lanthanide metal salt and organic ligand in a solvent for coordination reaction, cooling and drying.
5. 5. The method for preparing a lanthanide-series metal-organic framework material as claimed in claim 4, wherein the solvent is one or more of dimethylacetamide, N-dimethylformamide, methanol, ethanol and water.
6. 6. The method for preparing a lanthanide-series metal-organic framework material as claimed in claim 4, characterized in that the conditions of the coordination reaction are that the temperature is 100.+ -. 10 ℃ and the time is 12 hours to 72 hours.
7. 7. A lanthanide metal organic framework material obtained by the preparation method according to any one of claims 1 to 6.
8. 8. A fluorescence sensor comprising the lanthanide-metal organic framework material of claim 7.
9. 9. Use of the lanthanide metal organic framework material of claim 6 or the fluorescence sensor of claim 7 in pesticide detection.

Description

Lanthanide metal organic framework material, fluorescence sensor, preparation methods of lanthanide metal organic framework material and fluorescence sensor, and application of fluorescence sensor in pesticide detection Technical Field The invention belongs to the technical field of metal-organic frame materials, and relates to a lanthanide metal-organic frame material, a fluorescence sensor, a preparation method thereof and application thereof in pesticide detection. Background The agricultural chemical is an indispensable part of agricultural production, plays a vital role in protecting crops from pests, diseases and weeds, and especially, 2, 6-dichloro-4-nitroaniline is used as a broad-spectrum agricultural chemical commonly used for preventing and treating powdery mildew of wheat, cotton boll rot, fruit/vegetable diseases and the like, however, the decomposition rate of 2, 6-dichloro-4-nitroaniline is slow, and residual substances thereof exist in soil and water environments for a long time, so that the 2, 6-dichloro-4-nitroaniline is also classified as a class III dangerous agricultural chemical. Therefore, there is an urgent need to develop an effective method for detecting 2, 6-dichloro-4-nitroaniline. So far, common detection methods for nitroaniline pesticides include high performance liquid chromatography, gas chromatography, liquid chromatography-tandem mass spectrometry, and the like. For example, patent document CN116124929a discloses a method for simultaneously measuring trace amounts of dinitrobenzene, diaminotoluene and nitroaniline in a phenylenediamine reducing solution by liquid chromatography. However, these detection methods require complex pretreatment of the sample, and the detection instrument is expensive, greatly limiting its application in pesticide detection. In contrast, the fluorescence detection method based on the sensing material has received more and more attention in the field of pollutant detection because of the advantages of low cost, simple operation, short response time and the like. Currently, several sensing materials that have been reported are broadly classified into metal organic framework materials, covalent organic materials, carbon dot materials, and small molecule fluorescent probes. Among them, the fluorescent probe based on metal organic frame receives more and more attention because of its inherent characteristics (such as adjustable structure, adjustable aperture size and different fluorescence emission mechanisms), and the metal organic frame material is crystallized by stabilizing the metal site and the organic ligand with good coordination ability, thereby having adsorption or recognition function to the target pesticide, and realizing detection. In the prior art, metals used for constructing the metal-organic framework material comprise transition metals or rare earth metals, and the rare earth metal-organic framework has excellent light-emitting characteristics such as strong emission peak, long light-emitting service life, high light-emitting efficiency and the like because of inherent characteristics of metal ions and corresponding MOFs function guidance, so that the metal-organic framework material has more advantages in fluorescence detection. However, the rare earth metal ions have weak absorption capacity to excitation light due to 4f-4f transition forbidden by Laporte (Laporte) rule, so that the luminous efficiency is low, the fluorescence quantum yield and the luminous intensity of the target pesticide are further reduced, the sensitivity of a detection result is influenced, and the application of the rare earth metal ions in fluorescence sensing is greatly limited. Disclosure of Invention Aiming at the technical problems that in the existing rare earth metal organic frame material, the absorption capacity of rare earth metal ions to excitation light is weak due to 4f-4f transition forbidden by Laporte (Laporte) rule, so that the luminous efficiency is low, and further the fluorescence quantum yield and the luminous intensity of target pesticides are reduced, and the sensitivity of detection results is affected, the invention provides a lanthanide metal organic frame material, a fluorescence sensor, a preparation method thereof and application thereof in pesticide detection. The invention adopts the organic ligand with isomer and lanthanide metal ion to prepare lanthanide metal organic frame material by solvothermal method, effectively sensitizes lanthanide metal ion luminescence by antenna effect, improves fluorescence quantum yield and luminous intensity, further improves signal to noise ratio of lanthanide metal organic frame material, and has high sensitivity and accuracy for detecting 2, 6-dichloro-4-nitroaniline. The invention has the technical concept that in the lanthanide metal organic frame material, lanthanide metal ions (Ln 3+ ions) are sensitized by reasonably selecting organic ligands, and the lanthanide metal ions are effective