Search

CN-122011420-A - To Hg2+And NOR ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity and preparation method and application thereof

CN122011420ACN 122011420 ACN122011420 ACN 122011420ACN-122011420-A

Abstract

The invention belongs to the technical field of metal organic frame materials, and particularly relates to a carbon quantum dot-metal organic frame composite fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and Norfloxacin (NOR), a preparation method thereof and sensing colorimetric dual-mode detection application. And combining the Carbon Quantum Dots (CQDs), euCl 3 ·6H 2 O and ZrCl 4 with an organic ligand terephthalic acid (BDC) in DMF by adopting a solvothermal method to obtain the CQDs@Eu UiO-66 composite material. By combining excellent optical properties and pore structures of CQDs and Eu-UiO-66, the dual-emission ratio fluorescent probe has rapid and accurate specific recognition capability, lower detection limit and good practical application capability for Hg 2+ and NOR in water.

Inventors

  • ZHANG ZHIJUAN
  • LI PENGWEI
  • LI XINXIN
  • LI JINGYING
  • FAN LIANG
  • TANG HANXIAO
  • SU XING
  • ZHENG XIAOKE

Assignees

  • 河南中医药大学

Dates

Publication Date
20260512
Application Date
20260316

Claims (7)

  1. 1. A preparation method of a ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR is characterized by comprising the steps of mixing ZrCl 4 、EuCl 3 ·6H 2 O, CQDs with terephthalic acid, and preparing the CQDs@Eu-UiO-66 composite material by self-assembly by taking a DMF organic solvent as a reaction medium.
  2. 2. The preparation method of the ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR as claimed in claim 1 is characterized in that the reaction temperature is 120 ℃, the reaction time is 24 hours, and the addition amount of CQDs is 2-10 mg.
  3. 3. The method for preparing the ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR as claimed in claim 2, wherein the ratio of the amounts of the substances ZrCl 4 、EuCl 3 ·6H 2 O and BDC is 1:9:10.
  4. 4. A probe prepared by the preparation method of the fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR according to any one of claims 1-3 is characterized in that the specific BET surface area of the fluorescent probe is 641-737 m 2 /g, the specific Langmuir surface area is 747-832 m 2 /g, the pore volume is 0.344-0.3838 cm 3 /g, the micropore volume is 0.226-0.267 cm 3 /g, and the average pore diameter is 1.947-2.353 nm.
  5. 5. The probe of claim 4 for trace or trace detection of Hg 2+ ions with a detection limit in water for Hg 2+ as low as 2.08 nM.
  6. 6. The probe of claim 4 for detecting NOR in trace or trace amounts, which has a detection limit of NOR as low as 48.96 nM in water.
  7. 7. A portable sensing device for detecting Hg 2+ and NOR on site is characterized by comprising CQDs@Eu-UiO-66 and a UV cassette which are integrated into a smart phone, wherein color recognition software for converting fluorescent color signals into RGB values is also installed on the smart phone, and the ratio (R+G)/B of the sum of red and green values to blue value is used as an index of Hg 2+ and NOR detection.

Description

Ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR, and preparation method and application thereof Technical Field The invention belongs to the technical field of metal organic frame materials, and particularly relates to a ratio fluorescent probe CQDs@Eu UiO-66 with high selectivity to Hg 2+ and NOR, a preparation method thereof and sensing colorimetric dual-mode detection application. Background The problem of complex pollution in water environment is increasingly severe, and particularly, the coexistence of heavy metals and antibiotics makes the development of efficient and sensitive pollutant detection technology become a research hotspot in the current environment monitoring field. Mercury ions (Hg 2+) are a typical toxic heavy metal contaminant with strong mobility and bioaccumulation. Hg 2+ can be converted to more toxic organic mercury which enters the human body through the food chain, causing damage to the nervous, renal and immune systems and increasing the risk of cardiovascular disease and dysplasia. Meanwhile, norfloxacin (Norfloxacin, NOR) is widely used in human medicine and aquaculture as a representative of fluoroquinolone antibiotics. The chemical structure is stable, the microbial agent is difficult to completely degrade in natural environment, the long-term residue is easy to induce microorganisms to generate drug resistance genes, the aquatic ecological balance is destroyed, and the human health can be indirectly influenced through drinking water or food chains. Traditional heavy metal detection methods such as inductively coupled plasma emission spectrometry (ICP-AES), inductively coupled plasma mass spectrometry (ICP-MS), high Performance Liquid Chromatography (HPLC), atomic Absorption Spectrometry (AAS), atomic Fluorescence Spectrometry (AFS) and the like have higher precision, but generally rely on large-scale instruments, have complex pretreatment and are difficult to realize on-site rapid detection. In recent years, fluorescent sensing technology has received attention because of advantages such as low cost, fast response, high sensitivity, and the like. The carbon quantum dot is used as a novel fluorescent nano material, has the characteristics of wide raw materials, simple preparation and the like, and the metal organic frame material becomes a research hot spot by virtue of an adjustable pore structure and a high specific surface area. Aiming at the accumulation, migration and degradation-resistant characteristics of Hg 2+ and NOR, a fluorescent probe material capable of realizing rapid and accurate detection is developed, and the fluorescent probe material has important significance for objectively evaluating the composite pollution condition and guaranteeing the safety of water environment. Disclosure of Invention The invention aims to provide a ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR, and a preparation method and application thereof, and effectively solves the problems of low efficiency, time consumption, easiness in interference, poor portability and the like of the traditional inspection method. In order to achieve the above purpose, the invention adopts the following technical scheme: A preparation method of a ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR comprises the following steps of dissolving CQDs, euCl 3·6H2O、ZrCl4 and BDC in DMF ultrasonically, transferring to a reaction kettle for solvothermal synthesis, centrifuging, purifying and vacuum drying for 24 hours to obtain the CQDs@Eu-UiO-66 composite material. Further, the reaction temperature is 120 ℃, the reaction time is 24 hours, and the addition amount of the carbon quantum dots is 2-10 mg. Further, the ratio of the amounts of the substances of EuCl 3·6H2O、ZrCl4 and BDC was 1:9:10. The probe prepared by the preparation method of the ratio fluorescent probe CQDs@Eu-UiO-66 with high selectivity to Hg 2+ and NOR overcomes the aggregation quenching phenomenon of the carbon quantum dots, and has excellent fluorescent characteristic, high specific surface area and good thermal stability. Meanwhile, the composite probe shows remarkable specific recognition capability to Hg 2+ and NOR, and has good application potential. The probe is used for detecting Hg 2+ ions in trace or trace quantity, and the detection limit of Hg 2+ in an aqueous solution is as low as 2.08 nM. The probe is used for detecting NOR in trace or trace, and the detection limit of the probe in an aqueous solution is as low as 48.96 nM. The invention integrates CQDs@Eu-UIO-66 and UV cartridge through a smart phone, and detects Hg 2+ and NOR in real time by a visual quantification method. The color recognition software (Color Picker Application) installed on the smart phone is used for converting fluorescent color signals generated when the probe detects Hg 2+ and NOR with different concentrations into RGB values, and the ratio of the sum of red (R) and green