CN-122011423-A - Zirconium-based metal organic framework material and preparation method and application thereof

Abstract

The invention discloses a zirconium-based metal organic framework material, a preparation method and application thereof, and belongs to the technical field of electrochemical luminescence (ECL). The zirconium-based metal-organic framework material is of a typical fcu topology of UiO series, a hexanuclear metal cluster taking Zr 6 O 4 (OH) 4 as a core is taken as a secondary structural unit (SBU), each Zr 4+ is coordinated with carboxyl oxygen of a ligand, and the hexanuclear Zr clusters are bridged by the ligand to form a three-dimensional porous framework. The synthesis method for preparing the luminophor Zr-MOF is simple, has high stability and good electrochemiluminescence performance, can be used for ECL luminescence detection, and has excellent naphthalene ring and anthracene ring in the ligand.

Inventors

• XU ZHIQIANG
• SUN HUIPING
• ZOU ZHUO
• GUO CHUNXIAN

Assignees

• 苏州科技大学

Dates

Publication Date

20260512

Application Date

20260402

Claims (10)

1. 1. A method for preparing a zirconium-based metal organic framework material, which is characterized by comprising the following steps: (1) Mixing, heating and refluxing by using 4-bromo-1-naphthoic acid, methanol and concentrated H 2 SO 4 to obtain 4-bromo-1-naphthoic acid methyl ester; (2) Mixing 4-bromo-1-methyl naphthoate, bisboronic acid pinacol ester, a first catalyst and an alkaline substance in a reaction solvent, and heating to react in an inert atmosphere to obtain 4-boron pinacol ester-1-methyl naphthoate; (3) Mixing the obtained 4-boron pinacolate-1-methyl naphthoate, 10-bromine-9-methyl anthranilate, a second catalyst and cesium carbonate in a reaction solvent, and heating and reacting in AN inert atmosphere to obtain H 2 bpdc-AN-Me; (4) Heating and refluxing by using aqueous solution of H 2 bpdc-AN-Me, methanol and alkali to obtain a product H 2 bpdc-AN; (5) Mixing H 2 bpdc-AN with ZrCl 4 , placing the mixture into a mixed solution containing AN organic solvent and a growth regulator, and carrying out heating reaction in stages to obtain the zirconium-based metal organic framework material.
2. 2. The process according to claim 1, wherein in step (1), the temperature of the heated reflux is 60 to 70 ℃ for 24 to 48 hours.
3. 3. The preparation method according to claim 1, wherein in the step (2), the mass ratio of the methyl 4-bromo-1-naphthoate, the bisboronic acid pinacol ester, the first catalyst and the alkaline substance is 10.60 (11.17-35.1): 0.44-1.32): 11.78-35.34; The first catalyst comprises [1, 1-bis (diphenylphosphine) ferrocene ] palladium dichloride; The alkaline substance is selected from one or more of potassium acetate, sodium formate and sodium acetate; the reaction solvent is selected from dioxane.
4. 4. The process according to claim 1, wherein in the step (2), the inert atmosphere inert gas comprises nitrogen and/or argon, and the heating reaction is carried out at a temperature of 100 to 120 ℃ for a period of 1 to 3 days.
5. 5. The preparation method according to claim 1, wherein in the step (3), the mass ratio of the 4-boron pinacolate-1-methyl naphthoate, the 10-bromo-9-methyl anthranilate, the second catalyst and cesium carbonate is 5 (12.60-37.80): 0.92-2.76): 39.10-117.3; the inert gas in inert atmosphere is selected from nitrogen and/or argon, the heating reaction temperature is 80-100 ℃, and the reaction time is 3-7 days; the second catalyst comprises palladium tetraphenyl phosphine.
6. 6. The method according to claim 1, wherein in the step (4), the concentration of the aqueous alkali solution is 5M, the temperature of the heat reflux is 80 to 100 ℃ and the time is 3 to 7 days; The alkali in the aqueous solution of the alkali is selected from one or more of sodium hydroxide, potassium hydroxide and tetramethylammonium hydroxide.
7. 7. The method according to claim 1, wherein in the step (5), the mass ratio of H 2 bpdc-AN to ZrCl 4 is (5:3) - (5:5); the organic solvent comprises DMF; The growth regulator is acetic acid.
8. 8. The preparation method according to claim 1, wherein the heating reaction is carried out in stages, the first stage having a temperature of 100 ℃ for 24 hours and the second stage having a temperature of 120 ℃ for 48 hours.
9. 9. A zirconium-based metal-organic framework material prepared by the preparation method of any one of claims 1 to 8, wherein the zirconium-based metal-organic framework material is of a fcu topology typical of UiO series, a hexanuclear metal cluster with Zr 6 O 4 (OH) 4 as a core is used as a secondary structural unit SBU, each Zr 4+ is coordinated with carboxyl oxygen of a ligand, and the hexanuclear Zr clusters are bridged by the ligand to form a three-dimensional porous framework.
10. 10. An electrochemical light-emitting device comprising the zirconium-based metal-organic framework material of claim 9.

Description

Zirconium-based metal organic framework material and preparation method and application thereof Technical Field The invention relates to the technical field of electrochemiluminescence, in particular to a zirconium-based metal organic framework material and a preparation method and application thereof. Background The electrochemical luminescence (ECL) detection technology is a novel analysis technology integrating chemical reaction and chemiluminescence, has the advantages of controllability of electrochemical analysis, high sensitivity, low background interference and the like of the chemiluminescence analysis, triggers a system to generate redox reaction through applying a specific potential to an electrode to generate an excited state substance, releases photons when the excited state substance jumps back to a ground state, and realizes quantitative analysis of a target substance through detecting photon intensity, so that the ECL detection technology has become one of important technical means in the modern analysis detection field. The technology has the advantages of simple operation, wide linear range and no radioactive pollution, and has unique advantages in detection of extremely low-content substances in complex samples such as biological tissues, body fluids and the like, and is particularly suitable for ultrasensitive detection of disease biomarkers, environmental trace pollutants and the like. At present, the core bottleneck of the electrochemiluminescence detection technology is the optimization of the performance of an electrochemiluminescence system, namely, how to improve the luminescence efficiency, reduce the triggering potential and enhance the detection stability and selectivity. In the existing electrochemical luminescence system, the commonly used luminophore comprises nano materials such as terpyridyl ruthenium (Ru (bpy) 32+), molybdenum disulfide (MoS 2) and the like, wherein the Ru (bpy) 32+ system has the problems of limited luminous efficiency, higher cost, complex marking process and the like although the Ru (bpy) 32+ system is widely applied, and the two-dimensional nano materials such as MoS 2 and the like have larger specific surface area and excellent electronic characteristics, but have lower electrochemical luminous efficiency and limit the application range thereof. To solve the above problems, the person skilled in the art tries to introduce catalysts or support materials for modifying the light-emitting system. Because of the ordered porous structure, the larger specific surface area and the adjustable metal active sites, the Metal Organic Frameworks (MOFs) become ideal anchoring substrates for carrier materials, and can realize stable anchoring of the materials under milder conditions compared with the traditional carbon nitrogen-based materials. Currently, MOFs are partly studied for ECL sensing, for example, ZIF-8, uiO-66 or UiO-67 series are utilized, but MOFs of the UIO series are basically used as carriers of ECL luminophores and cannot emit light. The problem group of Wei Qin in 2018 encapsulates ruthenium (II) complex Ru (bpy) 32+ in UiO-67 metal organic framework (ACS appl. Mater. Interfaces 2018, 10, 22932-22938) to form UiO-67/Ru (bpy) 32+ nanocomposite, and UiO-67 MOF has the characteristics of large specific surface area and high porosity, and can load more Ru (bpy) 32+ on the surface and holes of the nanocomposite, thereby obviously improving ECL efficiency. In the prior art, the stability of the UiO-67/Ru (bpy) 32+ compound is poor, ru (bpy) 32+ is loaded in a MOF pore canal through physical encapsulation, the leakage risk possibly exists, and a luminophor possibly oozes out of a MOF framework during long-term storage or repeated use, so that the signal attenuation and the reproducibility are poor. The loading of Ru (bpy) 32+ during synthesis is difficult to control accurately. If the load is too high, partial ruthenium complex can be accumulated on the outer surface or pore opening of the MOF to cause self-quenching, and if the load is too low, the signal enhancement effect is limited, and the fluctuation of the load between different batches can directly influence the quantitative accuracy of the sensor. The above drawbacks significantly limit the versatility of MOFs as carrier-supported luminophore strategies. Disclosure of Invention In order to solve the technical problems, the invention provides a zirconium-based metal organic framework material and a preparation method and application thereof. The first object of the present invention is to provide a method for preparing a zirconium-based metal organic framework material, comprising the steps of: (1) Mixing, heating and refluxing by using 4-bromo-1-naphthoic acid, methanol and concentrated H 2SO4 to obtain 4-bromo-1-naphthoic acid methyl ester; (2) Mixing 4-bromo-1-methyl naphthoate, bisboronic acid pinacol ester, a first catalyst and an alkaline substance in a reaction solvent, and heating to react