阅读说明：本技术 一种用于苯胺污染物检测的金属有机骨架的制备方法与应用 (Preparation method and application of metal organic framework for aniline pollutant detection ) 是由 王晓军 俞玲菲 李长云 李秋艳 罗隹瑶 于 2020-11-23 设计创作，主要内容包括：本发明公开了一种用于苯胺污染物检测的金属有机骨架的制备方法与应用,该方法具体步骤为：(1)将L有机配体与三联苯二甲基二羧酸配体放入N,N-二甲基甲酰胺溶液中,使其充分溶解；(L有机配体的结构式如下)；(2)加入四氯化锆和乙酸,超声溶解；(3)90-150℃下反应72小时；(4)冷却至室温后,离心收集沉淀；(5)将沉淀用N,N-二甲基甲酰胺和乙醇分别洗三遍,得到的黄绿色粉末即为金属有机骨架。本发明的金属有机骨架应用于苯胺污染物的检测。本发明的金属有机骨架材料的制备方法简单、稳定性好,其制备的金属有机骨架实现了苯胺的快速检测,肉眼就可以观察到明显的淬灭,方便、灵敏、响应速度快且成本低廉。(The invention discloses a preparation method and application of a metal organic framework for aniline pollutant detection, wherein the method comprises the following specific steps: (1) putting the L organic ligand and the terphenyl dimethyl dicarboxylic acid ligand into an N, N-dimethylformamide solution to be fully dissolved; (the structural formula of the organic ligand L is shown as follows); (2) adding zirconium tetrachloride and acetic acid, and performing ultrasonic dissolution; (3) reacting for 72 hours at 90-150 ℃; (4) cooling to room temperature, centrifuging and collecting precipitate; (5) and (3) washing the precipitate with N, N-dimethylformamide and ethanol respectively for three times to obtain yellow-green powder, namely the metal organic framework. The metal organic framework is applied to detection of aniline pollutants. The preparation method of the metal organic framework material is simple and has good stability, the prepared metal organic framework realizes the rapid detection of aniline, obvious quenching can be observed by naked eyes, and the metal organic framework material is convenient, sensitive, high in response speed and low in cost.)

1. A preparation method of a metal organic framework for aniline pollutant detection is characterized by being a solvothermal method, and comprising the following specific steps:

(1) putting 34mg L of organic ligand and 82mg of terphenyl dimethyl dicarboxylic acid ligand into a reaction container containing 100mL of N, N-dimethylformamide solution to fully dissolve the organic ligand and the terphenyl dimethyl dicarboxylic acid ligand;

the structural formula of the L organic ligand is

(2) Adding 108mg of zirconium tetrachloride and 5.5mL of acetic acid into the mixed solution obtained in the step (1), and putting the reaction container into an ultrasonic machine for ultrasonic dissolution;

(3) taking the reaction container out of the ultrasonic machine, and putting the reaction container into an oil bath kettle for reaction for 48 to 72 hours at the reaction temperature of between 90 and 150 ℃;

(4) cooling the solution after the reaction in the step (3) to room temperature, and then putting the solution into a centrifuge to collect precipitates;

(5) and (3) washing the collected precipitate with N, N-dimethylformamide and ethanol for three times respectively to obtain yellow-green powder, namely the metal organic framework for detecting the aniline pollutants.

2. The method for preparing a metal organic framework for aniline contaminant detection according to claim 1, wherein the reaction time in step (3) is 72 hours, and the reaction temperature is 100 ℃.

3. The application of the metal organic framework for detecting the aniline pollutants is characterized in that the metal organic framework is applied to the detection of the aniline pollutants.

Technical Field

The invention relates to a preparation method and application of a metal organic framework material, in particular to a preparation method and application of a metal organic framework for aniline pollutant detection.

Background

With the rapid development of industry and explosive growth of population, environmental pollution issues are drawing more and more attention. Aniline has been widely used as an important intermediate for organic synthesis in agricultural chemicals, rubbers, dyes, and the like. However, even when released into the environment at low concentrations, it can cause a number of health problems, including skin cancer, liver damage and anemia, to be considered as potential carcinogens. Aniline has been classified by the International agency for research on cancer in the third group of carcinogen lists. Common analytical methods for detecting aniline to date are gas chromatography-mass spectrometry, electrochemical methods, raman spectroscopy, and ion mobility spectroscopy. However, these methods have certain disadvantages, such as complicated processing procedure, poor stability, high price, and slow detection speed.

Disclosure of Invention

In order to solve the problems, the invention aims to provide a preparation method of a metal organic framework for aniline pollutant detection, the method is simple and easy to operate, and the prepared metal organic framework material is simple and convenient in aniline detection treatment process, strong in stability, high in speed and low in price. The invention also provides application of the metal organic framework for detecting the aniline pollutants, and the metal organic framework can be applied to detection of aniline.

In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a metal organic framework for aniline pollutant detection is a solvothermal method, and comprises the following specific steps:

(1) putting an L organic ligand and a terphenyl dimethyl dicarboxylic acid ligand into a reaction vessel containing an N, N-dimethylformamide solution to be fully dissolved;

the structural formula of the L organic ligand is L structural formula

(2) Adding zirconium tetrachloride and acetic acid into the mixed solution obtained in the step (1), and putting the reaction container into an ultrasonic machine for ultrasonic dissolution;

(3) taking the reaction container out of the ultrasonic machine, and putting the reaction container into an oil bath pot for reaction for 72 hours, wherein the reaction temperature is 90-150 ℃;

(4) cooling the solution after the reaction in the step (3) to room temperature, and then putting the solution into a centrifuge to collect precipitates;

(5) and (3) washing the collected precipitate with N, N-dimethylformamide and ethanol for three times respectively to obtain yellow-green powder, namely the metal organic framework for detecting the aniline pollutants.

Preferably, the reaction temperature in the step (3) is 100 ℃.

The application of the metal organic framework for detecting the aniline pollutants is disclosed.

The invention has the following beneficial effects:

1. the preparation method of the luminescent metal organic framework material is simple and has good stability.

2. The metal organic framework of the present invention, when interacting with the analyte aniline, causes a change in fluorescence intensity: with the addition of aniline, the fluorescence is quenched significantly. The invention utilizes the change to realize the rapid detection of aniline.

3. The metal organic framework material has obvious selectivity in the aspect of aniline compound detection, obvious quenching can be observed by naked eyes, and the metal organic framework material is convenient, sensitive, high in response speed and low in cost.

Drawings

FIG. 1 is a graph of the fluorescence response of a metal organic framework synthesized in accordance with the present invention to 0.1-15 μ M aniline;

FIG. 2 is the I of the metal organic frameworks synthesized according to example 2 in the invention in aqueous aniline solutions of different concentrations₀the/I curve;

FIG. 3 is a plot of photoluminescence intensity of metal organic frameworks synthesized according to example 2 of the present invention versus the detection limit of linear fit of aniline in the aqueous phase.

Detailed Description

The present invention will be described in further detail with reference to examples.

Example 1

By adopting a mixed ligand strategy, 34mg of L organic ligand containing a thiazole functional group and 82mg of terphenyldimethyldicarboxylic acid ligand are put into a reaction vessel containing 100mL of N, N-dimethylformamide solution to be fully dissolved, 108mg of zirconium tetrachloride and 5.5mL of acetic acid are added to be ultrasonically dissolved, and the reaction is carried out for 72 hours at 90 ℃. After the reaction is finished, cooling to room temperature, and centrifuging to collect precipitate. The resulting precipitate was washed three times with N, N-dimethylformamide and ethanol, respectively, to give a yellowish green powder with a yield of about 40.2%.

Example 2

By adopting a mixed ligand strategy, 34mg of L organic ligand containing a thiazole functional group and 82mg of terphenyldimethyldicarboxylic acid ligand are put into a reaction vessel containing 100mL of N, N-dimethylformamide solution to be fully dissolved, 108mg of zirconium tetrachloride and 5.5mL of acetic acid are added to be ultrasonically dissolved, and the reaction is carried out for 72 hours at the temperature of 100 ℃. After the reaction is finished, cooling to room temperature, and centrifuging to collect precipitate. The resulting precipitate was washed three times with N, N-dimethylformamide and ethanol, respectively, to give a yellow-green powder with a yield of about 56.8%.

Example 3

By adopting a mixed ligand strategy, 34mg of L organic ligand containing a thiazole functional group and 82mg of terphenyldimethyldicarboxylic acid ligand are put into a reaction vessel containing 100mL of N, N-dimethylformamide solution to be fully dissolved, 108mg of zirconium tetrachloride and 5.5mL of acetic acid are added to be ultrasonically dissolved, and the reaction is carried out for 72 hours at 120 ℃. After the reaction is finished, cooling to room temperature, and centrifuging to collect precipitate. The resulting precipitate was washed three times with N, N-dimethylformamide and ethanol, respectively, to give a yellow-green powder with a yield of about 38.9%.

Example 4

By adopting a mixed ligand strategy, 34mg of L organic ligand containing a thiazole functional group and 82mg of terphenyldimethyldicarboxylic acid ligand are put into a reaction vessel containing 100mL of N, N-dimethylformamide solution to be fully dissolved, 108mg of zirconium tetrachloride and 5.5mL of acetic acid are added to be dissolved by ultrasound, and the reaction is carried out for 72 hours at 150 ℃. After the reaction is finished, cooling to room temperature, and centrifuging to collect precipitate. The resulting precipitate was washed three times with N, N-dimethylformamide and ethanol, respectively, to give a yellowish green powder with a yield of about 26.8%.

Examples 1-4 are the preparation process and the yield of the present invention under different temperature conditions, and it can be seen that the reaction temperature is 100 ℃ and the yield is the highest.

The use method of the metal organic framework in the aniline concentration determination comprises the following steps:

(1) preparing a metal organic framework solution: putting 1mg of metal organic framework into 50ml of deionized water, and fully dissolving;

(2) a response curve of fluorescence intensity and amount of substance was prepared: first, the fluorescence intensity I of an organometallic skeleton solution in the absence of aniline was measured₀Then aniline of gradient substance amount is added, fluorescence intensity I of the sensing material in the presence of aniline is measured, and a fluorescence response graph of the luminescent metal organic framework aniline is drawn (as shown in figure 1). The gradient of the amount of aniline substance is 0.1. mu.M, 0.2. mu.M, 0.3. mu.M, 0.4. mu.M, 0.5. mu.M, 1. mu.M, 1.5. mu.M, 2. mu.M, 2.5. mu.M, 3. mu.M, 3.5. mu.M, 4. mu.M, 4.5. mu.M, 5. mu.M, 5.5. mu.M, 6. mu.M, 9. mu.M, 12. mu.M, 15. mu.M in this order.

(3) Mixing the same amount of sample to be detected with the metal organic framework solution, detecting the fluorescence intensity in real time, if the fluorescence is obviously quenched, proving that the sample contains aniline substances, otherwise, not detecting the sample.

The test result shows that the fluorescence intensity of the metal organic framework material is gradually reduced along with the increasing of the amount of the aniline substance, and when the amount of the added aniline substance reaches 15 mu M, the quenching degree reaches 86 percent, so that the sensing effect of the sensing material on the aniline is very obvious.