CN110240706B - Cd-MOF material and preparation method and application thereof - Google Patents

Cd-MOF material and preparation method and application thereof Download PDF

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CN110240706B
CN110240706B CN201910491515.9A CN201910491515A CN110240706B CN 110240706 B CN110240706 B CN 110240706B CN 201910491515 A CN201910491515 A CN 201910491515A CN 110240706 B CN110240706 B CN 110240706B
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mof
picric acid
mof material
mixture
ligand
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王石
陆敏铭
麦婷
许景文
苏艳荣
黄维
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Nanjing University of Posts and Telecommunications
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Abstract

The invention discloses a novel Cd-MOF material and a preparation method and application thereof, belonging to the technical field of organic metal framework material preparation. The MOF is synthesized by adopting a solvothermal method, and is prepared by mixing a reducing solvent such as N, N-dimethylformamide, ethanol and the like and a ditetrazole triphenylamine-carboxylic acid ligand, adding the mixture into a polytetrafluoroethylene reaction kettle, and heating the mixture. The Cd-MOF material prepared by the method has the advantages of good stability, high yield and the like, is easy to prepare and store, and can have potential application in the aspect of gas adsorption; the method has good selectivity on picric acid, can detect the picric acid by utilizing the fluorescence quenching effect of the picric acid on Cd-MOF, realizes the specific identification and detection of the picric acid, and has simple operation and high sensitivity.

Description

Cd-MOF material and preparation method and application thereof
Technical Field
The invention relates to a Cd-MOF material and a preparation method and application thereof, belonging to the technical field of organic metal framework material preparation.
Background
The Metal Organic Framework (MOF) is a porous material which is developed rapidly in recent decades and is formed by 3D extension and assembly of a space formed by taking metal ions and organic ligands as pillars, the pore diameter and the surface performance of the MOF can be regulated and controlled by changing the types of the metal and the organic ligands and the synthesis conditions, and the MOF has wide application prospects in the fields of luminescence, separation, gas storage, catalysis, sensors and biochemistry.
In recent years, nitro explosives are constituting a huge threat to international safety and ecological environment, wherein nitro aromatic compounds, such as: dinitrobenzene (DMB), trinitrotoluene (TNT), 2, 4-dinitrotoluene (4-DNT), 2, 6-dinitrotoluene (2, 6-DNT), 2,4, 6-Trinitrophenol (TNP) and the like have strong explosive power and strong toxicity (belonging to carcinogens), so that how to efficiently detect the explosives is called one of the hot spots of scientific research. The traditional detection methods, such as gas chromatography, Raman spectroscopy and the like, have certain problems in the aspects of stability, selectivity and usability, and the chemical fluorescence sensor is widely researched due to simple operation, fast response and high sensitivity, and is expected to become a new generation of detection means and be put into application. So far, fluorescent probes based on high molecular materials, organic metal frameworks, nanomaterials and organic dyes have been successfully applied to explosive detection.
Disclosure of Invention
The purpose is as follows: in order to overcome the defects in the prior art, the invention provides a novel Cd-MOF material and a preparation method and application thereof.
The technical scheme is as follows: in order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a novel Cd-MOF material with a molecular formula of C24H19Cd1.5N10O3Molar mass M =664.09g/mol, hexagonal system, unit cell parameters:a = 28.888(12) Å, b= 28.888(12) Å, c = 27.78(2) Å，V = 20080(20) Å3, α/°=90，β/° =90，γ/°=120，Volume/Å3=20080（20），Z = 18。
preferably, the Cd-MOF is a metal-organic framework material which is composed of cadmium ions as nodes and bitetrazole triphenylamine-carboxylic acid ligands as pillars.
A preparation method of a novel Cd-MOF material comprises the following steps:
(1) adding a mixture of 2.5 cadmium chloride hydrate, ditetrazole triphenylamine-carboxylic acid ligand, DMF (dimethyl formamide) solvent and ethanol into a reaction kettle of polytetrafluoroethylene, and ultrasonically vibrating for 30 minutes;
(2) then putting the mixture into a 110 ℃ oven to be heated for 2 days, and then cooling the mixture to room temperature at the speed of 5 ℃/h;
(3) cooling to room temperature, repeatedly cleaning with ethanol, and air drying to obtain yellow transparent rice grain crystal; the final product yield was 75% calculated on ligand.
Preferably, the molar ratio of the ligand to the 2.5 hydrated cadmium chloride in the step (1) is 1: 2-3.
The application of Cd-MOF in detecting picric acid adopts a fluorescence quenching method to detect picric acid: and (3) detecting the picric acid by taking the Cd-MOF as a fluorescent probe and utilizing the fluorescence quenching effect of the picric acid on the Cd-MOF.
Has the advantages that: the preparation method of the Cd-MOF material provided by the invention is simple, the yield is high, the prepared complex is good in stability and beneficial to storage, has good selectivity on picric acid, can realize specific identification and detection on picric acid, and is simple and convenient to detect and operate and high in sensitivity.
Drawings
FIG. 1 is a minimum asymmetric unit of a complex of the present invention;
FIG. 2 is a structural formula of bitertamine-monocarboxylic acid ligand;
FIG. 3 is an XRD pattern of a complex of the present invention;
FIG. 4 is a graph of the infrared spectrum of a complex of the present invention;
FIG. 5 is a solid state fluorescence spectrum of a complex and ligand of the present invention;
FIG. 6 is a thermogravimetric analysis of a complex of the present invention;
FIG. 7 shows the respective nitro explosives (10)-2mol/L) 40. mu.L of percent fluorescence quenching after titration to a suspension of the complex of the invention (1 g/ml);
FIG. 8 is a sensitivity test spectrum of the complex of the invention for nitro explosive picric acid TNP;
FIG. 9 is a plot of the S-V linear fit of the complex of the present invention titrated with TNP at a concentration of 0.01M;
FIG. 10 Cd-MOF vs N at 77K2Adsorption isotherm curve of (d);
FIG. 11 Cd-MOF vs CO at 273K2Adsorption isotherm curve of (1).
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
The preparation method of Cd-MOF provided by the invention comprises the following steps:
(1) weighing CdCl2•2.5H2O (0.103 mmol,23.6 mg) and bitetrazole triphenylamine-carboxylic acid ligand (0.051 mmol, 21.7 mg) are put into a reaction kettle of polytetrafluoroethylene; measuring solvent DMF2ml with pipette gun, and collectingAdding 2ml of water ethanol into a reaction kettle made of polytetrafluoroethylene, sealing the reaction kettle, and carrying out ultrasonic treatment for 30 minutes;
(2) putting the reaction kettle into a 110 ℃ oven to be heated for 2 days, and then reducing the temperature to room temperature at the speed of 5 ℃/h;
(3) and taking out the product, repeatedly washing with ethanol, and airing to obtain yellow rice-shaped transparent crystals, wherein the yield is 75% calculated by ligand.
The structural formula of the bitetrazole triphenylamine monocarboxylic acid is shown in figure 2.
The corresponding crystal structure, XRD and infrared spectrum are shown in figure 1, figure 3 and figure 4 respectively.
The structure of the complex is shown in figure 1, and the minimum asymmetric unit comprises 3 crystallographically independent Cd ions and 1 bitetrazole triphenylamine-carboxylic acid ligand.
The purity of the crystalline material of the complex was confirmed by powder X-ray diffraction (PXRD) measurement at room temperature. FIG. 3 shows that the experimental data for this complex shows that the position of all peaks is substantially consistent with the position of all peaks in a simulated PXRD pattern generated by corresponding single crystal X-ray diffraction. These data clearly show that samples of the complex are of very high purity.
The solid state fluorescence spectra of the bitetrazole-triphenylamine-carboxylic acid ligand and complex were measured at room temperature, and as shown in FIG. 5, the emission and absorption of the fluorescent material are generally mirror images. The wavelengths corresponding to the highest peaks of the excitation spectrum and the emission spectrum of the bitetrazole triphenylamine-carboxylic acid ligand are 390nm and 482nm respectively, and the wavelengths corresponding to the highest peaks of the excitation spectrum and the emission spectrum of the complex are 395nm and 488nm respectively.
Thermal stability is an important parameter indicator of the complex. To investigate the thermal stability of the complex, a thermogravimetric test was carried out on it, at N2Under protection, with 10oThe temperature of the mixture is increased from 30 ℃ to 800 ℃ at a speed of C/min. As shown in FIG. 6, the TG curve shows that the first step weight loss of the complex is from 31 ℃ to 220 ℃ due to free solvent molecule H2Releasing O; the second weight loss was initiated at 320 ℃ due to the collapse of the complex structure; the complex has good thermal stability.
The concentration of the mixture is 10 when the absolute ethyl alcohol is used for preparing-2A solution of 2-nitrotoluene (2-NT), 4-nitrotoluene (4-NT), 2,4, 6-Trinitrophenol (TNP), 2, 4-dinitrotoluene (2, 4-DNT), 2, 3-dimethyl-2, 3-Dinitrobutane (DMNB), 3, 4-dinitrotoluene (3, 4-DNT), 4-nitrobenzaldehyde (4-NT) and 4-nitrophenol (4-NF) in mol/L.
And adding 40 mu L of different nitro compound solutions into the Cd-MOF fluorescent probe solution to detect the influence of different nitro compounds on the fluorescent signal, wherein the result is shown in figure 7, only TNP has obvious quenching on the fluorescent intensity, and other phenol compounds have almost no influence on the intensity of the fluorescent probe, which shows that the Cd-MOF fluorescent probe has good selectivity on TNP and can realize specific identification and detection on TNP.
As shown in fig. 8, as the volume of the added PA increased, the fluorescence intensity gradually decreased; when more than 40. mu.L of PA was added, there was a significant quenching of fluorescence intensity.
FIG. 9 is a S-V linear fit curve of the complex using the Stern-Volmer (SV) equation: i is0/I=1+Ksv[C]Investigating the efficiency of quenching, where [ C]Represents the concentration of TNP. From the figure we can obtain the quenching constantK SVIs 0.967.
Using the limit detection formula LOD 3 δ ═ 4-K SVThe detection limit was found to be 3.85X 10-7 M。
The MOF material is a new type of organic-inorganic hybrid porous material and is a good novel adsorbent. Has attracted extensive attention due to the abundance of designable and tailorable frame and aperture structures. As shown in FIGS. 10 and 11, the Cd-MOF complex pair N2And CO2And (5) absorbing the attached drawings.
At lower relative pressure to N2The adsorption amount of (A) increases sharply with the increase of pressure, indicating that the microporous membrane is abundant; then, the adsorption quantity of the material continuously and slowly increases along with the increase of the pressure, and the material has a mesoporous structure. To CO2The adsorption quantity of the material is gradually increased along with the increase of the pressure, and the material has good adsorption effect.
The above description is only of the preferred embodiments of the present invention, and it should be noted that: it will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the principles of the invention and these are intended to be within the scope of the invention.

Claims (6)

1. A Cd-MOF material characterized by: molecular formula C24H19Cd1.5N10O3Molar mass M =664.09g/mol, hexagonal system, unit cell parameters:a = 28.888(12) Å, b= 28.888(12) Å, c = 27.78(2) Å，V = 20080(20) Å3, α/°=90，β/° =90，γ/°=120，Volume/Å3=20080（20），Z = 18。
2. the Cd-MOF material of claim 1, wherein: the Cd-MOF is a metal organic framework material which is composed of cadmium ions as nodes and bitetrazole triphenylamine-carboxylic acid ligands as pillars.
3. A method of preparing a Cd-MOF material according to claim 1 or 2, characterized in that: the method comprises the following steps:
(1) adding a mixture of 2.5 cadmium chloride hydrate, ditetrazole triphenylamine-carboxylic acid ligand, DMF (dimethyl formamide) solvent and ethanol into a reaction kettle of polytetrafluoroethylene, and ultrasonically vibrating for 30 minutes;
(2) then putting the mixture into a 110 ℃ oven to be heated for 2 days, and then cooling the mixture to room temperature at the speed of 5 ℃/h;
(3) cooling to room temperature, washing with ethanol repeatedly, and air drying to obtain yellow transparent rice-grain crystal.
4. A method of preparing a Cd-MOF material according to claim 3, wherein: the molar ratio of the bitetrazole-monocarboxylic acid ligand to the 2.5 hydrated cadmium chloride in the step (1) is 1: 2-3.
5. A method of preparing a Cd-MOF material according to claim 3, wherein: the final product yield was 75% calculated on ligand.
6. Use of a Cd-MOF material according to claim 1 or 2 for the detection of picric acid, characterized in that: the Cd-MOF is used as a fluorescent probe, and the picric acid is detected by utilizing the fluorescence quenching effect of the picric acid on the Cd-MOF.
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CN106188108A (en) * 2016-07-08 2016-12-07 北京工业大学 The metal-organic framework materials of a kind of Cd and preparation method and applications
CN109776504A (en) * 2019-02-27 2019-05-21 北京工业大学 A kind of metal-organic framework material and preparation method and applications based on low symmetrical pyrazoles-Carboxylic acid ligand Zn

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106188108A (en) * 2016-07-08 2016-12-07 北京工业大学 The metal-organic framework materials of a kind of Cd and preparation method and applications
CN109776504A (en) * 2019-02-27 2019-05-21 北京工业大学 A kind of metal-organic framework material and preparation method and applications based on low symmetrical pyrazoles-Carboxylic acid ligand Zn

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