CN110240706A - A kind of novel C d-MOF material and its preparation method and application - Google Patents
A kind of novel C d-MOF material and its preparation method and application Download PDFInfo
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- CN110240706A CN110240706A CN201910491515.9A CN201910491515A CN110240706A CN 110240706 A CN110240706 A CN 110240706A CN 201910491515 A CN201910491515 A CN 201910491515A CN 110240706 A CN110240706 A CN 110240706A
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Abstract
The invention discloses a kind of novel C d-MOF materials and its preparation method and application, belong to organic metal framework material preparation technical field.The present invention synthesizes MOF using solvent heat seal, and by using n,N-Dimethylformamide, the reproducibilities such as ethyl alcohol solvent is mixed in the reaction kettle that polytetrafluoroethylene (PTFE) is added with two tetrazolium triphenylamine monocarboxylic acid ligands and is made after heating.The Cd-MOF material that the present invention is prepared has many advantages, such as that stability is good, yield is high, easily prepared and preservation, and can have potential application in terms of gas absorption；There is good selectivity to picric acid, detects picric acid using fluorescence quenching of the picric acid to Cd-MOF, realize and picric acid specific recognition is detected, easy to operate and high sensitivity.
Description
Technical field
The present invention relates to a kind of novel C d-MOF materials and its preparation method and application, belong to organic metal framework material system
Standby technical field.
Background technique
Metal-organic framework materials (MOF) are that quickly grow in recent decades is pillar by metal ion and organic ligand
The porous material that space 3D extends, assembles is constituted, aperture and surface property can be by changing metal and organic ligand
Type and synthesis condition regulate and control, shine, separation, gas storage, catalysis, sensor and biochemical field have wide answer
Use prospect.
In recent years, nitro explosive is just constituting huge threat to world security and ecological environment, wherein nitryl aromatic race
Class compound, such as: dinitrobenzene (DMB), trinitrotoluene (TNT), 2,4- dinitrotoluene (DNT) (4-DNT), 2,6- dinitro first
There is powerful brisance and stronger toxicity (to belong to carcinogenic for benzene (2,6-DNT), 2,4,6- trinitrophenols (TNP) etc.
Object), therefore how efficiently to detect these explosives and be known as one of hot spot of scientific research.Traditional detection method, such as gas phase
Chromatography, Raman spectrum etc. deposit some problems in terms of stability, selectivity, usability, and chemiluminescence sensing is because of its operation
Simply, it responds fast, high sensitivity and is widely studied, be expected to the detection means as a new generation and put into application.So far,
Fluorescence probe based on high molecular material, organometallic skeletal, nano material and organic dyestuff has been successfully applied to quick-fried
In fried analyte detection.
Summary of the invention
Purpose: in order to overcome the deficiencies in the prior art, the present invention provides a kind of novel C d-MOF material and its system
Preparation Method and application.
Technical solution: in order to solve the above technical problems, the technical solution adopted by the present invention are as follows:
A kind of novel C d-MOF material, molecular formula C24H19Cd1.5N10O3, molal weight M=664.09g/mol, hexagonal crystal system,
Cell parameter are as follows:a = 28.888(12) Å, b= 28.888(12) Å, c=27.78 (2),V = 20080(20)
Å3, α/°=90, β/°=90, γ/°=120, Volume/3=20080(20),Z = 18。
Preferably, the Cd-MOF be by cadmium ion be node, two tetrazolium triphenylamine monocarboxylic acid ligands be pillar constitute
Metal-organic framework materials.
A kind of preparation method of novel C d-MOF material, includes the following steps:
(1) polytetrafluoro is added in the mixture of 2.5 chloride hydrate cadmiums, two tetrazolium triphenylamine monocarboxylic acid ligands and solvent DMF, ethyl alcohol
In the reaction kettle of ethylene, ultrasonic vibration 30 minutes；
(2) 110 DEG C of baking ovens are then placed in heat 2 days, then room temperature is down to the rate of 5 DEG C/h；
(3) it is cooled to room temperature the rice-shaped transparent crystal for being cleaned repeatedly with ethyl alcohol and drying to obtain yellow；It is calculated with ligand, is finally obtained
The products collection efficiency obtained is 75%.
Preferably, the molar ratio of ligand and 2.5 chloride hydrate cadmiums is 1:2 ~ 3 in step (1).
Application of the Cd-MOF in detection picric acid, uses fluorescence quenching method to detect picric acid: visiting by fluorescence of Cd-MOF
Needle detects picric acid using fluorescence quenching of the picric acid to Cd-MOF.
The utility model has the advantages that Cd-MOF material preparation method provided by the invention is simple, yield is high, and the complex being prepared is steady
It is qualitative good, it is conducive to save, and have good selectivity, it can be achieved that detecting picric specific recognition to picric acid, detects
Simple to operate and high sensitivity.
Detailed description of the invention
Fig. 1 is a minimum asymmetric cell of complex of the invention；
Fig. 2 is the structural formula of two tetrazolium triphenylamine monocarboxylic acid ligands；
Fig. 3 is complex XRD spectrum of the invention；
Fig. 4 is the infrared spectrogram of complex of the invention；
Fig. 5 is the solid state fluorescence spectrogram of complex and ligand of the invention；
Fig. 6 is the thermogravimetric analysis figure of complex of the invention；
Fig. 7 is each nitro explosive (10-2Mol/L) 40 μ L are titrated to the suspension (1g/ml) of complex of the present invention fluorescence afterwards
Quench percentage；
Fig. 8 is sensitivity test spectrogram of the complex of the present invention to nitro explosive picric acid TNP；
The S-V Linear Fit Chart that Fig. 9, which is complex concentration of the present invention, to be titrated with TNP when being 0.01M；
Figure 10 is for Cd-MOF to N at 77K2Adsorption isothermal curve；
Figure 11 is for Cd-MOF to CO at 273K2Adsorption isothermal curve.
Specific embodiment
The present invention will be further explained with reference to the accompanying drawing.
It is provided by the invention Cd-MOF's the preparation method is as follows:
(1) CdCl is weighed2•2.5H2O(0.103 mmol, 23.6 mg), two tetrazolium triphenylamine monocarboxylic acid ligands (0.051
Mmol, 21.7 mg) it is put into the reaction kettle of polytetrafluoroethylene (PTFE)；Solvent DMF 2ml, dehydrated alcohol 2ml are measured with liquid-transfering gun, is added
In the reaction kettle of polytetrafluoroethylene (PTFE), ultrasound 30 minutes after reaction kettle is sealed；
(2) reaction kettle is put into 110 DEG C of baking ovens and is heated 2 days, room temperature is then down to the rate of 5 DEG C/h；
(3) product taking-up ethyl alcohol is cleaned to the rice-shaped transparent crystal for drying to obtain yellow repeatedly, production is calculated with ligand
Rate is 75%.
The structural formula of two tetrazolium triphenylamine monocarboxylic acids is as shown in Figure 2.
Corresponding crystal structure, XRD and infrared spectroscopy difference are as shown in figure 1, figure 3 and figure 4.
The structure of the complex is as shown in Figure 1, minimum asymmetric cell includes independent Cd ion in 3 crystallography, and 1
Two tetrazolium triphenylamine monocarboxylic acid ligands.
The purity of the crystalline material of the complex is confirmed by powder x-ray diffraction (PXRD) measurement at room temperature.
Fig. 3 shows the position at all peaks and the simulation PXRD generated by corresponding single crystal X-ray diffraction in the experimental data of the complex
The position at all peaks is almost the same in figure.Show to these data dumps that the sample of the complex has very high purity.
The solid state fluorescence spectrogram of two tetrazolium triphenylamine monocarboxylic acid ligands and complexes is measured at room temperature, as shown in figure 5,
The transmitting and its absorption of usual fluorescent material are in mirror symmetry relationship.The excitation spectrum and hair of two tetrazolium triphenylamine monocarboxylic acid ligands
The corresponding wavelength in top for penetrating spectrum is 390nm and 482nm respectively, the excitation spectrum of the complex and the highest of emission spectrum
The corresponding wavelength in peak is 395nm and 488nm respectively.
Thermal stability is an important parameter index of complex.In order to study the thermal stability of the complex, to its into
Thermogravimetric test is gone, in N2Under protection, with 10oThe speed of C/min is warming up to 800 DEG C from 30 DEG C.As shown in fig. 6, TG curve is shown
The complex first step weightlessness is from 31 DEG C to 220 DEG C, due to free solvent molecule H2The release of O；Second step weightlessness be from
320 DEG C beginning, due to the collapsing of the complex structure；Illustrate that the complex has good thermal stability.
It is 10 with dehydrated alcohol compound concentration-22- nitrotoleune (2-NT), the 4- nitrotoleune (4-NT), 2 of mol/L,
4,6- trinitrophenol (TNP), 2,4-DNT (2,4-DNT), 2,3- dimethyl -2,3- dinitrobutane (DMNB),
3,4- dinitrotoluene (DNT) (3,4-DNT), 4- nitrobenzaldehyde (4-NT), 4- nitrophenol (4-NF) solution.
Different 40 μ L of nitro compound solution are added into Cd-MOF fluorescence probe solution, detect different nitro compounds pair
The influence of fluorescence signal, as a result as shown in fig. 7, only TNP has obvious quenching to fluorescence intensity, other phenol compounds are to glimmering
The intensity of light probe has little effect, and shows that Cd-MOF fluorescence probe has good selectivity TNP, it can be achieved that TNP
Specific recognition detection.
As shown in figure 8, fluorescence intensity gradually decreases as the volume of the PA of dropwise addition increases；As the PA that 40 μ L or more are added
When, fluorescence intensity has apparent quenching.
Fig. 9 is the S-V linear fit curve of the complex, uses Stern-Volmer (SV) equation: I0/I=1+Ksv[C]
Research quenching efficiency, wherein [C] represents the concentration of TNP.Our available quenching constants from figureK SVIt is 0.967.
Limit of utilization detection formula LOD=3 δ/K SVAcquiring detectable limit is 3.85 × 10-7 M。
MOF material is a kind of emerging hybrid inorganic-organic porous material, is good new adsorbent.It is rich because having
Rich multiplicity, can design and cut-out frame and pore structure and attracted extensive concern.It as shown in Figure 10, Figure 11, is that the Cd-MOF matches
Object is closed to N2And CO2Absorption figure.
To N under lower relative pressure2Adsorbance sharply increased with the increase of pressure, show to have abundant micro-
Hole；Its subsequent adsorbance with the increase of pressure, continues to be slowly increased, and shows that the material has central hole structure.And to CO2Suction
Attached amount gradually rises with the increase of pressure, and showing the material has good suction-operated.
The above is only a preferred embodiment of the present invention, it should be pointed out that: for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (6)
1. a kind of novel C d-MOF material, it is characterised in that: molecular formula C24H19Cd1.5N10O3, molal weight M=664.09g/
Mol, hexagonal crystal system, cell parameter are as follows:a = 28.888(12) Å, b= 28.888(12) Å, c=27.78 (2),V =
20080(20) Å3, α/°=90, β/°=90, γ/°=120, Volume/3=20080(20),Z = 18。
2. novel C d-MOF material according to claim 1, it is characterised in that: it is section that the Cd-MOF, which is by cadmium ion,
Point, two tetrazolium triphenylamine monocarboxylic acid ligands are the metal-organic framework materials that pillar is constituted.
3. the preparation method of novel C d-MOF material of any of claims 1 or 2, characterized by the following steps:
(1) polytetrafluoro is added in the mixture of 2.5 chloride hydrate cadmiums, two tetrazolium triphenylamine monocarboxylic acid ligands and solvent DMF, ethyl alcohol
In the reaction kettle of ethylene, ultrasonic vibration 30 minutes；
(2) 110 DEG C of baking ovens are then placed in heat 2 days, then room temperature is down to the rate of 5 DEG C/h；
(3) it is cooled to room temperature the rice-shaped transparent crystal for being cleaned repeatedly with ethyl alcohol and drying to obtain yellow.
4. the preparation method of novel C d-MOF material according to claim 3, it is characterised in that: two in the step (1)
The molar ratio of tetrazolium monocarboxylic acid ligand and 2.5 chloride hydrate cadmiums is 1:2 ~ 3.
5. the preparation method of novel C d-MOF material according to claim 3, it is characterised in that: calculated with ligand, finally
The products collection efficiency of acquisition is 75%.
6. application of the novel C d-MOF material of any of claims 1 or 2 in detection picric acid, it is characterised in that: by Cd-
MOF is used as fluorescence probe, detects picric acid using fluorescence quenching of the picric acid to Cd-MOF.
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| CN111471038A (en) * | 2020-03-12 | 2020-07-31 | 广西师范大学 | Tetragonal system Cd-MOF crystal material and synthesis method and application thereof |
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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 |
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Patent Citations (2)
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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 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111471038A (en) * | 2020-03-12 | 2020-07-31 | 广西师范大学 | Tetragonal system Cd-MOF crystal material and synthesis method and application thereof |
| CN111471038B (en) * | 2020-03-12 | 2022-09-30 | 广西师范大学 | Tetragonal system Cd-MOF crystal material and synthesis method and application thereof |
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