CN109517185B - Rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nPreparation method and application of - Google Patents
Rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nPreparation method and application of Download PDFInfo
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- RMBFBMJGBANMMK-UHFFFAOYSA-N 2,4-dinitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O RMBFBMJGBANMMK-UHFFFAOYSA-N 0.000 claims description 7
- XTRDKALNCIHHNI-UHFFFAOYSA-N 2,6-dinitrotoluene Chemical compound CC1=C([N+]([O-])=O)C=CC=C1[N+]([O-])=O XTRDKALNCIHHNI-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
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Abstract
Rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nRelates to the technical field of preparation and application of rare earth metal-organic framework materials. Dissolving and uniformly mixing terephthalic acid by using DMF to obtain a solution A; DyCl is added3·6H2Dissolving and uniformly mixing O by using DMF to obtain a solution B; placing the solution A and the solution B in a beaker A and uniformly mixing; placing DMF and triethylamine in a beaker B, uniformly mixing, and sealing the opening of the beaker through a preservative film; firstly, placing a beaker B in a beaker A, then placing the beaker A in an ultrasonic instrument, and reacting under the ultrasonic condition to obtain the rare earth metal-organic framework material [ Dy ] taking rare earth metal Dy as a metal center and terephthalic acid as a ligand2(BDC)3(H2O)4]n. The rare earth metal-organic framework material has fluorescence sensitivity to trace nitro explosives, and nitro compounds have strong fluorescence quenching effect on the trace nitro explosives.
Description
Technical Field
The invention relates to the technical field of preparation and application of rare earth metal-organic framework materials, in particular to a rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nThe preparation method and the application thereof.
Background
Metal-organic framework Materials (MOFs) are materials of one-dimensional, two-dimensional, or three-dimensional structure assembled from metal ions and organic ligands by coordination bonds. Compared with the traditional inorganic porous material, the MOFs material has wider selection range of metal ions and organic ligands, so that the MOFs material can be designed and synthesized into materials with various structural forms and characteristics. The MOFs material has potential application prospects in the aspects of gas storage, separation, catalysis, magnetism and the like, and has attracted wide attention of various researchers. The MOFs have the advantages of both inorganic materials and organic materials, and have made great progress so far, and many scholars at home and abroad make great contributions to this purpose, such as m.eddaodi, o.kazuya, a.zacaraiae, etc., and their research results all make research on the MOFs rapidly develop and achieve remarkable results.
The introduction of multifunctional metal centers is an important functional approach of metal-organic framework compounds, and rare earth metals are widely favored by scientists due to their unique 4f internal layer electronic structures. Rare earth metals are located in group IIIB of the periodic table, and the total number of 17 elements are not completely filled in the 4f inner electron shells, and the properties are very similar, but due to the difference of the electron numbers of the 4f inner electron shells, the rare earth metals have respective characteristics, particularly optical and magnetic properties. The coordination mode and the geometric configuration of the rare earth elements are variable, the control in the synthesis needs to be difficult for transition metals, but simultaneously, a richer network structure can be brought to a metal-organic framework compound. Rare earth elements tend to coordinate with oxygen (O) and nitrogen (N) atoms, particularly the organocarboxylic ligands, which are particularly prevalent in metal-organic framework materials of rare earths. The excellent optical, electric and magnetic properties also provide powerful conditions for the multi-functionalization of metal-organic framework compounds. In recent years, more and more metal organic framework compounds with rare earth metals as the center are synthesized, some of the compounds show good performances in the aspects of catalysis, adsorption, optics and magnetism, and particularly have wide application values in the aspects of small molecule fluorescence detection, cation detection, anion detection, temperature sensing, pH value and the like by taking rare earth metal-organic framework materials as fluorescence sensing materials.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a rare earth metal-organic framework material [ Dy ] for preparing a fluorescent detection material applicable to trace nitro explosives2(BDC)3(H2O)4]nThe method of (1).
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nThe preparation method comprises the following steps:
1) reacting dysprosium oxide with hydrochloric acid solution until the dysprosium oxide is completely dissolved, evaporating water after complete reaction to obtain solid DyCl3(ii) a Filtering on a filter, washing with water, washing with alcohol, and naturally drying to obtain powder solid DyCl3·6H2O；
2) Dissolving and uniformly mixing terephthalic acid by using N, N-dimethylformamide to obtain a solution A;
3) DyCl3·6H2Dissolving and uniformly mixing O by using N, N-dimethylformamide to obtain a solution B;
4) uniformly mixing the solution A and the solution B in a beaker A, and keeping for later use;
5) placing the N, N-dimethylformamide and the triethylamine in the beaker B, uniformly mixing, sealing the opening of the beaker through a preservative film, and keeping for later use;
6) firstly placing a beaker B in a beaker A, then placing the beaker A in an ultrasonic instrument, reacting under the ultrasonic condition to obtain a precipitate, finally filtering, washing and drying to obtain the rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]n。
As the rare earth metal-organic framework material [ Dy ] of the present invention2(BDC)3(H2O)4]nDyCl3·6H2The molar ratio of O, terephthalic acid and triethylamine is 1.5-1.7: 1: 1.4-1.6. The molar ratio of dysprosium oxide to HCl in the step 1) is 1: 5 to 7, and the molar concentration of the hydrochloric acid solution is 5.5 to 6.5 mol/L. Dissolving every 1g of terephthalic acid in the step 2) by using 80-100mL of N, N-dimethylformamide. DyCl per 1g in step 3)3·6H2O was dissolved with 10-20mL of N, N-dimethylformamide. In step 5), 5 to 15mL of N, N-dimethylformamide are mixed per 1mL of triethylamine. Adjusting the ultrasonic power to be 40-60W in the step 6), and adjusting the reaction time to be 1-30min under the ultrasonic condition in the step 6) and the reaction temperature to be 60-80 ℃.
The invention synthesizes the rare earth metal-organic framework material [ Dy ] taking Dy as a metal center and terephthalic acid as a ligand by a simple and rapid ultrasonic diffusion combined method2(BDC)3(H2O)4]n. The ultrasonic diffusion combined method has the advantages of short synthesis time, high efficiency, convenient operation and the like. We analyzed the structure of the sample by XRD and showed that the product obtained by this method was the target product. And the size and the shape of the synthesized material are regulated and controlled by controlling the ultrasonic time. The synthesized material has strong photoluminescence property, and the invention systematically studies the fluorescence sensitivity of the obtained material to trace nitro explosives (nitrobenzene, 2-nitrotoluene, 4-nitrotoluene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene). The results show that: with the increase of the volume of nitro explosives added, [ Dy2(BDC)3(H2O)4]nUntil quenched, indicating that the material has a strong sensitivity to nitro explosives.
Compared with the prior art, the invention also has the following advantages:
1) compared with the defects of complex processes, low yield, high pollution, energy waste and the like of most of the traditional methods for synthesizing the rare earth metal-organic framework material, the method can realize rapid synthesis and mass preparation of the rare earth metal-organic framework material, and has effective, rapid, simple and pollution-free preparation method and important practical significance.
2) The invention quickly synthesizes the rare earth metal-organic framework material [ Dy ] which takes rare earth element Dy as metal central ion and terephthalic acid as ligand by an ultrasonic diffusion method2(BDC)3(H2O)4]nAnd products with different shapes and sizes can be obtained by regulating and controlling the ultrasonic time.
3) The rare earth metal-organic framework material prepared by the invention has fluorescence sensitivity to five kinds of nitro explosives such as 4-nitrotoluene, 2, 4-dinitrotoluene, 2, 6-dinitrotoluene and the like, and has the characteristics of high response speed and strong sensitivity to the nitro explosives. By researching the fluorescence property of the sample, the nitro compound is found to have stronger fluorescence quenching effect on the sample, and the nitro compound has extremely important significance for developing fluorescent probes and fluorescent sensors applied to explosive detection in the future.
Drawings
The following examples and drawings show the rare earth metal-organic framework material [ Dy ] of the present invention2(BDC)3(H2O)4]nThe preparation method and the application are further detailed.
FIG. 1 is an XRD spectrum of the product prepared in example 1.
FIG. 2 is a scanning electron micrograph of the products obtained by controlling different ultrasonic times in example 1.
In the figure 3-5, 4-nitrotoluene, 2, 4-dinitrotoluene and 2, 6-dinitrotoluene with different concentrations are added with [ Dy2(BDC)3(H2O)4]nInfluence curve on change of fluorescence intensity in solution.
Detailed Description
Example 1
Rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nThe preparation method comprises the following steps:
1) 0.8952g (2.4mmol) of dysprosium oxide (Dy)2O3) Reacting with 2.4mL of 6mol/L hydrochloric acid solution in a water bath at 60 ℃ until the solution is completely dissolved, and evaporating water after complete reaction to obtain solid DyCl3. Filtering on a filter, washing with water and alcohol for multiple times, and naturally drying to obtain white powder solid DyCl3·6H2O。
2) 0.1118g (0.48mmol) of terephthalic acid was dissolved in 10mL of N, N-Dimethylformamide (DMF) and mixed well for use.
3) 0.3g (0.78mmol) of DyCl was weighed3·6H2O was dissolved in 5mL of N, N-Dimethylformamide (DMF) and mixed well for use.
4) And transferring the two solutions prepared in the step 2) and the step 3) into a 50mL beaker together, and fully shaking up and keeping the solution for later use.
5) And transferring 1mL of N, N-Dimethylformamide (DMF) and 0.1mL of triethylamine into a 25mL beaker, uniformly mixing, sealing the opening of the beaker by a preservative film, and keeping for later use.
6) Firstly placing a 25mL small beaker into a 50mL big beaker, then placing the 50mL big beaker into an ultrasonic instrument, adjusting the ultrasonic power to 50W, controlling the water bath temperature to be 70 ℃, respectively carrying out ultrasonic reaction for 5min, 10min, 15min and 20min to obtain white precipitates, finally filtering, washing with alcohol, and carrying out vacuum drying for 4h at 70 ℃.
In the figure 1, a-d are XRD spectrograms of products obtained by ultrasonic reaction for 5min, 10min, 15min and 20min in sequence. As shown in FIG. 1, the product rapidly synthesized by the ultrasonic diffusion method of the invention is exactly the target product [ Dy2(BDC)3(H2O)4]nThe rare earth metal-organic framework material is highly crystallized as seen from the powder diffraction peak of XRD.
According to the Debye-Scherrer formula:
where k is a constant (k ═ 0.89), λ is the wavelength (λ ═ 1.54184nm), and β and θ are the half-peak width and diffraction angle, respectively. The grain size calculated was consistent with that shown by the SEM.
FIG. 2 is a scanning electron microscope image of the product obtained by adjusting and controlling different ultrasonic times in example 1, and as can be seen from FIG. 2a, when the ultrasonic treatment is carried out for 5min, the product is in the form of small particles with uniform size distribution, the length is about 1 μm, and the diameter is about 0.2 μm; at 10min of sonication, the sample gradually increased in size, appearing in rod-like structures (FIG. 2b), about 2 μm in length and about 0.3 μm in diameter; when the ultrasound is continuously added for 15min, the appearance of the generated product tends to be more regular, the length of the rod-shaped product is gradually reduced, the diameter is increased, the distribution is more uniform, the rod-shaped product tends to be a sheet structure (figure 2c), the length is about 1 μm, and the diameter is about 0.5 μm; when the sonication time was increased to 20min, the product continued to increase in length and diameter, gradually growing into a massive structure (FIG. 2d), with a length of about 4 μm and a diameter of about 2 μm. This suggests that differences in sonication time can affect the morphology and size of the resulting product.
Example 2
Rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nFluorescence sensitivity study of
(1) Fluorescence sensitivity to 4-nitrotoluene
To further investigate the effect of 4-nitrotoluene on its fluorescence intensity, as shown in FIG. 3, when 1. mu.L of 0.1 mol/L4-nitrotoluene was added (v/v: 0.5 ‰), its fluorescence intensity decreased from 245a.u to 200a.u., and its fluorescence intensity decreased by 18.4%. The fluorescence intensity of the solution continues to decrease as the solution of 4-nitrotoluene is added. When 15. mu.L of 4-nitrotoluene was added (v/v: 7.5 ‰), the sample underwent fluorescence quenching
(2) Fluorescence sensitivity to 2, 4-dinitrotoluene
Continuing to examine the fluorescence sensitivity of the product to 2, 4-dinitrotoluene, as shown in FIG. 4, when 2. mu.L of 0.1 mol/L2, 4-dinitrotoluene (v/v: 1 ‰) was added, the fluorescence intensity decreased from the initial 230a.u to 180a.u., which was 21.7%. The addition of the 2, 4-dinitrotoluene solution continued to decrease the fluorescence intensity. When the amount is 22. mu.L (v/v: 11 ‰), significant fluorescence quenching is caused
(3) Fluorescence sensitivity to 2, 6-dinitrotoluene
Further examining the fluorescence sensitivity of the product to 2, 6-dinitrotoluene, as shown in FIG. 5, when 2. mu.L of 0.1 mol/L2, 6-dinitrotoluene (v/v: 1 ‰) was added, the fluorescence intensity decreased from the initial 245a.u to 185a.u., and the fluorescence intensity decreased by 24.5%. The addition of 2, 6-dinitrotoluene solution at 25. mu.L (v/v: 12.5%) results in a significant quenching of fluorescence
Nitro explosives (quenchers) and [ Dy ] according to the mechanism of interaction between an excited species and a quencher2(BDC)3(H2O)4]nFluorescence quenching effect is generated between the excited substances through resonance energy transfer effect, and donor ([ Dy)2(BDC)3(H2O)4]n) And the receptor (nitro-explosive) through dipole-dipole coupling. Transfer efficiency is related to a number of factors such as: the acceptor concentration and the average distance between the dipole centers of the donor and the acceptor are increased, the transfer efficiency is increased along with the decrease of the average distance along with the increase of the acceptor concentration, and when the donor is in an excited state, non-radiative transition is carried out to an energy level with lower energy due to the loss of resonance energy, so that [ Dy ] is generated2(BDC)3(H2O)4]nThe fluorescence intensity of (a) decreases with increasing concentration of nitro-explosives. Therefore, the rare earth metal-organic framework material [ Dy ] prepared by the invention2(BDC)3(H2O)4]nHas the characteristics of high response speed and strong sensitivity to nitro explosives. By researching the fluorescence property of the sample, the nitro compound is found to have stronger fluorescence quenching effect on the sample, and the nitro compound has extremely important significance for developing a fluorescent probe and a fluorescent sensor applied to explosive detection.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (1)
1. Rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nThe preparation method is characterized by comprising the following steps:
1) 0.8952g of dysprosium oxide Dy2O3Reacting with 2.4mL of 6mol/L hydrochloric acid solution in a water bath at 60 ℃ until the solution is completely dissolved, and evaporating water after complete reaction to obtain solid DyCl3(ii) a Filtering on a filter, washing with water and alcohol for multiple times, and naturally drying to obtain white powder solid DyCl3·6H2O；
2) Weighing 0.1118g of terephthalic acid, dissolving in 10mL of N, N-dimethylformamide DMF, and uniformly mixing for later use;
3) 0.3g of DyCl was weighed out3·6H2Dissolving O in 5mL of N, N-dimethylformamide DMF, and uniformly mixing for later use;
4) transferring the two solutions prepared in the step 2) and the step 3) into a 50mL beaker together, and fully shaking up and then keeping the solution for later use;
5) transferring 1mL of N, N-dimethylformamide DMF and 0.1mL of triethylamine into a 25mL beaker, uniformly mixing, sealing the opening of the beaker by a preservative film, and keeping for later use;
6) firstly placing a small beaker with the volume of 25mL in a big beaker with the volume of 50mL, then placing the big beaker with the volume of 50mL in an ultrasonic instrument, adjusting the ultrasonic power to 50W, controlling the water bath temperature to be 70 ℃, carrying out ultrasonic reaction for 5-20 min to obtain white precipitate, finally filtering, washing with alcohol, and carrying out vacuum drying at the temperature of 70 ℃ for 4h to obtain the rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]n；
Performing ultrasonic treatment for 5min to obtain small particles with uniform size distribution, length of 1 μm and diameter of 0.2 μm; performing ultrasonic treatment for 10min to generate product with gradually increased size and rod-like structure with length of 2 μm and diameter of 0.3 μm; performing ultrasonic treatment for 15min, wherein the shape of the generated product tends to be more regular, the length of the rod-shaped product is gradually reduced, the diameter of the rod-shaped product is increased, the distribution of the rod-shaped product is more uniform, the rod-shaped product tends to be of a sheet structure, the length of the rod-shaped product is 1 mu m, and the diameter of the rod-shaped product is 0.5 mu m; performing ultrasonic treatment for 20min to generate product with length and diameter of 4 μm and diameter of 2 μm, and gradually increasing to form block structure;
the rare earth metal-organic framework material [ Dy2(BDC)3(H2O)4]nThe fluorescent sensitivity performance of the fluorescent material is as follows:
when 1 mu L of 0.1 mol/L4-nitrotoluene is added (v/v: 0.5 per thousand), the fluorescence intensity of the fluorescent material is reduced from 245a.u to 200a.u., and the fluorescence intensity is reduced by 18.4%; continuously adding the 4-nitrotoluene solution, and continuously weakening the fluorescence intensity of the solution; when 15. mu.L of 4-nitrotoluene was added (v/v: 7.5 ‰), the sample was quenched for fluorescence;
when 2 mu L of 0.1 mol/L2, 4-dinitrotoluene (v/v: 1 per thousand) is added, the fluorescence intensity is reduced from the initial 230a.u to 180a.u., and the fluorescence intensity is reduced by 21.7 percent; continuously adding the 2, 4-dinitrotoluene solution, and continuously reducing the fluorescence intensity; when the addition amount is 22 mu L (v/v: 11 per thousand), obvious fluorescence quenching phenomenon can be caused;
when 2 mu L of 0.1 mol/L2, 6-dinitrotoluene (v/v: 1 per thousand) is added, the fluorescence intensity is reduced from the initial 245a.u to 185a.u., and the fluorescence intensity is reduced by 24.5 percent; the addition of 2, 6-dinitrotoluene solution, when added in an amount of 25. mu.L (v/v: 12.5 ‰), leads to a pronounced quenching of fluorescence.
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