CN110330666B - Rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, preparation method and application - Google Patents
Rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, preparation method and application Download PDFInfo
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
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- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
- G01N2021/6432—Quenching
Abstract
The invention discloses a rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, a preparation method and application, and belongs to the technical field of rare earth-organic framework material preparation, wherein the preparation method comprises the step of mixing 2- (4-pyridyl) terephthalic acid (H)2pta) is dissolved in distilled water, and rare earth nitrate Eu (NO) is added3)2·6H2O phase is filled into a polytetrafluoroethylene lining, then the polytetrafluoroethylene lining is placed into an oven, the temperature is kept constant at 150 ℃ and 170 ℃ for 24h, and then the temperature is reduced to room temperature at the speed of 2-4 ℃/h to obtain a target complex, and the complex can be used for detecting Fe3+The luminescence experiment shows that the quenching efficiency can reach more than 98 percent, and the quenching efficiency is higher than that of Fe3+The lowest detection line is 3.5 multiplied by 10‑5mol/L, the invention can prepare products with higher purity and yield in a short time.
Description
Technical Field
The invention relates to the technical field of metal-organic framework material preparation, in particular to a rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, a preparation method and application.
Background
Luminescent metal-organic frameworks (LMOFs) are receiving increasing attention as an effective sensing material due to their abundant structure, outstanding optical properties, and longer emission wavelength. Among them, rare earth metal-organic frameworks (Ln-MOFs) have the advantages of high luminescent quantum yield, strong and narrow emission band, long luminescent lifetime, etc., and have attracted great interest and extensive research. The comprehensive literature reports that most of rare earth metal-organic framework materials with fluorescence sensing are synthesized by aromatic carboxylic acid or pyridine carboxylic acid ligands, and have wide prospects in practical applications such as biomedicine, small molecule detection, ion detection and the like.
The solvothermal method is a method in which a substance having poor solubility is dissolved in a solvent at high temperature and high pressure, and the resultant is reacted with another substance under a critical condition to produce a target compound. The method can directly obtain the target object with high purity, has short reaction time, and is widely applied to the fields of organic and inorganic synthesis, single crystal growth, material preparation and the like, thereby being valued by chemists and pharmacologists.
At present, the synthesis method of the complex has long reaction time and generally low yield. For example, Zhao Jian et al (RSC Advances,2015,5,14897) reacted at 170 ℃ for 72h under hydrothermal conditions with a cooling rate of 10 ℃/h to give the complex { [ Cd (pta) (1, 4-bdb)0.5]·2H2O}nThe yield is 59%; anfengqin and the like (New Journal of Chemistry,2019,43,4800) react for 72 hours at 160 ℃ under the hydrothermal condition to obtain a complex { [ Cd (pta)]H2O)}nThe yield was 60%.
Disclosure of Invention
The invention aims to provide a rare earth fluorescent sensing material with short synthesis time and high yield so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of a rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, which comprises the following steps:
(1) dissolving 2- (4-pyridyl) terephthalic acid in distilled water, and adding rare earth nitrate to obtain a mixed solution;
(2) putting the mixed solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, and putting the reaction kettle into an oven for reaction;
(3) then cooling to room temperature to obtain the target product.
Preferably, the rare earth nitrate in step (1) is Eu (NO)3)2·6H2O。
Preferably, 2- (4-pyridyl) terephthalic acid (H) in step (1)2pta) and Eu (NO)3)2·6H2The molar ratio of O is 1: 1-3: 1.
Preferably, 2- (4-pyridyl) terephthalic acid (H) in step (1)2pta) and Eu (NO)3)2·6H2The molar ratio of O is 2: 1.
Preferably, the step (2) is carried out in an oven at a constant temperature of 150 ℃ and 170 ℃ for 24 h.
Preferably, the cooling rate in step (3) is 2-4 ℃/h.
The invention also provides a rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid prepared by the preparation method, and the general structural formula of the fluorescent sensing material is as follows: [ Eu ] as a source of electric potential4(pta)5(Hpta)2(H2O)4]·10H2And O. Elemental analysis calculated C, 42.81%; h, 3.10%; n, 3.84%; the experimental value is C, 42.76%; h, 3.02%; and N,3.70 percent. Infrared analysis IR (KBr, cm)-1): 3394(vs),1604(vs),1375(vs),1573(s),1534(vs),1418(s),1290(m), 865(m),777(m),531(w),625(w),558(w)。
The invention also provides the rare earth metal-organic framework fluorescent sensing material based on the 2- (4-pyridyl) terephthalic acid for detecting Fe3+The use of (1).
The invention discloses the following technical effects:
the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid with high purity and yield can be prepared in a short time by using water as a solvent and using a hydrothermal method, and the yield is over 80%.
The fluorescence intensity of the rare earth metal-organic framework fluorescence sensing material based on 2- (4-pyridyl) terephthalic acid is related to Fe3+The concentration is from 0 μ L to 42Increasing 0 μ L and gradually decreasing until the fluorescence intensity is completely quenched, wherein the quenching efficiency can reach more than 98%, and the lowest detection line is 3.5 × 10-5mol/L, can solve the traditional Fe3+The detection method has low sensitivity (detection limit is 10)-3mol/L), long response time and the like.
The fluorescence sensing material has the advantages of high crystallinity, large crystal size, good stability, simple synthesis process and high yield.
Drawings
FIG. 1 is a theoretical X-ray powder diffraction pattern prepared in example 1 of the present invention and an X-ray powder diffraction Pattern (PXRD) of the prepared rare earth metal-organic framework fluorescent sensing material;
FIG. 2 is a crystal three-dimensional structure diagram of a rare earth metal-organic framework fluorescent sensing material of example 1;
FIG. 3 is the fluorescence emission intensity of the rare earth metal-organic framework fluorescence sensing material of example 1 in different metal ion aqueous solutions;
FIG. 4 shows the rare earth metal-organic framework fluorescent sensing material of example 1 in different Fe3+Graph of fluorescence intensity in aqueous solution of concentration, in which Fe is represented by upper to lower curves in FIG. 43+The concentration of the aqueous solution is 0. mu.L, 30. mu.L, 60. mu.L, 90. mu.L, 120. mu.L, 150. mu.L, 180. mu.L, 210. mu.L, 240. mu.L, 270. mu.L, 300. mu.L, 330. mu.L, 360. mu.L, 390. mu.L, 420. mu.L;
FIG. 5 shows the rare earth metal-organic framework fluorescent sensing material of example 1 of the present invention at low Fe3+A Stern-Volmer line plot at concentration;
FIG. 6 is a graph of the cycle number of the fluorescence intensity of the rare earth metal-organic framework fluorescent sensing material in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
0.0122g (0.05mmol) of 2- (4-pyridyl) terephthalic acid (H)2pta) was dissolved in 6mL of distilled water, after which 0.0117g (0.025mmol) of Eu (NO) was added3)3·6H2O，H2pta and Eu (NO)3)3·6H2Adding the mixture into a polytetrafluoroethylene inner lining in a 15mL stainless steel reactor, sealing, putting into a temperature-controlled oven, heating from room temperature to 160 ℃ within 60min, reacting at the constant temperature of 160 ℃ for 24h, cooling to room temperature at the cooling rate of 3 ℃/h, finally washing the product with distilled water, and naturally drying to obtain the target product with the yield of 85%.
FIG. 1 is a powder diffraction pattern of the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid prepared in this example, all diffraction peaks are consistent with simulated crystal data, which shows that the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid has good solvent stability; FIG. 2 is a crystal three-dimensional structure diagram of the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid; FIG. 3 shows the emission intensity of the complex in different metal ion aqueous solutions, showing that the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid is paired with Fe3+Has fluorescence quenching effect and can well identify Fe3+(ii) a FIG. 4 shows the complex in different Fe3+Fluorescence intensity profile in aqueous solution of concentration; FIG. 5 shows that the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid is in low Fe3+Stern-Volmer linear graph under concentration, FIG. 5 shows that rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid is in low Fe3+Has good linear relation under concentration, and the detection limit is 3.5 multiplied by 10-5mol/L; FIG. 6 is a graph of cycle times of fluorescence intensity of rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, and after 5 cycles, the fluorescence intensity is basically kept unchanged and has good stability.
Example 2
0.0122g (0.05mmol) of 2- (4-pyridyl) terephthalic acid (H)2pta) was dissolved in 6mL of distilled water, and 0.0233g (0.05mmol) of Eu (NO) was added3)3·6H2O，H2pta and Eu (NO)3)3·6H2Adding the mixture into a polytetrafluoroethylene inner lining in a 15mL stainless steel reactor, sealing, putting the mixture into a temperature-controlled oven, heating the mixture from room temperature to 150 ℃ within 60min, reacting at the constant temperature of 150 ℃ for 24h, cooling the mixture to room temperature at the cooling rate of 4 ℃/h, finally washing the product with distilled water, and naturally drying to obtain a target product with the yield of 82%.
Example 3
0.0122g (0.05mmol) of 2- (4-pyridyl) terephthalic acid (H)2pta) was dissolved in 6mL of distilled water, after which 0.0093g (0.02mmol) of Eu (NO) was added3)3·6H2O, i.e. H2pta and Eu (NO)3)3·6H2Adding the mixture into a polytetrafluoroethylene inner lining in a 15mL stainless steel reactor, sealing, putting the mixture into a temperature-controlled oven, heating the mixture from room temperature to 170 ℃ within 60min, reacting at the constant temperature of 170 ℃ for 24h, cooling the mixture to room temperature at the cooling rate of 2 ℃/h, finally washing the product with distilled water, and naturally drying to obtain a target product with the yield of 80%.
Example 4
The only difference from example 1 is that the solvents are water and CH3Mixed solvent of CN, water and CH3CN is 1:2, and the target compound is obtained by a solvothermal method with the yield of 62%.
Example 5
The same as example 1 except that the solvent was a mixed solvent of water and ethanol in a molar ratio of 1:2, the solvothermal method gave the objective compound in a yield of 65%.
Example 6
The same as example 1 except that the oven reaction temperature was 120 deg.c, the objective compound was obtained in 64% yield.
Example 7
The same as example 1 except that the oven temperature reaction time was 12 hours, the objective compound was obtained in 58% yield.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (5)
1. A preparation method of a rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid is characterized by comprising the following steps:
(1) dissolving 2- (4-pyridyl) terephthalic acid in distilled water, and adding rare earth nitrate to obtain a mixed solution, wherein the rare earth nitrate is Eu (NO)3)3·6H2O, 2- (4-pyridyl) terephthalic acid and Eu (NO)3)3·6H2The molar ratio of O is 1: 1-3: 1;
(2) putting the mixed solution obtained in the step (1) into a reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into a drying oven for reaction, and reacting in the drying oven at a constant temperature of 150-170 ℃ for 24 hours;
(3) then cooling to room temperature to obtain the target product.
2. The method for preparing rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid according to claim 1, wherein the 2- (4-pyridyl) terephthalic acid and Eu (NO) in step (1)3)3·6H2The molar ratio of O is 2: 1.
3. The preparation method of the rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid as claimed in claim 1, wherein the cooling rate in the step (3) is 2-4 ℃/h.
4. A rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid, which is characterized by being prepared by the preparation method of any one of claims 1 to 3.
5. The rare earth metal-organic framework fluorescent sensing material based on 2- (4-pyridyl) terephthalic acid as claimed in claim 4 for detecting Fe3+The use of (1).
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