CN112480426B - Metal organic framework material for detecting copper ions and pH, and preparation method and application thereof - Google Patents
Metal organic framework material for detecting copper ions and pH, and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a rare earth metal post-synthesis modified metal organic framework material for detecting copper ions and pH (potential of hydrogen) with long wavelength, a preparation method and application thereof, and belongs to the technical field of fluorescent probe materials. The fluorescent probe material is prepared in water under the condition of stirring at room temperature, so compared with the prior art, the fluorescent probe material has the following remarkable advantages: the fluorescent probe has the advantages of simple preparation process, environmental protection and energy saving. The fluorescent probe material prepared by the process has high purity, strong stability, good selectivity and high sensitivity, can be observed by naked eyes in fluorescence change, and is an ideal metal organic framework fluorescent probe material for detecting copper ions and pH.
Description
Technical Field
The invention relates to a copper ion identified metal organic framework material fluorescent probe, in particular to a rare earth metal post-synthesis modified metal organic framework material and a preparation method and application thereof.
Background
With the development of industrialization, more and more heavy metal ions are discharged into water, causing serious environmental pollution. The copper element is a trace element necessary for human body, is an active center of some enzymes, and plays an important role in body functions. In the human body, too low copper content can cause decrease of hematopoiesis function, increase of cholesterol, corresponding decrease of some synthetase components and the like, and even can cause coronary heart disease. However, if copper is excessively taken, the activity of intracellular enzymes in the human body is inhibited, resulting in copper poisoning of the human body, gastrointestinal symptoms and acute renal tubular necrosis of the kidney, cirrhosis, hemolysis, and the like. The U.S. environmental protection agency specifies a maximum allowable copper concentration of 1.3 ppm. The World Health Organization (WHO) recommends Cu in drinking water2+The content of (A) is about 2.0mg/L, and the average intake of copper per day of an adult is regulated not to exceed 10-12mg, so that the establishment of a full-speed, simple and sensitive method for measuring copper ions is of great significance. At present, the methods for measuring copper ions mainly include electrochemical methods, atomic absorption methods, atomic emission methods, chromatographic methods, and the like. Compared with other copper ion determination methods, the copper ion fluorescent probe determination method established based on optical signal change has attracted wide attention due to the advantages of high sensitivity, good selectivity and short reaction time.
In the aspects of environmental analysis, chemical reaction process control, biomedicine and the like, pH is an important parameter, and the determination of the pH value has very important significance. Currently, pH measurement methods mainly include an indicator method, a glass electrode method, an optical sensor method, and the like. The pH probe assay method established based on the change of optical signals has drawn much attention due to its advantages of high sensitivity, good selectivity, and short reaction time, as compared to other pH assay methods. Some pH fluorescent probes have been reported, but most pH fluorescent molecular probes have a wide detection range, which reduces the sensitivity of the probes. At present, there are few reports on fluorescent probes in low pH and high pH ranges. Therefore, the preparation of the pH fluorescent probe with narrow detection range and higher sensitivity has important significance.
As a novel crystalline porous material, a Metal Organic Framework (MOFs) has excellent properties such as high porosity, super-large specific surface area, porosity, order, adjustable pore channel structure and the like, so that the MOFs has excellent performance and application prospects in the aspects of adsorption, separation, catalysis, sensing, ion conduction and the like. At present, a great deal of literature reports that MOFs are used as fluorescent probes for detecting metal ions, biological small molecules, organic volatile solvents and the like. In the aspect of metal ion measurement, the MOFs fluorescent probe material not only can detect the concentration of metal ions, but also has the advantages of adsorption and enrichment compared with other MOFs fluorescent probes, so that the MOFs fluorescent probe material has higher sensitivity in the aspect of ion detection and has lower detection limit. At present, reports on copper ion MOFs fluorescent probe (J.Luo, B.S.Liu, X.R.Zhang, et al.A novel fluorescent sensor with high fluorescence response of Cu) have been made2+ based on Eu3+post-modified metal-organic framework in aqueous media,J.Mol. Struct.,2020,1202,12734；X.X.Peng,G.M.Bao,Y.F.Zhong,et al.Highly selective detection of Cu2+in aqueous media based on Tb3+-functionalized metal-organic frame.Spectrochim.acta A,2020,240,118621; xu, Q.Y.Meng, Q.Cao, et al.Selective Sensing of hopper Ions by Mesoporous Metal-Organic Framework nanoovils. anal. chem.2020,92, 2201-. However, the above MOFs fluorescent probe is complicated to synthesize, and reacts in a toxic solvent under high temperature and high pressureThe preparation method is carried out in a kettle, so that the development of the preparation method of the copper ion MOFs probe material which is rapid, convenient and environment-friendly has important significance.
Disclosure of Invention
Based on the defects of the prior art, the invention aims to provide a rapid, simple, convenient and pollution-free preparation process of a copper ion MOFs probe material, and the process is used for detecting copper ions and hydroxyl ions in a water body. The method for preparing the rare earth metal europium post-modified metal organic framework material by stirring the rare earth metal europium post-modified metal organic framework material in the environment-friendly solvent water or methanol at room temperature has the advantages of simple preparation process, environmental friendliness, high purity and high stability of the synthesized luminous MOFs material, and has the advantages of rapidness, simplicity and convenience in the aspect of detection of copper ions and hydroxyl ions and high sensitivity.
In order to achieve the experimental purpose, the technical scheme of the invention is as follows:
(1) histidine, 2-methylimidazole and Zn (NO)3)2·6H2Mixing O, stirring for 24 hours at room temperature, stopping reaction, centrifuging, washing and drying to obtain a white solid powder product 1;
(2) weighing a certain amount of the product 1 obtained in the step (1), ultrasonically dispersing the product in water, and adding a certain amount of Eu (NO)3)3·6H2O, stirring for 30 minutes at room temperature, and then centrifuging, washing and drying to obtain a product 2;
(3) weighing a certain amount of the product 2 obtained in the step (2), ultrasonically dispersing the product into water, adding a certain amount of molecular 2-thenoyltrifluoroacetone (Htta) capable of being used as antenna molecules to excite europium ions to emit light, stirring the mixture at room temperature for 30 minutes, and then centrifuging, washing and drying the mixture to obtain the long-wavelength metal organic framework material with copper ion identification detection.
In order to achieve the above experimental purpose, another technical solution of the present invention is as follows: the metal organic framework material prepared by the method is used for detecting copper ions and pH.
In order to achieve the above experimental purpose, another technical solution of the present invention is as follows: the application of the metal organic framework material for detecting copper ions and pH is based on the application of the metal organic framework material after rare earth metal synthesis modification in the aspect of selective recognition of copper ions.
In order to achieve the above experimental purpose, another technical solution of the present invention is as follows: the application of the metal organic framework material for detecting copper ions and pH is based on the application of the metal organic framework material modified by rare earth metal post-synthesis in the aspect of detecting hydroxide ions.
The application of the europium post-modified metal organic framework material obtained by the preparation process is that the metal organic framework material fluorescent probe is used for high-selectivity and high-sensitivity identification of copper ions and pH value in water.
The invention has the beneficial effects that:
compared with the prior art, the invention has the following remarkable advantages: the metal organic framework material which can be used for high-selectivity and high-sensitivity identification of copper ions is prepared in water under the condition of stirring at room temperature for the first time, and the preparation method of the copper ion and pH MOFs fluorescent probe material provided by the invention is synthesized in environment-friendly solvent water and methanol, and toxic and harmful byproducts can not be generated, so that the preparation process is green and environment-friendly;
(1) according to the preparation method of the copper ion and pH MOFs fluorescent probe material, complex equipment such as a high-pressure reaction kettle, a constant temperature box and the like is not needed, and only a common reaction vessel and a simple stirring device are needed, so that the preparation process is low in cost;
(2) the preparation method of the copper ion MOFs and pH fluorescent probe material provided by the invention is prepared at room temperature, and a target product can be obtained without heating, so that the preparation process is mild in condition and simple and convenient to operate;
(3) the copper ion and pH metal organic framework fluorescent probe material obtained by the preparation process provided by the invention has strong stability, the fluorescence intensity of suspension prepared in water cannot be attenuated for several days, and the complete framework structure of the suspension is still maintained.
(4) The copper ion metal organic framework fluorescent probe material obtained by the preparation process provided by the invention emits long-wavelength red light, has strong luminescence, and can identify copper ions by observing the luminescence intensity through naked eyesAnd (4) concentration. In addition, Ni is not accepted in the detection of copper ions and pH2+、Cu2+、Cr2+、Na+、K+、Mg2+、Ca2+、Mn2+、 Al3+、、Zn2+、Ba2+The interference of plasma metal ions, therefore, the fluorescent probe has the advantage of higher selectivity. In the process of detecting copper ions and pH, the fluorescence intensity of the probe material can be quickly weakened after a trace amount of copper ion aqueous solution is added, so that the probe has quick response and high sensitivity.
Drawings
In order to facilitate further understanding of the present application, some of the specification figures are provided. The contents of the present application are explained by taking histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone as an example, but the present application is not limited thereto.
FIG. 1 is a powder X-ray diffraction pattern of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone, simulated ZIF-8, histidine @ ZIF-8 and histidine @ ZIF-8/Eu, prepared according to the present invention;
FIG. 2 is a scanning electron micrograph and an EDS spectrum of histidine @ ZIF-8/Eu prepared in the present invention;
FIG. 3 is an X-ray photoelectron spectrum of histidine @ ZIF-8 and histidine @ ZIF-8/Eu, prepared in the present invention;
FIG. 4 is a graph showing the color of solid powders of histidine @ ZIF-8/Eu (left) and histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone (right) prepared in the present invention emitted under the irradiation of an ultraviolet lamp at 365 nm;
FIG. 5 shows a diffusion solution of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone +3.0uM Cu in water according to the present invention2+Luminescence pattern under excitation of ultraviolet lamp 365nm wavelength (left panel); (iv) diffusion luminescence of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone in water (right panel);
FIG. 6 is a time-varying fluorescence emission spectrum of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone prepared in the present invention;
FIG. 7 is a change of fluorescence spectrum of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone prepared in the present invention with increasing copper ion concentration;
FIG. 8 is a response diagram of the fluorescent probe material histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone of the copper ion MOFs probe material prepared in the present invention to different metal ions, wherein the concentration of copper ions is 2.0uM, and the concentration of other metal ions is 0.1 mM;
FIG. 9 is a graph of luminescence from histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone in a pH 11.80 diffusion solution under excitation of an ultraviolet lamp at 365nm in accordance with the present invention (left panel); (iv) diffusion luminescence of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone in water (right panel);
FIG. 10 shows the change of fluorescence spectrum of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone prepared in the present invention with the increase of hydroxyl concentration.
Detailed Description
The contents of the present invention will be further clarified by the following examples, which are not intended to limit the scope of the present invention, and various modifications that can be made by those skilled in the art without inventive efforts based on the technical solution of the present invention are still within the scope of the present invention.
Example 1
Synthesis of histidine @ ZIF-8
465mg of histidine are dissolved in 40mL of distilled water, and 0.25mL of triethylamine is added dropwise and stirred for 2 minutes. Weighing 1.785g Zn (NO)3)·6H2O was dissolved in 80mL of water. 1.72g of 2-methylimidazole are weighed out and dissolved in 60mL of distilled water. Mixing the prepared histidine solution, 2-methylimidazole and Zn (NO)3)·6H2And O is mixed and stirred for 24 hours, and then the mixture is filtered, washed by ethanol and dried to obtain the histidine @ ZIF-8 doped target product.
Example 2
Synthesis of histidine @ ZIF-8/Eu
100.0mg histidine @ ZIF-8 was weighed out and diffused into 20.0mL distilled water, followed by 300mg Eu (NO)3)·6H2And O, stirring for 0.5 hour at room temperature, then centrifugally separating, washing with water and ethanol in sequence, and vacuum drying at room temperature to obtain histidine @ ZIF-8/Eu post-modified europium ion.
Example 3
Synthesis of histidine @ ZIF-8/Eu/2-thenoyl trifluoroacetone
Weighing 50.0mg of histidine @ ZIF-8/Eu, diffusing the histidine @ ZIF-8/Eu into 10.0mL of distilled water, then adding 100.0mg of 2-thenoyl trifluoroacetone, stirring for 0.5 hour at room temperature, then carrying out centrifugal separation, washing with water and ethanol in sequence, and carrying out vacuum drying at room temperature to obtain the histidine @ ZIF-8/Eu/2-thenoyl trifluoroacetone for post-modifying europium ions.
Example 4
The solid powder materials of histidine @ ZIF-8/Eu and histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone were observed to emit light under the irradiation of an ultraviolet lamp at a wavelength of 365nm, and the results are shown in FIG. 4. Histidine @ ZIF-8/Eu did not emit light, while histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone emitted characteristic red light of europium ions and had high luminous intensity. In addition, histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone was diffused into water, and observed to emit light under irradiation of an ultraviolet lamp at a wavelength of 365nm without adding copper ions and with adding 3.0uM of copper ions, and the results are shown in FIG. 5. The histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone aqueous diffusion solution shines a red light, while the fluorescence is completely quenched by the addition of 3.0uM copper ions, which also indicates that the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone prepared in this application recognizes the concentration of copper ions by naked eyes.
Histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone photostability experiment. The method comprises the following specific operations: weighing 5.0mg of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material, ultrasonically diffusing the probe material into 5.0mL of water to prepare 1.0mg/L of test solution, then testing the emission spectrum once a day, ultrasonically mixing the emission spectrum uniformly before each test, and continuously monitoring for 9 days, wherein the experimental result is shown in figure 6. The result shows that the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone prepared by the method has good light stability, and the emission signal cannot be weakened along with the prolonging of time.
The fluorescence spectrum change of the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material under the condition of copper ions with different concentrations is shown in figure 7. The method comprises the following specific operations: weighing 5.0mg histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material, and ultrasonically diffusing the fluorescent probe material to 5.0mLSequentially adding different amounts of Cu into water2+After each addition, the mixture is fully and uniformly mixed, and then the change of an emission spectrum is measured by taking 365nm as an excitation wavelength. As can be seen from the fluorescence spectrogram, the fluorescence intensity is quenched sharply along with the increase of the concentration of the copper ions, which indicates that the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material has the capability of identifying the copper ions by fluorescence. In addition, the detection limit of copper ions was calculated to be 42nM (detection limit is 3 × blank standard deviation/slope, blank standard deviation is standard deviation of 11 blank samples) according to the linear regression equation, which indicates that the fluorescent probe has high sensitivity. The mechanism of detecting the copper ions by using histidine @ ZIF-8/Eu/2-thenoyl trifluoroacetone is that the copper ions are coordinated with histidine in the histidine @ ZIF-8/Eu/2-thenoyl trifluoroacetone, and the copper ions have a spinning single electron and can quench luminescence.
The histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material has strong anti-interference capability. The method comprises the following specific operations: weighing 5.0mg of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material, ultrasonically diffusing the probe material into 5.0mL of water, preparing 12 parts of 1.0mg/L test solution by adopting the same experimental operation, measuring a fluorescence emission spectrum of each test solution, then respectively adding different metal ions (0.1mM) with the concentration 50 times that of copper ions, measuring the emission spectra, and finally calculating the ratio of the fluorescence intensity after adding the metal ions to the fluorescence intensity of a blank test solution, wherein the result is shown in figure 8. Experimental results show that the fluorescence of the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material is remarkably quenched after copper ions are added, and other metal ions even being 50 times of the concentration of the copper ions cannot cause remarkable change of fluorescence spectrum, so that the probe material prepared in the application has strong capability of selectively identifying the copper ions.
Example 5
Histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone was diffused into water, and emission was observed under irradiation of an ultraviolet lamp at a wavelength of 365nm without adding hydroxyl group and at a pH of 11.80, and the results are shown in FIG. 9. When a trace amount of hydroxyl is added, the luminescence can be quenched sharply.
The fluorescence spectrum change of the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material added with hydroxide radicals with different concentrations is shown in figure 10. The method comprises the following specific operations: weighing 5.0mg of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material, ultrasonically diffusing the probe material into 5.0mL of water, sequentially adding different amounts of hydroxide ions, fully and uniformly mixing the hydroxide ions after each addition, and measuring the change of an emission spectrum by taking 365nm as an excitation wavelength, wherein the result is shown in a figure 10. As can be seen from the fluorescence spectrogram, the fluorescence intensity is quenched sharply along with the increase of the concentration of the hydroxyl, which indicates that the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone fluorescent probe material has the capability of identifying the hydroxyl by fluorescence. As can be seen from a graph of the change of a fluorescence spectrum along with pH, the histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone prepared by the method has the advantages of narrow response range and high sensitivity. The mechanism of detecting hydroxide radical by histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone is mainly because the change of pH can influence the coordination capacity of 2-thenoyltrifluoroacetone and europium ions, thereby influencing the luminous capacity of histidine @ ZIF-8/Eu/2-thenoyltrifluoroacetone.
Comparative example
At present, reports about copper ion MOFs fluorescent probes are available. For example, Luo et al prepared MOFs material having characteristic emission spectrum of europium ion by introducing europium ion into MIL-116 skeleton by post-synthesis modification method and used it for copper ion detection, with detection limit of 0.88uM (J.Luo, B.S.Liu, X.R.Zhang, et al. A novel fluorescence sensor with high reactivity of Cu2+based on Eu3+post-modified metal-organic frame in aqueous media, j.mol.struct.,2020,1202,127347). Peng et al introduced the terbium ion into UIO-66- (COOH)2MOFs fluorescent probe material with a metal terbium characteristic emission spectrum is prepared on a framework, and the detection limit of the probe is 0.23uM (X.X.Peng, G.M.Bao, Y.F. Zhong, et al.high selectivity detection of Cu2+in aqueous media based on Tb3+-functionalized metal-organic frame. Spectrochim. acta A,2020,240, 118621). Xu et al hydrothermally synthesized PCN-222MOFs materials and used for detecting copper ions with detection limits of 50nM (Z.Y.Xu, Q.Y.Meng, Q.Cao, et al.Selective sensing ofcoppers by mesoporous metallic-organic framework nanoovils, anal, chem.2020,92, 2201-. The reported copper ion MOFs fluorescent probe materials are prepared in a toxic solvent and a high-temperature high-pressure reaction kettle by adopting hydrothermal synthesis and complex synthesis.
In addition, there are few reports of metal-organic framework probe materials for pH detection (P.das, S.K.Manual. Nanoporus Zn-based metallic organic framework nanoparticles for fluorescent pH sensing and for thermochromism. ACS appl. Nano mater, 2020,3,9480-3+post-synthetic modification of a metal-organic frame, Ind. Eng. chem. Res.,2020,59, 1764-1771). The reported copper ion MOFs fluorescent probe materials are prepared in a toxic solvent and a high-temperature high-pressure reaction kettle by hydrothermal synthesis, are complex in synthesis and have wide pH response range. The probe provided by the invention is simple and convenient to synthesize, green and environment-friendly, has higher sensitivity in the aspect of pH detection, and can cause the rapid change of the luminescence of the probe material due to the tiny change of the hydroxide concentration.
The invention is not limited to the specific technical solutions described in the above embodiments, and all technical solutions formed by equivalent substitutions are within the scope of the invention as claimed.
Claims (4)
1. A preparation method of a metal organic framework material for detecting copper ions and pH is characterized by comprising the following steps: the method comprises the following steps:
(1) histidine, 2-methylimidazole and Zn (NO)3)2·6H2Mixing O, stirring at room temperature for 24 hours, stopping reaction, centrifuging, washing and drying to obtain a white solid powder product 1;
(2) weighing a certain amount of the product 1 obtained in the step (1), ultrasonically dispersing the product in water, and adding a certain amount of Eu (NO)3)3·6H2O, stirring for 30 minutes at room temperature, and then centrifuging, washing and drying to obtain a product 2;
(3) weighing a certain amount of the product 2 obtained in the step (2), ultrasonically dispersing the product into water, adding a certain amount of 2-thenoyltrifluoroacetone, stirring the mixture at room temperature for 30 minutes, and then centrifuging, washing and drying the mixture to obtain the long-wavelength metal organic framework material with copper ion identification detection.
2. A metal organic framework material for copper ion and pH detection prepared according to the method of claim 1.
3. The use of metal organic framework material for copper ion and pH detection according to claim 2, characterized in that: the application of the metal organic framework material based on post-synthesis modification of rare earth metal in the aspect of selective recognition of copper ions.
4. The use of metal organic framework material for copper ion and pH detection according to claim 2, characterized in that: the application of the metal organic framework material based on post-synthesis modification of rare earth metal in the aspect of detecting hydroxide ions.
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| CN104672476A (en) * | 2015-01-26 | 2015-06-03 | 江苏大学 | Preparation method of rare-earth fluorescent molecularly imprinted membrane and application of rare-earth fluorescent molecularly imprinted membrane |
| CN109265704A (en) * | 2018-11-29 | 2019-01-25 | 绍兴文理学院 | A kind of efficient method for preparing ZIF-8 material |
| CN111808295A (en) * | 2020-08-06 | 2020-10-23 | 西华师范大学 | Double-ligand europium-based metal organic framework material and preparation method and application thereof |
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