CN111269434B - Preparation of two-dimensional Cu-MOF nanosheet and application of nanosheet in fluorescence detection of TNP - Google Patents
Preparation of two-dimensional Cu-MOF nanosheet and application of nanosheet in fluorescence detection of TNP Download PDFInfo
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Abstract
The invention discloses a preparation method of a two-dimensional Cu-MOF nanosheet and application of the nanosheet in fluorescence detection of TNP (trinitrotoluene), which comprises the steps of completely dissolving copper chloride and polyvinylpyrrolidone in ultrapure water, dropwise adding an aqueous sodium hydroxide solution, dropwise adding an aqueous ascorbic acid solution, centrifuging to obtain a first product, and washing to obtain a cuprous oxide nanocube; dispersing the cuprous oxide nanocubes in an ethanol solution to obtain a mixed solution; 2-amino terephthalic acid is completely dissolved in N, N-dimethylformamide to obtain an organic phase solution; and adding the mixed solution into an organic phase solution, standing, centrifuging to obtain a second product, washing, removing the solvent, and drying to obtain the two-dimensional Cu-MOF nanosheet. The nanosheet is applied to fluorescence detection of TNP. The nanosheet synthesized by the solvothermal method has ultrathin thickness, directional growth and excellent crystallinity, and the nanosheet fluorescent probe has good stability, is easy to store and has good selectivity on TNP.
Description
Technical Field
The invention belongs to the technical field of fluorescence detection, and relates to a preparation method of a two-dimensional Cu-MOF nanosheet; the invention also relates to application of the fluorescent probe in fluorescence detection of TNP.
Background
The rapid, high-sensitivity and high-selectivity determination of high-energy explosives has become one of the most urgent problems for national security, military application, forensic investigation and mine analysis. 2,4, 6-Trinitrophenol (TNP), also known as picric acid, is mainly used in the fields of explosives, acid dyes, fireworks, pesticides, glass, leather industry and the like. TNP has high toxicity and may damage soil and water environment. In addition, the medicine can enter human body through the contact of mouth, nose, skin and the like, and causes chronic poisoning, and in severe cases, the medicine can cause peripheral neuritis, bladder irritation symptoms and liver and kidney damage. Therefore, the selective detection and the sensitive detection of TNP in soil and water bodies have great significance for tracking buried explosives and monitoring the environment nearby an industrial area.
The two-dimensional metal organic framework layer material has ultrathin atomic layer thickness and strong in-plane covalent bond effect, and shows excellent flexibility, mechanical strength and optical transparency. And secondly, the two-dimensional material has a large transverse plane size and can keep a certain atom thickness, so that the two-dimensional metal-organic framework layer material has a large specific surface area. The atoms with highly exposed surface provide possible means of surface modification and functionalization, element doping or atom defect and the like to easily regulate and control the material. Therefore, the two-dimensional metal organic framework material has wide application prospect in the fields of catalysis, separation, sensing, imaging and the like.
Currently, on-site monitoring for high energy explosives is usually done with police dogs or with expensive, complex, inconvenient to carry precision instruments. It is worth noting that while TNP is more explosive than TNT and is widely used in the field of rocket fuel, paints, fireworks, matches, glass, leather, etc., TNP measurements are less attractive. Therefore, it is necessary to develop an analytical method for rapidly, conveniently and selectively determining TNP. Currently, methods for detecting TNP mainly include gas chromatography and colorimetric methods, and in contrast, fluorescence methods are increasingly attracting attention because of their advantages of high sensitivity, simple operation, short response time, and the like, and can be used for analysis of solution and solid phase samples.
Disclosure of Invention
The invention aims to provide a simple and quick preparation method of a two-dimensional Cu-MOF nanosheet with easily-obtained materials.
The invention also aims to provide an application of the nanosheet in fluorescence detection of TNP.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a preparation method of a two-dimensional Cu-MOF nanosheet comprises the following steps:
1) respectively taking copper chloride and polyvinylpyrrolidone according to a mass ratio of 1: 5-6, and then taking a sodium hydroxide aqueous solution and an ascorbic acid aqueous solution, wherein the mass ratio of the copper chloride to sodium hydroxide contained in the sodium hydroxide aqueous solution is 8.5-10: 1, and the concentration ratio of the sodium hydroxide aqueous solution to the ascorbic acid aqueous solution is 2-1: 2.2;
completely dissolving copper chloride and polyvinylpyrrolidone in ultrapure water, then dropwise adding a sodium hydroxide aqueous solution under the condition of magnetic stirring, continuously magnetically stirring for 5-8 minutes after the addition is finished, then dropwise adding an ascorbic acid aqueous solution under the condition of magnetic stirring, continuously magnetically stirring for 5-8 minutes after the addition is finished, centrifuging to obtain a first product, washing the first product with an ethanol solution (analytically pure) at least twice to obtain cuprous oxide (Cu)2O) nanocubes;
2) dispersing cuprous oxide nanocubes into an ethanol solution (analytically pure) according to the proportion of 0.005mmol cuprous oxide nanocubes dispersed in 10mL of the ethanol solution (analytically pure) to obtain a mixed solution;
completely dissolving 2-aminoterephthalic acid in N, N-dimethylformamide according to the proportion of adding 0.05mmol of 2-aminoterephthalic acid in 10mL of N, N-dimethylformamide to obtain an organic phase solution;
3) respectively taking a mixed solution and an organic phase solution according to a volume ratio of 1: 1-1.5, adding the mixed solution into the organic phase solution, standing for 4-5 hours at room temperature, centrifuging to obtain a second product, washing the second product once with an ethanol solution (analytically pure), washing the second product once with a methanol solution (analytically pure), removing the solvent, and drying at 60-70 ℃ for 12-14 hours to obtain the two-dimensional Cu-MOF nanosheet.
All steps in the preparation method of the invention are carried out at room temperature.
After the two-dimensional Cu-MOF nanosheet is prepared by solvothermal, 2-aminoterephthalic acid is used as an organic ligand, and the organic ligand not only forms a two-dimensional metal organic framework, but also remains on the surface of the two-dimensional Cu-MOF nanosheet, so that the two-dimensional Cu-MOF nanosheet is washed once by ethanol and methanol respectively.
The invention is achieved by using Cu2O nanocubes (-60 nm) as a source of confined metal ions, 2-amino terephthalic acid (NH)2-BDC) as organic linking group. During the reaction, Cu2O nanocubes gradually releasing Cu+And Cu+The ions are further oxidized by dissolved oxygen and act as nutrients for the two-dimensional framework building. Cu-NH in two-dimensional Cu-MOF nanosheets2The basic unit skeleton of BDC comprises two penta-coordinate copper cations, bridged in a paddle-wheel type structure, a 2-aminoterephthalic acid ligand (NH)2BDC) are coordinated by a bidentate bridge. In addition to the carboxyl ligand, one terminal Dimethylformamide (DMF) is coordinated, thereby forming a stable two-dimensional sheet structure having an ultra-thin thickness, a directional growth, and an excellent crystallinity.
The other technical scheme adopted by the invention is as follows: an application method of the nanosheet prepared by the preparation method in fluorescence detection of TNP comprises the following steps: two-dimensional Cu-MOF nanosheets (metal organic framework nanosheet materials) are used as fluorescent probes for detecting TNP, and fluorescence of the two-dimensional Cu-MOF nanosheets is used as response signals. The method specifically comprises the following steps:
1) mixing the two-dimensional Cu-MOF nanosheets with water to prepare a fluorescent probe solution with the mass volume concentration of 50-52 mg/L;
2) preparing TNP standard solutions with a series of concentrations;
3) mixing the TNP standard solutions with different concentrations prepared in the step 2) with the fluorescent probe solution prepared in the step 1), and detecting the fluorescence intensity of the two-dimensional Cu-MOF nanosheets respectively to obtain a standard curve or a linear equation of the fluorescence intensity ratio of the two-dimensional Cu-MOF nanosheets to the TNP concentration;
4) mixing the TNP solution to be detected with the fluorescent probe solution prepared in the step 1), detecting the fluorescence intensity of the two-dimensional Cu-MOF nanosheet under the excitation wavelength of 335-339 nm, and then obtaining the concentration of TNP in the TNP solution to be detected through the standard curve or linear equation obtained in the step 3).
The TNP has a quenching effect on the fluorescence of an organic ligand in a two-dimensional Cu-MOF nanosheet, and can be used as a response signal for fluorescence analysis and detection. The fluorescence intensity of the two-dimensional Cu-MOF nanosheet is in a linear relationship with the concentration of TNP.
The preparation method is simple and quick, the materials are easy to obtain and cheap, and the two-dimensional Cu-MOF nanosheet synthesized by the solvothermal method in the prior art has ultrathin thickness, directional growth and excellent crystallinity. The prepared two-dimensional Cu-MOF nanosheet fluorescent probe is good in stability, easy to store and good in selectivity on TNP.
As the amino groups existing in the two-dimensional Cu-MOF nanosheets prepared by the method can form strong hydrogen bonds with the hydroxyl groups in the TNP, and the two-dimensional Cu-MOF nanosheets are of sheet-shaped planar structures and have a pi-pi stacking effect with the TNP, the two-dimensional Cu-MOF nanosheets and the TNP have strong binding capacity, and quenching of fluorescence can be accelerated. In addition, the internal filtering effect of fluorescence can also cause the weakening of fluorescence. Therefore, the two-dimensional Cu-MOF nanosheet prepared by the method has high-sensitivity specific recognition on TNP.
Drawings
FIG. 1 is a fluorescence spectrum of excitation and emission wavelengths of the fluorescent probe of the present invention.
FIG. 2 is a graph showing the influence of different interferents on the fluorescence intensity of a two-dimensional Cu-MOF nanosheet fluorescent probe.
FIG. 3 is a time response graph of a two-dimensional Cu-MOF nanosheet fluorescent probe.
FIG. 4 is a graph showing the influence of TNP with different concentration levels on the fluorescence intensity of a two-dimensional Cu-MOF nanosheet fluorescent probe.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
A50 mL beaker was charged with 40mL of ultrapure water, and 0.02g of copper chloride and 0.1g of polyvinylpyrrolidone were dissolved in the ultrapure water. Weighing 0.2mol of sodium hydroxide, dissolving the sodium hydroxide in 2.5mL of ultrapure water to obtain a sodium hydroxide aqueous solution, weighing 0.1mol of ascorbic acid, dissolving the ascorbic acid in 2.5mL of ultrapure water to obtain an ascorbic acid aqueous solution, dropwise adding the sodium hydroxide aqueous solution into a beaker at the speed of 30 mu L/s under the condition of magnetic stirring, after the addition is finished, continuously stirring for 5 minutes, dropwise adding the ascorbic acid aqueous solution into the beaker at the speed of 10 mu L/s under the condition of magnetic stirring, after the addition is finished, continuously stirring for 5 minutes, centrifuging to obtain a first product, washing the first product with an ethanol solution (analytically pure) for 2 times to obtain a yellow cuprous oxide cube, and dispersing the cuprous oxide cube in 10mL of ethanol to obtain a mixed solution. 0.05mmol of 2-aminoterephthalic acid was completely dissolved in 10mL of N, N-dimethylformamide to obtain an organic phase solution. Adding the mixed solution into the organic phase solution, standing for 4 hours at room temperature, centrifuging to obtain a second product, washing once with an ethanol solution (analytically pure), washing once with a methanol solution (analytically pure), removing the solvent, placing in a drying oven, and drying at 60 ℃ for 12 hours to obtain the two-dimensional Cu-MOF nanosheet.
Detection of TNP by fluorescence assay:
1) adding the two-dimensional Cu-MOF nanosheets into ultrapure water to prepare a fluorescent probe solution with the mass volume concentration of 50 mg/L;
2) sample solution: the configured concentration levels are respectively 10-7mol、10-6mol、10-4mol、10-3mol、10-2Preparing five kinds of TNP standard solutions by mol, and preparing other nine kinds of TNP standard solutions with concentration magnitude of 10-4mols of other interferents including Cu2+、Fe2+、Fe3+、Hg2+Nitrobenzene (NB), Phenol (PHE), o-nitrotoluene (ONT), p-nitrotoluene (PNT) and M-dinitrobenzene (M-dinitrobenzene) for standby.
3) Taking 2mL of the fluorescent probe solution prepared in the step 1) into five quartz cuvettes with four sides transmitting light, respectively, adding the TNP standard solution of the step 2) with a concentration magnitude into one cuvette, detecting the fluorescence intensity by using a fluorescence spectrometer, setting the slit width of the fluorescence spectrometer to be 5nm, setting the wavelength of the excitation light to be 339nm, and detecting the fluorescence intensity of the emission peak at the wavelength of 429nm, as shown in figure 1. FIG. 1 shows that, when TNP standard solution is added, as the concentration of TNP increases, 429nm shows fluorescence quenching, and the fluorescence intensity decreases continuously.
Adding different interferents to the fluorescent probe solution (10)-4M) solution, and detecting the influence of different substances to be detected on fluorescence signals, wherein the result is shown in figure 2, only TNP has obvious quenching on fluorescence intensity, and other substances to be detected hardly have influence on the intensity of a fluorescence probe, which shows that the two-dimensional Cu-MOF nanosheet prepared by the preparation method has good selectivity on TNP, and can realize specific identification and detection on TNP.
The fluorescence intensity detection is respectively carried out on the two-dimensional Cu-MOF nanosheet and the two-dimensional Cu-MOF nanosheet dropwise added with TNP, the result is shown in figure 3, and figure 3 shows that the fluorescence intensity hardly changes along with time, which shows that the fluorescence probe prepared by the preparation method provided by the invention has good stability.
Adding a series of different concentrations (0-10) into the fluorescent probe solution-4mol) TNP solution, and respectively detecting the influence of different concentrations of TNP on the fluorescence signal of the probe, wherein the fluorescence intensity at 429nm is reduced more and more obviously and is in good linearity with the increase of the TNP concentration, and the result is shown in FIG. 4, and the linear equation is as follows: y =0.7744x +0.0971, linear range: 0 to 40 μmol, wherein x is F/F0And y is the TNP concentration.
4) Taking 2mL of the fluorescent probe solution obtained in the step 1) to be placed in a quartz cuvette with light transmission on four sides, adding the TNP solution to be detected with unknown concentration, detecting the fluorescence intensity at 429nm according to the conditions obtained in the step 3), and obtaining the concentration of TNP in the TNP solution to be detected through the linear equation obtained in the step 3).
Example 2
Respectively taking copper chloride and polyvinylpyrrolidone according to a mass ratio of 1: 6, and then taking a sodium hydroxide aqueous solution and an ascorbic acid aqueous solution, wherein the mass ratio of the copper chloride to sodium hydroxide contained in the sodium hydroxide aqueous solution is 10: 1, and the concentration ratio of the sodium hydroxide aqueous solution to the ascorbic acid aqueous solution is 2-2.2; completely dissolving copper chloride and polyvinylpyrrolidone in ultrapure water, dropwise adding sodium hydroxide aqueous solution at the rate of 40 mu L/s under the condition of magnetic stirring, continuing to magnetically stir for 8 minutes after the addition is finished, dropwise adding ascorbic acid aqueous solution at the rate of 20 mu L/s under the condition of magnetic stirring, and continuing to add ascorbic acid aqueous solution after the addition is finishedMagnetic stirring is continued for 8 minutes, centrifugation is carried out to obtain a first product, the first product is washed three times by ethanol solution (analytically pure) to obtain cuprous oxide (Cu)2O) nanocubes; dispersing cuprous oxide nanocubes into an ethanol solution (analytically pure) according to the proportion of 0.005mmol cuprous oxide nanocubes dispersed in 10mL of the ethanol solution (analytically pure) to obtain a mixed solution; completely dissolving 2-aminoterephthalic acid in N, N-dimethylformamide according to the proportion of adding 0.05mmol of 2-aminoterephthalic acid in 10mL of N, N-dimethylformamide to obtain an organic phase solution; respectively taking a mixed solution and an organic phase solution according to a volume ratio of 1: 1.5, adding the mixed solution into the organic phase solution, standing for 5 hours at room temperature, centrifuging to obtain a second product, washing the second product once with an ethanol solution (analytically pure), washing the second product once with a methanol solution (analytically pure), removing the solvent, and drying for 14 hours at the temperature of 70 ℃ to obtain the two-dimensional Cu-MOF nanosheet.
Example 3
Respectively taking copper chloride and polyvinylpyrrolidone according to a mass ratio of 1: 5.5, and then taking a sodium hydroxide aqueous solution and an ascorbic acid aqueous solution, wherein the mass ratio of the copper chloride to sodium hydroxide contained in the sodium hydroxide aqueous solution is 9.25: 1, and the concentration ratio of the sodium hydroxide aqueous solution to the ascorbic acid aqueous solution is 2-1.6; completely dissolving copper chloride and polyvinylpyrrolidone in ultrapure water, then dropwise adding sodium hydroxide aqueous solution at the speed of 35 mu L/s under the condition of magnetic stirring, continuing to magnetically stir for 6.5 minutes after the addition is finished, then dropwise adding ascorbic acid aqueous solution at the speed of 15 mu L/s under the condition of magnetic stirring, continuing to magnetically stir for 7 minutes after the addition is finished, centrifuging to obtain a first product, washing the first product with ethanol solution (analytically pure) at least twice to obtain cuprous oxide (Cu)2O) nanocubes; dispersing cuprous oxide nanocubes into an ethanol solution (analytically pure) according to the proportion of 0.005mmol cuprous oxide nanocubes dispersed in 10mL of the ethanol solution (analytically pure) to obtain a mixed solution; completely dissolving 2-aminoterephthalic acid in N, N-dimethylformamide according to the proportion of adding 0.05mmol of 2-aminoterephthalic acid in 10mL of N, N-dimethylformamide,obtaining an organic phase solution; respectively taking a mixed solution and an organic phase solution according to a volume ratio of 1: 1.25, adding the mixed solution into the organic phase solution, standing for 4.5 hours at room temperature, centrifuging to obtain a second product, washing the second product once with an ethanol solution (analytically pure), washing the second product once with a methanol solution (analytically pure), removing the solvent, and drying for 13 hours at a temperature of 65 ℃ to obtain the two-dimensional Cu-MOF nanosheet.
Claims (3)
1. An application of a two-dimensional Cu-MOF nanosheet in fluorescence detection of 2,4, 6-trinitrophenol is characterized in that the two-dimensional Cu-MOF nanosheet is prepared by the following steps:
1) respectively taking copper chloride and polyvinylpyrrolidone according to a mass ratio of 1: 5-6, and then taking a sodium hydroxide aqueous solution and an ascorbic acid aqueous solution, wherein the mass ratio of the copper chloride to sodium hydroxide contained in the sodium hydroxide aqueous solution is 8.5-10: 1, and the concentration ratio of the sodium hydroxide aqueous solution to the ascorbic acid aqueous solution is 2-1: 2.2;
completely dissolving copper chloride and polyvinylpyrrolidone in ultrapure water, then dropwise adding a sodium hydroxide aqueous solution at the speed of 30-40 mu L/s under the condition of magnetic stirring, continuing to magnetically stir after the addition is finished, then dropwise adding an ascorbic acid aqueous solution at the speed of 10-20 mu L/s under the condition of magnetic stirring, continuing to magnetically stir after the addition is finished, centrifuging to obtain a first product, and washing the first product with an ethanol solution to obtain a cuprous oxide nanocube;
2) dispersing cuprous oxide nanocubes into an ethanol solution according to the proportion of 0.005mmol cuprous oxide nanocubes dispersed in 10mL of the ethanol solution to obtain a mixed solution;
completely dissolving 2-aminoterephthalic acid in N, N-dimethylformamide according to the proportion of adding 0.05mmol of 2-aminoterephthalic acid in 10mL of N, N-dimethylformamide to obtain an organic phase solution;
3) respectively taking the mixed solution and the organic phase solution according to the volume ratio of 1: 1-1.5, adding the mixed solution into the organic phase solution, standing, centrifuging to obtain a second product, washing the second product with an ethanol solution, then washing with a methanol solution, removing the solvent, drying, and drying at the temperature of 60-70 ℃ for 12-14 hours to obtain the two-dimensional Cu-MOF nanosheet.
2. The application of the two-dimensional Cu-MOF nanosheet in the fluorescence detection of 2,4, 6-trinitrophenol according to claim 1, wherein the two-dimensional Cu-MOF nanosheet is used as a fluorescence probe for the fluorescence detection of 2,4, 6-trinitrophenol, and the fluorescence of the two-dimensional Cu-MOF nanosheet is used as a response signal.
3. The application of the two-dimensional Cu-MOF nanosheet of claim 2 in fluorescence detection of 2,4, 6-trinitrophenol, wherein the application method specifically comprises:
1) mixing the two-dimensional Cu-MOF nanosheets with water to prepare a fluorescent probe solution with the mass volume concentration of 50-52 mg/L;
2) preparing 2,4, 6-trinitrophenol standard solutions with series concentrations;
3) mixing the 2,4, 6-trinitrophenol standard solutions with different concentrations prepared in the step 2) with the fluorescent probe solution prepared in the step 1), and respectively detecting the fluorescence intensity of the two-dimensional Cu-MOF nanosheets to obtain a standard curve or linear equation of the fluorescence intensity ratio of the two-dimensional Cu-MOF nanosheets to the 2,4, 6-trinitrophenol concentration;
4) mixing the 2,4, 6-trinitrophenol solution to be detected with the fluorescent probe solution prepared in the step 1), detecting the fluorescence intensity of the two-dimensional Cu-MOF nanosheet under the excitation wavelength of 335-339 nm, and then obtaining the concentration of the 2,4, 6-trinitrophenol in the 2,4, 6-trinitrophenol solution to be detected through the standard curve or linear equation obtained in the step 3).
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