CN112940718A - Cu2+Fluorescent covalent organic framework material and preparation method and application thereof - Google Patents
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Abstract
Cu2+A fluorescent covalent organic framework material, a preparation method and an application thereof relate to Cu2+A fluorescence detection material and a preparation method and application thereof. It aims to solve the problem of the existing Cu2+The fluorescent probe is easy to be influenced by the environment, has poor chemical stability and poor recognition selectivity. Cu of the invention2+The fluorescent covalent organic framework material comprises periodic structural fragments as follows:
the preparation method comprises the following steps: using 2- (4-aminophenyl) -1H-phenanthrene [9,10-d]Imidazole-6, 9-diamine and terephthalaldehyde. It is used for Cu2+Qualitative and quantitative detection. The qualitative detection is performed by adding a detection sample and then performing fluorescenceLight emission intensity TBFluorescence emission intensity T before addition to the sampleAIn contrast, if TB≤TAAnd/5, judging that the sample contains Cu2+. Quantitative detection is carried out by a standard curve method, and Cu in an actual water sample can be realized2+And (4) carrying out quantitative detection.
Description
Technical Field
The invention relates to Cu2+Preparation and application of fluorescent covalent organic framework material.
Technical Field
Copper is a metal element which is commonly existing in the nature, is one of essential trace elements of human bodies, animals and plants, and has an important regulation effect on the metabolism of living bodies. When the content of copper ions in a human body is more than or less than 15.7-23.6 mu mol/L, serious nervous system diseases can be caused. Copper is also widely applied to the fields of metallurgy, dye, information engineering, medical biology and the like, and excessive copper element is discharged into the environment due to the large use of copper, so that great harm is brought to the ecological environment and animals and plants. Therefore, it is of great significance to develop a sensor with high selectivity, good sensitivity and rapid response for detecting trace copper ions in biological and environmental samples.
At present, methods for detecting copper ions in trace amounts include atomic absorption spectrometry, voltammetry, X-ray absorption spectrometry, chemical colorimetry, raman spectrometry, and the like. However, the above methods are difficult to satisfy the dual requirements of simple processing method and high measurement accuracy of the sample to be measured. In recent years, small molecule fluorescent probe-based fluorescence spectroscopy method for detecting Cu2+Is of great interest. In 2020, 40 vol.9 of organic chemistry, 9 of 'off-on' type near infrared fluorescent probe for detecting copper ions in living cells reports recognition of N, N-dimethylamino flavone as fluorophore and 2-picolinate as recognition groupCu2+Fluorescent probes emitting in the near infrared region, but which are chemically unstable in acidic or basic media, limit the scope of applications for such probes. The covalent organic framework is discovered by the advantages of unique porous rigid structure, large conjugated space, low density, high stability, reusability and the like, and is applied to constructing the fluorescent probe. Journal of Microporous and Mesoporous Materials (microporus and mesoporus Materials) in 2020, 299 volume covalent organic scaffolds with bidentate ligand sites as reagents for detecting Cu2+The fluorescence sensor synthesizes a fluorescence covalent organic framework material, and the fluorescence spectrum analysis result shows that the material can be used as a fluorescence probe to realize Cu2+Identification, but Fe in the course of identification3+For Cu2+Has larger interference, and Cu can not be obviously distinguished by a fluorescence analysis method2+And Fe3+。
Based on the present covalent organic frameworks and Cu2+The invention aims to solve the problem of small molecule Cu in the current research situation of fluorescent probes2+The fluorescent probe has the defects of poor chemical stability, difficult reuse and low use efficiency, and the fluorescent covalent organic framework is easily interfered by the environment and has poor recognition effect, thereby providing the Cu with stable structure and high selectivity2+Fluorescent covalent organic framework material and realization of the same for Cu2+And (4) carrying out quantitative detection.
Disclosure of Invention
The invention aims to solve the problem of the existing Cu2+The fluorescent probe is easy to be influenced by the environment, has poor chemical stability and low recognition selectivity, and provides the Cu with stable structure and high selectivity2+Fluorescent covalent organic framework material and realizes the effect of the fluorescent covalent organic framework material on Cu in an actual water sample2+And (4) carrying out quantitative detection.
The invention provides a Cu2+The fluorescent covalent organic framework material comprises periodic structural fragments as follows:
a Cu as described above2+Preparation of fluorescent covalent organic framework materialsThe method comprises the following steps: using 2- (4-aminophenyl) -1H-phenanthrene [9,10-d]Imidazole-6, 9-diamine and terephthalaldehyde, and the reaction formula is as follows:
cu as described above2+The preparation method of the fluorescent covalent organic framework material specifically comprises the following steps:
adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde in a mixed solvent according to a mass ratio of 1 (1-5), uniformly dispersing by using ultrasonic waves, adding acid serving as a catalyst, wherein the mass of the added acid is 1-10% of that of the 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine, and obtaining a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing for 3 times to obtain a reaction mixture;
heating the reaction mixture to 80-150 ℃, keeping the reaction for 48-72 hours, cooling after the reaction is finished, performing suction filtration, washing a filter cake with an organic solvent, placing the filter cake in a vacuum drying oven, heating to 100-180 ℃, and performing vacuum drying for 4-5 hours to obtain Cu2+Fluorescent covalent organic framework materials.
A Cu as described above2+The fluorescent covalent organic framework material is applied to Cu as a fluorescent material2+Qualitative and quantitative detection.
Using one of the above Cu2+Fluorescent covalent organic framework materials for Cu2+The qualitative detection method comprises the following steps:
firstly, mixing Cu2+Uniformly dispersing the fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with a volume ratio of 8 (1-5) to obtain a probe solution A, wherein Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.1-0.5 g/L;
secondly, adding a sample to be detected containing metal ions into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmA；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmB；
Fifth, compare TAAnd TBIf T isB≤TAAnd 5, judging that the sample to be detected contains Cu2+。
Using the above-mentioned Cu2+Quantitative detection of Cu in actual water sample by using fluorescent covalent organic framework material2+The method is a standard curve method and specifically comprises the following steps:
firstly, mixing Cu2+Uniformly dispersing the fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with a volume ratio of 8 (1-5) to obtain a probe solution A, wherein Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, gradually adding the probe solution A into the probe solution A to obtain the probe solution C1、C2、C3……CnCu of (2)2+Respectively obtaining sample solutions B1、B2、B3……Bn；
Thirdly, with 330nm as the excitation wavelength, the sample solution B is measured1～BnRespectively recording the emission intensity at an emission wavelength of 450nm, and recording as TB1～TBn；
Fourthly, with Cu2+Concentration C1～CnAbscissa, in emission intensity T of sample solutionB1～TBnDrawing a standard curve for a vertical coordinate;
fifthly, adding an actual water sample into the probe solution A, and uniformly mixing to prepare a sample solution Bx；
Sixthly, with 330nm as the excitation wavelength, the sample solution B is measuredxRecording the emission intensity at an emission wavelength of 450nm, denoted TBx；
Seventhly, combining TBxComparing the ordinate of the standard curve in step four, looking up TBxAbscissa Cu corresponding to strength2+Concentration of Cu in actual water sample2+And (4) concentration.
Cu of the invention2+Fluorescent covalent organic framework material as fluorescent probe pair Cu2+Shows stronger sensitivity and anti-interference capability and can be used for Cu2+The method realizes the unity identification, is not interfered by other metal ions in the environment, and is not influenced by the acid-base environment. Compared with other fluorescent probes, the Cu of the invention2+The fluorescent covalent organic framework material as a fluorescent probe can be applied to Cu in environments and biological systems2+Detection expands the application range and application field of the covalent organic framework. Using the Cu provided by the invention2+Fluorescent covalent organic framework material detection of Cu2+The method is simple, the response is rapid, and Cu is in the testing process2+The fluorescent covalent organic framework material can keep stable fluorescence intensity, shows that the fluorescent covalent organic framework material has good chemical stability, is not influenced by external environment in recognition, and can realize the effect of Cu in an actual water sample2+And (4) carrying out quantitative detection.
Drawings
FIG. 1 is Cu prepared in example 12+Scanning electron microscopy of fluorescent covalent organic framework materials.
FIG. 2 is Cu prepared in example 12+Transmission electron microscopy of fluorescent covalent organic framework materials.
FIG. 3 is Cu prepared in example 12+Fluorescent covalent organic framework materials (0.3g/L, V)MeCN:VHEPES8:2, pH 7.4) with 0.2 μmol/L Cu2+The abscissa of the fluorescence spectrum in the presence of the fluorescent dye is the wavelength, and the ordinate thereof is the fluorescence intensity.
FIG. 4 Cu prepared in example 12+Fluorescent covalent organic framework materials (0.3g/L, V)MeCN:VHEPES8:2, pH 7.4) with 0.2 μmol/L Cu2+In the case of coexistence, the abscissa represents the metal ion and the ordinate represents the fluorescence intensity in the presence of other metal ions.
FIG. 5Cu prepared in example 12+Concentration of fluorescent covalent organic framework materials (V)MeCN:VHEPES8:2, pH 7.4) and fluorescence intensity, concentration on the abscissa and fluorescence intensity on the ordinate.
Detailed Description
The first embodiment is as follows: cu of the present embodiment2+The fluorescent covalent organic framework material comprises periodic structural fragments as follows:
。
the second embodiment is as follows: cu according to the first embodiment2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde in a mixed solvent according to a mass ratio of 1 (1-5), uniformly dispersing by using ultrasonic waves, adding acid serving as a catalyst, wherein the mass of the added acid is 1-10% of that of the 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine, and obtaining a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing for 3 times to obtain a reaction mixture;
heating the reaction mixture to 80-150 ℃, keeping the reaction for 48-72 hours, cooling after the reaction is finished, performing suction filtration, washing a filter cake with an organic solvent, placing the filter cake in a vacuum drying oven, heating to 100-180 ℃, and performing vacuum drying for 4-5 hours to obtain Cu2+Fluorescent covalent organic framework materials.
The third concrete implementation mode: the difference between the second embodiment and the first embodiment is that the mixed solvent in the first step is any two of mesitylene, dioxane, p-dichlorobenzene, N-butanol and N, N-dimethylformamide; the rest is the same as the second embodiment.
The fourth concrete implementation mode: this embodiment differs from the second or third embodiment in that the acid catalyst is glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid or p-toluenesulfonic acid; the other is the same as the second or third embodiment.
The fifth concrete implementation mode: the difference between the second embodiment and the fourth embodiment is that the organic solvent for washing the filter cake in the third step is methanol, ethanol, acetone, tetrahydrofuran, dichloromethane, chloroform, acetonitrile or diethyl ether; the other is the same as one of the second to fourth embodiments.
The sixth specific implementation mode: detailed description of the invention2+Fluorescent covalent organic framework materials for Cu2 +The qualitative detection method comprises the following steps:
firstly, mixing Cu2+Uniformly dispersing the fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with a volume ratio of 8 (1-5) to obtain a probe solution A, wherein Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.1-0.5 g/L;
secondly, adding a sample to be detected containing metal ions into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmA；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmB；
Fifth, compare TAAnd TBIf T isB≤TAAnd 5, judging that the sample to be detected contains Cu2+。
The seventh embodiment: cu according to the first embodiment2+Quantitative detection of Cu in actual water sample by using fluorescent covalent organic framework material2+The method of concentration is a standard curve method.
The specific implementation mode is eight: cu of the present embodiment2+Quantitative detection of Cu in actual water sample by using fluorescent covalent organic framework material2+The concentration method comprises the following steps:
one, adding one kind of Cu2+Uniformly dispersing a fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with a volume ratio of 8 (1-5) to obtain a probe solution A, wherein one Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, gradually adding the probe solution A into the probe solution A to obtain the probe solution C1、C2、C3……CnCu of (2)2+Respectively obtaining sample solutions B1、B2、B3……Bn；
Thirdly, with 330nm as the excitation wavelength, the sample solution B is measured1～BnRespectively recording the emission intensity at an emission wavelength of 450nm, and recording as TB1～TBn；
Fourthly, with Cu2+Concentration C1～CnAbscissa, in emission intensity T of sample solutionB1～TBnDrawing a standard curve for a vertical coordinate;
fifthly, adding an actual water sample into the probe solution A, and uniformly mixing to prepare a sample solution Bx；
Sixthly, with 330nm as the excitation wavelength, the sample solution B is measuredxRecording the emission intensity at an emission wavelength of 450nm, denoted TBx；
Seventhly, combining TBxComparing the ordinate of the standard curve in step four, looking up TBxAbscissa Cu corresponding to strength2+Concentration of Cu in actual water sample2+And (4) concentration.
The specific implementation method nine: the difference between the embodiment and the eighth embodiment is that the actual water sample is tap water, bottled water, river water or lake water; the rest is the same as the embodiment eight.
The following examples were used to demonstrate the beneficial effects of the present invention:
example 1: cu of the present example2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
firstly, adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde with the mass ratio of 1:1.5 into a mixed solvent of 1mL of trimethylbenzene and 0.5mL of dioxane, and adding 0.5mL of 6M acetic acid serving as a catalyst after uniform ultrasonic dispersion to obtain a mixed solution;
secondly, freezing, vacuumizing and unfreezing the mixed liquid obtained in the first step by using liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing the liquid nitrogen for 3 times to obtain a reaction mixture;
thirdly, heating the reaction mixture to 120 ℃, keeping the reaction for 72 hours, cooling and filtering after the reaction is finished, washing a filter cake with ethanol to obtain Cu2+Fluorescent covalent organic framework materials. Yield: 85% melting Point>320℃。
Cu prepared in this example by XRD testing2+The crystal structure of the fluorescent covalent organic framework material is characterized, and the junction has strong diffraction peaks at 2 theta of 10.42 degrees and 22.86 degrees, which respectively represent a (220) plane and a (224) plane.
Cu prepared in this example by Fourier Infrared Spectroscopy2+The fluorescent covalent organic framework material is characterized and proved to be at 1610cm-1The characteristic absorption peak of C-N appears.
For Cu prepared in this example2+XPS tests are carried out on the fluorescent covalent organic framework material, the binding energy of the 1s orbit of N is 399.28eV, which shows that the fluorescent covalent organic framework material is successfully prepared and mutually proves with infrared spectroscopy.
Cu prepared in this example2+The scanning electron micrograph of the fluorescent covalent organic framework material is shown in figure 1, the transmission electron micrograph is shown in figure 2, and as can be seen from figures 1 and 2, Cu2+The fluorescent covalent organic framework material is spherical in structure and has a large number of micropores.
From the above characterization results, Cu prepared in this example2+The periodic structural fragments of the fluorescent covalent organic framework material are:
the structural formula containing two periodic structural fragments is as follows:
cu prepared in example 12+The fluorescence covalent organic framework material is used for carrying out spectrum performance test, and the steps are as follows:
first, spectrum test
Cu prepared in example 12+The fluorescence spectrum determination method of the fluorescent covalent organic framework material and different metal ions comprises the following steps: weigh 1.0mmol of metal salt: KNO3、Ba(NO3)2、Mg(NO3)2·6H2O、Ca(NO3)2·4H2O、Cu(NO3)2·3H2O、Cr(NO3)3·9H2O、Fe(NO3)3·9H2O、Al(NO3)3·9H2O、Ni(NO3)2·6H2O、Zn(NO3)2·6H2O、Co(NO3)2·4H2O、AgNO3、Cd(NO3)2·4H2O、Hg(NO3)2And Pb (NO)3)2The solution was put into a 10mL volumetric flask, and the volume was fixed with 0.01mol/L HEPES buffer solution having pH of 7.4, and the solution was uniformly shaken with ultrasound to completely dissolve the metal salt, thereby obtaining a metal cation stock solution having a concentration of 0.1 mol/L.
Acetonitrile and a HEPES buffer solution having a pH of 7.4 were mixed at a volume ratio of 8:2 to obtain a mixed solution, and the Cu prepared in example 1 was added to the mixed solution2+Fluorescence covalent organic framework material to obtain 0.3g/L probe test solution, respectively adding 0.2 mu mol/L metal cation stock solution into the probe test solution, after ultrasonic oscillation for 5min, taking 330nm as excitation wavelength, and respectively measuring fluorescence emission spectra of the fluorescence covalent organic framework material and the fluorescence material after adding different metal ions under the condition that the excitation slit width is 8nm, wherein the result is shown in figure 3. As can be seen from FIG. 3, Cu prepared in this example2+Of fluorescent covalent organic framework materialsThe fluorescence emission wavelength is 450nm, and the fluorescence intensity is 712a.u. After addition of different metal cations (Fe)3+、Al3+、Cr3+、Zn2+、Ag+、Mg2+、Hg2+、K+、Co2+、Pb2+、Ba2+、Ca2+、Ni2Or+Cd2+)，Cu2+The fluorescence intensity of the fluorescent covalent organic framework material is not changed greatly, and the intensity is about 712a.u. While adding Cu2+When the fluorescence intensity is reduced to 123a.u., the fluorescence intensity is reduced to about one sixth of the original intensity. Thus, from the fluorescence emission spectrum, it can be preliminarily inferred that2+Fluorescent covalent organic framework material pair Cu2+Has selective recognition performance.
Cu prepared in example 12+The fluorescent covalent organic framework material is in Cu2+The method for testing the metal ion interference resistance during detection comprises the following steps: acetonitrile and a HEPES buffer solution having a pH of 7.4 were mixed at a volume ratio of 8:2 to obtain a mixed solution, and the Cu prepared in example 1 was added to the mixed solution2+Fluorescent covalent organic framework material to obtain a probe solution with the concentration of 0.3 mg/mL; then, various ion solutions (Mg) were added to the probe solution at a concentration of 0.2. mu. mol/L2+、Ca2+、K+、Al3+、Zn2+、Fe3+、Hg2+、Ag+、Cd2+、Ni2+、Pd2+、Cr3+、Ba2+、Co2+) Shaking up, then adding 0.2 mu mol/L Cu respectively2+And ions are prepared into a mixed test solution of a probe, identification ions and interference ions. After shaking thoroughly, the fluorescence test was immediately carried out after 5min of ultrasonic oscillation. The results are shown in FIG. 4. As can be seen from FIG. 3, the fluorescence emission spectrum was measured at an excitation wavelength of 330nm and an excitation slit width of 8 nm. Cu2+Fluorescent covalent organic framework materials and Cu2+In the coexistence, the histogram of fluorescence intensity in the presence of other metal ions is shown in fig. 4, with the abscissa representing the metal ion and the ordinate representing the fluorescence intensity. As can be seen from FIG. 4, in the case where other metal cations are presentUnder the condition of Cu2+The fluorescence intensity was 123a.u. in the presence of other ions, and was not changed, but was still Cu2+About one sixth of the intensity of fluorescent covalent organic framework materials, i.e. Cu2+Fluorescent covalent organic framework material pair Cu2+The fluorescence detection of (2) is not interfered by other metal ions.
Cu prepared by example 12+Fluorescent covalent organic framework materials for Cu2+The qualitative detection method comprises the following steps:
firstly, mixing Cu2+The fluorescent covalent organic framework material is uniformly dispersed in a solvent with the volume ratio of 8:2 acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) to obtain a probe solution A, wherein Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, adding a sample I to be detected containing metal ions into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmA，TA＝712；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmB，TB＝123；
Fifth, compare TAAnd TBIf T isB≤TAAnd 5, judging that the sample I to be detected contains Cu2+。
Cu prepared by example 12+Quantitative detection of Cu in actual water sample by using fluorescent covalent organic framework material2+The concentration method comprises the following steps:
firstly, mixing Cu2+Uniformly dispersing the fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid (HEPES) with a volume ratio of 8:2 to obtain a probe solution A, wherein Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, gradually adding the probe solution A into the probe solution A with the concentration of 0.02, 0.04, 0.06,0.08, 0.1, 0.12, 0.14, 0.16, 0.18, 0.2 μ M Cu2+Respectively obtaining sample solutions B1、B2、B3……Bn；
Thirdly, with 330nm as the excitation wavelength, the sample solution B is measured1～BnRespectively recording the emission intensity at an emission wavelength of 450nm, and recording as TB1～TBn；
Fourthly, with Cu2+Concentration C1～CnAbscissa, in emission intensity T of sample solutionB1～TBnAs ordinate, a standard curve is plotted as shown in fig. 5;
fifthly, adding an actual water sample into the probe solution A, and uniformly mixing to prepare a sample solution Bx；
Sixthly, with 330nm as the excitation wavelength, the sample solution B is measuredxRecording the emission intensity at an emission wavelength of 450nm, denoted TBx；
Seventhly, combining TBxComparing the ordinate of the standard curve in step four, looking up TBxAbscissa Cu corresponding to strength2+Concentration of Cu in actual water sample2+And (4) concentration.
Eighthly, calculating Cu in actual water sample2+The concentration, the standard recovery rate experiment, the repeated 3 times of measurement, the results are shown in Table 1, and it can be seen from Table 1 that the Cu2+Fluorescent covalent organic framework material for Cu in water sample2+The detection, the recovery rate and the RSD all meet the requirements, and the method is expected to be used for Cu in a life system2+Accuracy of selection of (2).
TABLE 1 sample recovery method Cu2+Concentration detection result
From the data in Table 1, it can be seen that Cu2+When the method of adding the sample is used for quantitative detection, the recovery rate is more than 95 percent, which shows that the precision of the method of adding the sample is high, and the results show that the fluorescent probe can be applied toDetecting Cu in water sample2+。
Cu during testing2+The fluorescent covalent organic framework material can keep stable fluorescence intensity, shows that the fluorescent covalent organic framework material has good chemical stability, is not influenced by external environment in recognition, and can realize the effect of Cu in an actual water sample2+And (4) carrying out quantitative detection.
Example 2: cu of the present example2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
firstly, adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde with the mass ratio of 1:1.5 into a mixed solvent of 0.8mL of mesitylene and 1.2mL of dioxane, and adding 0.7mL of 6M acetic acid as a catalyst after uniform ultrasonic dispersion to obtain a mixed solution;
secondly, freezing, vacuumizing and unfreezing the mixed solution obtained in the first step by using liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing the liquid nitrogen for 3 times to obtain a reaction mixture;
thirdly, the reaction mixture is heated to 120 ℃ and reacted for 72 hours. After the reaction is finished, cooling and filtering the mixture, washing a filter cake with ethanol, putting the filter cake into a vacuum drying oven, and drying the filter cake for 4 hours in vacuum at the temperature of 160 ℃ to obtain Cu2+Fluorescent covalent organic framework material, yield: 68 percent.
Example 3: cu of the present example2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde in a mass ratio of 1:1.5 into a mixed solvent of 1mL of dioxane and 0.5mL of p-dichlorobenzene, and adding 0.5mL of 6M acetic acid serving as a catalyst after uniform ultrasonic dispersion to obtain a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by using liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing the liquid nitrogen for 3 times to obtain a reaction mixture;
thirdly, the reaction mixture is heated to 120 ℃ and reacted for 72 hours. After the reaction is finished, the mixture is cooled and filtered, and a filter cake is washed by methanol and then placed in a vacuum drying ovenVacuum drying at 150 deg.C for 5 hr to obtain Cu2+Fluorescent covalent organic framework material, yield: 70 percent.
Example 4: cu of the present example2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
firstly, adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde with the mass ratio of 1:1.5 into a mixed solvent of 0.8mL of mesitylene and 1.2mL of dioxane, and adding 0.7mL of 6M acetic acid as a catalyst after uniform ultrasonic dispersion to obtain a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by using liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing the liquid nitrogen for 3 times to obtain a reaction mixture;
thirdly, the reaction mixture is heated to 120 ℃ and reacted for 72 hours. After the reaction is finished, cooling and filtering the mixture, washing a filter cake with ethanol, putting the filter cake into a vacuum drying oven, and drying the filter cake for 4 hours in vacuum at the temperature of 170 ℃ to obtain Cu2+Fluorescent covalent organic framework material, yield: 72 percent.
Example 5: cu of the present example2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde in a mass ratio of 1:1.5 into a mixed solvent of 0.5mL of ethanol and 0.5mL of p-dichlorobenzene, and adding 0.1mL of 6M acetic acid serving as a catalyst after uniform ultrasonic dispersion to obtain a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by using liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing the liquid nitrogen for 3 times to obtain a reaction mixture;
thirdly, the reaction mixture is heated to 120 ℃ and reacted for 72 hours. After the reaction is finished, cooling and filtering the mixture, washing a filter cake with acetone to obtain Cu2+Fluorescent covalent organic framework material, yield: 57 percent.
Example 6: cu of the present example2+The preparation method of the fluorescent covalent organic framework material comprises the following steps:
adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde with the mass ratio of 1:1.5 into a mixed solvent of 0.5mL of N, N-dimethylformamide and 1mL of p-dichlorobenzene, and adding 0.5mL of 6M acetic acid serving as a catalyst after uniform ultrasonic dispersion to obtain a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by using liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing the liquid nitrogen for 3 times to obtain a reaction mixture;
thirdly, the reaction mixture is heated to 120 ℃ and reacted for 72 hours. After the reaction is finished, cooling and filtering the mixture, washing a filter cake with acetone, putting the filter cake into a vacuum drying oven, and drying the filter cake for 5 hours in vacuum at the temperature of 150 ℃ to obtain Cu2+Fluorescent covalent organic framework material, yield: 65 percent.
Claims (10)
1. Cu2+The fluorescent covalent organic framework material is characterized in that the periodic structural fragments of the material are as follows:
2. preparation of a Cu as claimed in claim 12+A method of fluorescent covalent organic framework material, characterized in that the method is performed as follows:
adding 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine and terephthalaldehyde in a mixed solvent according to a mass ratio of 1 (1-5), uniformly dispersing by using ultrasonic waves, adding acid serving as a catalyst, wherein the mass of the added acid is 1-10% of that of the 2- (4-aminophenyl) -1H-phenanthrene [9,10-d ] imidazole-6, 9-diamine, and obtaining a mixed solution;
freezing, vacuumizing and unfreezing the mixed solution by liquid nitrogen, and repeating the operations of freezing, vacuumizing and unfreezing for 3 times to obtain a reaction mixture;
thirdly, heating the reaction mixture to 80-150 ℃, keeping the reaction for 48-72 hours, cooling after the reaction is finished, performing suction filtration, washing a filter cake with an organic solvent, and then performing vacuum filtrationPlacing the mixture in a vacuum drying oven, heating to 100-180 ℃, and vacuum drying for 4-5 hours to obtain Cu2+Fluorescent covalent organic framework materials.
3. Cu according to claim 22+The preparation method of the fluorescent covalent organic framework material is characterized in that the mixed solvent in the step one is any two of mesitylene, dioxane, p-dichlorobenzene, N-butanol and N, N-dimethylformamide.
4. Cu according to claim 2 or 32+The preparation method of the fluorescent covalent organic framework material is characterized in that the acid catalyst in the step one is glacial acetic acid, trifluoroacetic acid, benzenesulfonic acid or p-toluenesulfonic acid.
5. Cu according to claim 2 or 32+The preparation method of the fluorescent covalent organic framework material is characterized in that the organic solvent for washing the filter cake in the third step is methanol, ethanol, acetone, tetrahydrofuran, dichloromethane, trichloromethane, acetonitrile or diethyl ether.
6. A Cu as claimed in claim 12+The use of fluorescent covalent organic framework materials, characterized in that the Cu is2+Fluorescent covalent organic framework materials for Cu2+Detection of (3).
7. Cu according to claim 62+Use of fluorescent covalent organic framework materials, characterized in that Cu is used2+Fluorescent covalent organic framework material pair Cu2+The qualitative detection method comprises the following steps:
firstly, mixing Cu2+Uniformly dispersing the fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid with a volume ratio of 8 (1-5) to obtain a probe solution A, wherein Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.1-0.5 g/L;
secondly, adding a sample I to be detected containing metal ions into the probe solution A, and uniformly mixing to prepare a sample solution B;
thirdly, measuring the fluorescence emission spectrum of the probe solution A by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmA；
Fourthly, measuring the fluorescence emission spectrum of the sample solution B by taking 330nm as the excitation wavelength, and recording the emission intensity as T when the emission wavelength is 450nmB；
Fifth, compare TAAnd TBIf T isB≤TAAnd 5, judging that the sample I to be detected contains Cu2+。
8. Cu according to claim 62+Use of fluorescent covalent organic framework materials, characterized in that Cu is used2+Quantitative detection of Cu in actual water sample by using fluorescent covalent organic framework material2+The method of concentration is a standard curve method.
9. Cu according to claim 82+Use of fluorescent covalent organic framework materials, characterized in that Cu is used2+Quantitative detection of Cu in actual water sample by using fluorescent covalent organic framework material2+The concentration standard curve method specifically comprises the following steps:
one, adding one kind of Cu2+Uniformly dispersing the fluorescent covalent organic framework material in a mixed solution of acetonitrile and 4-hydroxypiperazine ethanesulfonic acid with a volume ratio of 8 (1-5) to obtain a probe solution A, wherein one Cu in the probe solution A2+The concentration of the fluorescent covalent organic framework material is 0.3 g/L;
secondly, gradually adding the probe solution A into the probe solution A to obtain the probe solution C1、C2、C3……CnCu of (2)2+Respectively obtaining sample solutions B1、B2、B3……Bn；
Thirdly, with 330nm as the excitation wavelength, the sample solution B is measured1～BnRespectively recording the emission intensity at an emission wavelength of 450nm, and recording as TB1～TBn；
Fourthly, with Cu2+Concentration C1～CnAbscissa, in emission intensity T of sample solutionB1～TBnDrawing a standard curve for a vertical coordinate;
fifthly, adding an actual water sample into the probe solution A, and uniformly mixing to prepare a sample solution Bx；
Sixthly, with 330nm as the excitation wavelength, the sample solution B is measuredxRecording the emission intensity at an emission wavelength of 450nm, denoted TBx；
Seventhly, combining TBxComparing the ordinate of the standard curve in step four, looking up TBxAbscissa Cu corresponding to strength2+Concentration of Cu in actual water sample2+And (4) concentration.
10. A Cu according to claim 8 or 92+The application of the fluorescent covalent organic framework material is characterized in that the actual water sample is tap water, bottled water, river water or lake water.
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