CN114149593B - Metal organic framework UiO-66-NH 2 And preparation method and application thereof - Google Patents
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- G01N21/64—Fluorescence; Phosphorescence
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Abstract
The invention provides a metal organic framework UiO-66-NH 2 The material is prepared by a water phase synthesis method of a formic acid aqueous solution of zirconium salt and an organic ligand in ethanol. The invention provides the metal organic framework UiO-66-NH 2 The material can be based on a three-dimensional fluorescence detection method, is convenient and quick to use, has high accuracy, can be used for detecting the concentration of the phosphate radical in water, can be prepared into test paper for detecting the concentration of the phosphate radical, has the advantages of high sensitivity, no interference of inorganic anions and humic acid, cyclic use of the material and the like, is simple to operate, quick in reaction speed and low in detection cost, only needs to drop a sample on the test paper, can quickly detect the sample by means of a three-dimensional fluorescence instrument to obtain a result, and is convenient to analyze. Meanwhile, the detection limit is as low as 0.1 micromole per liter, the kit is suitable for screening and field monitoring of a large number of samples, the measurement result of an actual sample is accurate, the response to phosphate radical is sensitive, and the detection of the phosphate radical in natural environment and drinking water can be realized.
Description
Technical Field
The invention relates to the technical field of analytical chemistry, in particular to a metal organic framework UiO-66-NH 2 And a preparation method and application thereof, in particular to a metal organic framework UiO-66-NH 2 A preparation method thereof and application thereof in phosphate radical detection.
Background
Phosphate is one of the nutrients needed by human body, and contains 600-700 g of phosphorus in normal human body. Phosphorus in the human body exists mainly in the form of phosphate radical and participates in various important physiological activities, including the regulation of energy metabolism and acid-base balance in the body. However, excessive phosphate intake causes joint pain, muscle pain and muscle weakness, induces various diseases, and affects physical health. The sewage and wastewater discharge in the fields of food industry, detergent manufacturing industry, pesticide production and the like can bring a large amount of phosphate to the natural environment, the water eutrophication can be caused by excessive phosphate radicals in the environment, the growth of aquatic organisms is not facilitated, and meanwhile, industrial water can be influenced, so that the production activity is influenced; therefore, accurately and quickly detecting the content of phosphate radicals in the environmental water body becomes an important means for monitoring the water body quality and preventing diseases.
The existing phosphate radical detection method comprises a chromatography method, a fluorescence method, an electrochemical method, a biosensing method and the like, and can meet the requirement of detecting phosphate radicals in partial scenes. However, the above technical solutions still have disadvantages, such as the requirement of high temperature, high pressure and organic solvent for material preparation; the detection conditions are harsh, the requirement on the reagent storage conditions is high, the cost is relatively high, and the operation is relatively complex; the detection precision and the detection limit are to be improved. Therefore, the development of the phosphate radical detection method which is simple and convenient to operate, low in cost and high in applicability is of great significance.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a metal organic framework UiO-66-NH 2 The preparation method and the application in the phosphate radical detection can realize the convenient and rapid detection of the phosphate radical.
The invention provides a metal organic framework UiO-66-NH 2 The material is prepared by a water phase synthesis method of a formic acid aqueous solution of zirconium salt and an organic ligand in ethanol.
Preferably, the zirconium salt is zirconium tetrachloride; the organic ligand is 2-amino terephthalic acid.
The invention also provides a metal organic framework UiO-66-NH 2 The preparation method of the material comprises the following steps:
mixing the aqueous solution of zirconium salt formic acid, organic ligand and ethanol, and reacting to obtain the metal organic framework UiO-66-NH 2 A material.
Preferably, the zirconium salt is zirconium tetrachloride.
The molar volume ratio of the zirconium salt to the aqueous formic acid solution is preferably 2mmol:23ml.
The volume concentration of the formic acid aqueous solution is preferably 30-50%.
Preferably, the organic ligand is 2-amino terephthalic acid.
The molar ratio of 2-aminoterephthalic acid to zirconium salt is preferably 1:1.
The molar volume ratio of the organic ligand to ethanol is preferably 1mmol.
In some embodiments of the invention, the preparation method specifically comprises:
1) Dissolving zirconium salt in aqueous solution of formic acid, and uniformly rotating and stirring;
2) Adding the organic ligand and ethanol into the solution, and continuing stirring;
3) After stirring for a long time, rotating and centrifuging, washing with ethanol and acetone, and centrifuging.
In some embodiments of the invention, the zirconium salt is zirconium tetrachloride in an amount of 2mmol, and the aqueous formic acid solution is prepared from 7 ml of formic acid and 16 ml of water.
In some embodiments of the invention, the organic ligand is 2-aminoterephthalic acid in an amount of 2mmol and absolute ethanol in an amount of 20 ml.
In some embodiments of the present invention, the stirring speed is 300-600 rpm, the reaction time is 12-18 hours, and the ethanol and acetone washing is respectively washed and centrifuged three times.
The invention provides a solvent thermal synthesis method which is different from the traditional solvent thermal synthesis method, is developed based on the green principle and synthesizes a metal organic framework UiO-66-NH under the water phase condition 2 The preparation process of the material is simple to operate, the material synthesis process is green and environment-friendly, and toxic solvents are not required. The aqueous phase synthesis method avoids the influence of the combination of organic solvent guest in the pore canal on the fluorescence intensity, and improves the detection accuracy.
In another aspect of the invention, the metal organic framework UiO-66-NH is provided 2 Material or metal organic framework UiO-66-NH prepared by the preparation method 2 Application of the material in quantitative detection of phosphate radical.
Drawing a three-dimensional fluorescence intensity-phosphate radical concentration standard working curve, and then using the metal organic framework material UiO-66-NH 2 Adding the solution into aqueous solution containing phosphate radical, and measuring the concentration of the phosphate radical through a working curve by measuring the change of fluorescence intensity.
The invention is based on a metal organic framework UiO-66-NH 2 The zirconium ions are combined with the ligand to quench the fluorescence of the ligand; the coordination of phosphate radicals and zirconium ions in a test sample enables the fluorescence of the ligand to be recovered, and the fluorescence intensity is in direct proportion to the concentration of the phosphate radicals, so that the sensitive detection of the phosphate radicals is realized.
Specifically, the invention provides a method for quantitatively detecting phosphate radical, which comprises the following steps:
s1) preparing a metal organic framework UiO-66-NH 2 A solution of a material;
adjusting the pH value of the solution to be measured to 6-8;
s2) preparing a metal organic framework UiO-66-NH 2 Mixing the solution of the material and the solution to be detected to obtain a mixed solution;
and S3) carrying out fluorescence measurement on the mixed solution by using a three-dimensional fluorescence instrument, and calculating to obtain the concentration of phosphate in the solution to be measured according to a standard curve of fluorescence intensity-phosphate concentration.
The metal organic framework UiO-66-NH 2 The concentration of the solution of the material is preferably 30 to 50mg/L.
In the step S2), the metal organic framework UiO-66-NH 2 The volume ratio of the solution of the material to the solution to be measured is preferably 500.
In some embodiments of the present invention, the detection method specifically comprises the following steps:
1) 50mg/L of the metal organic framework material UiO-66-NH is prepared 2 The solution of (1);
2) Taking 5 ml of liquid to be measured, and adjusting the pH value to 6-8;
3) Taking 500 microliters of the liquid in the step 2), and mixing with 3.5 milliliters of the solution in the step 1) for 1 minute;
4) And (4) pouring the liquid obtained in the step 3) into a cuvette, carrying out fluorescence measurement by using a three-dimensional fluorescence instrument, and calculating to obtain the phosphate radical concentration according to a standard curve of fluorescence intensity-phosphate radical concentration.
In the present invention, the metal organic framework material UiO-66-NH is used 2 In the solution of (3), the solvent is preferably water.
In the invention, the metal organic framework material UiO-66-NH is used 2 Can be recycled.
The invention also provides UiO-66-NH for quantitatively detecting the concentration of phosphate radical 2 The test paper is prepared from the metal organic framework UiO-66-NH 2 Material or metal organic framework UiO-66-NH prepared by preparation method 2 The material is obtained by solution impregnation.
The invention is based on the metal organic framework UiO-66-NH 2 The material provides a test paper material which can realize the rapid detection of phosphate radical.
The invention also provides a method for preparing the catalyst by adopting UiO-66-NH 2 The method for quantitatively detecting phosphate radical by using the test paper comprises the following steps:
adjusting the pH value of the solution to be measured to 6-8, and adding a small amount of the solution to be measured to the UiO-66-NH 2 Incubating the surface of the test paper for 1-3 min at a constant temperature of 15-30 ℃, performing solid fluorescence measurement on the test paper by using a three-dimensional fluorescence instrument, and calculating the content of phosphate radical in the solution according to the dilution times and fluorescence intensity of the sample.
In some embodiments of the present invention, the detection method specifically comprises the following steps:
1) Providing UiO-66-NH for the detection of phosphate 2 Test paper;
2) Taking 5 ml of liquid to be measured, putting the liquid into a sample tube, and adjusting the pH value to 6-8;
3) Taking 100-300 microliter of the sample in the step 2), and spotting the sample on a metal organic framework UiO-66-NH 2 Incubating at 30 deg.C for 1 min, and three-dimensional fluorescenceAnd (3) carrying out solid fluorescence measurement on the test strip by using the instrument, and calculating the content of phosphate radicals in the solution according to the dilution times and the fluorescence intensity of the sample.
In the preferred embodiment of the present invention, the detection device used in the above method is a three-dimensional fluorescence device, the excitation wavelength is 249 nm and 327nm, and the emission wavelength is 425nm.
Compared with the prior art, the invention provides a metal organic framework UiO-66-NH 2 The material is prepared by a water phase synthesis method of a formic acid aqueous solution of zirconium salt and an organic ligand in ethanol. The invention provides the metal organic framework UiO-66-NH 2 The material can be based on a three-dimensional fluorescence detection method, is convenient and quick to use, has high accuracy, can be used for detecting the concentration of the phosphate radical in water, can be prepared into test paper for detecting the concentration of the phosphate radical, has the advantages of high sensitivity, no interference of inorganic anions and humic acid, cyclic use of the material and the like, is simple to operate, quick in reaction speed and low in detection cost, only needs to drop a sample on the test paper, can quickly detect the sample by means of a three-dimensional fluorescence instrument to obtain a result, and is convenient to analyze. Meanwhile, the detection limit is as low as 0.1 micromole per liter, and the detection range is as wide as 0.1 to 100 micromole per liter; the method is suitable for screening and field monitoring of a large number of samples, accurate in measurement result of actual samples, sensitive in response to phosphate radicals, and capable of detecting the phosphate radicals in natural environments and drinking water. The test paper developed based on the method has good detection effect and can be suitable for various scenes.
Drawings
FIG. 1 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 A real object diagram of (1);
FIG. 2 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 An infrared spectrum of (1);
FIG. 3 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 X-ray diffraction patterns of (a);
FIG. 4 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 Three-dimensional fluorescence images before and after blending reaction with phosphate;
FIG. 5 shows gold prepared in example 1 of the present inventionBelongs to an organic framework material UiO-66-NH 2 X-ray photoelectron spectroscopy before and after blending reaction with phosphate radical;
FIG. 6 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 Detecting an effect graph;
FIG. 7 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 Detecting an effect graph after recovery;
FIG. 8 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 Comparing fluorescence intensity in the presence of chloride ions;
FIG. 9 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 A standard curve diagram in the presence of humic acid;
FIG. 10 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 Dipping to obtain a standard curve chart of the test paper;
FIG. 11 shows a metal organic framework material UiO-66-NH prepared in example 1 of the present invention 2 And (5) dipping to obtain a test paper detection effect graph.
Detailed Description
To further illustrate the present invention, the following examples are given to illustrate the metal organic framework UiO-66-NH provided by the present invention 2 And a method for preparing the same and use thereof in phosphate detection, it will be apparent that the described embodiments are only a few, but not all, embodiments of the present invention. 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.
The following preparation steps are given for the purpose of illustration and are based on the comparative nature of the respective examples and the person skilled in the art is fully enabled to generalize from the prior knowledge the process of the invention for preparing the products of the invention.
In the present invention, the sources of all raw materials are not particularly limited, and they may be commercially available.
Example 1: metal organic framework material UiO-66-NH 2 System of (1)Is provided with
Dissolving 2mmol of zirconium tetrachloride in a solution prepared from 7 ml of formic acid and 16 ml of water, and stirring for 1 minute at a rotating speed of 60 revolutions per minute to uniformly stir; after stirring well, 2mmol of 2-aminoterephthalic acid and 20 ml of ethanol were added to the solution, and stirring was continued. Stirring and reacting for 12 hours, centrifuging at 8000 rpm, washing with ethanol for three times, washing with acetone for three times, and getting the water-phase synthesized metal organic framework material UiO-66-NH 2 Then, it was dried in a vacuum oven at 60 ℃.
FIG. 1 shows a metal organic framework material UiO-66-NH synthesized by the method described in this example 2 And (5) a real object picture. FIG. 2 shows a metal organic framework material UiO-66-NH synthesized by the method of this example 2 And (4) performing Fourier infrared characterization on the result. FIG. 3 shows a metal organic framework material UiO-66-NH synthesized by the method of this example 2 FIG. 4 shows the results of X-ray diffraction characterization of the metal-organic framework material UiO-66-NH synthesized by the method of this example 2 Three-dimensional fluorescence before and after blending reaction with phosphate, FIG. 5 is a metal organic framework material UiO-66-NH synthesized by the method described in this example 2 The result is characterized by X-ray photoelectron spectroscopy.
The invention uses a simple and universal method, and synthesizes the metal organic framework material UiO-66-NH under the environment and temperature conditions of more environmental protection without using dangerous organic solvent 2 And detecting phosphate radical with the material.
Example 2: metal organic framework UiO-66-NH 2 Application for detecting phosphate radical concentration
The metal-organic framework material UiO-66-NH obtained in example 1 was added 2 Preparing into solution with concentration of 50mg/L, respectively taking 3.5 ml of the prepared solution, respectively adding 0.1-100 micromole/L of sodium phosphate solution, and uniformly mixing the solutions.
The three-dimensional fluorescence spectrum of the mixed solution is measured by a three-dimensional fluorescence instrument, and a standard curve of fluorescence intensity and phosphate radical concentration can be established, as shown in fig. 6. Then 3.5 ml of the solution described in the embodiment is uniformly mixed with 0.5 ml of the actual sample solution, a fluorescence spectrum is measured by using a three-dimensional fluorescence spectrometer, and the concentration of the phosphate radical can be measured by contrasting a fluorescence intensity and phosphate radical concentration standard curve.
Example 3: metal organic framework UiO-66-NH 2 Is recycled and reused
The metal organic framework material UiO-66-NH detected in the example 2 2 Centrifuging, washing with 0.01 mol/L sodium hydroxide solution, centrifuging, drying, preparing into 50mg/L solution, collecting 3.5 ml of the prepared solution, adding 0.1-100 micromol/L sodium phosphate solution, and mixing.
The three-dimensional fluorescence spectrum of the mixed solution is measured by a three-dimensional fluorescence instrument, and a standard curve of fluorescence intensity and phosphate radical concentration can be established, as shown in fig. 7. Then 3.5 ml of the solution described in the embodiment is taken and mixed with 0.5 ml of the actual sample solution uniformly, a fluorescence spectrum is measured by using a three-dimensional fluorescence spectrometer, and the concentration of the phosphate radical can be measured by contrasting a fluorescence intensity and phosphate radical concentration standard curve.
Example 4: metal organic framework UiO-66-NH in the presence of chloride ion 2 Application for detecting phosphate radical concentration
The metal-organic framework material UiO-66-NH obtained in example 1 was added 2 Preparing into solution with concentration of 50mg/L, respectively taking 3.5 ml of the prepared solution, respectively adding 0.1-100 micromole/L sodium phosphate solution, and then uniformly mixing the solutions.
The three-dimensional fluorescence spectrum of the mixed solution is measured by a three-dimensional fluorescence instrument, and a standard curve of fluorescence intensity and phosphate radical concentration can be established, as shown in fig. 6. Adding different amounts of sodium chloride into an actual test sample solution, uniformly mixing 0.5 ml of the actual sample containing sodium chloride with 3.5 ml of the solution, measuring a fluorescence spectrum by using a three-dimensional fluorescence spectrometer, measuring the concentration of the phosphate radical by contrasting a standard curve of fluorescence intensity and the concentration of the phosphate radical, and measuring the concentration of the phosphate radical according to the testChlorine ion is added to the metal organic framework material UiO-66-NH 2 Detection of phosphate had no effect, as shown in fig. 8, chloride addition did not affect the change in fluorescence intensity. Therefore, the metal organic framework material UiO-66-NH constructed by the invention 2 The method for detecting the phosphate radical has stronger anti-interference capability on common chloride ions in the environment.
Example 5: metal organic framework UiO-66-NH in the presence of humic acid 2 Application for detecting phosphate radical concentration
The metal-organic framework material UiO-66-NH obtained in example 1 was added 2 Preparing a solution, wherein the concentration is 50mg per liter, adding a certain amount of humic acid to enable the concentration to be equivalent to the environmental level, respectively taking 3.5 milliliters of the prepared solution, respectively adding 0.1 to 100 micromole per liter of sodium phosphate solution, and then uniformly mixing the solutions.
The three-dimensional fluorescence spectrum of the mixed solution is measured by a three-dimensional fluorometer, and a standard curve of the fluorescence intensity and the phosphate radical concentration can be established, as shown in fig. 9. 0.5 ml of actual sample containing humic acid is uniformly mixed with 3.5 ml of the solution, the fluorescence spectrum is measured by using a three-dimensional fluorescence spectrometer, the phosphate radical concentration can be measured by contrasting the fluorescence intensity with the phosphate radical concentration standard curve, and according to the test, the humic acid in the environment can be eliminated from being applied to the metal organic framework material UiO-66-NH 2 The effect of phosphate was measured. Therefore, the metal organic framework material UiO-66-NH constructed by the invention 2 The method for detecting phosphate radicals can be applied to environments containing humic acid.
Example 6: based on a metal organic framework UiO-66-NH 2 Application of developed test paper for detecting phosphate radical concentration
The metal-organic framework material UiO-66-NH obtained in example 1 2 Preparing a solution with the concentration of 50mg per liter, soaking the test paper in the solution, drying after five minutes, respectively taking 0.3 ml of 10-100 micromole per liter sodium phosphate solution, dripping the solution on a test paper card soaked with a metal organic frame, incubating for 1 minute at the constant temperature of 30 ℃, drying the test paper, and carrying out solid fluorescence determination on the test paper by using a three-dimensional fluorescence spectrometer to obtain the fluorescence intensityThe standard curve of degree versus phosphate concentration is shown in fig. 10.
0.3 ml of actual sample is dropped on the prepared test paper, a three-dimensional fluorescence spectrometer is used for measuring the solid fluorescence spectrum, and as shown in figure 11, the concentration of the phosphate radical can be measured by contrasting the fluorescence intensity with the standard curve of the concentration of the phosphate radical.
As can be seen from the above examples, the metal organic framework UiO-66-NH prepared by the invention 2 The method can be used for measuring the concentration of phosphate radicals in the environment, and has the characteristics of low detection limit, high sensitivity, no interference of inorganic anions and humic acid, material recycling and the like.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (9)
1. Metal organic framework UiO-66-NH 2 The material is characterized in that the material is prepared by a water phase synthesis method of a methanoic acid aqueous solution of zirconium salt and an organic ligand in ethanol;
the aqueous phase synthesis method comprises the following steps:
1) Dissolving zirconium salt in aqueous solution of formic acid, and uniformly rotating and stirring;
2) Adding the organic ligand and ethanol into the solution, and continuing stirring;
3) Stirring for a long time for reaction, rotating and centrifuging, washing with ethanol and acetone, and centrifuging;
the reaction time is 12 to 18 hours;
the zirconium salt is zirconium tetrachloride; the organic ligand is 2-amino terephthalic acid.
2. Metal organic framework UiO-66-NH 2 The preparation method of the material is characterized by comprising the following steps:
1) Dissolving zirconium salt in aqueous solution of formic acid, and uniformly rotating and stirring;
2) Adding the organic ligand and ethanol into the solution, and continuing stirring;
3) Stirring for a long time for reaction, rotating and centrifuging, washing with ethanol and acetone, and centrifuging;
the reaction time is 12 to 18 hours;
the zirconium salt is zirconium tetrachloride; the organic ligand is 2-amino terephthalic acid.
3. The method according to claim 2, wherein the molar volume ratio of the zirconium salt to the aqueous formic acid solution is 2mmol:23ml;
the volume concentration of the formic acid aqueous solution is 30-50%.
4. The method of claim 2, wherein the molar ratio of 2-aminoterephthalic acid to zirconium salt is 1:1;
the molar volume ratio of the organic ligand to ethanol is 1mmol.
5. The metal organic framework UiO-66-NH as claimed in claim 1 2 Material or metal-organic framework UiO-66-NH prepared by the preparation method of any one of claims 2~4 2 Application of the material in quantitative detection of phosphate radical.
6. A method for quantitatively detecting phosphate, comprising the steps of:
s1) preparing a metal organic framework UiO-66-NH 2 A solution of a material; the metal organic framework UiO-66-NH 2 The material is the metal organic framework UiO-66-NH of claim 1 2 Material or metal-organic framework UiO-66-NH prepared by the preparation method of any one of claims 2~4 2 A material;
adjusting the pH value of the solution to be detected to 6~8;
s2) preparing a metal organic framework UiO-66-NH 2 Mixing the solution of the material and the solution to be detected to obtain a mixed solution;
and S3) carrying out fluorescence measurement on the mixed solution by using a three-dimensional fluorescence instrument, and calculating to obtain the concentration of phosphate in the solution to be measured according to a standard curve of fluorescence intensity-phosphate concentration.
7. The method of claim 6, wherein the metal-organic framework UiO-66-NH 2 The solution concentration of the material is 30 to 50mg/L;
in the step S2), the metal organic framework UiO-66-NH 2 The volume ratio of the solution of the material to the solution to be measured is 500.
8. UiO-66-NH for quantitatively detecting phosphate radical concentration 2 A test paper comprising the metal-organic framework UiO-66-NH of claim 1 2 Material or metal organic framework UiO-66-NH prepared by the method of preparation of any of claims 2~4 2 The material is obtained by solution impregnation.
9. Adopts UiO-66-NH 2 The method for quantitatively detecting phosphate radical by using the test paper comprises the following steps:
adjusting the pH value of the solution to be measured to 6~8, and dropping a small amount of the solution to be measured on the UiO-66-NH of claim 8 2 And (3) incubating the surface of the test paper for 1-3 min at a constant temperature of 15-30 ℃, performing solid fluorescence measurement on the test paper by using a three-dimensional fluorescence instrument, and calculating the content of phosphate radicals in the solution according to the dilution times and fluorescence intensity of the sample.
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