CN115838470B - Hollow porphyrin-based porous organic polymer, preparation method thereof and application thereof in colorimetric detection of Cr (VI) - Google Patents
Hollow porphyrin-based porous organic polymer, preparation method thereof and application thereof in colorimetric detection of Cr (VI) Download PDFInfo
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- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Abstract
The invention provides a hollow porphyrin-based porous organic polymer, a preparation method thereof and application thereof in colorimetric detection of Cr (VI). The preparation method of the hollow porphyrin-based porous organic polymer comprises the following steps: taking a silicon dioxide nanosphere as a template, tetraphenyl iron porphyrin and tetraphenyl methane as monomers, and dimethanol formal as a cross-linking agent, and carrying out a reaction under the catalysis of anhydrous ferric trichloride to obtain SiO 2 @Fe-POP; and etching the silica nanosphere template, washing and drying to obtain the nano-silica gel. The polymer has rich active sites and hierarchical pore structures, so that the polymer has excellent catalytic performance, and has the advantages of strong specificity, high sensitivity, wide linear range and the like in the aspect of colorimetric detection of Cr (VI).
Description
Technical Field
The invention belongs to the technical field of colorimetric detection of heavy metals, and particularly relates to a hollow porphyrin-based porous organic polymer, a preparation method thereof and application thereof in colorimetric detection of Cr (VI).
Background
Cr (VI) is a heavy metal ion which is extremely toxic and easily soluble in water, directly damages DNA, can change human chromosomes, is established as a human carcinogen, has the carcinogenic efficacy 2-3 times that of some heavy metals, and can induce lung cancer, nasal cancer and other diseases after long-term inhalation of Cr (VI). Cr (VI) mainly originates from natural environment and industrial production, and a large amount of chromium-containing waste water and waste residues, polluted soil and underground water and seriously endangered human health are generated due to the production of materials such as textiles, leather, stainless steel, paper, dye and the like, so that a simple, visual, rapid and efficient Cr (VI) detection method is urgently needed.
Currently, methods for detecting Cr (vi) include inductively coupled plasma mass spectrometry, atomic absorption spectrometry, electrochemistry, fluorescence spectrometry, and colorimetry. Most methods require expensive analytical equipment, are complex and time-consuming to operate, and are inconvenient to carry to the field for real-time detection of Cr (VI). However, the colorimetric method has the advantages of simple operation, low cost, strong intuitiveness and the like, and has become an important method for rapidly and efficiently detecting Cr (VI) in real time. Currently, researchers have developed a variety of nano-enzyme materials for colorimetric detection of Cr (vi), such as noble metals (Au, ag), metal oxides (Fe 3O4, coO), and the like. However, these nanoenzyme materials are easily aggregated, have few exposed active sites, and have an undesirable catalytic effect. The colorimetric platform for detecting Cr (VI) is constructed based on the nano enzyme material, most of the colorimetric platform has the defects of narrow linear range, low sensitivity, poor specificity and the like, the Cr (VI) in a larger range is difficult to detect rapidly, and the practical application of the colorimetric platform is severely limited.
Therefore, a novel nano enzyme material is developed, so that a colorimetric platform for detecting Cr (VI) with high sensitivity, wide linear range and strong specificity is constructed, and the colorimetric platform has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, in particular to the problems of few active sites, narrow linear range and poor selectivity in Cr (VI) detection of the existing nano enzyme material, the invention provides a hollow porphyrin-based porous organic polymer, a preparation method thereof and application thereof in colorimetric detection of Cr (VI). The invention regulates and controls the internal structure of the polymer by regulating the size of the inorganic template, so that more active sites are exposed, and the hollow porphyrin-based porous organic polymer with rich active sites and macroporous structures is obtained. The hollow porphyrin-based porous organic polymer is applied to colorimetric detection of Cr (VI), and a colorimetric platform for rapidly detecting Cr (VI) is constructed based on the oxidase-like activity of the hollow porphyrin-based porous organic polymer, and has the advantages of high sensitivity, wide linear range, strong specificity and the like.
The technical scheme of the invention is as follows:
a hollow porphyrin-based porous organic polymer having a structural unit represented by the following formula (I):
According to the invention, the preparation method of the hollow porphyrin-based porous organic polymer comprises the following steps:
Taking a silicon dioxide nanosphere as a template, tetraphenyl iron porphyrin and tetraphenyl methane as monomers, and dimethanol formal as a cross-linking agent, and carrying out a reaction under the catalysis of anhydrous ferric trichloride to obtain SiO 2 @Fe-POP; and etching the silica nanosphere template, and washing and drying to obtain the hollow porphyrin-based porous organic polymer.
According to the invention, the tetraphenyl ferriporphyrin and the tetraphenyl methane have the following structures:
according to the invention, the diameter of the silica nanospheres is 180-200 nm; the mass ratio of the silicon dioxide nanospheres to the tetraphenyl ferriporphyrin is 1-5:1.
According to the invention, the molar ratio of tetraphenyl ferriporphyrin to tetraphenyl methane is preferably 1:0.5-3.5, more preferably 1:1-2.
According to the invention, the molar ratio of the dimethanol formal to the tetraphenyl ferriporphyrin is preferably 2-6:1.
According to the invention, the molar ratio of the anhydrous ferric trichloride to the tetraphenylferriporphyrin is preferably 1-4:1.
According to a preferred embodiment of the invention, the reaction is carried out in an organic solvent, which is 1, 2-dichloroethane; the ratio of the volume of the organic solvent to the mass of the tetraphenyl ferriporphyrin is 100-200 mL/1 g.
Preferably, according to the present invention, the reaction is carried out under a nitrogen atmosphere; the reaction temperature is 80-85 ℃, and the reaction time is 20-24 h.
According to the invention, the reaction further comprises a post-treatment step after completion, specifically comprising the following steps: naturally cooling the obtained reaction liquid to room temperature, centrifuging, washing the obtained solid for 3-5 times by using dichloromethane, methanol, acetone and ethyl acetate, and then vacuum drying for 20-30 h at 45-65 ℃ to obtain the SiO 2 @Fe-POP.
According to the invention, the silica nanosphere template is etched away using sodium hydroxide solution; the concentration of the sodium hydroxide solution is 1-3 mol/L, and more preferably 2mol/L; the addition amount of the sodium hydroxide solution is not particularly limited, and may be an addition amount commonly used in the art.
According to the invention, the post-etching of the template is preferably performed by washing 3-5 times with absolute ethanol, and then vacuum drying is performed at 45-65 ℃ for 20-30 hours.
According to the invention, the hollow porphyrin-based porous organic polymer is applied to colorimetric detection of Cr (VI).
According to the application of the invention, a preferred method for colorimetric detection of Cr (VI) by using a hollow porphyrin-based porous organic polymer comprises the following steps:
(1) Preparing Cr (VI) ion solutions with different concentrations;
(2) Adding a hollow porphyrin-based porous organic polymer aqueous dispersion solution, an 8-hydroxyquinoline aqueous solution, the Cr (VI) ion solution in the step (2) and A3, 3', 5' -tetramethyl benzidine aqueous solution into a buffer solution, reacting to obtain a standard solution, and detecting absorbance A 1 of the standard solution at 652 nm;
(3) Replacing the Cr (VI) ion solution in the step (2) with the buffer solution with the same volume, obtaining a blank control solution after the reaction, detecting the absorbance A 0 of the blank control solution at 652nm, and calculating to obtain the difference delta A of the absorbance: Δa=a 1-A0; drawing a working curve by taking the concentration of the Cr (VI) ion solution as an abscissa and the difference delta A of absorbance as an ordinate to obtain a linear equation;
(4) And (3) replacing the Cr (VI) ion solution in the step (2) with a sample to be detected, reacting to obtain a solution to be detected, detecting the absorbance of the solution to be detected at 652nm, and calculating the content of Cr (VI) ions in the sample to be detected by contrasting a linear equation.
According to the present invention, the concentration of the Cr (VI) ion solution in the step (1) is preferably 2 to 130. Mu. Mol/L.
Preferably according to the invention, the buffer solution in step (2) is a NaAc/HAc buffer solution; the pH of the buffer solution is 3.2 to 6, and more preferably 4.
According to the present invention, the concentration of the hollow porphyrin-based porous organic polymer aqueous dispersion liquid in the step (2) is preferably 0.1 to 1mg/mL, and more preferably 0.5mg/mL; the concentration of the hollow porphyrin-based porous organic polymer in the standard solution is 0.01-0.1 mg/mL, and more preferably 0.05mg/mL.
According to the present invention, the concentration of the 8-hydroxyquinoline aqueous solution in the step (2) is preferably 5 to 15mmol/L, more preferably 12mmol/L; the concentration of 8-hydroxyquinoline in the standard solution is 0.5 to 1.5mmol/L, and more preferably 1.2mmol/L.
According to a preferred embodiment of the invention, the volume ratio of the Cr (VI) ion solution to the buffer solution in step (2) is 1:6.
According to the invention, the concentration of the 3,3', 5' -tetramethylbenzidine aqueous solution in step (2) is preferably 5 to 15mmol/L, more preferably 10mmol/L; the concentration of 3,3', 5' -tetramethylbenzidine in the standard solution is 0.5 to 1.5mmol/L, and more preferably 1mmol/L.
According to a preferred embodiment of the invention, the reaction time in step (2) is 1min.
According to the invention, the buffer solution and the reaction time in the step (3) are the same as those in the step (2).
According to the invention, preferably, the reaction time in step (4) is the same as that in step (2); the calculation method comprises the following steps: and (3) calculating the absorbance of the sample to be detected and the absorbance of the blank control solution to obtain delta A, and comparing the linear equation to obtain the content of Cr (VI) ions in the sample to be detected.
The invention has the technical characteristics and beneficial effects that:
1. According to the invention, the regulation and control of the inner surface area of the hollow porphyrin-based porous organic polymer can be realized by regulating the dosage and proportion of the silica template, so that more active sites are exposed, and the hollow porphyrin-based porous organic polymer with abundant active sites and macropore structures is obtained; the amount of the silica template used in the method is critical to the catalytic performance of the obtained polymer, and the ratio is too low or too high, so that the catalytic performance of the obtained hollow porphyrin-based porous organic polymer is reduced.
2. The hollow porphyrin-based porous organic polymer provided by the invention has a hollow spherical structure, and can provide abundant active sites for substrates; the pore structure of the polymer is a medium pore and macroporous structure, so that a substrate can more easily enter the inner surface of the material to be combined with an active site, and the catalytic performance of the polymer is remarkably improved by the internal hollow sphere and the multistage pore structure, so that the polymer has an excellent catalytic effect.
3. The hollow porphyrin-based porous polymer provided by the invention has the similar oxidase activity, generates a large amount of superoxide anions (O 2 ·-) in the catalysis process, has excellent catalytic activity, and changes the catalytic colorless TMB into blue ox-TMB, thereby realizing colorimetric detection of Cr (VI). The method based on the colorimetric method for quantitatively detecting Cr (VI) has the advantages of wide linear range, high sensitivity, strong specificity and the like, the linear range is 2-130 mu mol/L, the minimum detection limit is 0.28 mu mol/L, and when the interference cation concentration is 20 times that of Cr (VI), the method still shows a strong response signal to Cr (VI).
Drawings
FIG. 1 is a transmission electron microscope image of H-Fe-POP prepared in example 1.
FIG. 2 is an infrared spectrum of H-Fe-POP prepared in example 1.
FIG. 3 is a nitrogen adsorption-desorption chart and a pore size distribution chart (inset) of H-Fe-POP prepared in example 1.
FIG. 4 is a graph and a linear relationship (bottom right inset) of the H-Fe-POP versus Cr (VI) detection in test example 2.
Detailed Description
The invention is further illustrated, but not limited, by the following examples.
Meanwhile, the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials, unless otherwise specified, are commercially available.
The silica nanospheres and tetraphenyl ferriporphyrin used in the examples were prepared according to the methods of preparation example 1 and preparation example 2, respectively.
Preparation example 1
Synthesis of silica nanospheres:
7mL of tetraethyl silicate is added into 28mL of ethanol to obtain a tetraethyl silicate solution; adding 3.5mL of ammonia water (the concentration is 25-28 wt%) into a mixed solution of 72mL of ethanol and 9mL of water to obtain an alkali solution; adding the tetraethyl silicate solution into the alkali solution, and stirring the mixture for 12 hours at room temperature; and centrifuging the obtained reaction solution to recover solid, washing the obtained solid with absolute ethyl alcohol by ultrasonic for three times, and vacuum drying at 55 ℃ for 24 hours to obtain the silica nanospheres with the diameter of 180-200 nm.
Preparation example 2
Synthesis of tetraphenyl ferriporphyrin (FeTPP) monomer:
tetraphenylporphyrin (0.2024 g) was dissolved in 50mL of DMF, sonicated for 10min, and then added to a 100mL three-necked flask; feCl 2·4H2 O (0.4166 g) was added in three equal portions (10 min apart), magnetically stirred and refluxed at 165 ℃, fully purged with nitrogen, and reacted for 3h. After the completion of the reaction, the mixture was cooled to room temperature, then HCl solution (30 mL,6 mol/L) was added, the mixture was sufficiently stirred at room temperature, and the obtained precipitate was recovered by centrifugation. The precipitate was washed with HCl solution (1 mol/L) until the filtrate was colorless and then washed 5 times with deionized water. The obtained solid is dissolved in 5mL of dichloromethane, 200mL of petroleum ether is poured into the solution, the solution is recrystallized for 2 times, the solid is recovered by filtration and is dried in vacuum for 24 hours at 55 ℃ to obtain purple-black powder, namely the tetraphenyl ferriporphyrin (FeTPP) monomer.
Example 1
A preparation method of a hollow porphyrin-based porous organic polymer comprises the following steps:
(1) Silica nanospheres (0.6150 g), tetraphenyl ferriporphyrin (0.3305 g) and tetraphenyl methane (0.1751 g) were dissolved in 50mL of 1, 2-dichloroethane and sonicated for 1h.
(2) The mixture obtained in step (1) was placed in a 100mL three-necked flask, nitrogen was introduced thereinto, and dimethyl formal (0.2 mL) and anhydrous FeCl 3 (0.2466 g) were added thereto, followed by stirring and refluxing at 80℃for 24 hours.
(3) After the reaction is finished, naturally cooling to room temperature, centrifuging to recover solid, washing the obtained solid with dichloromethane, methanol, acetone and ethyl acetate for 3 times respectively, and vacuum drying at 65 ℃ for 24 hours to obtain SiO 2 @Fe-POP.
(4) And etching the obtained SiO 2 @Fe-POP by using a NaOH solution (2 mol/L) to remove a silica nanosphere template (the volume ratio of the mass of the SiO 2 @Fe-POP to the sodium hydroxide solution is 0.01g:5 mL), washing for 5 times by using absolute ethyl alcohol, and vacuum drying at 65 ℃ for 24 hours to obtain black powder, namely the hollow porphyrin-based porous organic polymer, which is marked as H-Fe-POP.
The transmission electron microscope image of the hollow porphyrin-based porous organic polymer prepared in the embodiment is shown in fig. 1, and as can be seen from fig. 1, the internal silicon dioxide is completely etched, a plurality of hollow sphere structures are shown, and the size of the hollow sphere is 180-200 nm.
The infrared spectrogram of the hollow porphyrin-based porous organic polymer prepared in the embodiment is shown in fig. 2, and an N-Fe vibration peak appears at 1006cm -1 to indicate that iron ions are coordinated with the nitrogen atom of TPP, and in addition, a C-H stretching vibration peak (2922 cm -1) in H-Fe-POP is formed to indicate that the polymerization of two monomers is successful.
The nitrogen adsorption-analysis diagram and the pore size distribution diagram of the hollow porphyrin-based porous organic polymer prepared by the embodiment are shown in fig. 3, the specific surface area of the obtained hollow porphyrin-based porous organic polymer is 10-100 m 3/g, the pore size is mainly distributed at 15-25 nm, and the pore structure is a mesopore and a macropore, so that a substrate can more easily enter the inner surface of the material to be combined with an active site, and the catalytic performance is improved.
Comparative example 1
A method of preparing a hollow porphyrin-based porous organic polymer as described in example 1, except that: monomers are tetraphenylporphyrin and tetraphenylmethane.
The method comprises the following specific steps: silica nanospheres (0.6150 g), tetraphenylporphyrin (0.2766 g) and tetraphenylmethane (0.1751 g) were dissolved in 50mL of 1, 2-dichloroethane and sonicated for 1h. The mixture was placed in a 100mL three-necked flask, nitrogen was introduced thereinto, and dimethyl formal (0.2 mL) and anhydrous FeCl 3 (0.2466 g) were added thereto, and the mixture was heated at 80℃under stirring and refluxed for 24 hours. After the reaction is finished, naturally cooling, centrifuging to recover solid, washing the obtained solid with dichloromethane, methanol, acetone and ethyl acetate for 3 times respectively, and vacuum drying at 65 ℃ for 24 hours to obtain the polymer. The silica nanospheres were etched with NaOH (1.6 g,2 mol/L) solution, then washed 5 times with absolute ethanol, and dried under vacuum at 65℃for 24 hours to give a polymer (abbreviated as H-POP).
Comparative example 2
A porphyrin-based porous organic polymer was synthesized as in example 1, except that: the silicon dioxide ball template is not etched in the follow-up process; other steps and conditions were the same as in example 1, and the resulting polymer was SiO 2 @ Fe-POP.
Test example 1
The polymers prepared in example 1 and comparative examples 1-2 were tested for catalytic performance.
An aqueous dispersion of H-Fe-POP (200. Mu.L, 0.5 mg/mL), an aqueous TMB solution (200. Mu.L, 10 mmol/L) was added to a NaAc/HAc buffer solution (1.6 mL, pH=4), and the mixture was kept at room temperature for 14min, and then the absorbance at 652nm was measured; the test was performed using an aqueous dispersion of H-POP (200. Mu.L, 0.5 mg/mL), siO 2 @ Fe-POP (200. Mu.L, 0.5 mg/mL) and NaAc/HAc buffer solution (200. Mu.L, pH=4) in place of the aqueous dispersion of H-Fe-POP (200. Mu.L, 0.5 mg/mL), respectively, and the results are shown in Table 1.
TABLE 1 absorbance at 652nm for different systems
| System of | TMB | H-Fe-POP+TMB | H-POP+TMB | SiO2@Fe-POP+TMB |
| Absorbance of light | 0.0055 | 0.5784 | 0.3470 | 0.4485 |
As is clear from Table 1, TMB alone was added to the buffer solution, and the absorbance at 652nm was almost 0, indicating that TMB did not undergo oxidation reaction. When the system has H-Fe-POP, the system has obvious absorbance at 652nm, which indicates that the H-Fe-POP can catalyze and oxidize TMB to change color, and has excellent catalytic activity. Compared with the hollow porphyrin-based porous organic polymer prepared in example 1, the catalytic performance of the polymer prepared in comparative example 1 is reduced by 40%, and it is seen that iron ions coordinated by tetraphenylporphyrin centers are particularly important for the catalytic performance; the catalytic performance of the polymer prepared by the comparative example is reduced by 22%; it can be seen that the hollow structure can significantly improve the catalytic performance.
Test example 2
The test of the series of concentrations Cr (VI) for the hollow porphyrin-based porous organic polymer prepared in example 1 is given below.
(1) 0.0147G of potassium dichromate is weighed and dissolved in 50mL of deionized water, and a series of Cr (VI) ion solutions (2, 6, 10, 30, 50, 70, 90, 110, 130, 150, 170, 200, 250 and 300 mu mol/L) with concentration are prepared by stepwise dilution;
(2) To NaAc/HAc buffer solution (1.2 mL, pH=4), aqueous dispersion of H-Fe-POP (200. Mu.L, 0.5 mg/mL), aqueous 8-HQ solution (200. Mu.L, 12 mmol/L), aqueous TMB solution (200. Mu.L, 10 mmol/L) and ionic Cr (VI) (200. Mu.L) were added in this order, and after reacting at room temperature for 1min, a standard solution was obtained; measuring absorbance A 1 of standard solution added with Cr (VI) ion solutions with different concentrations at 652 nm; and to NaAc/HAc buffer solution (1.4 mL, pH=4), aqueous dispersion of H-Fe-POP (200. Mu.L, 0.5 mg/mL), aqueous 8-HQ solution (200. Mu.L, 12 mmol/L), aqueous TMB solution (200. Mu.L, 10 mmol/L) were added in this order, and after reacting at room temperature for 1min, a blank control solution was obtained, absorbance A 0 of the blank control solution at 652nm was measured, and the difference DeltaA in absorbance was calculated according to the following formula: Δa=a 1-A0; the concentration of Cr (VI) ion solution is taken as an abscissa, the difference of absorbance delta A is taken as an ordinate, a working curve is drawn, as shown in a figure 4, as the concentration of Cr (VI) is increased, delta A is firstly increased and then slowly decreased, in the range of 2-130 mu mol/L, the concentration of delta A and the concentration of Cr (VI) show good linear relation, and a linear equation is as follows: y=0.0164 x-0.0281, the linear correlation coefficient is 0.999, and the lowest detection limit is 0.28 mu mol/L, which indicates that the method can quantitatively detect Cr (VI).
Test example 3
The response of the hollow porphyrin-based porous organic polymer prepared in example 1 to Cr (VI) and other interfering cations (Pb2+、Co2+、Cd2+、Ba2+、Al3+、Mg2+、Zn2+、Na+、Fe3+) is shown below, and the specific test method is described in test example 2. The concentration of Cr (VI) was 0.05mmol/L and the interfering ion concentration was 1mmol/L, although the interfering ion concentration was 20 times that of Cr (VI), table 2 shows that the response signal of Cr (VI) was significantly higher than that of other interfering cations, indicating that the method has good specificity for Cr (VI).
TABLE 2 absorbance change for different cations
| Cations (cationic) | Pb2+ | Co2+ | Cd2+ | Ba2+ | Al3+ | Mg2+ | Zn2+ | Na+ | Fe3+ | Cr6+ |
| ΔA | 0.072 | 0.039 | 0.080 | 0.086 | 0.060 | 0.054 | 0.075 | 0.061 | 0.036 | 0.779 |
Test example 4
The hollow porphyrin-based porous organic polymer prepared in example 1 was used to detect Cr (VI) in an actual water sample. Two water samples (tap water and industrial wastewater) are selected for measuring the Cr (VI) content, and the specific test method is as described in test example 2, and the sample to be tested is used for replacing the Cr (VI) ion solution in the step (2). Cr (VI) is not detected in tap water, and the content of Cr (VI) is possibly lower than the detection limit of the method, and the concentration of Cr (VI) in industrial wastewater is 10.3 mu mol/L. Further, cr (VI) with different concentrations is added into the actual water sample, and the standard concentration is 10, 50 and 100 mu mol/L. As can be seen from Table 3, the recovery rate of tap water and industrial wastewater is between 95% and 103.2%, which demonstrates the feasibility of the method for detecting Cr (VI) in an actual water sample.
TABLE 3 Experimental results of the inventive method on the recovery rates of actual water samples with different concentrations of Cr (VI)
The foregoing is merely a preferred embodiment of the present invention, and the present invention is not limited thereto, and equivalent embodiments using some modifications and equivalent variations made by the foregoing are included in the scope of the present invention without departing from the scope of the present invention.
Claims (12)
1. A hollow porphyrin-based porous organic polymer is characterized by having a structural unit represented by the following formula (I):
2. The method for preparing the hollow porphyrin-based porous organic polymer of claim 1, comprising the steps of:
Taking a silicon dioxide nanosphere as a template, tetraphenyl iron porphyrin and tetraphenyl methane as monomers, and dimethanol formal as a cross-linking agent, and carrying out a reaction under the catalysis of anhydrous ferric trichloride to obtain SiO 2 @Fe-POP; and etching the silica nanosphere template, and washing and drying to obtain the hollow porphyrin-based porous organic polymer.
3. The method for preparing a hollow porphyrin-based porous organic polymer according to claim 2, wherein the diameter of the silica nanospheres is 180-200 nm; the mass ratio of the silicon dioxide nanospheres to the tetraphenyl ferriporphyrin is 1-5:1.
4. The method for preparing a hollow porphyrin-based porous organic polymer according to claim 2, wherein the molar ratio of tetraphenyl ferriporphyrin to tetraphenyl methane is 1:0.5-3.5.
5. The method for preparing a hollow porphyrin-based porous organic polymer according to claim 2, wherein the molar ratio of tetraphenyl ferriporphyrin to tetraphenyl methane is 1:1-2.
6. The method for preparing a hollow porphyrin-based porous organic polymer according to claim 2, wherein the molar ratio of dimethanol formal to tetraphenyl iron porphyrin is 2-6:1; the molar ratio of the anhydrous ferric trichloride to the tetraphenyl ferriporphyrin is 1-4:1.
7. The method for preparing a hollow porphyrin-based porous organic polymer according to claim 2, wherein the reaction is performed in an organic solvent, which is 1, 2-dichloroethane; the ratio of the volume of the organic solvent to the mass of the tetraphenyl ferriporphyrin is 100-200 mL/1 g;
the reaction is carried out under nitrogen atmosphere; the reaction temperature is 80-85 ℃, and the reaction time is 20-24 h.
8. The method for preparing a hollow porphyrin-based porous organic polymer according to claim 2, further comprising a post-treatment step after the reaction is completed, specifically comprising the following steps: naturally cooling the obtained reaction liquid to room temperature, centrifuging, washing the obtained solid for 3-5 times by using dichloromethane, methanol, acetone and ethyl acetate respectively, and then vacuum drying for 20-30 h at 45-65 ℃ to obtain SiO 2 @Fe-POP;
Etching the silica nanosphere template by using sodium hydroxide solution, wherein the concentration of the sodium hydroxide solution is 1-3 mol/L; and washing the etched template for 3-5 times by using absolute ethyl alcohol, and then vacuum drying at 45-65 ℃ for 20-30 h.
9. Use of the hollow porphyrin-based porous organic polymer according to claim 1 for colorimetric detection of Cr (vi).
10. Use according to claim 9, characterized in that the method for the colorimetric detection of Cr (vi) by means of a hollow porphyrin-based porous organic polymer comprises the following steps:
(1) Preparing Cr (VI) ion solutions with different concentrations;
(2) Adding a hollow porphyrin-based porous organic polymer aqueous dispersion solution, an 8-hydroxyquinoline aqueous solution, the Cr (VI) ion solution in the step (1) and A3, 3', 5' -tetramethyl benzidine aqueous solution into a buffer solution, reacting to obtain a standard solution, and detecting absorbance A 1 of the standard solution at 652 nm;
(3) Replacing the Cr (VI) ion solution in the step (2) with the buffer solution with the same volume to obtain a blank control solution, detecting the absorbance A 0 of the blank control solution at 652nm, and calculating to obtain the absorbance difference delta A: Δa=a 1-A0; drawing a working curve by taking the concentration of the Cr (VI) ion solution as an abscissa and the difference delta A of absorbance as an ordinate to obtain a linear equation;
(4) And (3) replacing the Cr (VI) ion solution in the step (2) with a sample to be detected, reacting to obtain a solution to be detected, detecting the absorbance of the solution to be detected at 652nm, and calculating the content of Cr (VI) ions in the sample to be detected by contrasting a linear equation.
11. The use according to claim 10, wherein the concentration of the Cr (vi) ion solution in step (1) is 2 to 130 μmol/L;
The buffer solution in the step (2) is NaAc/HAc buffer solution; the pH value of the buffer solution is 3.2-6; the concentration of the hollow porphyrin-based porous organic polymer aqueous dispersion liquid is 0.1-1 mg/mL; the concentration of the hollow porphyrin-based porous organic polymer in the standard solution is 0.01-0.1 mg/mL; the concentration of the 8-hydroxyquinoline water solution is 5-15 mmol/L; the concentration of 8-hydroxyquinoline in the standard solution is 0.5-1.5 mmol/L; the volume ratio of the Cr (VI) ion solution to the buffer solution is 1:6; the concentration of the 3,3', 5' -tetramethyl benzidine aqueous solution is 5-15 mmol/L; the concentration of 3,3', 5' -tetramethyl benzidine in the standard solution is 0.5-1.5 mmol/L; the reaction time was 1min.
12. The use according to claim 10, wherein the pH of the buffer solution in step (2) is 4; the concentration of the hollow porphyrin-based porous organic polymer aqueous dispersion liquid is 0.5mg/mL; the concentration of the hollow porphyrin-based porous organic polymer in the standard solution is 0.05mg/mL; the concentration of the 8-hydroxyquinoline aqueous solution is 12mmol/L; the concentration of 8-hydroxyquinoline in the standard solution is 1.2mmol/L; the concentration of the 3,3', 5' -tetramethyl benzidine aqueous solution is 10mmol/L;
The concentration of 3,3', 5' -tetramethyl benzidine in the standard solution is 1mmol/L.
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| CN111848932A (en) * | 2020-08-08 | 2020-10-30 | 青岛科技大学 | Preparation of porphyrin-based porous polymer and application of porphyrin-based porous polymer in styrene oxidation catalysis |
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| CN111848932A (en) * | 2020-08-08 | 2020-10-30 | 青岛科技大学 | Preparation of porphyrin-based porous polymer and application of porphyrin-based porous polymer in styrene oxidation catalysis |
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