CN117960162A - Preparation of porous organic material loaded with platinum nano particles and colorimetric detection and Hg removal method thereof2+Application in (a) - Google Patents
Preparation of porous organic material loaded with platinum nano particles and colorimetric detection and Hg removal method thereof2+Application in (a) Download PDFInfo
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- 239000000047 product Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 10
- 238000002835 absorbance Methods 0.000 claims description 10
- FUPNEGLNSFQSCQ-UHFFFAOYSA-N 2,5-bis(methylsulfanyl)terephthalaldehyde Chemical compound CSc1cc(C=O)c(SC)cc1C=O FUPNEGLNSFQSCQ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 8
- 229910020820 NaAc-HAc Inorganic materials 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 7
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- 239000011591 potassium Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
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Abstract
The invention relates to the technical field of colorimetric detection and heavy metal removal, in particular to preparation of a porous organic material loaded with platinum nanoparticles and application of the porous organic material in colorimetric detection and Hg 2+ removal. The porous organic material comprises a porous organic polymer loaded with platinum nano particles, and the average particle size of the platinum nano particles is 2.65nm; the porous organic material loaded with the platinum nano particles provided by the invention has Hg 2+ activated oxidase-like activity. Based on the activity of Hg 2+ activated oxidase-like enzyme, a colorimetric detection method of Hg 2+ is constructed. The porous organic material can also remove Hg 2+ efficiently, and the removal rate is up to 99.4%.
Description
Technical Field
The invention relates to the technical field of colorimetric detection and heavy metal removal, in particular to preparation of a porous organic material loaded with platinum nanoparticles and application of the porous organic material in colorimetric detection and Hg 2+ removal.
Background
In recent years, heavy metal pollution has become a global environmental problem. Hg 2+ is a highly toxic and non-biodegradable heavy metal ion that can exert toxic effects on a variety of tissues and organs. The industrially discharged Hg 2+ wastewater increases the mercury deposition amount in lakes and soil, hg 2+ can be absorbed and amplified by organisms, and the ecological system and human health are seriously threatened. Therefore, detection and removal of Hg 2+ is particularly important.
Among various analytical methods, including atomic absorption spectroscopy, inductively coupled plasma mass spectrometry, electrochemistry, fluorescence spectroscopy, colorimetry, etc., colorimetry is becoming more favored for its simplicity, low cost, rapid and macroscopic color change, and has been widely used for detecting toxic ions, biological small molecules, organic pollutants, etc. Currently, nanoenzyme-based colorimetry has been used for sensitive detection of Hg 2+. However, most nanomaterials are not effective in removing Hg 2+ and only detection of Hg 2+ is achieved. Therefore, there is a need to develop bifunctional nanoezymes for detecting and removing Hg 2+. In previous reports, hg 2+ can enhance or inhibit the catalytic activity of noble metal nano-enzymes (Au, ag, pt, etc.), noble metal catalysts have been used to detect Hg 2+. It is known that the catalytic performance of noble metal nano-enzymes is reduced due to severe aggregation phenomenon and poor stability. Notably, uniformly immobilized Pt NPs generally have excellent catalytic performance. Thus, loading Pt NPs onto porous organic materials of customizable units is a new idea.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a porous organic material loaded with platinum nanoparticles, which is characterized in that sulfide groups are introduced into the porous organic material to fix the platinum nanoparticles, so that the platinum nanoparticles are uniformly loaded on the porous material. It is another object of the present invention to provide the use of porous organic polymers loaded with platinum nanoparticles for colorimetric detection and removal of Hg 2+. Importantly, the constructed colorimetric method has the advantages of strong specificity, wide detection range, rapidness and the like in detection of Hg 2+. Meanwhile, when the nano material prepared by the method is used for removing Hg 2+ in an aqueous solution, higher removal efficiency is shown.
The invention is realized by the following technical scheme:
a porous organic material loaded with platinum nanoparticles, the porous organic material comprising a porous organic polymer loaded with platinum nanoparticles, the platinum nanoparticles having an average particle diameter of 2.65nm;
The porous organic polymer comprises the following chemical structure:
；
The porous organic polymer is prepared by one-step condensation of pyrrole and 2, 5-bis (methylthio) terephthalaldehyde.
A preparation method of a porous organic material loaded with platinum nano particles comprises the following steps: adding a porous organic polymer and polyvinylpyrrolidone into ethanol, deionized water and potassium chloroplatinate solution, ultrasonically mixing and stirring for 3 hours, heating to react under intense stirring, wherein the heating temperature is 70-90 ℃, centrifuging after the reaction is finished, recovering a product, and washing for three times by using a mixed solution of ethanol and water in a volume ratio of 1:1; and (3) drying in vacuum at 60 ℃ for 24 hours to obtain the porous organic material loaded with the platinum nano particles.
Further, the preparation method of the porous organic polymer comprises the following steps:
(1) Preparation of 2, 5-bis (methylthio) terephthalaldehyde:
Firstly, adding 2, 5-dibromoterephthalaldehyde, DMF and NaSCH 3 into a three-neck flask, and stirring at room temperature for 12h in an atmosphere of N 2; secondly, adding 1 mol/L hydrochloric acid into the product; then the product is extracted three times by chloroform and is washed by deionized water for several times; obtaining a crude product by reduced pressure distillation, and further purifying the crude product by silica gel chromatography; finally, vacuum drying is carried out for 24 hours to obtain light orange solid;
(2) Preparation of Porous Organic Polymer (POP):
2, 5-bis (methylthio) terephthalaldehyde, feCl 2.4H2 O, propionic acid and pyrrole were added to a 50ml three-necked flask under an atmosphere of N 2, and refluxed at 150℃for 48 hours; the product was recovered by centrifugation and then washed several times with methanol, 0.1mol/L hydrochloric acid, tetrahydrofuran and deionized water; vacuum drying at 60deg.C for 24 hr to obtain black powder.
Further, the mass ratio of polyvinylpyrrolidone to porous organic polymer is 3:1.
Further, the concentration of the potassium chloroplatinate solution is 0.05-0.2 mol/L, preferably 0.1mol/L.
Further, the volume ratio of the ethanol to the deionized water to the potassium chloroplatinate solution is 10:9:1.
Further, the heating temperature is 70-90 ℃, preferably 80 ℃.
The invention also provides application of the porous organic material loaded with platinum nano particles in colorimetric detection of Hg 2+.
A method for colorimetric detection of Hg 2+ by a porous organic material loaded with platinum nanoparticles, comprising the steps of:
(1) Adjusting the pH value of a NaAc-HAc buffer solution, wherein the pH value of the buffer solution is 2-8, and preferably the pH value is 4;
(2) Preparing Hg 2+ solutions with different concentrations, wherein the concentration of the Hg 2+ solution is 0-1 mmol/L;
(3) And (3) adding the porous organic material solution loaded with the platinum nano particles, the Hg 2+ solution obtained in the step (2) and the 3,3', 5' -Tetramethylbenzidine (TMB) solution into the NaAc-HAc buffer solution to react for 30-180 s, and measuring the absorbance value at 652nm after 120s reaction.
The invention also provides application of the porous organic material loaded with platinum nano particles in removing Hg 2+.
A method for removing Hg 2+ from a platinum nanoparticle-loaded porous organic material, comprising the steps of:
(1) Adjusting the pH value of the Hg 2+ solution; the pH is 4-9, preferably 7;
(2) Preparing Hg 2+ solutions with different concentrations; the concentration of the Hg 2+ solution is 60-100 ppm;
(3) Dispersing the porous organic polymer loaded with the platinum nano particles into Hg 2+ aqueous solution, then oscillating the mixture for 0.5-12 h, preferably 8h, centrifugally separating the supernatant, filtering residual materials, and measuring the concentration of Hg 2+ after adsorption.
Compared with the prior art, the invention has the technical characteristics and beneficial effects as follows:
(1) According to the technical scheme, thioether groups are introduced into the porous organic polymer, so that nano platinum particles are successfully fixed on the polymer, and the ultra-small nano platinum particles are uniformly distributed on the polymer and have good stability.
(2) Compared with the single porous organic polymer, the catalytic activity of the porous organic polymer loaded with the platinum nano particles is obviously improved by 11 times after Hg 2+ is added.
(3) The porous organic material loaded with the platinum nano particles provided by the invention has Hg 2+ activated oxidase-like activity. Based on the activity of Hg 2+ activated oxidase-like enzyme, a colorimetric detection method of Hg 2+ is constructed. Compared with other methods for detecting Hg 2 +, the method is simpler, and hydrogen peroxide or substances acting with Hg 2+ are not needed to be added. In addition, the method has the advantages of strong specificity, wide linear range, short detection time and the like when detecting Hg 2+.
(4) The porous organic material provided by the invention can also efficiently remove Hg 2+, and the removal rate is as high as 99.4%.
Drawings
FIG. 1 is a transmission electron microscope image of a porous organic material prepared in accordance with the practice of the present invention.
FIG. 2 is an infrared spectrum of a porous organic material prepared in accordance with the practice of the present invention.
FIG. 3 is a diagram showing nitrogen adsorption-desorption and pore size distribution of a porous organic material prepared by the practice of the present invention.
Fig. 4 is a linear calibration graph of detection Hg 2+ for porous organic materials prepared in accordance with the practice of the present invention.
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.
Example 1
The preparation method of the porous organic polymer loaded with platinum nanoparticles is given below.
1. Preparation of 2, 5-bis (methylthio) terephthalaldehyde:
First, 2, 5-dibromoterephthalaldehyde (0.2 g,0.685 mmol), DMF (25 mL) and NaSCH 3 (200. Mu.L, 3.26 mmol) were charged into a three-necked flask, and stirred at room temperature for 12h under an atmosphere of N 2. Next, 1 mol/L hydrochloric acid (50 mL) was added to the product. The product was then extracted three times with chloroform and washed several times with deionized water. The crude product was obtained by distillation under reduced pressure and further purified by silica gel chromatography. Finally, the mixture was dried in vacuo for 24h to obtain a pale orange solid. 1H NMR(400MHz,CDCl3 Delta), 10.33 (s, 2H), 7.76 (s, 2H), 2.50 (s, 6H).
2. Preparation of Porous Organic Polymer (POP):
2, 5-bis (methylthio) terephthalaldehyde (0.0549 g,0.243 mmol), feCl 2.4H2 O (0.137 g,0.689 mmol), propionic acid (20 ml) and pyrrole (40. Mu.L, 0.571 mmol) were charged into a 50ml three-necked flask under an atmosphere of N 2, and refluxed at 150℃for 48 hours. The product was recovered by centrifugation and then washed several times with methanol, 0.1mol/L hydrochloric acid, tetrahydrofuran and deionized water. Vacuum drying at 60deg.C for 24 hr to obtain black powder.
3. Preparation of platinum nanoparticle-loaded porous organic material (Pt/POP):
10mg of the porous organic polymer and 30mg of polyvinylpyrrolidone were added to a 20mL glass bottle, followed by 5mL of ethanol, 4.5mL of deionized water and 0.5mL of potassium chloroplatinate solution (0.1 mol/L), ultrasonic mixing and stirring for 3 hours. The reaction was carried out at 80℃for 3h with vigorous stirring. The product was recovered by centrifugation and washed three times with a mixed solution of ethanol and water (1:1). Vacuum drying at 60deg.C for 24 hr to obtain black powder.
TEM image of Pt/POP prepared in this example shows (FIG. 1) that ultra-small Pt NPs are uniformly distributed in porous organic materials. As shown in fig. 2, in the infrared spectrum of POP, the stretching vibration peak of-c=o in 2, 5-bis (methylthio) terephthalaldehyde (1688 cm -1) almost disappeared, and the C-H stretching vibration peak of methyl group (2918 cm -1) appeared, indicating successful preparation of POP. The characteristic peaks of Pt/POP and POP are almost identical, which indicates that the POP structure remains intact even if Pt NPs are formed. The pore size distribution of Pt/POP was checked by nitrogen adsorption-desorption isotherms. As shown in FIG. 3, the specific surface area of Pt/POP is 252.8m 2/g, and the main pore diameters of Pt/POP are concentrated to 4.3 nm and 4.49nm.
Example 2
To NaAc-HAc buffer (1.4 mL, pH=4) were added Pt/POP solution (200. Mu.L, 20 mg/L), hg 2+ solution (200. Mu.L, 10. Mu. Mol/L) and TMB (200. Mu.L, 100. Mu. Mol/L), the mixed solution was 2mL in total, the mixed system was reacted at room temperature for 2 minutes, and an ultraviolet-visible spectrophotometer was scanned for absorbance at 652 nm. As is clear from Table 1, when TMB or Hg 2+ alone was present in the buffer solution, the absorbance at 652nm was close to 0, indicating that the system did not react. When Pt/POP exists in the system, the absorbance value at 652nm is very small, which indicates that TMB undergoes weak oxidation reaction. However, when Pt/POP and Hg 2+ coexist, there is a large absorbance at 652nm, indicating that both can catalyze the oxidation of TMB to blue when they coexist.
TABLE 1 absorbance values at 652nm for different systems
As can be seen from table 2, the catalytic performance of Pt/POP was improved 16 times after addition of Hg 2+, compared with pure Pt/POP, confirming that Pt/POP catalyst has excellent Hg 2+ enhanced oxidase-like activity. In contrast, the catalytic performance was not significantly improved after the addition of Hg 2+ to POP. It can be seen that the inclusion of the nano-platinum particles significantly enhanced the Hg 2+ -activated oxidase-like activity of the porous organic material.
Table 2 comparison of Hg 2+ enhanced catalytic performance for POP and Pt/POP
Example 3
The method for colorimetric detection of Hg 2+ by using the porous organic polymer loaded with platinum nanoparticles prepared by the invention is given below.
A series of Hg 2+ solutions (0-1 mmol/L) were prepared, pt/POP solutions (200. Mu.L, 25 mg/L) and TMB (200. Mu.L, 80. Mu. Mol/L) were added to NaAc-HAc buffer (1.6 mL, pH=4), and after 2 minutes reaction at room temperature, absorbance at 652nm (A 0) was measured as a blank. Then, pt/POP solution (200. Mu.L, 25 mg/L), TMB (200. Mu.L, 80. Mu. Mol/L) and Hg 2+ of various concentrations were added to NaAc-HAc buffer (1.4 mL, pH=4), and reacted at room temperature for 2 minutes, and the absorbance was recorded as A 1. Δa=a 1-A0 was calculated and plotted against Hg 2+ concentration. Different concentrations of Hg 2+ can catalyze the color reaction of TMB to varying degrees in the presence of Pt/POP. As shown in FIG. 4, with the increase of Hg 2+ concentration, the delta A increases and then becomes gentle, and in the range of 0.2-50 mu mol/L, the delta A and Hg 2+ concentration show good linear relation, and the detection limit is 36.5nmol/L through calculation.
Example 4
The response effect of the platinum nanoparticle-loaded porous organic polymer prepared by the present invention on Hg 2+ and other interfering ions （Hg2+、Pb2+、Cd2+、Al3+、Ba2+、Mg2+、Zn2+、Co2+、Cu2+、Na+） is given below to evaluate the selectivity of Pt/POP to Hg 2+. As is clear from Table 3, hg 2+ has a response intensity of about 10 times that of other interfering ions at 652nm, and the results show that Pt/POP has good selectivity to Hg 2+.
TABLE 3 variation of absorbance values for different cations
Example 5
The Hg 2+ in the actual water sample is detected by the porous organic polymer loaded with the platinum nano particles prepared by the invention. And verifying the feasibility of the Pt/POP+TMB sensing platform to detect Hg 2+ in an actual water sample (industrial wastewater). Different concentrations of Hg 2+ standard solutions (5, 10, and 30. Mu. Mol/L) were added to the actual samples and analyzed using a Pt/POP+TMB colorimetric platform. As shown in Table 4, the recovery rate is 93.40% -108.27%, and the result shows that the Pt/POP+TMB colorimetric platform has good accuracy and practicability for measuring Hg 2+ in an actual water sample.
TABLE 4 Experimental results of the inventive method on recovery rates of actual water samples with different concentrations of Hg 2+
Example 6
The removal efficiency of Hg 2+ in an aqueous solution using the platinum nanoparticle-loaded porous organic material prepared according to the present invention as an adsorbent is given below.
The pH of the Hg 2+ aqueous solution was adjusted to 7 using HNO 3 and NaOH. 1mg Pt/POP was dispersed in 5mL Hg 2+ aqueous solution (60, 70, 80, 90, and 100 ppm). The mixture was shaken for 6 hours, the supernatant was separated by centrifugation, the remaining material was filtered off, and the concentration of Hg 2+ after adsorption was measured. Table 5 shows the Pt/POP removal efficiency for different concentrations of Hg 2+, with a maximum removal efficiency exceeding 99%. The results indicate that Pt/POP is a promising adsorbent that can effectively capture Hg 2+ from aqueous solutions.
TABLE 5 Pt performance of Hg 2+ removal with POP as adsorbent
And (3) adjusting the pH value (4-9) of the Hg 2+ aqueous solution by using HNO 3 and NaOH, and preparing the initial concentration of Hg 2+ to be 150ppm. 1mg of Pt/POP was dispersed in 5mL of Hg 2+ aqueous solution, shaken for 6 hours, the supernatant was separated, the remaining material was filtered off, and the concentration of Hg 2+ after adsorption was measured. As can be seen from table 6, pH has a great influence on Hg 2+ adsorption, with maximum removal efficiency at ph=7.
TABLE 6 pH influence on removal efficiency
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 (9)
1. A porous organic material loaded with platinum nanoparticles, characterized in that: the porous organic material comprises a porous organic polymer loaded with platinum nano particles, and the average particle size of the platinum nano particles is 2.65nm;
The porous organic polymer comprises the following chemical structure:
；
The porous organic polymer is prepared by one-step condensation of pyrrole and 2, 5-bis (methylthio) terephthalaldehyde.
2. A method for preparing the platinum nanoparticle-supported porous organic material according to claim 1, wherein: the method comprises the following steps: a preparation method of a porous organic material loaded with platinum nano particles comprises the following steps: adding a porous organic polymer and polyvinylpyrrolidone into ethanol, deionized water and potassium chloroplatinate solution, ultrasonically mixing and stirring for 3 hours, heating to react under intense stirring, centrifuging after the reaction is finished to recover a product, and washing for three times by using a mixed solution of ethanol and water in a volume ratio of 1:1; and (3) drying in vacuum at 60 ℃ for 24 hours to obtain the porous organic material loaded with the platinum nano particles.
3. The method for preparing a platinum nanoparticle-supported porous organic material according to claim 2, wherein: the preparation method of the porous organic polymer comprises the following steps:
(1) Preparation of 2, 5-bis (methylthio) terephthalaldehyde:
Firstly, adding 2, 5-dibromoterephthalaldehyde, DMF and NaSCH 3 into a three-neck flask, and stirring at room temperature for 12h in an atmosphere of N 2; secondly, adding 1 mol/L hydrochloric acid into the product; then the product is extracted three times by chloroform and is washed by deionized water for several times; obtaining a crude product by reduced pressure distillation, and further purifying the crude product by silica gel chromatography; finally, vacuum drying is carried out for 24 hours to obtain light orange solid;
(2) Preparation of Porous Organic Polymer (POP):
2, 5-bis (methylthio) terephthalaldehyde, feCl 2.4H2 O, propionic acid and pyrrole were added to a 50ml three-necked flask under an atmosphere of N 2, and refluxed at 150℃for 48 hours; the product was recovered by centrifugation and then washed several times with methanol, 0.1mol/L hydrochloric acid, tetrahydrofuran and deionized water; vacuum drying at 60deg.C for 24 hr to obtain black powder.
4. The method for preparing a platinum nanoparticle-supported porous organic material according to claim 2, wherein:
the mass ratio of the polyvinylpyrrolidone to the porous organic polymer is 3:1;
the volume ratio of the ethanol to deionized water to the potassium chloroplatinate solution is 10:9:1, a step of;
The concentration of the potassium chloroplatinate solution is 0.05-0.2 mol/L, and the preferable concentration is 0.1mol/L.
5. The method for preparing a platinum nanoparticle-supported porous organic material according to claim 2, wherein:
The heating temperature is 70-90 ℃, preferably 80 ℃.
6. Use of the platinum nanoparticle-loaded porous organic material according to claim 1 or the platinum nanoparticle-loaded porous organic material prepared by the preparation method according to any one of claims 2 to 4 in colorimetric detection of Hg 2+.
7. A method for colorimetric detection of Hg 2+ from a platinum nanoparticle-loaded porous organic material as defined in claim 1 or a platinum nanoparticle-loaded porous organic material prepared by the method of any one of claims 2 to 4, comprising the steps of:
(1) Adjusting the pH value of a NaAc-HAc buffer solution, wherein the pH value of the buffer solution is 2-8, and preferably the pH value is 4;
(2) Preparing Hg 2+ solutions with different concentrations, wherein the concentration of the Hg 2+ solution is 0-1 mmol/L;
(3) And (3) adding the porous organic material solution loaded with the platinum nano particles, the Hg 2+ solution and the TMB solution in the step (2) into the NaAc-HAc buffer solution to react for 30-180 s, and measuring the absorbance value at 652nm after 120s reaction.
8. Use of the platinum nanoparticle-loaded porous organic material according to claim 1 or the platinum nanoparticle-loaded porous organic material prepared by the preparation method according to any one of claims 1 to 4 for removing Hg 2+, wherein: the porous organic material has excellent Hg 2+ enhanced oxidase-like activity; at ph=7, there was maximum Hg 2+ removal efficiency.
9. A method for removing Hg 2+ from a platinum nanoparticle-loaded porous organic material as claimed in claim 1 or a platinum nanoparticle-loaded porous organic material prepared by the method of any one of claims 1 to 4, comprising the steps of:
Adjusting the pH value of the Hg 2+ solution; the pH is 4-9, preferably 7;
Preparing Hg 2+ solutions with different concentrations; the concentration of the Hg 2+ solution is 60-100 ppm;
Dispersing the porous organic polymer loaded with the platinum nano particles into Hg 2+ aqueous solution, then oscillating the mixture for 0.5-12 h, preferably 8h, centrifugally separating the supernatant, filtering residual materials, and measuring the concentration of Hg 2+ after adsorption.
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