CN110272110B - Method for degrading iodo-substituted drug based on MOF template method - Google Patents
Method for degrading iodo-substituted drug based on MOF template method Download PDFInfo
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- CN110272110B CN110272110B CN201910610480.6A CN201910610480A CN110272110B CN 110272110 B CN110272110 B CN 110272110B CN 201910610480 A CN201910610480 A CN 201910610480A CN 110272110 B CN110272110 B CN 110272110B
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Abstract
The invention discloses an iodomedicine degradation method based on an MOF template method, and particularly relates to a method for degrading iodomedicines in water by using sulfate radicals generated by activating sulfite with copper-iron composite oxide prepared based on an MOF template method. According to the method, an MOF material can be used as a self-sacrifice template, the copper-iron composite oxide is prepared after calcination, and the characteristics of high specific surface area and strong catalytic activity of the copper-iron composite oxide are utilized to activate sulfite to generate sulfate radicals to degrade iodo drugs. The copper-iron composite oxide prepared based on the MOF template method is easy to recycle and has good activation effect after being recycled for many times. The method is suitable for degrading various iodophors, has high activation efficiency, is simple and easy to operate, can effectively activate sulfite to degrade the iodophors under a neutral condition, and has better advantages.
Description
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to a method for degrading an iodo-substituted drug based on an MOF template method.
Background
Micro-drug pollutants are frequently detected in water bodies around the world, wherein iododrugs are an important class of drugs. Iodophors are difficult to remove in conventional wastewater treatment, resulting in higher detected concentrations in surface water bodies. Iodinated drugs are important precursors for generating iodinated disinfection byproducts, and studies show that the formation of iodotrihalomethanes is in positive correlation with the content of iodinated drugs.
At present, the reaction activity of conventional oxidants (ozone, hypochlorous acid and monochloramine) and iodomedicine is low in the water treatment process, so that the degradation of the iodomedicine is difficult to realize, and the advanced oxidation method can generate free radicals (hydroxyl free radicals, sulfate free radicals and the like) with high reaction activity, so that the rapid oxidative degradation of pollutants can be realized. Compared with hydroxyl free radical, the sulfate radical-based advanced oxidation technology has the advantages of long half-life period, high selectivity, small influence by water background substances, weak competitive consumption of coexisting components (phosphate ions, carbonate ions, sulfate ions, natural organic matters and the like) in water and the like, and is widely applied to the field of water environment pollution remediation and treatment.
The sulfite is an industrial product with environment-friendly characteristics, the raw materials are cheap and easy to obtain, the risk of secondary pollution is low, and the sulfite is used as a precursor for generating sulfate radicals and has obvious advantages when being applied to a water treatment process. Activators to promote the sulfite autoxidation process may generally be used as homogeneous transition metal ions, heterogeneous activators, and the like. The transition metal ion activator has the advantages of low technical difficulty, high activation efficiency and low energy consumption, but has the problem of metal ion release and certain environmental risk. The preparation of the heterogeneous phase activation material which is cheap and easy to obtain, can be recycled and has no secondary pollution replaces the activation of homogeneous phase transition metal ions, and the preparation method is gradually concerned. However, when the heterogeneous activating material is adopted to activate the organic pollutants in the sulfite processing water at present, the problem of low organic matter degradation efficiency under the neutral condition exists.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for degrading iodomedicine based on an MOF template method.
The technical scheme adopted by the invention for solving the technical problems is as follows: provided is an iodo-drug degradation method based on an MOF template method, which comprises the following steps:
(1) dissolving copper nitrate trihydrate, iron acetylacetonate and terephthalic acid in a mixed solution of N, N-dimethylformamide and ethanol, and fully mixing and dissolving to obtain a precursor solution; reacting the precursor solution at the temperature of 100-180 ℃ for 10-36 h; after the reaction is finished, cooling to room temperature, washing and drying to obtain the copper/iron bimetallic organic framework material;
(2) cleaning the copper/iron bimetallic organic framework material obtained in the step (1) with ethanol, drying, heating to 500 ℃ at the speed of 1 ℃/min, and calcining for 1h to obtain a copper-iron composite oxide;
(3) placing the copper-iron composite oxide obtained in the step (2) in a water body to be treated containing iodomedicine, adjusting the pH value to 5-9, then adding sulfite with the use amount of 0.250-0.980 mM, taking a water sample after the reaction is finished, and then determining the concentration of the residual iodomedicine;
(4) and taking out the copper-iron composite oxide, washing with deionized water, and adding the copper-iron composite oxide into untreated water to be treated containing the iodophor for recycling for 1-5 times.
In a preferred embodiment of the present invention, in the step (1), the molar ratio of the copper nitrate trihydrate, the iron acetylacetonate and the terephthalic acid is 1: 0.2-3: 2 to 5. The volume ratio of the N, N-dimethylformamide to the ethanol in the mixed solution is 1: 0.5 to 2.
In a preferred embodiment of the invention, the concentration of the iodomedicine in the water to be treated containing the iodomedicine is 0.5-3 mg/L.
In a preferred embodiment of the invention, in the step (3), the copper-iron composite oxide obtained in the step (2) is placed in a water body to be treated containing an iodine-containing drug, the dosage of the copper-iron composite oxide is 50-500 mg/L, the pH value is adjusted to 7-8, and then a sulfite, the dosage of which is 0.250-0.980 mM, is added, wherein the sulfite is sodium sulfite and/or potassium sulfite.
Compared with the background technology, the technical scheme has the following advantages:
1. the invention adopts MOF template method to prepare copper-iron composite oxide, can realize the efficient activation of sulfite to generate sulfate radical free radical under neutral condition to degrade iodo-containing drug in water, is easy to recycle, and avoids secondary pollution.
2. The MOF material can be used as a self-sacrifice template, and the porous copper-iron composite oxide is prepared after calcination, has a large specific surface area and excellent physicochemical properties, can efficiently degrade iodomedicine, and has obvious advantages in the aspect of pollutant treatment.
Drawings
FIG. 1 is a plot of the iohexol decay at different reaction time points.
FIG. 2 is a graph showing the effect of iohexol removal at different pH values.
FIG. 3 is a graph showing the effect of iohexol removal by repeating the cycle 1 to 5 times.
Detailed Description
Example 1
The method for degrading the iodo-substituted drug based on the MOF template method comprises the following steps:
(1) dissolving 0.241g of copper nitrate trihydrate, 0.353g of ferric acetylacetonate and 0.332g of terephthalic acid in a mixed solution (50mL, v: v ═ 1) of N, N-dimethylformamide and ethanol, and sufficiently mixing and dissolving to obtain a precursor solution;
putting the precursor solution into a hydrothermal kettle, controlling the reaction temperature at 120 ℃, and reacting for 12 h;
after the reaction is finished, cooling to room temperature, washing and drying to obtain a copper/iron bimetallic organic framework material MOFs which is constructed by copper, iron bimetallic ions and rigid organic ligands;
(2) cleaning and drying the copper/iron bimetallic organic framework material by using ethanol, placing the material in a muffle furnace, heating the material to 500 ℃ at the speed of 1 ℃/min, and calcining the material for 1h to obtain a copper-iron composite oxide; the copper-iron composite oxide takes a copper/iron bimetallic organic framework material as a self-sacrificial template, so that the copper-iron composite oxide has a large specific surface area and excellent physical and chemical properties, and can effectively activate sulfite to degrade iodo-substituted drugs;
(3) placing the obtained copper-iron composite oxide (0.08g/L) in a water body to be treated (pH is adjusted to 7) with an iodophor of iohexol (2mg/L), adding 0.450mM of sodium sulfite, stirring the mixture for reaction by a stirrer at room temperature, setting different reaction time points (0, 5, 10, 20, 30, 40, 50 and 60min), taking a water sample to measure the concentration of residual iohexol, and drawing an attenuation curve of iohexol at different reaction time points (figure 1);
as shown in fig. 1, the addition of the copper-iron composite oxide can significantly promote the effective degradation of iohexol, compared to the sodium sulfite system alone; with the prolonging of the reaction time, the concentration of iohexol in the water body to be treated is gradually reduced; after the reaction is carried out for 30min, the residual concentration of the iohexol is only about 1% of the initial concentration of the iohexol, which shows that the copper-iron composite oxide prepared based on the MOF template method can effectively activate sodium sulfite to degrade the iohexol.
Example 2
Steps (1) and (2) of this example are the same as those of example 1, except that:
(3) adding the obtained copper-iron composite oxide (0.08g/L) into a water body to be treated, wherein the iodine medicine is iohexol (2mg/L), respectively adjusting the pH values to 5, 6, 7, 8 and 9, then adding 0.450mM sodium sulfite, stirring and reacting by using a stirrer at room temperature, taking a water sample after reacting for 30min to determine the concentration of residual iohexol, and drawing a curve (shown in figure 2) of the removal effect of iohexol at different pH values;
as shown in fig. 2, the ordinate represents the ratio of the residual quantity to the initial quantity of iohexol, the effect of degrading the iodol can be achieved at a pH value of 5-9, and particularly, at a pH value of 7-9, after reaction for 30min, the residual concentration of iohexol in the water body to be treated is only about 1% of the initial concentration, which indicates that the copper-iron composite oxide prepared based on the MOF template method can efficiently activate sulfite to remove iohexol under a neutral condition.
Example 3
Steps (1) and (2) of this example are the same as those of example 1, except that:
(3) adding the obtained copper-iron composite oxide (0.08g/L) into a water body to be treated, wherein the iodine medicine is iohexol (2mg/L), adjusting the pH value to 7, then adding 0.450mM sodium sulfite, stirring for reaction by using a stirrer at room temperature, setting different sampling time points (0, 1, 3, 5, 10, 15, 20 and 30min), and taking a water sample to determine the residual concentration of the iohexol;
(4) after the reaction is finished, taking out the copper-iron composite oxide, washing the copper-iron composite oxide by deionized water, continuously putting the copper-iron composite oxide into a new water body to be treated containing iohexol (the concentration of the iohexol is 2mg/L, the pH value is 7, the concentration of sodium sulfite is 0.450mM), stirring the mixture for reaction, measuring the residual concentration of the iohexol at different sampling time points, repeatedly utilizing the copper-iron composite oxide for 5 times according to the method, and drawing a removal effect curve (figure 3);
as shown in fig. 3, the ordinate represents the ratio of the remaining amount of iohexol to the initial amount, and it can be seen that the degradation effect of the copper-iron composite oxide on iohexol is better, the removal effect of iohexol is only slightly reduced with the increase of the number of times of use, but the residual concentration of iohexol after reaction for 30min is only about 8% of the initial concentration after 5 times of recycling, which indicates that the copper-iron composite oxide can be repeatedly used for many times.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims and their equivalents.
Claims (7)
1. An iodo-drug degradation method based on an MOF template method is characterized by comprising the following steps:
(1) dissolving copper nitrate trihydrate, iron acetylacetonate and terephthalic acid in a mixed solution of N, N-dimethylformamide and ethanol, and fully mixing and dissolving to obtain a precursor solution; reacting the precursor solution at the temperature of 100-180 ℃ for 10-36 h; after the reaction is finished, cooling to room temperature, washing and drying to obtain the copper/iron bimetallic organic framework material;
(2) cleaning the copper/iron bimetallic organic framework material obtained in the step (1) with ethanol, drying, heating to 500 ℃ at the speed of 1 ℃/min, and calcining for 1h to obtain a copper-iron composite oxide;
(3) placing the copper-iron composite oxide obtained in the step (2) in a water body to be treated containing the iodomedicine, adjusting the pH value to 7, adding sulfite with the use amount of 0.250-0.980 mM, taking a water sample after the reaction is finished, and then determining the concentration of the residual iodomedicine; the iodo-drug is iohexol;
(4) and taking out the copper-iron composite oxide, washing with deionized water, and adding the copper-iron composite oxide into untreated water containing the iodophor for recycling.
2. The MOF template method-based method for degrading iodo-substituted drugs according to claim 1, wherein: in the step (1), the molar ratio of copper nitrate trihydrate, iron acetylacetonate and terephthalic acid is 1: 0.2-3: 2 to 5.
3. The MOF template method-based method for degrading iodo-substituted drugs according to claim 1, wherein: in the step (1), the volume ratio of the N, N-dimethylformamide to the ethanol in the mixed solution is 1: 0.5 to 2.
4. The MOF template method-based method for degrading iodo-substituted drugs according to claim 1, wherein: the concentration of the iodomedicine in the water body to be treated containing the iodomedicine is 0.5-3 mg/L.
5. The MOF template method-based method for degrading iodo-substituted drugs according to claim 1, wherein: in the step (3), the dosage of the copper-iron composite oxide is 50-500 mg/L.
6. The MOF template method-based method for degrading iodo-substituted drugs according to claim 1, wherein: in the step (3), the sulfite is sodium sulfite and/or potassium sulfite.
7. The MOF template method-based method for degrading iodo-substituted drugs according to claim 1, wherein: in the step (4), the number of times of recycling is 1-5 times.
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| CN110404526B (en) * | 2019-07-25 | 2021-09-14 | 中国科学院城市环境研究所 | La derived based on MOFs2O3Method for removing PPCPs and As (III) by using @ C activated persulfate |
| CN110862130A (en) * | 2019-12-05 | 2020-03-06 | 广州大学 | Method for disinfecting water and degrading iodo-contrast agent in water |
| CN112520834B (en) * | 2020-11-10 | 2022-08-30 | 华侨大学 | Method for degrading iodo-drug by using activated sulfite system |
| CN113354057B (en) * | 2021-05-19 | 2023-02-10 | 同济大学 | Degradation treatment method for copper complexing reinforced tetracycline pollutants |
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