CN112844475B - Preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride - Google Patents

Preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride Download PDF

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CN112844475B
CN112844475B CN202011556704.9A CN202011556704A CN112844475B CN 112844475 B CN112844475 B CN 112844475B CN 202011556704 A CN202011556704 A CN 202011556704A CN 112844475 B CN112844475 B CN 112844475B
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type magnetic
cyclodextrin
janus
carbon nitride
phase carbon
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王慧
张秀莲
燕少玮
丁杰
邓力铭
李想
阿斯哈尔·艾比罗哈甫
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Harbin Institute of Technology
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Abstract

A preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and an experimental method for removing polychlorinated biphenyl in water by using the Janus type magnetic cyclodextrin-graphite phase carbon nitride. The invention belongs to the field of water treatment. The invention aims to solve the technical problems that polychlorinated biphenyl pollutants are difficult to treat, and the existing iron-based Fenton method is easy to agglomerate, poor in chemical stability, high in energy consumption of a photocatalytic method and low in degradation efficiency. According to the invention, a high-temperature hydrolysis method is combined with a sol-gel method to prepare Janus type magnetic mesoporous silica, the Janus type magnetic cyclodextrin-graphite phase carbon nitride is used as a precursor, and a derivatization grafting technology is utilized to prepare the Janus type magnetic cyclodextrin-graphite phase carbon nitride, and the Janus type magnetic mesoporous silica is a material with selective adsorption, heterogeneous Fenton oxidation and visible light catalysis functions, and is used for removing polychlorinated biphenyl in water. The material prepared by the invention has magnetism, is easy to separate from water, has low price and stable property, and can be recycled, and the removal rate of polychlorinated biphenyl in water by the Janus type magnetic cyclodextrin-graphite phase carbon nitride reaches 78-90%.

Description

Preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride
Technical Field
The invention belongs to the field of water treatment, and particularly relates to a preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and an experimental method for removing polychlorinated biphenyl in water by using the Janus type magnetic cyclodextrin-graphite phase carbon nitride.
Background
Polychlorinated biphenyls, which are the most representative class of persistent organic pollutants, have carcinogenic, teratogenic, and mutagenic effects, and are widely present in various environmental media due to their once mass-produced and applied to various industrial fields, and are considered by UNEP as one of the "largest environmental challenges facing the world". The town sewage is an important carrier for discharging various pollutants in the life and production process of people, and is an important environmental medium for the existence of polychlorinated biphenyl. Polychlorinated biphenyl spread from town sewage to water environment or recycled water is a great hidden danger for human health and safety. In recent years, a great deal of research has been carried out by scholars at home and abroad on the degradation and removal of polychlorinated biphenyl in water. Among them, the heterogeneous Fenton method and the photocatalytic technique are considered as one of the most promising new techniques for controlling such contaminants in water.
The heterogeneous Fenton method is a typical advanced oxidation technology and has the advantages of strong oxidation capacity, wide application range, high reaction speed and the like. The core of which is based on Fe2+Catalysis H2O2Generating hydroxyl radical OH with strong oxidizing property to remove organic pollutants. However, the common Fenton-like system has the problems of high toxicity, poor chemical stability, easy agglomeration of the catalyst and the like.
The photocatalysis technology is that the generated photohole and active oxygen free radicals such as OH are used as 'green' oxidant to gradually dechlorinate and mineralize polychlorinated biphenyl into inorganic substance by irradiating the semiconductor photocatalyst through ultraviolet-visible light. However, due to the characteristics of the semiconductor energy band structure and the restriction of high recombination rate of photo-generated electrons and holes, the photocatalytic efficiency is low, and most materials need an additional ultraviolet light source, which increases energy consumption.
For the two catalytic degradation processes, all reactions occur on the interface of a solid-phase catalyst and a liquid phase containing a target degradation product, and the target product can be quickly adsorbed and enriched on the surface of the solid phase so as to react with a photoinduced cavity or an active free radical generated on the surface of the catalyst to achieve the purpose of degradation. Therefore, an experimental method which is green, low in energy consumption, high in degradation efficiency, strong in adsorption selectivity and capable of being recycled is urgently needed to be developed, and the key problem that polychlorinated biphenyl pollutants in the water body are difficult to treat at present is solved.
Disclosure of Invention
The invention aims to solve the technical problems that polychlorinated biphenyl pollutants are difficult to treat and an existing iron-based Fenton method is easy to agglomerate, poor in chemical stability, high in energy consumption of a photocatalytic method and low in degradation efficiency, and provides a preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and an experimental method for removing polychlorinated biphenyl in water by using the preparation method.
The preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride provided by the invention comprises the following steps:
step one, preparing magnetic nanoparticles: anhydrous ferric trichloride is taken as a raw material, diethylene glycol is taken as a solvent, polyacrylic acid is taken as a surfactant, a high-temperature hydrolysis method is adopted for reaction under the protection of nitrogen, alkali liquor is added in the reaction process for continuous reaction, and magnetic nanoparticles are obtained;
step two, preparing the aminated asymmetric Janus type magnetic mesoporous silica: taking the aqueous solution of the magnetic nanoparticles obtained in the step one as a raw material, cetyl trimethyl ammonium bromide as a template agent and tetraethoxysilane as a silicon source to prepare asymmetric Janus type magnetic mesoporous silica containing the template agent, and removing the template agent to obtain the asymmetric Janus type magnetic mesoporous silica; introducing amino on the surface of the asymmetric Janus type magnetic mesoporous silica by taking a silane coupling agent as a bridge to obtain aminated asymmetric Janus type magnetic mesoporous silica;
step three, preparing Janus type magnetic cyclodextrin: connecting the carboxylated beta-cyclodextrin with the aminated asymmetric Janus type magnetic mesoporous silica obtained in the step two through carbodiimide activation reaction to obtain Janus type magnetic cyclodextrin;
step four, preparing Janus type magnetic cyclodextrin-graphite phase carbon nitride: and (4) occupying oxygen-containing functional groups-OH in the Janus type magnetic cyclodextrin obtained in the step three at the N atom of the graphite phase carbon nitride to form N-OH, so as to prepare the Janus type magnetic cyclodextrin-graphite phase carbon nitride.
Further limiting, the specific process for preparing the magnetic nanoparticles in the first step is as follows: adding polyacrylic acid, anhydrous ferric trichloride and diethylene glycol into a reaction container, heating the mixture to 210-220 ℃ from room temperature under the conditions of nitrogen protection and stirring, condensing and refluxing the mixture at the temperature, adding alkali liquor at the speed of 300-500 mL/min when the color of the reaction solution is changed into transparent light yellow, continuously reacting for 0.8-1.2 h to obtain black turbid solution, and centrifuging to obtain magnetic nanoparticles.
Further limiting, the mass ratio of the polyacrylic acid to the anhydrous ferric chloride is 58: (12-14).
Further defined, the ratio of the mass of polyacrylic acid to the volume of diethylene glycol is 1.5 g: (85-95) mL.
Further defined, the ratio of the mass of the polyacrylic acid to the volume of the lye is 1.5 g: (9-10) mL.
Further defined, the lye is a diethylene glycol solution of sodium hydroxide, wherein the ratio of the mass of the sodium hydroxide to the volume of the diethylene glycol is 1 g: (9-11) mL.
Further limiting, the preparation process of the lye is as follows: mixing sodium hydroxide and diethylene glycol, heating the mixture to 110-120 ℃ from room temperature under the protection of nitrogen and stirring, keeping the temperature for 0.8-1.2 h, and then cooling the mixture to 70-90 ℃ for later use.
Further limiting, the specific process for preparing the asymmetric Janus type magnetic mesoporous silica in the second step is as follows: mixing hexadecyl trimethyl ammonium bromide and deionized water, then carrying out ultrasonic treatment for 15-25 min, adding the aqueous solution of the magnetic nanoparticles obtained in the step one, continuing to carry out ultrasonic treatment for 15-25 min, then carrying out mechanical stirring at 100-200 rpm, adding ammonia water at the speed of 300-500 mL/min during stirring, then increasing the rotating speed to 250-350 rpm, then adding ethyl orthosilicate at the speed of 0.1-0.2 mL/min, reacting for 80-100 min to obtain asymmetric Janus type magnetic mesoporous silica containing a template, removing the template, drying for 5-7 h under the vacuum condition of 50-70 ℃ to obtain the asymmetric Janus type magnetic mesoporous silica containing the template
Further defined, the ratio of the mass of the hexadecyl trimethyl ammonium bromide to the volume of the deionized water is (350-450) mg: 100 mL.
Further defined, the ratio of the mass of the hexadecyl trimethyl ammonium bromide to the volume of the aqueous solution of the magnetic nanoparticles is (350-450) mg: 3mL, wherein the concentration of the aqueous solution of the magnetic nanoparticles is 32 mg/mL-34 mg/mL.
Further limiting, the ratio of the mass of the hexadecyl trimethyl ammonium bromide to the volume of the ammonia water is (350-450) mg: 4 mL.
Further defined, the ratio of the mass of the hexadecyl trimethyl ammonium bromide to the volume of the tetraethoxysilane is (350-450) mg: 500 μ L.
Further defined, the specific operation process of removing the template agent is as follows: mixing an ammonium nitrate standard solution with absolute ethyl alcohol, then adding asymmetric Janus type magnetic mesoporous silica containing a template agent, mechanically stirring at 50-70 ℃, performing reflux condensation for 20-24 h, performing magnetic separation, then washing the magnetic separation product with ethyl alcohol and deionized water in sequence, repeating the steps of reflux condensation-magnetic separation-washing for 2-3 times, and removing the template agent of hexadecyl trimethyl ammonium bromide.
Further defined, the volume ratio of the ammonium nitrate standard solution to the absolute ethyl alcohol is 5 mL: (90-100) mL, wherein the mass concentration of the ammonium nitrate standard solution is 8% -12%.
Further defined, the ratio of the mass of the asymmetric Janus type magnetic mesoporous silica containing the template to the volume of the absolute ethyl alcohol is 0.2 g: (90-100) mL.
Further limiting, the second step is a specific process of introducing amino groups on the surface of the asymmetric Janus type magnetic mesoporous silica, which comprises the following steps: ultrasonically and uniformly mixing 3-aminopropyltriethoxysilane and isopropanol, then adding asymmetric Janus type magnetic mesoporous silica, continuing to perform ultrasonic treatment for 8-12 min, then stirring for 14-16 h at room temperature, heating to 80-90 ℃, performing reflux condensation for 2-4 h at the temperature, then alternately washing with deionized water and ethanol for multiple times, and finally drying at 50-70 ℃ in vacuum to obtain the aminated asymmetric Janus type magnetic mesoporous silica.
Further limiting, the volume ratio of the 3-aminopropyltriethoxysilane to the isopropanol is (3-4) mL: 30 mL.
Further defined, the ratio of the volume of the 3-aminopropyltriethoxysilane to the mass of the asymmetric Janus-type magnetic mesoporous silica is (3-4) mL: 0.2 g.
Further limiting, the specific process for preparing the Janus-type magnetic cyclodextrin in the third step is as follows: dissolving carboxylated beta-cyclodextrin into a buffer solution, adding 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and N-hydroxysuccinimide, and carrying out ultrasonic treatment for 15-25 min to obtain an activated carboxyl solution; dispersing the aminated asymmetric Janus type magnetic mesoporous silica obtained in the step two in a buffer solution, mixing with the activated carboxyl solution, carrying out ultrasonic treatment for 15-25 min, mechanically stirring for 9-11 h, then sequentially washing with ethanol and deionized water, and carrying out magnetic separation to obtain Janus type magnetic cyclodextrin.
Further defined, the ratio of the mass of the carboxylated beta-cyclodextrin to the volume of the buffer is (450-550) mg: 20mL, wherein the buffer is 0.03M phosphate solution, pH 5.9.
Further limiting, the mass ratio of the carboxylated beta-cyclodextrin to the 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide is (1.8-2.2): 1.
further limiting, the mass ratio of the carboxylated beta-cyclodextrin to the N-hydroxysuccinimide is (1.8-2.2): 1.
further, the ratio of the mass of the aminated and asymmetric Janus type magnetic mesoporous silica obtained in the second step to the volume of the buffer solution is (450-550) mg: 20mL, wherein the buffer is 0.03M phosphate solution, pH 5.9.
Further, the mass ratio of the carboxylated beta-cyclodextrin to the aminated asymmetric Janus-type magnetic mesoporous silica obtained in the second step is (0.8-1.2): 1.
further limiting, the specific process for preparing the Janus type magnetic cyclodextrin-graphite phase carbon nitride in the step four is as follows: mixing the blocky nitrogen carbide with the Janus type magnetic cyclodextrin, then adding a mixed solution of water and ethanol, carrying out ultrasonic treatment for 10-14 h, and carrying out magnetic separation to obtain the Janus type magnetic cyclodextrin-graphite phase carbon nitride.
Further limiting, the mass ratio of the bulk nitrogen carbide to the Janus type magnetic cyclodextrin is (3.8-4.2): 1.
further defined, the ratio of the mass of the massive carbonized nitrogen to the volume of the mixed liquid of water and ethanol is 800 mg: (90-110) mL, wherein the volume fraction of ethanol in the mixed solution of water and ethanol is 20-30%.
The experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride is carried out according to the following steps:
adding hydrogen peroxide into a water sample containing polychlorinated biphenyl, adjusting the pH to 3-7, adding Janus type magnetic cyclodextrin-graphite phase carbon nitride, and finishing the removal of the polychlorinated biphenyl in the water under the irradiation of visible light.
Further, the polychlorinated biphenyl is a mixture of one or more of PCB 28, PCB 52, PCB 101, PCB 138 and PCB 180 according to any ratio.
Further limiting, the ratio of the amount of the hydrogen peroxide to the volume of the water sample is (30-60) mmol: 1L of the compound.
Further limiting, the ratio of the mass of the Janus type magnetic cyclodextrin-graphite phase carbon nitride to the volume of the water sample is (0.5-1.0) g: 1L of the compound.
Further limited, the time of the visible light irradiation is 100min to 220 min.
Compared with the prior art, the invention has the following remarkable effects:
1) the material has a Janus asymmetric structure, the bare magnetic core on one side is matched with hydrogen peroxide, active free radicals such as OH and the like are generated by utilizing an oxide surface oxygen vacancy mechanism and a Haber-Weiss mechanism, and polychlorinated biphenyl organic pollutants are degraded by heterogeneous Fenton oxidation; the graphite-phase carbon nitride on the other side has visible light response and lower forbidden bandwidth, and polychlorinated biphenyl can be degraded by a photocatalysis method. The material can be used as both an out-phase Fenton catalyst and a photocatalyst, and the degradation of a target object can be accelerated by utilizing the synergistic effect of the two catalysts.
2) The material modifies beta-cyclodextrin on the surface of mesoporous silica, has a large specific surface area, and can selectively adsorb polychlorinated biphenyl compounds in water. The host-guest complex formed by the beta-cyclodextrin cavity and the polychlorinated biphenyl changes the internal bond energy of polychlorinated biphenyl molecules, OH can enter the cavity to directly react with the polychlorinated biphenyl, and the degradation process of pollutants is accelerated.
3) Janus type magnetic cyclodextrin-graphite phase carbon nitride is matched with hydrogen peroxide for use, pollutants are degraded by utilizing the strong oxidizing property of free radicals such as OH and the like and the photocatalytic activity of N-OH-based graphite phase carbon nitride, in-situ regeneration of adsorption sites is completed, and recycling of the catalyst is realized. Overcomes the defect of the traditional FentonThe system is only suitable for acid conditions, and common Fenton-like systems (such as Co)2+PMS) has high toxicity, high price, poor chemical stability and the like.
4) The material prepared by the invention has excellent degradation performance on polychlorinated biphenyl compounds in a near-neutral pH range, and has an obvious mineralization effect.
5) The material prepared by the invention has the advantages of magnetism, easy separation from water, low price, stable property, repeated utilization, more contribution to industrial application and the like.
Drawings
FIG. 1 is a schematic representation of a TEM characterization of the Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in example 1;
FIG. 2 is a total ion flow graph of the GC-QQQ MS full scan of polychlorinated biphenyl compounds in a water sample subjected to standard addition in example 2;
FIG. 3 is a GC-QQQ MS extraction ion chromatogram of polychlorinated biphenyl compounds in example 2.
Detailed Description
Example 1: the preparation method of the Janus-type magnetic cyclodextrin-graphite phase carbon nitride provided by the embodiment comprises the following steps:
step one, preparing magnetic nanoparticles: adding 1.516g of polyacrylic acid, 0.342g of anhydrous ferric trichloride and 89.5mL of diethylene glycol into a reaction container, heating the mixture from room temperature to 220 ℃ under the conditions of nitrogen protection and stirring, condensing and refluxing the mixture at the temperature, adding 9.5mL of alkali liquor at the speed of 400mL/min when the color of the reaction solution is changed into transparent light yellow, continuing to react for 1h to obtain a black turbid solution, and centrifuging to obtain magnetic nanoparticles; the alkali liquor is a diethylene glycol solution of sodium hydroxide, wherein the ratio of the mass of the sodium hydroxide to the volume of the diethylene glycol is 1 g: 10mL, and the preparation process of the alkali liquor comprises the following steps: mixing sodium hydroxide and diethylene glycol, heating the mixture from room temperature to 120 ℃ under the protection of nitrogen and stirring, keeping the temperature for 1h, and then cooling the mixture to 80 ℃ for later use;
step two, preparing the aminated asymmetric Janus type magnetic mesoporous silica: mixing 400mg of hexadecyl trimethyl ammonium bromide with 100mL of deionized water, performing ultrasonic treatment for 20min, adding 3mL of aqueous solution (33.5mg/mL) of the magnetic nanoparticles obtained in the first step, performing continuous ultrasonic treatment for 20min, performing mechanical stirring at 150rpm, adding 4mL of ammonia water at the speed of 400mL/min in the stirring process, increasing the rotating speed to 300rpm, adding 500 mu L of tetraethoxysilane at the speed of 0.15mL/min, performing reaction for 90min to obtain asymmetric Janus type magnetic mesoporous silica containing a template, removing the template, and drying for 6h under the vacuum condition of 60 ℃ to obtain the asymmetric Janus type magnetic mesoporous silica; the specific operation process of removing the template agent comprises the following steps: mixing 5mL of ammonium nitrate standard solution (10 wt.%) with 95mL of absolute ethyl alcohol, then adding 0.2g of asymmetric Janus type magnetic mesoporous silica containing a template agent, mechanically stirring at 60 ℃, performing magnetic separation after refluxing and condensing for 24h, then washing a magnetic separation product by using ethyl alcohol and deionized water in sequence, repeating the steps of refluxing and condensing-magnetic separation-washing for 3 times, and removing the template agent of hexadecyl trimethyl ammonium bromide; uniformly mixing 3.6mL of 3-aminopropyltriethoxysilane with 30mL of isopropanol by ultrasonic treatment for 10min, adding 0.2g of asymmetric Janus type magnetic mesoporous silica, continuing ultrasonic treatment for 10min, stirring at room temperature for 15h, heating to 85 ℃, refluxing and condensing at the temperature for 3h, alternately washing with deionized water and ethanol for 3 times, and finally drying at 60 ℃ in vacuum to obtain aminated asymmetric Janus type magnetic mesoporous silica;
step three, preparing Janus type magnetic cyclodextrin: dissolving 0.5g of carboxylated beta-cyclodextrin in 20mL of phosphate buffer (0.03M, pH value is 5.9), adding 250mg of 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and 250mg of N-hydroxysuccinimide, and carrying out ultrasonic treatment for 20min to obtain an activated carboxyl solution; dispersing 0.5g of the aminated asymmetric Janus type magnetic mesoporous silica obtained in the second step in 20mL of phosphate buffer solution (0.03M, pH is 5.9), mixing with the activated carboxyl solution, performing ultrasonic treatment for 20min, mechanically stirring for 10h, sequentially washing with ethanol and deionized water for 3 times, and performing magnetic separation to obtain Janus type magnetic cyclodextrin;
step four, preparing the Janus type magnetic cyclodextrin-graphite phase carbon nitride, mixing 800mg of blocky nitrogen carbide and 200mg of Janus type magnetic cyclodextrin, then adding 100mL of mixed solution of water and ethanol (the ethanol accounts for 25 vol.%), carrying out ultrasonic treatment for 12h, and carrying out magnetic separation to obtain the Janus type magnetic cyclodextrin-graphite phase carbon nitride.
A TEM representation of the Janus-type magnetic cyclodextrin-graphite phase carbon nitride prepared in this example is shown in fig. 1. As can be seen from FIG. 1, the synthesized material has clear morphology, obvious Janus structure and Fe3O4The end diameter is about 130nm and the nonmagnetic end length is about 250 nm.
Example 2: the adsorption performance of the Janus-type magnetic cyclodextrin-graphite-phase carbon nitride prepared in example 1 on polychlorinated biphenyl compounds in water is examined, and the specific process is as follows:
1. respectively measuring 100mL of surface water as an environmental water sample, putting the surface water into 5 conical flasks, respectively adding 1mL of 5 polychlorinated biphenyl standard solutions (PCB 28, PCB 52, PCB 101, PCB 138 and PCB 180) with the concentration of 20mg/L, respectively adding 100mg of Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in the embodiment 1, uniformly mixing, putting the mixture into a light-proof constant temperature oscillator, oscillating the mixture for 30min under the condition of 100r/min, and adsorbing polychlorinated biphenyl in the environmental water sample into a cavity of the Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in the embodiment 1 in the process;
2. after the adsorption reaction is finished, obtaining a clear upper layer solution after magnetic field separation, carrying out liquid-liquid extraction (2mL multiplied by 3) on the clear upper layer solution by using normal hexane, combining normal hexane phases, dehydrating the normal hexane phases and concentrating the normal hexane phases to 0.5 mL;
3. the results of qualitative and quantitative analysis of polychlorinated biphenyls using GC-QQQ MS are shown in fig. 2 and 3, and the method was applied to determine the concentration of polychlorinated biphenyls remaining in water to examine the adsorption capacity of Janus-type magnetic cyclodextrin-graphite-phase carbon nitride prepared in example 1, and found that 5 polychlorinated biphenyls were adsorbed at 82% to 95%. Experimental results show that the Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in example 1 has good adsorption capacity on polychlorinated biphenyl compounds.
Example 3: the experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in example 1 is carried out according to the following steps
Adding 0.5mL of hydrogen peroxide (30 wt.%) into 100mL of a polychlorinated biphenyl-containing water sample (10.0mg/L), adjusting the pH to 4, adding 100mg of the Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in example 1, irradiating with visible light for 200min, and removing the polychlorinated biphenyl in the water; polychlorinated biphenyl in the water sample containing the polychlorinated biphenyl is a mixture of PCB 28, PCB 52, PCB 101, PCB 138 and PCB 180.
After the light irradiation is finished, magnetic field separation is carried out to obtain the Janus type magnetic cyclodextrin-graphite phase carbon nitride adsorbent prepared in example 1, acetonitrile is used for eluting the Janus type magnetic cyclodextrin-graphite phase carbon nitride adsorbent (1.5mL multiplied by 2), the acetonitrile is combined and concentrated to 0.2mL, then n-hexane is added for carrying out solvent replacement, and GC-QQQ MS is used for measuring the concentration change of the polychlorinated biphenyl compounds adsorbed on the Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared in example 1 so as to investigate the capability of removing the pollutants under the synergistic effect. Experimental results prove that the removal rate of the 5 polychlorinated biphenyls in the water is as high as 78-90%. Therefore, the Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared by the method has better removal capability on polychlorinated biphenyl compounds.

Claims (10)

1. A preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride is characterized by comprising the following steps:
step one, preparing magnetic nanoparticles: anhydrous ferric trichloride is taken as a raw material, diethylene glycol is taken as a solvent, polyacrylic acid is taken as a surfactant, a high-temperature hydrolysis method is adopted for reaction under the protection of nitrogen, alkali liquor is added in the reaction process for continuous reaction, and magnetic nanoparticles are obtained;
step two, preparing the aminated asymmetric Janus type magnetic mesoporous silica: taking the aqueous solution of the magnetic nanoparticles obtained in the step one as a raw material, cetyl trimethyl ammonium bromide as a template agent and tetraethoxysilane as a silicon source to prepare asymmetric Janus type magnetic mesoporous silica containing the template agent, and removing the template agent to obtain the asymmetric Janus type magnetic mesoporous silica; introducing amino on the surface of the asymmetric Janus type magnetic mesoporous silica by taking a silane coupling agent as a bridge to obtain aminated asymmetric Janus type magnetic mesoporous silica;
step three, preparing Janus type magnetic cyclodextrin: connecting the carboxylated beta-cyclodextrin with the aminated asymmetric Janus type magnetic mesoporous silica obtained in the step two through carbodiimide activation reaction to obtain Janus type magnetic cyclodextrin;
step four, preparing Janus type magnetic cyclodextrin-graphite phase carbon nitride: and (4) occupying oxygen-containing functional groups-OH in the Janus type magnetic cyclodextrin obtained in the step three at the N atom of the graphite phase carbon nitride to form N-OH, so as to prepare the Janus type magnetic cyclodextrin-graphite phase carbon nitride.
2. The preparation method of Janus-type magnetic cyclodextrin-graphite-phase carbon nitride as claimed in claim 1, wherein the specific process for preparing the magnetic nanoparticles in the first step is as follows: adding polyacrylic acid, anhydrous ferric trichloride and diethylene glycol into a reaction container, heating the mixture to 210-220 ℃ from room temperature under the conditions of nitrogen protection and stirring, condensing and refluxing the mixture at the temperature, adding alkali liquor at the speed of 300-500 mL/min when the color of a reaction solution is changed into transparent light yellow, continuously reacting for 0.8-1.2 h to obtain a black turbid solution, and centrifuging to obtain magnetic nanoparticles, wherein the mass ratio of the polyacrylic acid to the anhydrous ferric trichloride is 58: (12-14), wherein the ratio of the mass of the polyacrylic acid to the volume of the diethylene glycol is 1.5 g: (85-95) mL, wherein the ratio of the mass of the polyacrylic acid to the volume of the alkali liquor is 1.5 g: (9-10) mL.
3. The method for preparing Janus type magnetic cyclodextrin-graphite phase carbon nitride according to claim 2, wherein the alkali liquor is a diethylene glycol solution of sodium hydroxide, and the ratio of the mass of the sodium hydroxide to the volume of the diethylene glycol is 1 g: (9-11) mL, wherein the preparation process of the alkali liquor is as follows: mixing sodium hydroxide and diethylene glycol, heating the mixture to 110-120 ℃ from room temperature under the protection of nitrogen and stirring, keeping the temperature for 0.8-1.2 h, and then cooling the mixture to 70-90 ℃ for later use.
4. The preparation method of Janus-type magnetic cyclodextrin-graphite-phase carbon nitride according to claim 1, wherein the specific process for preparing asymmetric Janus-type magnetic mesoporous silica in the second step is as follows: mixing hexadecyl trimethyl ammonium bromide and deionized water, then carrying out ultrasonic treatment for 15-25 min, adding the aqueous solution of the magnetic nanoparticles obtained in the first step, continuing to carry out ultrasonic treatment for 15-25 min, then carrying out mechanical stirring at 100-200 rpm, adding ammonia water at the speed of 300-500 mL/min in the stirring process, then increasing the rotating speed to 250-350 rpm, then adding ethyl orthosilicate at the speed of 0.1-0.2 mL/min, reacting for 80-100 min to obtain Janus type magnetic mesoporous silica containing a template agent, removing the template agent, drying for 5-7 h under the vacuum condition of 50-70 ℃ to obtain asymmetric Janus type magnetic mesoporous silica, wherein the mass ratio of the hexadecyl trimethyl ammonium bromide to the volume of the deionized water is (350-450) mg: 100mL, wherein the ratio of the mass of the hexadecyl trimethyl ammonium bromide to the volume of the aqueous solution of the magnetic nanoparticles is (350-450) mg: 3mL, wherein the concentration of the aqueous solution of the magnetic nanoparticles is 32-34 mg/mL, and the ratio of the mass of the cetyl trimethyl ammonium bromide to the volume of the ammonia water is (350-450) mg: 4mL, wherein the ratio of the mass of the hexadecyl trimethyl ammonium bromide to the volume of the ethyl orthosilicate is (350-450) mg: 500 μ L.
5. The preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride as claimed in claim 4, wherein the specific operation process of removing the template agent is as follows: mixing an ammonium nitrate standard solution with absolute ethyl alcohol, then adding asymmetric Janus type magnetic mesoporous silica containing a template agent, mechanically stirring at 50-70 ℃, performing reflux condensation for 20-24 h, then performing magnetic separation, washing the magnetic separation product with ethanol and deionized water in sequence, repeating the steps of reflux condensation-magnetic separation-washing for 2-3 times, removing the template agent of hexadecyl trimethyl ammonium bromide, wherein the volume ratio of the ammonium nitrate standard solution to the absolute ethyl alcohol is 5 mL: (90-100) mL, wherein the mass concentration of the ammonium nitrate standard solution is 8-12%, and the ratio of the mass of the template-containing asymmetric Janus-type magnetic mesoporous silica to the volume of the absolute ethyl alcohol is 0.2 g: (90-100) mL.
6. The preparation method of Janus-type magnetic cyclodextrin-graphite-phase carbon nitride according to claim 1, wherein the second step of introducing amino groups on the surface of the asymmetric Janus-type magnetic mesoporous silica comprises the following specific steps: ultrasonically and uniformly mixing 3-aminopropyltriethoxysilane and isopropanol, then adding asymmetric Janus type magnetic mesoporous silica, continuing to perform ultrasonic treatment for 8min to 12min, then stirring for 14h to 16h at room temperature, heating to 80-90 ℃, performing reflux condensation for 2h to 4h at the temperature, then alternately washing with deionized water and ethanol for multiple times, and finally drying at 50-70 ℃ in vacuum to obtain aminated asymmetric Janus type magnetic mesoporous silica, wherein the volume ratio of the 3-aminopropyltriethoxysilane to the isopropanol is (3-4) mL: 30mL, wherein the ratio of the volume of the 3-aminopropyltriethoxysilane to the mass of the asymmetric Janus type magnetic mesoporous silica is (3-4) mL: 0.2 g.
7. The preparation method of Janus-type magnetic cyclodextrin-graphite-phase carbon nitride according to claim 1, wherein the specific process for preparing Janus-type magnetic cyclodextrin in the third step is as follows: dissolving carboxylated beta-cyclodextrin into a buffer solution, adding 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide and N-hydroxysuccinimide, and carrying out ultrasonic treatment for 15-25 min to obtain an activated carboxyl solution; dispersing the aminated asymmetric Janus type magnetic mesoporous silica obtained in the step two in a buffer solution, mixing the aminated asymmetric Janus type magnetic mesoporous silica with the activated carboxyl solution, performing ultrasonic treatment for 15-25 min, mechanically stirring for 9-11 h, sequentially washing with ethanol and deionized water, and performing magnetic separation to obtain Janus type magnetic cyclodextrin, wherein the ratio of the mass of the carboxylated beta-cyclodextrin to the volume of the buffer solution is (450-550) mg: 20mL, wherein the buffer is 0.03M phosphate solution, pH 5.9, and the mass ratio of the carboxylated β -cyclodextrin to 1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide is (1.8-2.2): 1, the mass ratio of the carboxylated beta-cyclodextrin to the N-hydroxysuccinimide is (1.8-2.2): 1, the mass ratio of the aminated asymmetric Janus type magnetic mesoporous silica obtained in the second step to the volume of the buffer solution is (450-550) mg: 20mL, wherein the buffer solution is 0.03M phosphate solution, the pH is 5.9, and the mass ratio of the carboxylated beta-cyclodextrin to the aminated asymmetric Janus-type magnetic mesoporous silica obtained in the second step is (0.8-1.2): 1.
8. the preparation method of Janus-type magnetic cyclodextrin-graphite phase carbon nitride according to claim 1, wherein the specific process for preparing Janus-type magnetic cyclodextrin-graphite phase carbon nitride in the fourth step is as follows: mixing blocky nitrogen carbide and Janus type magnetic cyclodextrin, adding a mixed solution of water and ethanol, carrying out ultrasonic treatment for 10-14 h, and carrying out magnetic separation to obtain Janus type magnetic cyclodextrin-graphite phase carbon nitride, wherein the mass ratio of the blocky nitrogen carbide to the Janus type magnetic cyclodextrin is (3.8-4.2): 1, the mass ratio of the massive carbonized nitrogen to the volume of the mixed liquid of water and ethanol is 800 mg: (90-110) mL, wherein the volume fraction of ethanol in the mixed solution of water and ethanol is 20-30%.
9. An experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride prepared by the method of any one of claims 1 to 8, which is characterized by comprising the following steps:
adding hydrogen peroxide into a water sample containing polychlorinated biphenyl, adjusting the pH to 3-7, adding Janus type magnetic cyclodextrin-graphite phase carbon nitride, and finishing the removal of the polychlorinated biphenyl in the water under the irradiation of visible light.
10. The experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride as claimed in claim 9, wherein the polychlorinated biphenyl is one or a mixture of more of PCB 28, PCB 52, PCB 101, PCB 138 and PCB 180, and the ratio of the amount of hydrogen peroxide to the volume of a water sample is (30-60) mmol: 1L, wherein the ratio of the mass of the Janus type magnetic cyclodextrin-graphite phase carbon nitride to the volume of a water sample is (0.5-1.0) g: 1L, and the time of visible light irradiation is 100 min-220 min.
CN202011556704.9A 2020-12-24 2020-12-24 Preparation method of Janus type magnetic cyclodextrin-graphite phase carbon nitride and experimental method for removing polychlorinated biphenyl in water by using Janus type magnetic cyclodextrin-graphite phase carbon nitride Expired - Fee Related CN112844475B (en)

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