CN113786805B - Preparation method and application of cobalt-based metal-organic framework derived magnetic carbon composite material - Google Patents
Preparation method and application of cobalt-based metal-organic framework derived magnetic carbon composite material Download PDFInfo
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Abstract
The invention discloses a preparation method and application of a cobalt-based metal-organic framework derived magnetic carbon composite material, wherein the preparation method comprises the following steps: 1) Preparing a cobalt-based metal organic framework compound Co-MONCs; 2) Carbonizing a cobalt-based metal-organic framework compound Co-MONCs at a high temperature to generate a cobalt-based metal-organic framework derivative magnetic carbon composite material; the cobalt-based metal-organic framework derived magnetic carbon composite material prepared by the preparation method is used as a drug pollutant adsorbent to adsorb chlorpromazine hydrochloride in water; the preparation method is simple, has sufficient raw material sources and low production cost, is suitable for expanding production requirements, and is convenient for industrial production; the cobalt-based metal-organic framework derived magnetic carbon composite material prepared by the preparation method has good adsorption capacity to chlorpromazine hydrochloride, good desorption capacity and recycling capacity, and magnetism, and can be quickly recovered through a magnet, and the recovery is convenient.
Description
Technical Field
The invention relates to the technical field of drug pollutant adsorbents, in particular to a preparation method and application of a cobalt-based metal-organic framework derived magnetic carbon composite material.
Background
With the progress of society and the development of the pharmaceutical industry, more and more drugs, drug metabolites and pharmaceutical adjuvant residues are detected in more and more aqueous environments in recent decades. Wherein the medicine mainly comprises antibiotics, hormones, anti-inflammatory medicines and the like, and the pharmaceutic adjuvant mainly comprises solubilizer, cosolvent, emulsifier, colorant, adhesive and the like. The medicines, the medicine metabolites and the pharmaceutic adjuvant have complex structures and various components and are slowly degraded by themselves under natural conditions. Meanwhile, along with continuous production and use of people, more and more medicines, medicine metabolites and medicinal auxiliary materials are discharged into the water body, and although the concentration of the medicines detected at present is far lower than the lowest concentration of the medicine effect, the substances can still have certain harm to human beings, animals and plants and ecological systems through the durable contact of the water body.
The existing method for removing the drug pollutants mainly comprises activated sludge adsorption, biodegradation, photocatalytic degradation, oxidization and the like, but the application of the method is limited due to the respective defects. Activated sludge adsorption is only used for transferring drug pollutants in a polluted wastewater system into soil, and the drug cannot be thoroughly removed from the environment. Biodegradation and photocatalytic degradation processes are slow enough to counteract the increasing emission of drug contaminants into the water. And for oxidation, it is difficult to apply widely due to its high cost consumption. In contrast, the adsorption method has the characteristics of simple operation, low cost, high efficiency, wide application and the like, and is suitable for being used as a method for removing the drug pollutants in the water body. At present, various materials can be used as adsorbents, such as activated carbon, carbon nano-tubes, ion exchange resins, metal oxides and the like, but the carbon nano-tubes have high production cost and are difficult to apply on a large scale; the active carbon is difficult to regenerate and reuse; the specific surface area of the materials such as metal oxide, ion exchange resin and the like is small, and the adsorption effect is not ideal. Therefore, there is still a need to continue to develop new materials with the advantages of good adsorption effect, low cost and recycling as adsorbents for removing drug pollutants in water.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a preparation method and application of a cobalt-based metal-organic framework-derived magnetic carbon composite material, the preparation method is simple and easy, the yield is high, the cobalt-based metal-organic framework-derived magnetic carbon composite material prepared by the method has good adsorption capacity to chlorpromazine hydrochloride, the cobalt-based metal-organic framework-derived magnetic carbon composite material also has certain desorption capacity and recycling capacity after adsorbing drug pollutants, the cobalt-based metal-organic framework-derived magnetic carbon composite material has magnetism, the magnet can be used for rapidly recovering the cobalt-based metal-organic framework-derived magnetic carbon composite material, and the cobalt-based metal-organic framework-derived magnetic carbon composite material has potential application in the aspect of adsorbing drug residues in environmental water.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the preparation method of the cobalt-based metal-organic framework derived magnetic carbon composite material comprises the following steps:
1) Dissolving methyl pyrogallol calix [4] arene and cobalt nitrate hexahydrate in acetonitrile aqueous solution, then dropwise adding triethylamine, shaking uniformly to obtain mixed solution A, placing a scintillation bottle filled with the mixed solution A in an oven for reacting for 22-26 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tube furnace for high-temperature carbonization, and cooling to room temperature to obtain the cobalt-based metal organic framework derivative magnetic carbon composite material.
As a preferred scheme, the molar ratio of the methyl pyrogallol calix [4] arene to the cobalt nitrate hexahydrate in the step 1) is 1:3.
as a preferred scheme, the volume ratio of acetonitrile to water in the acetonitrile aqueous solution in step 1) is 5:1.
as a preferred embodiment, the temperature of the drying oven is maintained at 80℃during the reaction in which the scintillation vial containing the mixed solution A is placed in the oven in step 1).
As a preferable scheme, in the high-temperature carbonization process, the calcining temperature of the tube furnace is 700-1000 ℃.
As a preferable scheme, the calcination time is 2-8 h
As a preferred embodiment, the heating rate of the tube furnace in step 2) is set to 5 ℃/min during the high temperature carbonization.
As a preferable scheme, nitrogen is introduced in the high-temperature carbonization process in the step 2), and the introducing speed of the nitrogen is 60mL/min.
The cobalt-based metal-organic framework derived magnetic carbon composite material prepared by the preparation method of the cobalt-based metal-organic framework derived magnetic carbon composite material is used as a drug pollutant adsorbent to adsorb chlorpromazine hydrochloride in water.
As a preferred scheme, the cobalt-based metal-organic framework-derived magnetic carbon composite material has magnetism, and the cobalt-based metal-organic framework-derived magnetic carbon composite material has a large number of adsorption active sites.
The cobalt-based metal-organic framework compound (Co-MONCs) is used as a precursor, the cobalt-based metal-organic framework-derived magnetic carbon composite material is directly obtained by high-temperature carbonization in a tube furnace, the framework of the precursor collapses after carbonization, the organic ligand in the precursor is converted into a porous carbon material, and metal (cobalt) in the precursor is inlaid into the porous carbon material in the carbonization process, so that the cobalt-based metal-organic framework-derived magnetic carbon composite material is formed. A large number of adsorption active sites exist in the cobalt-based metal-organic framework derived magnetic carbon composite material, so that the adsorption capacity of the cobalt-based metal-organic framework derived magnetic carbon composite material on medicine pollutants is greatly improved. The cobalt-based metal-organic framework derived magnetic carbon composite material has the advantages that the magnetic cobalt nano particles exist in the cobalt-based metal-organic framework derived magnetic carbon composite material and have stronger magnetization intensity, so that the cobalt-based metal-organic framework derived magnetic carbon composite material can attract magnetism of a magnet, and the cobalt-based metal-organic framework derived magnetic carbon composite material can realize quick recovery by means of the magnet after chlorpromazine hydrochloride is adsorbed.
The beneficial effects of the invention are as follows: the preparation method of the cobalt-based metal-organic framework derived magnetic carbon composite material is simple, the raw material sources are sufficient, the production cost is low, the cobalt-based metal-organic framework derived magnetic carbon composite material is suitable for expanding production requirements, and the industrial production is convenient; the cobalt-based metal-organic framework-derived magnetic carbon composite material has rich adsorption active sites, has good adsorption capacity to chlorpromazine hydrochloride, and still has good adsorption capacity to chlorpromazine hydrochloride in an acidic environment; the cobalt-based metal-organic framework derived magnetic carbon composite material also has good desorption capacity and recycling capacity after adsorbing drug pollutants; the cobalt-based metal-organic framework derived magnetic carbon composite material has magnetism, and can be recovered rapidly and conveniently through magnets.
Drawings
FIG. 1 is a crystal optical micrograph of a cobalt-based metal organic framework compound Co-MONCs;
FIG. 2 is a single crystal-X-ray diffraction analysis chart of cobalt-based metal organic framework compound Co-MONCs;
FIG. 3 is an X-ray diffraction pattern of cobalt-based metal-organic framework-derived magnetic carbon composites Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2;
FIG. 4 is a Raman spectrum of cobalt-based metal-organic framework derived magnetic carbon composite materials Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2;
FIG. 5 is a scanning electron microscope image of cobalt-based metal organic framework derived magnetic carbon composites Co@C-700-2, co@C-800-2 and Co@C-1000-2;
FIG. 6 is a scanning electron microscope, transmission electron micrograph and element map of a cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2;
FIG. 7 is a scanning electron microscope image of cobalt-based metal organic framework derived magnetic carbon composite materials Co@C-900-4 and Co@C-900-8;
FIG. 8 is a nitrogen adsorption isotherm plot of cobalt-based metal-organic framework derived magnetic carbon composites Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2;
FIG. 9 is a graph of pore size distribution of cobalt-based metal-organic framework-derived magnetic carbon composites Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2;
FIG. 10 is a graph of the adsorption capacity of cobalt-based metal-organic framework-derived magnetic carbon composites Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2 for chlorpromazine hydrochloride solutions;
FIG. 11 is a graph of the adsorption capacity of Co@C-900-2, co@C-900-4 and Co@C-900-8 of cobalt-based metal-organic framework derived magnetic carbon composite materials to chlorpromazine hydrochloride solution;
FIG. 12 is an analysis chart of adsorption conditions of cobalt-based metal organic framework derived magnetic carbon composite material Co@C-900-2 adsorbed chlorpromazine hydrochloride with different dosage;
FIG. 13 is a graph of adsorption of commercial activated carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2 to chlorpromazine hydrochloride of different concentrations;
FIG. 14 is a graph of adsorption equilibrium time analysis of commercial activated carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2 for chlorpromazine hydrochloride;
FIG. 15 is a graph of analysis of adsorption of chlorpromazine hydrochloride by commercial activated carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2 at different temperatures;
FIG. 16 is a graph of an analysis of the adsorption of chlorpromazine hydrochloride by commercial activated carbon AC and cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2 at different pH values;
FIG. 17 is a graph showing the adsorption of Co@C-900-2 of a cobalt-based metal-organic framework derived magnetic carbon composite material to chlorpromazine hydrochloride added with humic acid of different concentrations;
FIG. 18 is a Zeta potential test plot under different pH conditions;
FIG. 19 is a hysteresis loop diagram of a cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2;
FIG. 20 is a graph of the rapid recovery of cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2 after the adsorption of chlorpromazine hydrochloride with a magnet;
FIG. 21 is a graph of an analysis of 5 times of cyclic adsorption of chlorpromazine hydrochloride by Co@C-900-2 of a cobalt-based metal-organic framework-derived magnetic carbon composite material;
FIG. 22 is a simulation diagram of a quasi-first order kinetic model of a cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2 and a commercial activated carbon AC;
FIG. 23 is a simulation diagram of a cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2 and a commercial activated carbon AC pseudo-secondary kinetic model;
FIG. 24 is a simulation diagram of a Langmuir isothermal adsorption model of a cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2;
FIG. 25 is a simulated drawing of a Freundlich isothermal adsorption model of a cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2;
fig. 26 is a schematic diagram of a model of Temkin isothermal adsorption of cobalt-based metal organic framework-derived magnetic carbon composite co@c-900-2.
Detailed Description
The structural and operational principles of the present invention will be described in further detail below with reference to the accompanying drawings.
Example 1
Preparation of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-700-2
1) 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate were dissolved in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water was 5: 1) Adding 30 mu L of triethylamine dropwise, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tubular furnace to calcine for 2 hours at the calcination temperature of 700 ℃, wherein the heating rate of the tubular furnace is kept to be 5 ℃/min in the heating process, nitrogen is introduced into the tubular furnace in the working process, the introducing rate of the nitrogen is kept to be 60mL/min, and the cobalt-based metal organic framework derivative magnetic carbon composite material Co@C-700-2 is obtained after cooling to room temperature.
Example 2
Preparation of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-800-2
1) 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate were dissolved in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water was 5: 1) Adding 30 mu L of triethylamine dropwise, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tubular furnace to calcine for 2 hours at the calcination temperature of 800 ℃, wherein the heating rate of the tubular furnace is kept to be 5 ℃/min in the heating process, nitrogen is introduced into the tubular furnace in the working process, the introducing rate of the nitrogen is kept to be 60mL/min, and the cobalt-based metal organic framework derivative magnetic carbon composite material Co@C-800-2 is obtained after cooling to room temperature.
Example 3
Preparation of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2
1) 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate were dissolved in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water was 5: 1) Adding 30 mu L of triethylamine dropwise, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tubular furnace to be calcined for 2 hours under the condition that the calcining temperature is 900 ℃, wherein the heating rate of the tubular furnace is kept to be 5 ℃/min in the heating process, nitrogen is introduced into the tubular furnace in the working process, the introducing rate of the nitrogen is kept to be 60mL/min, and the cobalt-based metal organic framework derivative magnetic carbon composite material Co@C-900-2 is obtained after the crucible is cooled to room temperature.
Example 4
Preparation of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-1000-2
1) 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate were dissolved in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water was 5: 1) Adding 30 mu L of triethylamine dropwise, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tubular furnace to calcine for 2 hours at the calcination temperature of 1000 ℃, wherein the heating rate of the tubular furnace is kept to be 5 ℃/min in the heating process, nitrogen is introduced into the tubular furnace in the working process, the introducing rate of the nitrogen is kept to be 60mL/min, and the cobalt-based metal organic framework derivative magnetic carbon composite material Co@C-1000-2 is obtained after cooling to room temperature.
Comparative example 1
Preparation of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-4
1) 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate were dissolved in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water was 5: 1) Adding 30 mu L of triethylamine dropwise, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tubular furnace to be calcined for 4 hours under the condition that the calcining temperature is 900 ℃, wherein the heating rate of the tubular furnace is kept to be 5 ℃/min in the heating process, nitrogen is introduced into the tubular furnace in the working process, the introducing rate of the nitrogen is kept to be 60mL/min, and the cobalt-based metal organic framework derivative magnetic carbon composite material Co@C-900-4 is obtained after the crucible is cooled to room temperature.
Comparative example 2
Preparation of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-8
1) 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate were dissolved in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water was 5: 1) Adding 30 mu L of triethylamine dropwise, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tubular furnace to be calcined for 8 hours under the condition that the calcining temperature is 900 ℃, wherein the heating rate of the tubular furnace is kept to be 5 ℃/min in the heating process, nitrogen is introduced into the tubular furnace in the working process, the introducing rate of the nitrogen is kept to be 60mL/min, and the cobalt-based metal organic framework derivative magnetic carbon composite material Co@C-900-8 is obtained after the crucible is cooled to room temperature.
Comparative example 3
Preparation of cobalt-based metal organic framework compound Co-MONCs
Dissolving 0.1mmol of methyl pyrogallol calix [4] arene and 0.3mmol of cobalt nitrate hexahydrate in 12mL of acetonitrile aqueous solution (wherein the volume ratio of acetonitrile to water is 5:1), then dropwise adding 30 mu L of triethylamine, shaking uniformly to obtain a mixed solution A, placing a scintillation bottle filled with the mixed solution A into an oven with the temperature of 80 ℃ for reaction for 24 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain a cobalt-based metal organic framework compound Co-MONCs.
Cobalt-based metal-organic framework-derived magnetic carbon composite material Co@C-700-2 described in the following experiments 1-18 was prepared from example 1, cobalt-based metal-organic framework-derived magnetic carbon composite material Co@C-800-2 was prepared from example 2, cobalt-based metal-organic framework-derived magnetic carbon composite material Co@C-900-2 was prepared from example 3, cobalt-based metal-organic framework-derived magnetic carbon composite material Co@C-1000-2 was prepared from example 4, cobalt-based metal-organic framework-derived magnetic carbon composite material Co@C-900-4 was prepared from comparative example 1, cobalt-based metal-organic framework-derived magnetic carbon composite material Co@C-900-8 was prepared from comparative example 2, and cobalt-based metal-organic framework compound Co-MONCs were prepared from comparative example 3.
Experiment 1
Optical microscope experiment
The experimental steps are as follows: the cobalt-based metal organic framework compound Co-MONCs were subjected to optical microscopic measurement by an optical microscope.
Experimental results: as shown in fig. 1.
Experiment 2
Single crystal X-ray diffraction experiment
The experimental steps are as follows: the structure of Co-MONCs was measured with a single crystal X-ray diffractometer.
Experimental results: as shown in FIG. 2, wherein a) is methyl pyrogallol cup [4 ]]Aromatic hydrocarbon (PgC) l ) Is a structural diagram of (1); b) And c) is Co 1 Is a structural diagram of (1); (d) Is Co 2 Is a structural diagram of (1); (e) With three Co 1 Metal-ligand connection mode; (f) Having two Co and one Co 2 Metal-ligand connection mode; (g) Structure of Co-MONCs, the guest molecule is H 2 O; (h) Co-MONCs structure diagram, guest molecule is H 2 O and acetonitrile.
Experiment 3
Powder X-ray diffraction experiment
The experimental steps are as follows: and (3) carrying out X-ray diffraction measurement on the cobalt-based metal organic framework derived magnetic carbon composite material Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2 by using a powder X-ray diffractometer.
Experimental results: as shown in fig. 3.
Experiment 4
Raman Spectroscopy experiments
The experimental steps are as follows: raman spectrometry is carried out on cobalt-based metal organic framework derived magnetic carbon composite materials Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2 by using a Raman spectrometer.
Experimental results: as shown in fig. 4.
Experiment 5
Scanning electron microscope experiment
The experimental steps are as follows: and (3) respectively measuring the internal and external morphology of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-700-2, co@C-800-2, co@C-900-2 and Co@C-1000-2 by using a field emission scanning electron microscope and a high resolution transmission electron microscope.
Experimental results: as shown in fig. 5, a is a 5 μm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-700-2; b is a 2 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-700-2; c is a 200nm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-700-2; d is a 5 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-800-2; e is a 2 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-800-2; f is a 200nm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-800-2; g is a 5 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-1000-2; h is a 2 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-1000-2; i is a 200nm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-1000-2; as shown in fig. 6, a is a 10 μm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; b is a 200nm transmission electron micrograph of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; c is a 10nm transmission electron micrograph of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; d is a 5nm transmission electron micrograph of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; e is a 2 mu m element mapping image of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; f is a C element mapping diagram of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; g is a Co element mapping diagram of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; h is an O element mapping diagram of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2; as shown in fig. 7, a is a 5 μm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-4; b is a 2 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-4; c is a 200nm electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-4; d is a 5 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-8; e is a 2 mu m electron microscope image of a cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-8; f is a 200nm electron microscope image of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-8.
Experiment 6
Adsorption experiments of different adsorbents on chlorpromazine hydrochloride solutions
The experimental steps are as follows: 1) Weighing 5mg of adsorbent (commercial active carbon AC, cobalt-based metal organic framework compound Co-MONCs, cobalt-based metal organic framework derived magnetic carbon composite material Co@C-700-2, co@C-800-2, co@C-900-2, co@C-1000-2, co@C-900-4 and Co@C-900-8), respectively adding into a beaker filled with 25 mL concentration of 300 mg/L chlorpromazine hydrochloride (CPZ) aqueous solution, sealing the mouth of the beaker with a sealing film, placing the beaker into a shaking table (model TS-2, manufacturer is Jiangsu sea door Chemie Beber Instrument manufacturing Co., ltd.) for 10 hours under the condition that the shaking speed is 220 rpm, and then centrifuging with a centrifuge (model H1850R, manufacturer Hunan Xiang Instrument laboratory Co., ltd.) under the condition that the rotating speed is 10000R/min to remove the adsorbent, thereby obtaining chlorpromazine hydrochloride supernatant;
2) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), comparing with chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the supernatant, and determining the adsorption amount q=V (C) 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), calculating adsorption quantity, and recording data;
4) The specific surface area and pore volume of each adsorbent (commercial activated carbon AC, cobalt-based metal-organic framework compound Co-MONCs, cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-700-2, co@C-800-2, co@C-900-2, co@C-1000-2, co@C-900-4 and Co@C-900-8) are measured, data are recorded, and are summarized with the data obtained in the step 3) to form a table 1, and experimental results are obtained according to the adsorption amount data of each adsorbent to chlorpromazine hydrochloride in the table 1.
Table 1:
experimental results: as can be seen from fig. 8, 9, 10 and 11, among the above adsorbents, the cobalt-based metal organic framework-derived magnetic carbon composite material co@c-900-2 has the strongest adsorption capacity to chlorpromazine hydrochloride, while the other adsorbents have the adsorption capacities to chlorpromazine hydrochloride ranging from strong to weak: co@C-800-2> Co@C-1000-2> Co@C-900-4> Co@C-700-2> Co@C-900-8> Co-MONCs > commercial Activated Carbon (AC).
Experiment 7
Adsorption experiment of adsorbents Co@C-900-2 with different feeding amounts on chlorpromazine hydrochloride solution
The experimental steps are as follows: 1) Weighing 5mg, 10mg, 15mg, 20mg and 25mg of adsorbent (cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2), respectively adding into a beaker filled with a 25 mL aqueous solution of chlorpromazine hydrochloride (CPZ) with the concentration of 300 mg/L, sealing the mouth of the beaker by using a sealing film, placing the beaker into a shaking table (model TS-2, manufacturer is Jiangsu Siemens Riben Instrument manufacturing Co.) for shaking for 10 hours at an oscillation speed of 220rpm, and then centrifuging by using a centrifuge (model H1850R, manufacturer is Hunan instrument laboratory instrument development Co., ltd.) to remove the adsorbent at a rotation speed of 10000R/min to obtain chlorpromazine hydrochloride supernatant;
2) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the chlorpromazine hydrochloride supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meida Instrument Co., ltd.), comparing chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the chlorpromazine hydrochloride supernatant, and determining adsorption amount q=V (C) according to formula 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from FIG. 12, in the chlorpromazine hydrochloride solution having a concentration of 300mg/L, the adsorption capacity of Co@C-900-2 to chlorpromazine hydrochloride was decreased as the mass of the adsorbent was increased, and when the amount of the adsorbent was 5mg, the adsorption capacity of Co@C-900-2 to chlorpromazine hydrochloride was the strongest.
Experiment 8
Adsorption experiments of adsorbent Co@C-900-2 and commercial activated carbon AC on chlorpromazine hydrochloride solutions with different concentrations
The experimental steps are as follows: 1) Weighing 5mg of adsorbent (commercial activated carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2), respectively adding into beakers containing 25 mL aqueous solutions of 100mg/L, 150mg/L, 200mg/L, 250mg/L, 300mg/L, 350 mg/L and 400 mg/L chlorpromazine hydrochloride (CPZ), sealing the mouth of the beakers with sealing films, placing the beakers into a shaking table (model TS-2, manufacturer is Jiangsu sea door, linbell Instrument manufacturing Co.) and shaking for 10 hours at an oscillation speed of 220rpm, and then centrifuging to remove the adsorbent by using a centrifuge (model H1850R, manufacturer Hunan instrument laboratory instrument development Co.) at a rotation speed of 10000R/min to obtain chlorpromazine hydrochloride supernatant;
2) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), comparing with chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the supernatant, and determining the adsorption amount q=V (C) 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from fig. 13, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride is stronger than that of commercial activated carbon AC, and when the concentration of the chlorpromazine hydrochloride solution is 300mg/L, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride reaches the maximum value, and when the concentration of the chlorpromazine hydrochloride solution is lower than 300mg/L, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride increases with the increase of the concentration of chlorpromazine hydrochloride.
Experiment 9
Adsorption saturation time experiment of adsorbent Co@C-900-2 and commercial activated carbon AC on chlorpromazine hydrochloride solution with same concentration
The experimental steps are as follows: 1) Weighing 5mg of adsorbent (commercial active carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2), respectively adding into a beaker filled with 25 mL aqueous solution of chlorpromazine hydrochloride (CPZ) with the concentration of 300 mg/L, sealing the mouth of the beaker by using a sealing film, placing the beaker into a shaking table (model TS-2, manufacturer is manufactured by Jiangsu sea door Chemie Instrument Co., ltd.) and shaking at the shaking speed of 220rpm, and respectively using a centrifuge (model H1850R, manufacturer's Hunan Xiang instrument laboratory instrument development Co., ltd.) after shaking for 200min, 400min, 600min, 800min, 1000min, 1200min and 1400 min to centrifugally remove the adsorbent to obtain chlorpromazine hydrochloride supernatant at the rotation speed of 10000R/min;
2) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the chlorpromazine hydrochloride supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meida Instrument Co., ltd.), comparing chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the chlorpromazine hydrochloride supernatant, and determining adsorption amount q=V (C) according to formula 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from fig. 14, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride is stronger than that of commercial activated carbon AC to chlorpromazine hydrochloride, and the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 reaches an adsorption saturation state when the adsorption time in a chlorpromazine hydrochloride solution with an adsorption concentration of 300mg/L is 500 min; when the adsorption time is less than 500min, the adsorption capacity of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2 to chlorpromazine hydrochloride is increased along with the increase of the adsorption time, and when the adsorption time is more than 500min, the adsorption capacity of the cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2 to chlorpromazine hydrochloride is not changed obviously.
Experiment 10
Adsorption experiments of adsorbent Co@C-900-2 and commercial activated carbon AC on chlorpromazine hydrochloride at different temperatures
The experimental steps are as follows: 1) Weighing 5mg of adsorbent (commercial activated carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite Co@C-900-2), respectively adding into a beaker filled with a 25 mL aqueous solution of chlorpromazine hydrochloride (CPZ) with the concentration of 300 mg/L, sealing the mouth of the beaker by using a sealing film, placing the beaker in a shaker (model TS-2, manufactured by Jiangsu sea door, linbell instrument Co., ltd.) with the temperature of 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃ and 70 ℃ for 10 hours under the condition of the oscillation speed of 220rpm, and then centrifuging by using a centrifuge (model H1850R, manufactured by Hunan instrument laboratory instrument development Co., ltd.) to remove the adsorbent to obtain chlorpromazine hydrochloride supernatant;
2) Weighing 10mg of chlorpromazine hydrochloride standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting the standard solution with water to obtain chlorpromazine hydrochloride standard solutions with the concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring the absorbance of the chlorpromazine hydrochloride standard solution at 253nm by an ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing a chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the chlorpromazine hydrochloride supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meida Instrument Co., ltd.), comparing chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the chlorpromazine hydrochloride supernatant, and determining adsorption amount q=V (C) according to formula 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from fig. 15, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride is stronger than that of commercial activated carbon AC, and the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride gradually decreases with the increase of temperature under the condition that the temperature is 20-70 ℃.
Experiment 11
Adsorption experiment of adsorbent Co@C-900-2 and commercial activated carbon AC on chlorpromazine hydrochloride at different pH values
The experimental steps are as follows: 1) Putting 25mL of chlorpromazine hydrochloride (CPZ) aqueous solution with the concentration of 300 mg/L into a 100mL beaker, adjusting the pH value of the chlorpromazine hydrochloride solution to 2, 3, 4, 5, 6, 7, 8, 9 and 10 by using hydrochloric acid with the concentration of 0.01mol/L and sodium hydroxide with the concentration of 0.01mol/L, weighing 5mg of adsorbent (commercial activated carbon AC and cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2) respectively, sealing the mouth of a beaker by using a sealing film, putting the beaker into a shaking table (model TS-2, manufacturer is Jiangsu sea door, forest bell instrument manufacturing Co., ltd.) for 10 hours under the condition of 220rpm of shaking speed, and then centrifuging by using a centrifuge (model H1850R, manufacturer Hunan instrument laboratory Co., ltd.) under the condition of 10000R/min of rotating speed to remove the adsorbent, thereby obtaining chlorpromazine hydrochloride supernatant;
2) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the chlorpromazine hydrochloride supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meida Instrument Co., ltd.), comparing chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the chlorpromazine hydrochloride supernatant, and determining adsorption amount q=V (C) according to formula 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from fig. 16, at a pH value of less than 8, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride was stronger than that of the commercial activated carbon AC, and at a pH value of 4, the adsorption capacity of the cobalt-based metal-organic framework-derived magnetic carbon composite material co@c-900-2 to chlorpromazine hydrochloride reached a peak value.
Experiment 12
Adsorption experiment of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2 on chlorpromazine hydrochloride solution added with different humic acids
The experimental steps are as follows: 1) Putting 25mL of chlorpromazine hydrochloride (CPZ) aqueous solution with the concentration of 300 mg/L into a 100mL beaker, regulating the concentration of humic acid in the solution to be 20mg/L, 40mg/L, 60mg/L and 80mg/L, weighing 5mg of adsorbent (cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2) into the solution, sealing the mouth of a beaker by using a sealing film, putting the beaker into a shaking table (model TS-2, manufactured by Jiangsu sea door Linbell instrument Co., ltd.) for shaking for 10 hours under the condition of the shaking speed of 220rpm, and then centrifuging to remove the adsorbent by using a centrifuge (model H1850R, manufactured by NaHunan instrument laboratory instrument development Co., ltd.) at the rotating speed of 10000R/min to obtain chlorpromazine hydrochloride supernatant;
2) Weighing 10mg of chlorpromazine hydrochloride standard substance, dissolving in 50ml of water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with the concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring the absorbance of the chlorpromazine hydrochloride standard solution at 254nm by an ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing a chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the chlorpromazine hydrochloride supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meida Instrument Co., ltd.), comparing chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the chlorpromazine hydrochloride supernatant, and determining adsorption amount q=V (C) according to formula 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 Is chlorpromazine hydrochloride concentration before adsorption, CFor chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from FIG. 17, when the humic acid concentration is less than 40mg/L, the adsorption capacity of Co@C-900-2 of the cobalt-based metal-organic framework-derived magnetic carbon composite material to chlorpromazine hydrochloride is reduced along with the increase of the humic acid concentration, when the humic acid concentration is equal to 40mg/L, the adsorption capacity of Co@C-900-2 of the cobalt-based metal-organic framework-derived magnetic carbon composite material to chlorpromazine hydrochloride reaches a valley value, and when the humic acid concentration is more than 40mg/L, the adsorption capacity of Co@C-900-2 of the cobalt-based metal-organic framework-derived magnetic carbon composite material to chlorpromazine hydrochloride is almost the same.
Experiment 13
Zeta potential test experiment of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2 under different pH conditions
The experimental steps are as follows:
adding 5mg of Co@C-900-2 of a cobalt-based metal-organic framework derived magnetic carbon composite material into a beaker filled with 25mL of water to obtain Co@C-900-2 solution, adjusting the pH value of the Co@C-900-2 solution to 2, 3, 4, 5, 6, 7 and 8 by using hydrochloric acid with the concentration of 0.01mol/L and sodium hydroxide with the concentration of 0.01mol/L respectively, carrying out Zeta potential measurement on the Co@C-900-2 solution by using a Zeta potential measuring instrument respectively, recording data, and drawing to obtain experimental results.
Experimental results: as can be seen from FIG. 18, the isoelectric point of the cobalt-based metal organic framework-derived magnetic carbon composite material Co@C-900-2 is 4.
Experiment 14
Magnetization curve experiment
The experimental steps are as follows: and magnetically measuring the cobalt-based metal organic framework derived magnetic carbon composite material Co@C-900-2 by using a magnetic measuring instrument.
Experimental results: as shown in fig. 19.
Experiment 15
The experimental steps are as follows: 5mg of cobalt-based metal-organic framework-derived magnetic carbon composite Co@C-900-2 was placed in a vial containing a 25mL concentration of 300 mg/L chlorpromazine hydrochloride (CPZ) aqueous solution, and the vial was placed in a shaker (model TS-2, manufacturer was Jiangsu sea door, manufactured by Linbell instruments Co., ltd.) and shaken at an oscillation speed of 220rpm for 10 hours, after which the magnet was placed on one side of the vial.
Experimental results: as can be seen from fig. 20, the cobalt-based metal-organic framework derived magnetic carbon composite material co@c-900-2 can magnetically attract the magnet, and when the cobalt-based metal-organic framework derived magnetic carbon composite material co@c-900-2 adsorbs chlorpromazine hydrochloride, the purpose of rapidly recovering the cobalt-based metal-organic framework derived magnetic carbon composite material co@c-900-2 can be achieved by means of the magnet.
Experiment 16
Circulation experiment
The experimental steps are as follows: 1) Weighing 5mg of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2, adding into a beaker filled with 25 mL aqueous solution of chlorpromazine hydrochloride (CPZ) with the concentration of 300 mg/L, sealing the mouth of the beaker by using a sealing film, placing the beaker into a shaking table (model TS-2, manufactured by Jiangsu sea door, linbell instrument manufacturing Co.) for shaking for 10 hours at an oscillation speed of 220rpm, centrifuging by using a centrifuge (model H1850R, manufactured by Hunan instrument laboratory instrument development Co., ltd.) at a rotation speed of 10000R/min, and drying to obtain adsorption saturated Co@C-900-2;
2) Weighing 5mg of Co@C-900-2 saturated by adsorption obtained in the step 1), placing in a 100mL beaker, adding 20mL of ethanol and glycol mixed solution into the beaker, sealing a bottle mouth by using a sealing film, placing the beaker in an ultrasonic instrument for ultrasonic treatment, replacing fresh mixed solution every 10min until Co@C-900-2 saturated by adsorption chlorpromazine hydrochloride completely desorbs chlorpromazine hydrochloride, centrifuging by using a centrifuge (model H1850R, manufacturer is Hunan instrument laboratory instrument development Co., ltd.) at a rotating speed of 10000rpm, and drying to obtain Co@C-900-2 desorbed chlorpromazine hydrochloride;
3) Weighing 5mg of Co@C-900-2 obtained in the step 2) after chlorpromazine hydrochloride desorption, adding the mixture into a beaker filled with 25 mL aqueous solution of chlorpromazine hydrochloride (CPZ) with the concentration of 300 mg/L, sealing the mouth of the beaker by a sealing film, placing the beaker into a shaking table (model TS-2, manufacturer is Jiangsu sea door, manufactured by Linbell instrument Co., ltd.) and shaking the beaker for 10 hours at the shaking speed of 220rpm, and centrifuging the mixture by a centrifuge (model H1850R, manufacturer, hunan instrument laboratory instrument development Co., ltd.) at the rotating speed of 10000R/min to obtain chlorpromazine hydrochloride supernatant and adsorbed saturated Co@C-900-2;
4) Repeating the steps 2) -3) for 5 times, respectively measuring absorbance values of the chlorpromazine hydrochloride supernatant obtained in the step 3) at 254nm for a plurality of times by an ultraviolet spectrophotometer (model is UV-650, shanghai Meinada Instrument Co., ltd.), and recording data;
5) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
6) Comparing absorbance values of the chloropropion hydrochloride supernatant obtained in the step 3) at 254nm for a plurality of times with the chloropropion hydrochloride standard curve obtained in the step 5), obtaining the concentration of the chloropropion hydrochloride in the chloropropion hydrochloride supernatant, and obtaining the concentration of the chloropropion hydrochloride according to an adsorption quantity formula q=v (C) 0 -C)/m (V is chlorpromazine hydrochloride solution volume, C 0 For chlorpromazine hydrochloride concentration before adsorption, C is chlorpromazine hydrochloride concentration after adsorption, m adsorbent dosage), the adsorption amount is calculated, the data is recorded, and the experimental result is obtained by drawing.
Experimental results: as can be seen from FIG. 21, after 5 cycles of adsorption experiments, co@C-900-2 still maintains a higher adsorption amount to chlorpromazine hydrochloride, which indicates that Co@C-900-2 has good desorption capacity and recycling capacity after adsorbing drug pollutants.
Experiment 17
Kinetic simulation experiment
Experimental data obtained in experiments of adsorption saturation time of Co@C-900-2 and commercial activated carbon on chlorpromazine hydrochloride solution with the same concentration are respectively substituted into a first-order kinetic equation and a second-order kinetic equation for calculation, and the recorded data are obtained to obtain experimental results according to table 2.
TABLE 2
Experimental results: as shown in fig. 22 and 23.
Experiment 18
Isothermal adsorption experiments
The experimental steps are as follows:
The experimental steps are as follows: 1) Weighing 5mg of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2, respectively adding into a beaker filled with 25 mL aqueous solutions of chlorpromazine hydrochloride (CPZ) with the concentration of 100mg/L, 150mg/L, 200mg/L, 250mg/L, 300mg/L, 350mg/L and 400 mg/L, sealing the mouth of the beaker with a sealing film, placing the beaker into a shaking table (model TS-2, manufactured by Jiangsu sea door Linbell instrument Co., ltd.) and shaking for 10 hours at an oscillation speed of 220rpm (the temperature of the shaking table is kept constant at 298K, 308K and 318K during the period), and then centrifuging to remove the adsorbent by using a centrifuge (model H1850R, manufactured by Hunan instrument laboratory instrument development Co., ltd.) at a rotation speed of 10000R/min to obtain chlorpromazine hydrochloride supernatant;
2) Weighing 10mg chlorpromazine hydrochloride standard substance, dissolving in 50mL water to prepare 200mg/L standard solution, diluting with water to obtain chlorpromazine hydrochloride standard solutions with concentration of 4mg/L, 6mg/L, 8mg/L, 10mg/L and 12mg/L, measuring absorbance of the chlorpromazine hydrochloride standard solution at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meinada Instrument Co., ltd.), recording data, and drawing chlorpromazine hydrochloride standard curve;
3) Measuring absorbance of the chlorpromazine hydrochloride supernatant obtained in step 1) at 254nm with ultraviolet spectrophotometer (model UV-650, shanghai Meida Instrument Co., ltd.), comparing chlorpromazine hydrochloride standard curve, obtaining chlorpromazine hydrochloride concentration of the chlorpromazine hydrochloride supernatant, and determining adsorption amount q=V (C) according to formula 0 -C)/m (V is chlorpromazine hydrochlorideVolume of solution, C 0 For the pre-adsorption concentration of chlorpromazine hydrochloride, C is the post-adsorption concentration of chlorpromazine hydrochloride and the amount of m adsorbent), the adsorption amount was calculated, data was recorded, and the data was substituted into Langmuir (Langmuir) adsorption isothermal formula, francher (Freundlich) adsorption isothermal formula and Jiao Mjin (Temkin) adsorption isothermal formula, and the recorded data were obtained in Table 3, and the experimental results were plotted according to Table 3.
TABLE 3 Table 3
Experimental results: as shown in fig. 24, 25 and 26.
Experiment 19
Thermodynamic parameter calculation experiment of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2 adsorption chlorpromazine hydrochloride
The experimental steps are as follows: calculated from Langmuir (Langmuir) adsorption isotherms in the experimental results of the isothermal adsorption of experiment 18k L Value and maximum adsorption quantity q of cobalt-based metal-organic framework derived magnetic carbon composite material Co@C-900-2 to chlorpromazine hydrochloride m The equilibrium constant K of the adsorption kinetics is determined, and then the fatg is determined according to the van't Hoff equation. Plotting lnK against 1/T, substituting the slope and intercept of the straight line into the normal Hough equation to obtain fath and fats, and recording the data to obtain Table 4.
TABLE 4 Table 4
Experimental results: as can be seen from Table 4, the G values are negative at various temperatures, indicating that the adsorption of chlorpromazine hydrochloride on the adsorbent Co@C-900-2 is spontaneous and thermodynamically viable. And when the H value is negative, the adsorption of chlorpromazine hydrochloride on the adsorbent Co@C-900-2 is an exothermic reaction, the adsorption capacity of the cobalt-based metal organic framework derived magnetic carbon composite material Co@C-900-2 to chlorpromazine hydrochloride is reduced along with the increase of temperature, and in addition, when the S value is negative, the adsorption of the cobalt-based metal organic framework derived magnetic carbon composite material Co@C-900-2 to chlorpromazine hydrochloride reduces the chaotic degree of a system.
In the foregoing, only the preferred embodiment of the present invention is described, and any minor modifications, equivalent changes and modifications made to the above embodiments according to the technical solutions of the present invention fall within the scope of the technical solutions of the present invention.
Claims (10)
1. A preparation method of a cobalt-based metal-organic framework derived magnetic carbon composite material is characterized by comprising the following steps of: the method comprises the following steps:
1) Dissolving methyl pyrogallol calix [4] arene and cobalt nitrate hexahydrate in acetonitrile aqueous solution, then dropwise adding triethylamine, shaking uniformly to obtain mixed solution A, placing a scintillation bottle filled with the mixed solution A in an oven for reacting for 22-26 hours, naturally cooling to room temperature, filtering, washing with acetonitrile and drying to obtain cobalt-based metal organic framework compound Co-MONCs;
2) And (3) placing the crucible filled with the cobalt-based metal organic framework compound Co-MONCs into a tube furnace for high-temperature carbonization, and cooling to room temperature to obtain the cobalt-based metal organic framework derivative magnetic carbon composite material.
2. The method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 1, wherein the method comprises the following steps: in the step 1), the molar ratio of the methyl pyrogallol calix [4] arene to the cobalt nitrate hexahydrate is 1:3.
3. the method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 1, wherein the method comprises the following steps: the volume ratio of acetonitrile to water in the acetonitrile aqueous solution in the step 1) is 5:1.
4. the method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 1, wherein the method comprises the following steps: in the step 1), the temperature of the drying box is kept at 80 ℃ in the process of placing the scintillation flask filled with the mixed solution A in the oven for reaction.
5. The method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 1, wherein the method comprises the following steps: and 2) in the high-temperature carbonization process, the calcination temperature of the tube furnace is 700-1000 ℃.
6. The method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 5, wherein the method comprises the following steps: the calcination time is 2-8 h.
7. The method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 1, wherein the method comprises the following steps: in the step 2), the heating rate of the tube furnace is 5 ℃/min in the high-temperature carbonization process.
8. The method for preparing the cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 1, wherein the method comprises the following steps: and 2) introducing nitrogen in the high-temperature carbonization process, wherein the introducing rate of the nitrogen is 60mL/min.
9. An application of a cobalt-based metal-organic framework derived magnetic carbon composite material is characterized in that: the cobalt-based metal-organic framework-derived magnetic carbon composite material prepared by the preparation method of the cobalt-based metal-organic framework-derived magnetic carbon composite material according to any one of claims 1 to 8, which is used as a drug pollutant adsorbent for adsorbing chlorpromazine hydrochloride in water.
10. The use of a cobalt-based metal organic framework-derived magnetic carbon composite material according to claim 9, characterized in that: the cobalt-based metal-organic framework derived magnetic carbon composite material has magnetism, and the cobalt-based metal-organic framework derived magnetic carbon composite material has a large number of adsorption active sites.
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