CN108840878B - Preparation method and application of copper complex - Google Patents
Preparation method and application of copper complex Download PDFInfo
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- CN108840878B CN108840878B CN201810563915.1A CN201810563915A CN108840878B CN 108840878 B CN108840878 B CN 108840878B CN 201810563915 A CN201810563915 A CN 201810563915A CN 108840878 B CN108840878 B CN 108840878B
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
Abstract
The invention discloses a preparation method and application of a copper complex, wherein the preparation method comprises the following steps: 1) mixing copper chloride dihydrate and 1, 4-bis (triazole-1-yl) terephthalic acid, adding the mixture into a solvent, and uniformly stirring to obtain a mixed solution A; then adding nitric acid and stirring to obtain a mixed solution B; 2) under the sealing condition, the mixed solution B is placed at the temperature of 110-130 ℃ for reaction for 10-14h to obtain a crystal C; 3) and (3) cleaning the crystal C with ethanol for three times, then soaking the crystal C in methanol for 2 days, then soaking the crystal C in dichloromethane for 1 day, and finally drying the crystal C in an oven to obtain the copper complex. The method is simple and convenient to synthesize and high in yield, and the copper complex has high adsorption efficiency on diclofenac sodium and also has good desorption capacity and recycling capacity after adsorbing the drug pollutants, so that the copper complex has potential application in the aspect of adsorbing the drug pollutants in a water environment.
Description
Technical Field
The invention relates to the technical field of pharmaceutical pollutant adsorbents, and particularly relates to a preparation method and application of a copper complex.
Background
With the development of economy and the improvement of living standard, the use amount of medicines and personal care products is continuously increased, meanwhile, medicine pollutants are taken as a large class of medicines and personal care products, and are also a new pollutant which is widely concerned in recent years and are detected in more and more water environments, the pollutants mainly comprise antibiotics, anti-inflammatory drugs, antiepileptics, lipid-lowering drugs and the like, due to the fact that the pollutants are complex in structure and diverse in components, the pollutants are slowly degraded under natural conditions, meanwhile, the concentration of the medicine pollutants is continuously increased along with the continuous production, use and discharge of people, the medicines can cause the reaction of organisms under extremely low concentration, and the pollutants exist in water in large quantities and for a long time, so that the pollutants have certain harm to human beings, animals, plants and ecological systems.
The existing treatment methods for drug contamination mainly comprise activated sludge adsorption, biodegradation, photodegradation, advanced oxidation technology and the like, but the practical application of the treatment methods is limited due to respective defects. For example, the activated sludge adsorption only adsorbs and transfers the drug pollutants in the water body to the soil, and the drugs are not fundamentally removed from the environment; the degradation process of the biological and photodegradation methods is very slow and not enough to eliminate the increasing discharge of drugs into the water environment; although advanced oxidation technology is efficient at removing contaminants, it is costly and produces some toxic by-products, causing secondary pollution. In contrast, the adsorption method is simple and convenient to operate, low in economic cost and high in efficiency, various medicaments can be adsorbed and removed, various materials can be used as adsorbents at present, such as activated carbon, clay, molecular sieves, carbon nanotubes, metal oxides and the like, but the activated carbon is low in adsorption rate and difficult to recycle; the carbon nano tube has high production cost and is difficult to be applied in large scale; the metal oxide has a small specific surface area and a poor adsorption effect. Therefore, it is necessary to develop a new material with the advantages of high adsorption efficiency, low cost, recycling and the like as an adsorbent for adsorbing and removing drug pollutants in water environment.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of a copper complex and application thereof aiming at the defects in the prior art, the preparation method is simple and convenient to synthesize, high in yield and good in stability in water, the copper complex prepared by the method has high adsorption efficiency on diclofenac sodium, and also has good desorption capacity and recycling capacity after adsorbing drug pollutants, so that the copper complex has potential application in the aspect of adsorbing the drug pollutants in water environment.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a method for preparing a copper complex, comprising the steps of:
1) mixing copper chloride dihydrate and 1, 4-bis (triazole-1-yl) terephthalic acid, adding the mixture into a solvent, and uniformly stirring to obtain a mixed solution A; then adding nitric acid and stirring for 3-8min to obtain a mixed solution B;
2) under the sealing condition, the mixed solution B obtained in the step 1) is placed at the temperature of 110-130 ℃ for reaction for 10-14h to obtain a crystal C;
3) washing the crystal C obtained in the step 2) with ethanol for three times, then placing the washed crystal C in methanol for soaking for 2 days, then placing the crystal C in dichloromethane for soaking for 1 day, and finally placing the soaked crystal C in an oven at the temperature of 90-110 ℃ for drying for 8-12 hours to obtain the copper complex.
As a preferable scheme, the mass ratio of the copper chloride dihydrate to the 1, 4-bis (triazol-1-yl) terephthalic acid in the step 1) is 3-5: 1.
as a preferable scheme, the solvent in the step 1) is N, N-dimethylformamide, and the mass ratio of the copper chloride dihydrate and the 1, 4-bis (triazol-1-yl) terephthalic acid to the solvent is 1: 80-90.
As a preferable scheme, the mass ratio of the mixed solution A to the nitric acid in the step 1) is 16-20: 1.
As a preferable scheme, the methanol is replaced every 24 hours during the soaking of the washed crystal C in methanol in the step 3).
The application of the copper complex, namely the copper complex prepared by the preparation method is used as a drug pollutant adsorbent to adsorb diclofenac sodium in water.
As a preferable scheme, in the diclofenac sodium solution with the concentration of 400-1600mg/L, the adsorption capacity of the copper complex to the diclofenac sodium is enhanced along with the increase of the concentration of the diclofenac sodium solution.
As a preferable scheme, under the condition that the temperature is 20-60 ℃, the adsorption capacity of the copper complex to the diclofenac sodium is weakened along with the increase of the temperature.
As a preferred embodiment, the copper complex has an optimal ability to adsorb diclofenac sodium under weak acid conditions.
As a preferable scheme, the adsorption rate of the copper complex to diclofenac sodium reaches 65%, and the copper complex has good desorption capacity and recycling capacity after adsorbing drug pollutants.
The invention has the beneficial effects that: the preparation method of the copper complex is simple and convenient, and the yield is high; the copper complex prepared by the method shows regularly arranged nano-pore diameter, high surface area and high porosity, has good stability to water, is stably degraded at high temperature, still keeps good structural stability under the condition that the pH value is 2-12, has good adsorption capacity to diclofenac sodium, the adsorption rate reaches more than 65%, meanwhile, the adsorption capacity of the copper complex is gradually enhanced along with the reduction of temperature, the adsorption capacity of the copper complex is gradually enhanced along with the increase of the concentration of an adsorbate, the adsorption capacity of the copper complex to the diclofenac sodium under the weak acid condition is better, and the copper complex has good desorption capacity and recycling capacity after adsorbing drug pollutants, so the copper complex has potential application in the aspect of adsorbing the drug pollutants in water.
Drawings
FIG. 1 is a three-dimensional simulated structural view of a copper complex;
FIG. 2 is an X-ray diffraction diagram of a copper complex simulation, a copper complex crystal, a copper complex after solvent removal, a copper complex after diclofenac sodium adsorption, a copper complex after diclofenac sodium desorption and a copper complex after diclofenac sodium adsorption for 3 cycles;
FIG. 3 is an infrared spectrum of a copper complex, diclofenac sodium, a copper complex after adsorbing diclofenac sodium, a copper complex after desorbing diclofenac sodium, and a copper complex after adsorbing diclofenac sodium for 3 cycles;
FIG. 4 is a thermogravimetric plot of the copper complex, diclofenac sodium and the copper complex after adsorption of diclofenac sodium;
FIG. 5 is an analysis chart of the adsorption of diclofenac sodium at different concentrations of copper complex;
FIG. 6 is an analysis chart of adsorption equilibrium time of diclofenac sodium adsorbed by copper complex;
FIG. 7 is an analysis chart of the copper complex adsorbing diclofenac sodium at different temperatures;
FIG. 8 is an analysis chart of the adsorption of diclofenac sodium by the copper complex at different pH values;
FIG. 9 is an analysis chart of the copper complex adsorbing diclofenac sodium at different doses;
FIG. 10 is an analysis chart of desorption of copper complex after saturation of adsorbed diclofenac sodium;
FIG. 11 is a graph showing the analysis of the amount of the copper complex adsorbed after 3 cycles of adsorption of diclofenac sodium.
Detailed Description
The structural and operational principles of the present invention are explained in further detail below with reference to the accompanying drawings.
Example 1
A method for preparing a copper complex, comprising the steps of:
1) mixing 0.6g of copper chloride dihydrate and 0.2g of 1, 4-bis (triazol-1-yl) terephthalic acid, adding the mixture into 67mLN, N-dimethylformamide, and uniformly stirring to obtain a mixed solution A; then adding 2.85mL of nitric acid and stirring for 8min to obtain a mixed solution B;
2) taking 4mL of the mixed solution B obtained in the step 1) and subpackaging the mixed solution B into penicillin bottles with the specification of 15mL, and placing the penicillin bottles at the temperature of 110 ℃ for reaction for 14 hours to obtain crystals C;
3) cleaning the crystal C obtained in the step 2) with ethanol for three times, then placing the cleaned crystal C in methanol for soaking for 2 days, replacing the methanol every 24 hours, then placing the crystal C in dichloromethane for soaking for 1 day, and finally placing the soaked crystal C in an oven with the temperature of 90 ℃ for drying for 12 hours to obtain the copper complex.
Example 2
A method for preparing a copper complex, comprising the steps of:
1) 1g of copper chloride dihydrate and 0.2g of 1, 4-bis (triazol-1-yl) terephthalic acid are mixed and then added into 114mLN, N-dimethylformamide to be uniformly stirred, so as to obtain a mixed solution A; then adding 3.85mL of nitric acid and stirring for 3min to obtain a mixed solution B;
2) taking 4mL of the mixed solution B obtained in the step 1) and subpackaging the mixed solution B into penicillin bottles with the specification of 15mL, and placing the penicillin bottles at the temperature of 130 ℃ for reaction for 10 hours to obtain crystals C;
3) cleaning the crystal C obtained in the step 2) with ethanol for three times, then placing the cleaned crystal C in methanol for soaking for 2 days, replacing the methanol every 24 hours, then placing the crystal C in dichloromethane for soaking for 1 day, and finally placing the soaked crystal C in an oven with the temperature of 110 ℃ for drying for 8 hours to obtain the copper complex.
Example 3
A method for preparing a copper complex, comprising the steps of:
1) mixing 0.7g of copper chloride dihydrate and 0.2g of 1, 4-bis (triazol-1-yl) terephthalic acid, adding the mixture into 80mLN, N-dimethylformamide, and uniformly stirring to obtain a mixed solution A; then adding 3mL of nitric acid and stirring for 5min to obtain a mixed solution B;
2) taking 4mL of the mixed solution B obtained in the step 1) and subpackaging the mixed solution B into penicillin bottles with the specification of 15mL, and placing the penicillin bottles at the temperature of 120 ℃ for reaction for 12 hours to obtain crystals C;
3) cleaning the crystal C obtained in the step 2) with ethanol for three times, then placing the cleaned crystal C in methanol for soaking for 2 days, replacing the methanol every 24 hours, then placing the crystal C in dichloromethane for soaking for 1 day, and finally placing the soaked crystal C in an oven at the temperature of 100 ℃ for drying for 10 hours to obtain the copper complex.
In conclusion, the preparation method of the copper metal organic framework compound is simple and easy, and the yield is high.
In the above examples, example 3 was the most preferable, and the copper complexes used in examples 4 to 14 were each obtained in example 3.
Example 4
And (3) carrying out three-dimensional space structure simulation on the copper complex by using a computer to obtain a three-dimensional space simulation structure diagram of the copper complex, wherein an experimental result is shown in figure 1.
Example 5
P-XRD experiment
The experimental steps are as follows: respectively carrying out X-ray diffraction measurement on the copper complex, the copper complex loaded with the diclofenac sodium, the copper complex desorbed with the diclofenac sodium and the copper complex subjected to 3-time cyclic diclofenac sodium adsorption by using an X-ray diffractometer
The results of the experiment are shown in FIG. 2.
Example 6
Infrared spectroscopy experiment
The experimental steps are as follows:
1) mixing 1mg of copper complex, 1mg of diclofenac sodium, 1mg of copper complex loaded with diclofenac sodium, 1mg of copper complex desorbed with diclofenac sodium and copper complex adsorbed with diclofenac sodium for 3 times with 50mg of potassium bromide respectively, and grinding into powder with particle size less than 2.5 μm;
2) then pressing the powder obtained in the step 1 into tablets by using a hydraulic press at the pressure of 8 tons;
3) and (3) performing infrared spectrometry on the sheet obtained in the step 2) by using a Fourier infrared transform spectrometer (model WQF-510A, and the manufacturer is Beijing Bifen-Rayleigh Instrument analysis Co., Ltd.).
The results of the experiment are shown in FIG. 3.
Example 7
Thermogravimetric experiments
The experimental steps are as follows: respectively weighing 10mg of copper complex, 10mg of diclofenac sodium and 10mg of copper complex loaded with diclofenac sodium, placing the copper complex into a crucible (special for thermogravimetric analysis), and then placing the crucible into a thermogravimetric analyzer (the model is HCT-2, and the manufacturer is Beijing Hengjiu scientific instrument factory) to perform thermogravimetric experiment, wherein the thermogravimetric analyzer is set according to the following conditions during the experiment: the nitrogen flow was 150ml/min, the reaction temperature was raised from 25 ℃ to 800 ℃ and the rate of temperature rise was 10 ℃/min.
The results of the experiment are shown in FIG. 4.
Example 8
Adsorption experiments
Adsorption experiment of copper complex on diclofenac sodium solutions with different concentrations
The experimental steps are as follows:
1) taking 20mL of diclofenac sodium solution with the concentration of 400, 500, 600, 700, 800, 900, 1000, 1100, 1200, 1300, 1400, 1500 and 1600mg/L, respectively placing the diclofenac sodium solution into 100mL beakers, respectively weighing 10mg of copper complex, respectively adding the copper complex into the solution, sealing the bottle mouth with a sealing film, placing the bottle mouth into a shaking table (the model is TS-2, and the manufacturer is Jiangsu Haimengqin Linbei apparatus manufacturing limited company) and shaking at the shaking speed of 200rpm for 10 hours under the condition that the temperature is 25 ℃ to obtain reaction liquid; then standing for 3min, placing 4mL of reaction solution in a centrifuge (model H1850R, Hunan instrument laboratory development Co., Ltd.) and centrifuging at a rotation speed of 10000rpm to remove copper complexes to obtain a diclofenac sodium supernatant;
2) weighing 10mg of diclofenac sodium standard substance, dissolving the diclofenac sodium standard substance in 50mL of water to prepare 200mg/L standard solution, diluting the standard solution with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve;
3) measuring absorbance value of diclofenac sodium supernatant in the step 1) at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), comparing the standard curve of diclofenac sodium obtained in the step 2), calculating the concentration of diclofenac sodium in the diclofenac sodium supernatant, and then obtaining the concentration of diclofenac sodium according to an adsorption rate formula R = (C)Original source-C0)/COriginal sourceAnd calculating the adsorption rate by 100%, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as shown in FIG. 5, in the diclofenac sodium solution with the concentration of 400-1600mg/L, the adsorption capacity of the copper complex to the diclofenac sodium is enhanced with the increase of the concentration.
Example 9
Copper complex adsorption saturation time experiment on diclofenac sodium solution with same concentration
The experimental steps are as follows:
1) 20mL of diclofenac sodium solution with the concentration of 1200mg/L is placed in a 100mL beaker, 10mg of copper complex is weighed and added into the solution, the opening of the beaker is sealed by a sealing film, the beaker is placed in a shaking table (model TS-2, the manufacturer is Jiangsu Haimen Linbel instruments Co., Ltd.) to be shaken under the condition that the shaking amplitude is 200rpm, and the absorbance of the diclofenac sodium solution in the beaker at 274nm is respectively measured by an ultraviolet spectrophotometer (model UV-650, Shanghai Mei Banda instruments Co., Ltd.) when the beaker is shaken for 10, 30, 60, 100, 200, 300, 400, 600, 800, 1000, 1200, 1400 and 1600min, and data are recorded.
2) Weighing 10mg of diclofenac sodium standard substance, dissolving in 50mL of water to prepare 200mg/L standard solution, diluting with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve.
3) Comparing the absorbance of the sodium clofenate solution at 274nm obtained in the step 1) with the standard curve of the diclofenac sodium obtained in the step 2), calculating the concentration of the diclofenac sodium in the diclofenac sodium solution in the beaker, and then calculating the adsorption rate according to the formula R = (C)Original source-C0)/COriginal sourceAnd calculating the adsorption rate by 100%, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as shown in FIG. 6, diclofenac sodium in diclofenac sodium solution with copper complex adsorption concentration of 1200mg/L reaches adsorption saturation state at 400 min.
Example 10
Adsorption experiment of copper complex on diclofenac sodium at different temperatures
The experimental steps are as follows:
1) firstly, 20mL of diclofenac sodium solution with the concentration of 1200mg/L is placed in a 100mL beaker, 10mg of copper complex is weighed and added into the solution, a sealing film is used for sealing a bottle mouth, the beaker is placed in a shaking table (model number is TS-2, the manufacturer is Jiangsu Hainan Lin Berl apparatus manufacturing limited company) with the temperature condition of 20 ℃, 30 ℃, 40 ℃, 50 ℃ and 60 ℃ to shake for 8 hours under the condition that the shaking amplitude is 200rpm, and then a centrifuge (model number is H1850R, the manufacturer is Hunan instrument laboratory apparatus development limited company) is used for centrifuging and removing the copper complex under the condition that the rotating speed is 10000rpm to obtain the diclofenac sodium supernatant.
2) Weighing 10mg of diclofenac sodium standard substance, dissolving in 50mL of water to prepare 200mg/L standard solution, diluting with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve.
3) Measuring absorbance of the diclofenac sodium supernatant obtained in step 1) at 274nm with ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral apparatus Co., Ltd.), and comparing with the standard curve of diclofenac sodium obtained in step 2) to obtain diclofenac sodium of diclofenac sodium supernatantConcentration, then according to the adsorption rate formula R = (C)Original source-C0)/COriginal sourceAnd calculating the adsorption rate by 100%, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as shown in FIG. 7, the adsorption capacity of the copper complex to diclofenac sodium decreases with increasing temperature at a temperature of 20 ℃ to 60 ℃.
Example 11
Adsorption experiment of copper complex on diclofenac sodium at different pH values
The experimental steps are as follows:
1) firstly, 20mL of diclofenac sodium solution with the concentration of 1200mg/L is taken and placed in a 100mL beaker, then the pH value of the diclofenac sodium solution is adjusted to 6.5, 7.5, 8.5, 9.5 and 10.5 by using sodium hydroxide with the concentration of 0.01mol/L and hydrochloric acid with the concentration of 0.01mol/L, 10mg of copper complex is weighed and added into the solution, a bottle opening is sealed by a sealing film, the beaker is placed in a shaking table (the model is TS-2, the manufacturer is Jiangsu Haimen Linbeier apparatus manufacturing limited company) to shake for 8H under the condition that the swing amplitude is 200rpm, and then a centrifuge (the model is H1850R, the manufacturer is Hunan Xiang apparatus laboratory apparatus developing limited company) is used for centrifuging at the rotation speed of 10000rpm to remove the copper complex, thus obtaining the diclofenac sodium supernatant.
2) Weighing 10mg of diclofenac sodium standard substance, dissolving in 50mL of water to prepare 200mg/L standard solution, diluting with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve.
3) Measuring absorbance of the diclofenac sodium supernatant obtained in the step 1) at 274nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Mei spectral apparatus, Ltd.), comparing the standard curve of the diclofenac sodium obtained in the step 2), calculating the concentration of the diclofenac sodium in the diclofenac sodium supernatant, and then obtaining the concentration of the diclofenac sodium according to an adsorption rate formula R = (C)Original source-C0)/COriginal sourceAdsorption rate was calculated 100%, and data was recordedAnd drawing to obtain an experimental result.
The experimental results are as follows: as shown in FIG. 8, the copper complex has a decreased adsorption capacity for diclofenac sodium at pH 6.5-10.5 as the pH increases.
Example 12
Adsorption experiment of copper complex on diclofenac sodium under different doses
The experimental steps are as follows:
1) placing 20mL of diclofenac sodium solution with the concentration of 1200mg/L into a 100mL beaker, respectively weighing 5, 10, 15, 20 and 25mg of copper complex, adding the copper complex into the solution, sealing the bottle mouth with a sealing film, placing the beaker into a shaking table (model TS-2, manufacturer, HuntingHaimengqin Linbel instruments Co., Ltd.) to shake for 8H under the condition of the shaking amplitude of 200rpm, and then centrifuging by using a centrifuge (model H1850R, manufacturer, Huntingxiang instruments laboratory development Co., Ltd.) to remove the copper complex at the rotation speed of 10000rpm to obtain a diclofenac sodium supernatant.
2) Weighing 10mg of diclofenac sodium standard substance, dissolving in 50mL of water to prepare 200mg/L standard solution, diluting with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve.
3) Measuring absorbance value of the diclofenac sodium supernatant obtained in the step 1) at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), comparing the standard curve of the diclofenac sodium obtained in the step 2), calculating the concentration of the diclofenac sodium in the diclofenac sodium supernatant, and then obtaining the concentration of the diclofenac sodium according to an adsorption rate formula R = (C)Original source-C0)/COriginal sourceAnd calculating the adsorption rate by 100%, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as shown in FIG. 9, the adsorption capacity of the copper complex to diclofenac sodium decreases with increasing dosage at 5-25 mg.
Example 13
Desorption experiments
The experimental steps are as follows:
1) weighing 10mg of copper complex adsorbing saturated diclofenac sodium, placing the copper complex in a 100mL beaker, adding 20mL of pure water into the beaker, sealing the opening of the beaker by using a sealing film, placing the beaker in a shaking table (model TS-2, the manufacturer is Jiangsu Haimen Linbei apparatus manufacturing Co., Ltd.) to shake under the condition that the shaking amplitude is 200rpm, replacing fresh 20mL of pure water every other hour, repeating for 5 times, respectively measuring the absorbance value of the diclofenac sodium solution in each beaker at 274nm by using an ultraviolet spectrophotometer (model UV-650, Shanghai Meida apparatus Co., Ltd.), and recording data.
2) Weighing 10mg of diclofenac sodium standard substance, dissolving in 50mL of water to prepare 200mg/L standard solution, diluting with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve.
3) Measuring absorbance value of the diclofenac sodium supernatant obtained in the step 1) at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), comparing the standard curve of the diclofenac sodium obtained in the step 2), calculating the concentration of the diclofenac sodium in the diclofenac sodium supernatant, and then obtaining the concentration of the diclofenac sodium according to an adsorption rate formula R = (C)Original source-C0)/COriginal sourceAnd calculating the adsorption rate by 100%, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as shown in fig. 10, the desorption rate of the copper complex to the diclofenac sodium is gradually increased and then becomes stable with the passage of time, and the desorption rate of the copper complex to the diclofenac sodium reaches 90% after 300 min.
Example 14
Cycling experiments
The experimental steps are as follows:
1) placing 20mL of diclofenac sodium solution with the concentration of 1200mg/L into a 100mL beaker, weighing 10mg of copper complex, adding the copper complex into the solution, sealing the mouth of the beaker by using a sealing film, placing the beaker into a shaking table (model number TS-2, manufacturer is Jiangsu Haimen Linbeier apparatus manufacturing Limited) to shake for 8H under the condition that the shaking amplitude is 200rpm so as to ensure that the adsorption of the copper complex on the diclofenac sodium solution reaches an adsorption saturation state, then centrifuging the solution by using a centrifuge (model number H1850R, manufacturer is Hunan instrument laboratory apparatus development Limited) at the rotating speed of 10000rpm, and drying the solution to obtain the diclofenac sodium adsorption saturated copper complex;
2) weighing 10mg of the copper complex adsorbing saturated diclofenac sodium obtained in the step 1) and placing the copper complex into a 100mL beaker, adding 20mL of pure water into the beaker, sealing the opening of the beaker by using a sealing film, placing the beaker into a shaking table (model TS-2, the manufacturer is Jiangsu Haimengqin Lin Bell apparatus manufacturing Limited) and shaking the beaker under the condition that the shaking amplitude is 200rpm, replacing fresh 20mL of pure water every other hour until the copper complex adsorbing saturated diclofenac sodium completely desorbs diclofenac sodium, then centrifuging the beaker at the condition that the rotating speed is 10000rpm by using a centrifuge (model H185 1850R, the manufacturer is Hunan Xiang apparatus laboratory apparatus development Limited), and drying the beaker to obtain the copper complex after the diclofenac sodium is desorbed;
3) placing 20mL of diclofenac sodium solution with the concentration of 1200mg/L into a 100mL beaker, weighing 10mg of the copper complex obtained in the step 2) after the diclofenac sodium is desorbed, adding the copper complex into the solution, sealing the mouth of the beaker by using a sealing film, placing the beaker into a shaking table (model TS-2, manufacturer, HuntingHaimen Linbeier apparatus manufacturing company, Ltd.) and shaking for 8 hours under the condition that the shaking amplitude is 200rpm so that the adsorption of the copper complex on the diclofenac sodium solution is in an adsorption saturated state again, and then centrifuging by using a centrifuge (model H1850R, manufacturer, HuntingHainan Huntinginstrument laboratory apparatus development company, Ltd.) at the rotation speed of 10000rpm to obtain a diclofenac sodium supernatant and the copper complex saturated with adsorbed diclofenac sodium;
4) repeating the steps 2) -3) for 3 times, respectively measuring the absorbance values of the diclofenac sodium supernatant obtained in the step 3) at 274nm for multiple times by using an ultraviolet spectrophotometer (model is UV-650, Shanghai Meida instruments, Ltd.), and recording data;
5) weighing 10mg of diclofenac sodium standard substance, dissolving in 50mL of water to prepare 200mg/L standard solution, diluting with water to obtain 10, 15, 20, 25, 30 and 35mg/L diclofenac sodium standard solution, measuring the absorbance value of the diclofenac sodium standard solution at 274nm by using an ultraviolet spectrophotometer (UV-650, Shanghai Mei spectral instruments, Ltd.), recording data, and drawing a diclofenac sodium standard curve.
6) Respectively comparing the absorbance values of the diclofenac sodium supernatant obtained in the step 3) at 274nm with the standard curve of the diclofenac sodium obtained in the step 5) for many times, calculating the concentration of the diclofenac sodium in the diclofenac sodium supernatant, and then obtaining the concentration of the diclofenac sodium according to an adsorption rate formula R = (C)Original source-C0)/COriginal sourceAnd calculating the adsorption rate by 100%, recording data, and drawing to obtain an experimental result.
The experimental results are as follows: as shown in fig. 11, after 3 times of adsorption experiments, the adsorption rate of the copper complex to diclofenac sodium is close to 60%, which indicates that the copper complex has good desorption and recycling capability after adsorbing the drug pollutants.
The above description is only a preferred embodiment of the present invention, and all the minor modifications, equivalent changes and modifications made to the above embodiment according to the technical solution of the present invention are within the scope of the technical solution of the present invention.
Claims (5)
1. The application of a copper complex is characterized in that: the preparation method of the copper complex comprises the following steps:
1) mixing 0.7g of copper chloride dihydrate and 0.2g of 1, 4-bis (triazol-1-yl) terephthalic acid, adding the mixture into 80mL of N, N-dimethylformamide, and uniformly stirring to obtain a mixed solution A; then adding 3mL of nitric acid and stirring for 5min to obtain a mixed solution B;
2) taking 4mL of the mixed solution B obtained in the step 1) and subpackaging the mixed solution B into penicillin bottles with the specification of 15mL, and placing the penicillin bottles at the temperature of 120 ℃ for reaction for 12 hours to obtain crystals C;
3) cleaning the crystal C obtained in the step 2) for three times by using ethanol, then placing the cleaned crystal C in methanol for soaking for 2 days, replacing the methanol every 24 hours, then placing the crystal C in dichloromethane for soaking for 1 day, and finally placing the soaked crystal C in an oven with the temperature of 100 ℃ for drying for 10 hours to obtain a copper complex;
the copper complex prepared by the preparation method is used as a drug pollutant adsorbent to adsorb diclofenac sodium in water.
2. Use of a copper complex according to claim 1, wherein: in the diclofenac sodium solution with the concentration of 400-1600mg/L, the adsorption capacity of the copper complex to the diclofenac sodium is enhanced along with the increase of the concentration of the diclofenac sodium solution.
3. Use of a copper complex according to claim 1, wherein: under the condition of the temperature of 20-60 ℃, the adsorption capacity of the copper complex to the diclofenac sodium is weakened along with the increase of the temperature.
4. Use of a copper complex according to claim 1, wherein: under weak acid conditions, the copper complex has the best ability to adsorb diclofenac sodium.
5. Use of a copper complex according to claim 1, wherein: the adsorption rate of the copper complex on diclofenac sodium reaches 65%, and the copper complex has good desorption capacity and recycling capacity after adsorbing drug pollutants.
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