CN116177690A - Method for removing fluoride ions in water body based on polypyrrole/bimetallic MOF/graphite composite electrode capacitive deionization - Google Patents
Method for removing fluoride ions in water body based on polypyrrole/bimetallic MOF/graphite composite electrode capacitive deionization Download PDFInfo
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- 230000008569 process Effects 0.000 description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 8
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4691—Capacitive deionisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/12—Halogens or halogen-containing compounds
- C02F2101/14—Fluorine or fluorine-containing compounds
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- General Chemical & Material Sciences (AREA)
- Hydrology & Water Resources (AREA)
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Abstract
The invention relates to a method for removing fluoride ions in a water body based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization, which comprises the steps of preparation of the bimetal MOF, electropolymerization of pyrrole and electrophoretic deposition of the bimetal MOF. The inclusion of polypyrrole can improve the problem of poor conductivity of the MOF material. The specific and efficient adsorption of fluoride ions can be realized by utilizing the high specific surface area of the bimetallic MOF material, the bimetallic center and the special functional groups on the ligand. The electrode material prepared by the method of the invention is used as an anode, manganese dioxide is used as a cathode, and the high-efficiency removal of fluorine ions in water can be realized based on the advantages of pseudocapacitance, large adsorption capacity, capacitance deionization technology and the like of the system. After the adsorption is finished, the anode and the cathode are reversely connected, so that the regeneration of the electrode can be realized, and the electrode is safe and environment-friendly and is beneficial to sustainable development.
Description
Technical Field
The invention belongs to the technical field of water treatment, and relates to a method for removing fluoride ions in a water body based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization.
Background
Water is an essential element for human life, however, limited fresh water resources on earth have been limited by water pollution. Fluoride ions are common contaminating ions in water bodies, and it is known that ingestion of small amounts of fluorine can act to protect teeth and if the intake of fluorine is too low in daily life, the risk of caries increases. However, excessive intake of fluorine causes fluorosis, which is a serious hazard to bones, kidneys, etc. of the human body, and common symptoms are fluorosis teeth, fluorosis, etc. At present, the requirement of the world health organization on the fluorine content in drinking water is lower than 1.5mg/L, and the national standard is more strict and is lower than 1mg/L.
The natural high-fluorine underground water mainly has the source of releasing fluoride ions in fluorine-containing minerals. Natural activities such as wind blowing, rain, volcanic eruption and the like can promote release of fluorine ions into soil and groundwater, and high-fluorine groundwater is finally formed through accumulation for a long time. The investigation data according to the national statistical annual book of Chinese health shows that at present, the problem of fluorine poisoning is recorded in 28 provinces in China, and the national study is mainly concentrated in northern areas, because northern rainwater is rare, and the fluorine content is higher due to the action of strong evaporation. The fluorine pollution in Shandong area is serious, wherein the maximum of the lotus city can reach 7.8mg/L, and the maximum of the high density city can reach 11.0mg/L.
The main defluorination methods at present are a coagulating sedimentation method, an electrodialysis method, an ion exchange method, a membrane separation method, an adsorption method and the like. The adsorption method has the advantages of low cost, simple operation, regenerable adsorbent and the like, and is one of the most popular defluorination methods at present. The main adsorption materials at present are carbon materials, metal oxides, metal hydroxides, metal organic frameworks, natural materials and the like.
Electro-adsorption, also known as Capacitive Deionization (CDI), is an emerging water treatment technology. The main process is that under the action of electric field, anions and cations are transferred to the surface of the electrode, and finally the drinking water with standard fluorine content is obtained. It has the advantages of low energy consumption and simple operation. Compared with the traditional adsorption material, the CDI technology has the greatest advantages that the regeneration of the electrode can be realized only by reversely connecting the anode and the cathode of the electrode, and the problem that the traditional adsorbent needs to be added with alkali liquor to realize the regeneration so as to cause secondary pollution is avoided. The key point of the capacitive deionization technology is the selection of electrode materials, and materials with high conductivity, large specific surface area and specific active sites should be selected.
The traditional electrosorption defluorination electrode material is prepared by hot-press molding a conductive material and an adsorbent by using a hot melt adhesive. The traditional defluorination electrode material has poor fluorine adsorption capacity, complicated electrode preparation, high energy consumption and high cost, and as disclosed in Chinese patent document CN102234145A, the preparation method of the defluorination electroadsorption electrode for drinking water and the defluorination electroadsorption electrode prepared by the method comprises the following steps: 1) Uniformly mixing a conductive material and an adsorbent to prepare a conductive mixture, wherein the weight ratio of the conductive material to the adsorbent is 3-55:45-97; 2) Adding the hot melt adhesive into the conductive mixture prepared in the step 1), and uniformly mixing to prepare an electro-adsorption mixture, wherein the weight ratio of the hot melt adhesive to the conductive mixture is 5-50:50-95; 3) And placing the electro-adsorption mixture into a mould, and hot-pressing and forming. CN103641201a discloses a method for preparing a fluorine-removing electroadsorption lanthanum-carrying electrode for drinking water and a fluorine-removing electrode, the method comprises 1) loading lanthanum into a carbon aerogel material to prepare a conductive adsorbent, wherein the weight ratio of lanthanum to carbon aerogel material is 5-60:40-95; 2) Adding the hot melt adhesive into the lanthanum-loaded carbon aerogel material prepared in the step 1), and uniformly mixing to prepare an electro-adsorption mixture, wherein the weight ratio of the hot melt adhesive to the lanthanum-loaded carbon aerogel material is 10-40:60-90; 3) And placing the electro-adsorption mixture into a mould, and hot-pressing and forming.
Metal-organic frameworks (MOFs) are crystalline materials with periodic network structures formed by self-assembly of Metal ions and organic ligands. The fluorine ion adsorption catalyst has a high specific surface area and rich active sites, wherein the central metal can realize better combination with fluorine ions, and the ligand can realize adsorption of the fluorine ions by adding functional groups favorable for combination with the fluorine ions. However, most MOF materials have poor conductivity and are not suitable for direct use as CDI electrodes.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for removing fluoride ions in a water body based on polypyrrole/bimetallic MOF/graphite composite electrode capacitance deionization.
The invention can efficiently remove the fluoride ions in the water body, and the polypyrrole/bimetallic MOF/graphite has large fluoride removal capacity, can still keep better adsorption fluoride removal capacity after repeated cyclic regeneration, has no secondary pollution, and is safe and environment-friendly.
The invention realizes the aim through the following technical scheme:
a method for removing fluoride ions in water based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization uses a polypyrrole/bimetal MOF electrode as an anode and a manganese dioxide electrode as a cathode, and applies 1-2V working voltage to realize efficient removal of fluoride ions in water;
the polypyrrole/bimetal MOF/graphite composite electrode is prepared by the following method:
(1) Adding the mixed metal salt solution into the ligand solution, and reacting by a hydrothermal method to obtain the bimetallic MOF;
(2) Dissolving chitosan in CH 3 Adding pyrrole into the COOH solution to uniformly disperse the solution, taking graphite as a working electrode and graphite as a counter electrode, and performing anodic electropolymerization under the condition of constant current density to obtain a polypyrrole electrode;
(3) Dispersing the bimetal MOF obtained in the step (1) into ethanol to obtain a bimetal MOF suspension, dropwise adding a dilute hydrochloric acid solution, taking the polypyrrole electrode prepared in the step (2) as a working electrode, and performing cathode electrophoresis deposition under a constant potential condition to obtain the polypyrrole/bimetal MOF/graphite composite electrode.
According to the present invention, in the step (1), the mixed metal salt of the mixed metal salt solution is Ce (NO) 3 ) 3 And Zn (NO) 3 ) 2 The molar ratio of Ce to Zn is 1:0.25-4, and the solvent of the mixed metal salt solution is ethanol or DMF; the ligand of the ligand solution is 2-amino terephthalic acid, and the solvent used by the ligand solution is DMF.
According to the present invention, preferably, in the step (1), the concentration of the mixed metal salt in the mixed metal salt solution is 0.14 to 0.18mol/L, the concentration of the ligand in the ligand solution is 0.11 to 0.22mol/L, and the molar ratio of the mixed metal salt in the mixed metal salt solution to the ligand in the ligand solution is 1:0.8 to 1.2.
According to the invention, in the step (1), the reaction temperature of the hydrothermal method reaction is 130-150 ℃ and the reaction time is 18-24 hours.
According to the invention, in the step (1), after the reaction is completed, after slowly cooling to room temperature in an oven, the obtained solid material is centrifugally separated, the unreacted material is removed by washing with DMF three times, the solvent is replaced with anhydrous methanol for 3 times at intervals of 12 hours, the residual DMF in the pores of the MOF is removed, and finally, the obtained solid material is centrifugally separated, and is dried for 12-24 hours under the vacuum condition at 60-80 ℃ to obtain the bimetallic MOF.
According to a preferred embodiment of the invention, in step (2), CH 3 The concentration of the COOH solution is 1-3%.
According to the invention, in the step (2), the chitosan solution is electrolyte, the mass fraction of the chitosan solution is 0.4% -1.0%, and the addition amount of the pyrrole is such that the concentration of the pyrrole is 0.008-0.01 mol/L.
According to the invention, in the step (2), the dissolution time of chitosan is 10-12 h, the dispersion time of pyrrole is 10-20 min, and the stirring rotation speed is 400-600 r/min.
According to the present invention, in the step (2), the electropolymerization has a current density of 2 to 10mA/cm 2 The time is 10-20 min, and the stirring rotating speed is 100-200 r/min.
According to a preferred embodiment of the invention, in step (3), the concentration of the bimetallic MOF suspension is between 0.1 and 1g/L and the concentration of the dilute hydrochloric acid solution is between 0.1mol/L.
According to the present invention, in the step (3), the amount of the diluted hydrochloric acid solution added dropwise is preferably 0.05 to 0.1mL.
According to the invention, in the step (3), the working electrode is a polypyrrole electrode, the counter electrode is graphite, the cathode deposition is carried out, the potential is 30-80V, the deposition time is 20-30 min, and the stirring rotation speed is 50-100 r/min.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention improves the defect of insufficient conductivity of the bimetallic MOF material by introducing the polypyrrole as the conductive polymer, and the electrode material with high specific surface area, specific binding site and high conductivity is finally obtained by combining the two materials;
2. the invention removes fluorine ions in water based on Faraday's law and electric double layer principle, uses polypyrrole/bimetal MOF/graphite composite electrode material as anode to adsorb fluorine ions, uses MnO 2 As the cathode for adsorbing sodium ions, compared with the traditional capacitance deionization mode, the adsorption capacity is greatly improved;
3. the electrode prepared by the invention has high adsorption capacity, can still reach higher adsorption capacity after repeated cyclic regeneration, has no secondary pollution in the treatment process, and is safe, environment-friendly and low in energy consumption.
4. The polypyrrole/bimetal MOF/graphite composite electrode has good ion selectivity, has higher selectivity for removing ionic fluoride ions aiming at the target, and has no obvious influence on other common anions in water in the drinking water range;
5. the polypyrrole/bimetallic MOF/graphite electrode of the invention adsorbs and fixes fluorine compounds in drinking water through the actions of covalent bond chemical adsorption, electrostatic adsorption, ion exchange adsorption and the like, has high adsorption capacity to fluorine, and has a saturated adsorption capacity of 83.26mg/g when the voltage is 1.2V under the condition of neutral pH.
6. The polypyrrole/bimetal MOF/graphite composite electrode has the advantages of small quality loss, no dissolution, no swelling, no toxicity, no secondary pollution problem, standard water quality after treatment, safety and reliability in the use process.
Drawings
FIG. 1 is an SEM image of a polypyrrole/bimetallic MOF/graphite composite electrode material (PPy/CZTN 100) prepared in example 1;
FIG. 2 is a comparison of capacitance defluorination adsorption capacities of the graphite composite electrode material prepared in comparative example 1 and the polypyrrole/bimetallic MOF/graphite composite electrode materials prepared in examples 1-4;
FIG. 3 is a graph showing the relationship between the capacitance defluorination adsorption capacity of the polypyrrole/graphite composite electrode material prepared in comparative example 1 and the capacitance defluorination adsorption capacity of the polypyrrole/bimetallic MOF/graphite composite electrode materials prepared in examples 1 to 4 over time;
FIG. 4 is a graph showing the adsorption performance of fluoride ions after repeated cyclic regeneration of the polypyrrole/bimetallic MOF/graphite composite electrode material (PPy/CZTN 80) prepared in example 2.
FIG. 5 is a graph showing the capacitance defluorination adsorption capacity of the polypyrrole/bimetallic MOF/graphite composite electrode material (PPy/CZTN 50) prepared in example 3 at different operating voltages;
FIG. 6 is a graph showing the capacitance defluorination adsorption capacity of the polypyrrole/bimetallic MOF/graphite composite electrode material (PPy/CZTN 50) prepared in example 3 at different solution concentrations as a function of equilibrium concentration;
FIG. 7 is a graph of the fit isothermal adsorption of polypyrrole/bimetallic MOF/graphite composite electrode material (PPy/CZTN 50) prepared in example 3.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1:
a method for removing fluoride ions in water based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization uses a polypyrrole/bimetal MOF electrode as an anode and a manganese dioxide electrode as a cathode, and applies 1-2V working voltage to realize efficient removal of fluoride ions in water;
the polypyrrole/bimetal MOF/graphite composite electrode is prepared by the following method:
(1) 45mL of a DMF solution (mixed salt solution) of cerium nitrate and zinc nitrate (0.16 mol/L) is added dropwise to 45mL of a DMF solution of 2-amino terephthalic acid (0.16 mol/L), and the mixture is dispersed for 1h by ultrasonic; the molar ratio of Ce to Zn in the mixed salt solution is 3:2, then the mixed solution is poured into a reaction kettle with a polytetrafluoroethylene lining of 150mL, hydrothermal reaction is carried out for 24h at 150 ℃, after the reaction is completed, the obtained solid substance is centrifugally separated after being slowly cooled to room temperature in an oven, the solid substance is washed three times by DMF to remove unreacted substances, and solvent replacement is carried out for 3 times by anhydrous methanol, and the interval is 12h each time, so as to remove residual DMF in the pores of the MOF. Finally, the solid material obtained was dried under vacuum at 80℃for 12h by centrifugation to give the bimetallic MOF, designated CZTN.
(2) Adding 0.32g chitosan into 80mL acetic acid solution with 2% concentration, stirring for 10 hr at 500r/min to dissolve thoroughly, adding 0.556mL pyrrole into chitosan solution, stirring for 20min at 800r/min to disperse uniformly to obtain pyrrole electropolymerized electrolyte solution, using graphite sheet with thickness of 2×3cm and 0.5mm as working electrode and counter electrode, and stirring at 5mA/cm 2 Electropolymerization for 10min under the current density condition, and finally obtaining the graphite flake deposited with polypyrrole at the anode. The polypyrrole electrode sheet is washed clean by deionized water, dried for 12 hours at 60 ℃ for standby, and marked as PPy.
(3) 100mg of the bimetallic MOF prepared in the step (1) is added into 100mL of absolute ethyl alcohol, 2 drops of 0.1mol/L hydrochloric acid are added dropwise, and ultrasonic dispersion is carried out for 30min, so as to obtain MOF suspension. And (3) taking the PPy electrode prepared in the step (2) as a working electrode, taking a graphite sheet as a counter electrode, placing the counter electrode in MOF suspension, electrifying for 20min under a constant voltage of 50V, and obtaining the polypyrrole/bimetal MOF/graphite composite electrode by a cathode, which is marked as PPy/CZTN 100. SEM images of the polypyrrole/bimetallic MOF/graphite composite electrode material are shown in fig. 1.
Example 2:
a method for removing fluoride ions in water based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization uses a polypyrrole/bimetal MOF electrode as an anode and a manganese dioxide electrode as a cathode, and applies 1-2V working voltage to realize efficient removal of fluoride ions in water;
the polypyrrole/bimetal MOF/graphite composite electrode is prepared by the following method:
(1) 45mL of a DMF solution (mixed salt solution) of cerium nitrate and zinc nitrate (0.16 mol/L) was added dropwise to 45mL of a DMF solution of 2-amino terephthalic acid (0.16 mol/L), and the mixture was dispersed ultrasonically for 1h. Wherein the molar ratio of Ce to Zn in the mixed salt solution is 3:2. Then, the mixed solution was poured into a 150mL polytetrafluoroethylene-lined reaction vessel, and subjected to hydrothermal reaction at 150℃for 24 hours. After the reaction was completed, after slowly cooling to room temperature in an oven, the resulting solid material was centrifuged, washed three times with DMF to remove unreacted material, and solvent-displaced 3 times with anhydrous methanol at intervals of 12h in order to remove residual DMF in the MOF pores. Finally, the solid material obtained was dried under vacuum at 80℃for 12h by centrifugation to give the bimetallic MOF, designated CZTN.
(2) 0.32g of chitosan was added to 80mL of 2% acetic acid solution and stirred at 500r/min for 10 hours to allow sufficient dissolution. Then 0.556mL of pyrrole is added into the chitosan solution, and the mixture is stirred for 20min under the condition of 800r/min to be uniformly dispersed, so as to obtain the pyrrole electropolymerized electrolyte solution. Graphite sheet with a thickness of 2X 3cm and 0.5mm was used as the working electrode and the counter electrode at 5mA/cm 2 Electropolymerization for 10min under the current density condition, and finally obtaining the graphite flake deposited with polypyrrole at the anode. The polypyrrole electrode sheet is washed clean by deionized water, dried for 12 hours at 60 ℃ for standby, and marked as PPy.
(3) 80mg of the bimetallic MOF prepared in the step (1) is added into 100mL of absolute ethanol, 2 drops of 0.1mol/L hydrochloric acid are added dropwise, and ultrasonic dispersion is carried out for 30min, so as to obtain MOF suspension. And (3) taking the PPy electrode prepared in the step (2) as a working electrode, taking a graphite sheet as a counter electrode, placing the counter electrode in MOF suspension, electrifying for 20min under a constant voltage of 50V, and marking the polypyrrole/bimetal MOF/graphite composite electrode as PPy/CBN 80 by a cathode.
Example 3:
a method for removing fluoride ions in water based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization uses a polypyrrole/bimetal MOF electrode as an anode and a manganese dioxide electrode as a cathode, and applies 1-2V working voltage to realize efficient removal of fluoride ions in water;
the polypyrrole/bimetal MOF/graphite composite electrode is prepared by the following method:
(1) 45mL of a DMF solution (mixed salt solution) of cerium nitrate and zinc nitrate (0.16 mol/L) was added dropwise to 45mL of a DMF solution of 2-amino terephthalic acid (0.16 mol/L), and the mixture was dispersed ultrasonically for 1h. Wherein the molar ratio of Ce to Zn in the mixed salt solution is 3:2. Then, the mixed solution was poured into a 150mL polytetrafluoroethylene-lined reaction vessel, and subjected to hydrothermal reaction at 150℃for 24 hours. After the reaction was completed, after slowly cooling to room temperature in an oven, the resulting solid material was centrifuged, washed three times with DMF to remove unreacted material, and solvent-displaced 3 times with anhydrous methanol at intervals of 12h in order to remove residual DMF in the MOF pores. Finally, the solid material obtained was dried under vacuum at 80℃for 12h by centrifugation to give the bimetallic MOF, designated CZTN.
(2) 0.32g of chitosan was added to 80mL of 2% acetic acid solution and stirred at 500r/min for 10 hours to allow sufficient dissolution. Then 0.556mL of pyrrole is added into the chitosan solution, and the mixture is stirred for 20min under the condition of 800r/min to be uniformly dispersed, so as to obtain the pyrrole electropolymerized electrolyte solution. Graphite sheet with a thickness of 2X 3cm and 0.5mm was used as the working electrode and the counter electrode at 5mA/cm 2 Electropolymerization for 10min under the current density condition, and finally obtaining the graphite flake deposited with polypyrrole at the anode. The polypyrrole electrode sheet is washed clean by deionized water, dried for 12 hours at 60 ℃ for standby, and marked as PPy.
(3) 50mg of the bimetallic MOF prepared in the step (1) is added into 100mL of absolute ethanol, 2 drops of 0.1mol/L hydrochloric acid are added dropwise, and ultrasonic dispersion is carried out for 30min, so as to obtain MOF suspension. And (3) taking the PPy electrode prepared in the step (2) as a working electrode, taking a graphite sheet as a counter electrode, placing the counter electrode in MOF suspension, electrifying for 20min under a constant voltage of 50V, and obtaining the polypyrrole/bimetal MOF/graphite composite electrode by a cathode, which is marked as PPy/CZTN 50.
Example 4:
a method for removing fluoride ions in water based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization uses a polypyrrole/bimetal MOF electrode as an anode and a manganese dioxide electrode as a cathode, and applies 1-2V working voltage to realize efficient removal of fluoride ions in water;
the polypyrrole/bimetal MOF/graphite composite electrode is prepared by the following method:
(1) 45mL of a DMF solution (mixed salt solution) of cerium nitrate and zinc nitrate (0.16 mol/L) was added dropwise to 45mL of a DMF solution of 2-amino terephthalic acid (0.16 mol/L), and the mixture was dispersed ultrasonically for 1h. Wherein the molar ratio of Ce to Zn in the mixed salt solution is 3:2. Then, the mixed solution was poured into a 150mL polytetrafluoroethylene-lined reaction vessel, and subjected to hydrothermal reaction at 150℃for 24 hours. After the reaction was completed, after slowly cooling to room temperature in an oven, the resulting solid material was centrifuged, washed three times with DMF to remove unreacted material, and solvent-displaced 3 times with anhydrous methanol at intervals of 12h in order to remove residual DMF in the MOF pores. Finally, the solid material obtained was dried under vacuum at 80℃for 12h by centrifugation to give the bimetallic MOF, designated CZTN.
(2) 0.32g of chitosan was added to 80mL of 2% acetic acid solution and stirred at 500r/min for 10 hours to allow sufficient dissolution. Then 0.556mL of pyrrole is added into the chitosan solution, and the mixture is stirred for 20min under the condition of 800r/min to be uniformly dispersed, so as to obtain the pyrrole electropolymerized electrolyte solution. Graphite sheet with a thickness of 2X 3cm and 0.5mm was used as the working electrode and the counter electrode at 5mA/cm 2 Electropolymerization for 10min under the current density condition, and finally obtaining the graphite flake deposited with polypyrrole at the anode. The polypyrrole electrode sheet is washed clean by deionized water, dried for 12 hours at 60 ℃ for standby, and marked as PPy.
(3) 10mg of the bimetallic MOF prepared in the step (1) is added into 100mL of absolute ethanol, 2 drops of 0.1mol/L hydrochloric acid are added dropwise, and ultrasonic dispersion is carried out for 30min, so as to obtain MOF suspension. And (3) taking the PPy electrode prepared in the step (2) as a working electrode, taking a graphite sheet as a counter electrode, placing the counter electrode in MOF suspension, electrifying for 20min under a constant voltage of 50V, and obtaining the polypyrrole/bimetal MOF/graphite composite electrode by a cathode, which is marked as PPy/CZTN 10.
Comparative example 1:
the procedure is as described in example 1, except that,
the graphite composite electrode is not doped with bimetal MOF, and is prepared by the following method:
0.32g of chitosan was added to 80mL of 2% acetic acid solution and stirred at 500r/min for 10 hours to allow sufficient dissolution. Then 0.556mL of pyrrole is added into the chitosan solution, and the mixture is stirred for 20min under the condition of 800r/min to be uniformly dispersed, so as to obtain the pyrrole electropolymerized electrolyte solution. Graphite sheet with a thickness of 2X 3cm and 0.5mm was used as the working electrode and the counter electrode at 5mA/cm 2 Electropolymerization for 10min under the current density condition, and finally obtaining the graphite flake deposited with polypyrrole at the anode. The polypyrrole electrode sheet is washed clean by deionized water, dried for 12 hours at 60 ℃ for standby, and marked as PPy.
Application test example 1:
1. the method is used for examining the performance of the polypyrrole/MOF composite electrode materials prepared in examples 1-4 in the field of capacitance defluorination, and the specific process and the result are as follows:
the composite electrodes of examples 1 to 4 and comparative example 1 were used as anodes, mnO 2 The cathode is 2X 3cm in size, and a voltage of 1.2V is applied between the cathode and the anode to form the electroabsorption defluorination component. With 5mg/L aqueous sodium fluoride solution (with F - Meter) is simulated wastewater, the treatment capacity is 50mL, the process is carried out in a 100mL beaker, and the capacitor defluorination is completed by energizing for 90 min. Capacitance defluorination data are obtained, fig. 2 is a comparison of capacitance defluorination adsorption capacities of the graphite composite electrode material prepared in comparative example 1 and the polypyrrole/bimetal MOF/graphite composite electrode materials prepared in examples 1 to 4, and fig. 3 is a relationship of capacitance defluorination adsorption capacities of the polypyrrole/graphite composite electrode materials prepared in comparative example 1 and the polypyrrole/bimetal MOF/graphite composite electrode materials prepared in examples 1 to 4 over time.
The calculated fluoride ion adsorption capacities of the polypyrrole/bimetallic MOF/graphite composite electrodes PPy/CBN 10, PPy/CBN 50, PPy/CBN 80 and PPy/CBN 100 are respectively 1.32mg/L, 6.01mg/L, 8.53 and 6.83mg/g. The polypyrrole fluoride ion adsorption capacity of the electrode without MOF was 1.06mg/L. Therefore, when the MOF content in the polypyrrole/bimetallic MOF/graphite composite electrode is proper, the fluoride ion adsorption capacity is greatly improved, and the method has the potential of practical application in the aspect of removing fluoride ions in water.
2. Examine the cyclic regeneration process of polypyrrole/bimetallic MOF/graphite composite electrode PPy/CZBN80 of example 2: after the capacitor defluorination is completed, the anode of the cathode is transferred into deionized water, and the anode and the cathode of the electrode are converted, namely PPy/CZTN 80 is used as the cathode, mnO is used as the anode 2 Is an anode, and is used as a cyclic regeneration process of electric adsorption defluorination. As shown in FIG. 4, the PPy/CZTN 100 still has a high adsorption capacity after a plurality of recycling.
3. The polypyrrole/bimetallic MOF/graphite composite electrode PPy/CBN 50 prepared in example 3 was examined for performance in the field of capacitance defluorination, and the specific process and results are as follows:
an aqueous solution of sodium fluoride (100 mg/mL in F) - Meter) was stock solution, the experimental solutions were diluted with stock solution, and the initial pH of the solution was adjusted by dropwise addition of 0.1mol/L HCl or NaOH solution.
(1) Influence of operating voltage on the defluorination effect of capacitor
PPy/CZTN 50 is taken as an anode, mnO is carried out 2 The cathode electrode has an electrode size of 2X 3cm, and the electroabsorption defluorination component is formed. Voltages of 0.8V, 1.2V and 1.6V are applied between the cathode and the anode, respectively, at 50mg/L of sodium fluoride aqueous solution (at F - Meter) was simulated wastewater with a throughput of 50mL, and was performed in a 100mL beaker to obtain capacitance defluorination data of polypyrrole/MOF composite electrode material, as shown in fig. 5. The calculated fluoride ion adsorption capacities of the polypyrrole/bimetallic MOF/graphite composite electrode PPy/CBN 50 at the applied voltages of 0.8V, 1.2V and 1.6V are 32.39mg/L, 45.11mg/L and 58.42mg/g respectively. From this, it can be seen that as the applied voltage increases, the fluoride ion adsorbing capacity also increases.
(2) Effect of solution pH on capacitive defluorination Effect
7 parts of 50mL,50mg/L NaF solution (in F - Calculated as pH 3, 4, 5, 6, 7, 8 and 9 with 0.1mol/L HCl and NaOH. PPy/CZTN 50 is taken as an anode, mnO is carried out 2 The cathode electrode has an electrode size of 2X 3cm, and the electroabsorption defluorination component is formed. Applying a voltage of 1.2V between the cathode and the anode, and electrifying for 90min to complete capacitance defluorination to obtain polypyrrole/MOF composite electrode materials at different pH valuesAccording to the capacitance defluorination data, when the pH value of the solution is 3-7, the capacitance defluorination performance of the polypyrrole/bimetal MOF/graphite composite electrode reaches the highest level, and the proper pH value of the polypyrrole/bimetal MOF/graphite composite electrode is the initial pH value in consideration of economy and feasibility.
(3) Effect of initial concentration of solution on the defluorination Effect of capacitor
5 parts of 50mL of NaF solution (in F) with the concentration of 5mg/L, 20mg/L, 40mg/L, 60mg/L and 80mg/L respectively are taken - Meter), an initial pH was used. PPy/CZTN 50 is taken as an anode, mnO is carried out 2 The cathode electrode has an electrode size of 2X 3cm, and the electroabsorption defluorination component is formed. And applying a voltage of 1.2V between the cathode and the anode, and electrifying for 90min to complete capacitance defluorination, so as to obtain capacitance defluorination data of the polypyrrole/MOF composite electrode material under different initial conditions, wherein the result is shown in figure 6. The polypyrrole/bimetallic MOF/graphite composite electrode is well matched with the Langmuir model, and the maximum adsorption capacity calculated by the adsorption model is 83.26mg/g.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. The invention is therefore not limited to the embodiments described above, and those skilled in the art, based on the disclosure of the invention, shall make improvements and modifications without departing from the scope of the invention.
Claims (10)
1. A method for removing fluoride ions in water based on polypyrrole/bimetal MOF/graphite composite electrode capacitive deionization uses a polypyrrole/bimetal MOF electrode as an anode and a manganese dioxide electrode as a cathode, and applies 1-2V working voltage to realize efficient removal of fluoride ions in water;
the polypyrrole/bimetal MOF/graphite composite electrode is prepared by the following method:
(1) Adding the mixed metal salt solution into the ligand solution, and reacting by a hydrothermal method to obtain the bimetallic MOF;
(2) Dissolving chitosan in CH 3 Adding pyrrole into the COOH solution to uniformly disperse the solution, taking graphite as a working electrode and graphite as a counter electrode, and performing anodic electropolymerization under the condition of constant current density to obtain a polypyrrole electrode;
(3) Dispersing the bimetal MOF obtained in the step (1) into ethanol to obtain a bimetal MOF suspension, dropwise adding a dilute hydrochloric acid solution, taking the polypyrrole electrode prepared in the step (2) as a working electrode, and performing cathode electrophoresis deposition under a constant potential condition to obtain the polypyrrole/bimetal MOF/graphite composite electrode.
2. The method according to claim 1, wherein in the step (1), the mixed metal salt of the mixed metal salt solution is Ce (NO 3 ) 3 And Zn (NO) 3 ) 2 The molar ratio of Ce to Zn is 1:0.25-4, and the solvent of the mixed metal salt solution is ethanol or DMF; the ligand of the ligand solution is 2-amino terephthalic acid, and the solvent used by the ligand solution is DMF.
3. The method according to claim 1, wherein in the step (1), the concentration of the mixed metal salt in the mixed metal salt solution is 0.14 to 0.18mol/L, the concentration of the ligand in the ligand solution is 0.11 to 0.22mol/L, and the molar ratio of the mixed metal salt in the mixed metal salt solution to the ligand in the ligand solution is 1:0.8 to 1.2.
4. The method according to claim 1, wherein in the step (1), the reaction temperature of the hydrothermal reaction is 130 to 150 ℃ and the reaction time is 18 to 24 hours.
5. The method according to claim 1, wherein in the step (1), after the completion of the reaction, the obtained solid material is centrifuged after being slowly cooled to room temperature in an oven, washed three times with DMF to remove unreacted materials, solvent-displaced 3 times with anhydrous methanol at intervals of 12 hours each to remove residual DMF in the pores of the MOF, and finally centrifuged, and the obtained solid material is dried at 60 to 80 ℃ under vacuum for 12 to 24 hours to obtain the bimetal MOF.
6. The method of claim 1, wherein in step (2), CH 3 The concentration of the COOH solution is 1-3%.
7. The method of claim 1, wherein in the step (2), the chitosan solution is an electrolyte, the mass fraction of the chitosan solution is 0.4% -1.0%, the addition amount of the pyrrole is such that the concentration of the pyrrole is 0.008-0.01 mol/L, the dissolution time of the chitosan is 10-12 h, the dispersion time of the pyrrole is 10-20 min, and the stirring rotation speed is 400-600 r/min.
8. The method according to claim 1, wherein in the step (2), the electropolymerization has a current density of 2 to 10mA/cm 2 The time is 10-20 min, and the stirring rotating speed is 100-200 r/min.
9. The method according to claim 1, wherein in the step (3), the concentration of the bimetallic MOF suspension is 0.1-1 g/L, the concentration of the dilute hydrochloric acid solution is 0.1mol/L, and the dropping amount of the dilute hydrochloric acid solution is 0.05-0.1 mL.
10. The method according to claim 1, wherein in the step (3), the working electrode is a polypyrrole electrode, the counter electrode is graphite, the potential is 30-80V, the deposition time is 20-30 min, and the stirring rotation speed is 50-100 r/min.
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