CN115465924A - PPy/GO/MnO 2 Nano composite electrode, preparation method and application - Google Patents
PPy/GO/MnO 2 Nano composite electrode, preparation method and application Download PDFInfo
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- 238000004364 calculation method Methods 0.000 description 1
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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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
PPy/GO/MnO 2 The preparation method comprises the steps of fully mixing graphene oxide dispersion liquid with pyrrole monomers, adding sodium dodecyl benzene sulfonate solution, and uniformly stirring to obtain uniformly dispersed mixed liquid; then adding a manganese sulfate solution into the mixed solution, and performing ultrasonic dispersion to a uniform state to obtain a uniformly dispersed mixed solution; finally, the mixed solution is used as electrolyte, foamed nickel is used as an anode, an equal-area graphite plate is used as a cathode, and electrochemical deposition is carried out on the anode to obtain PPy/GO/MnO 2 The nano composite electrode material is used for adsorbing heavy metal ions in the wastewater; the invention is realized by adding MnO 2 Co-deposition with PPy and GO allows MnO to be incorporated 2 Nanocrystallization and improvement of PPy/GO/MnO 2 The capacitive properties of the nanocomposite; PPy/GO/MnO 2 The nano composite material can be used as a good capacitive deionization electrode material and adopts one-step electricityThe chemical deposition method ensures that the electrode forming condition is simple and the electrode material with high efficiency and uniformity can be prepared.
Description
Technical Field
The present invention belongs to the field of capacitive deionization technologyThe field, in particular to PPy/GO/MnO 2 A nano composite electrode material, a preparation method and application.
Background
The Capacitive Deionization (CDI) technology is one of the ways to solve the problems of heavy metal wastewater pollution and the like as a novel technology which is simple and convenient to operate, environment-friendly and resource-recoverable, and the research core of the CDI technology is still the preparation of high-performance electrode materials at present. Polypyrrole (PPy) is a common conductive polymer, and has the advantages of high specific capacitance, low cost, good chemical stability and the like, but PPy has some disadvantages as a CDI electrode material, such as poor mechanical properties, cycle stability, poor processability and the like.
The current common CDI electrode preparation process is to mix a certain mass ratio of conductive agent and adhesive and then brush or press the mixture on an electrode substrate by high pressure. The conductive agent and the binder can play an important role in the electrode manufacturing process (application number: 202011269215.5, namely preparation of a composite material for a capacitive deionization technology electrode and application thereof), but also bring problems, such as complex preparation process, reduced hydrophilicity, narrowed ion channels of the electrode material, blocked pore channels and increased resistance of the electrode. Furthermore, the electrodes are prone to deformation in the solution, which will affect the service life of the electrodes.
Disclosure of Invention
To overcome the disadvantages of the prior art, the invention provides a PPy/GO/MnO 2 A nano-class composite electrode material prepared from MnO through mixing 2 Co-deposition with PPy and GO allows MnO to be incorporated 2 Nanocrystallization and improvement of PPy/GO/MnO 2 The capacitive properties of the nanocomposite; PPy/GO/MnO 2 The nano composite material can be used as a good capacitive deionization electrode material, and the electrode forming condition is simple and the efficient and uniform electrode material can be prepared by adopting a one-step electrochemical deposition method.
In order to achieve the purpose, the invention adopts the technical scheme that:
PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials:graphene oxide dispersion liquid, pyrrole monomers, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid to the pyrrole monomer to the sodium dodecyl benzene sulfonate solution is (250-500) and 7 (250-500); the volume ratio of a mixed solution formed by the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution to the manganese sulfate solution is (1-2): 1.
The PPy/GO/MnO 2 The preparation method of the nano composite electrode material comprises the following steps:
the method comprises the following steps: fully mixing the graphene oxide dispersion liquid with a pyrrole monomer, adding a sodium dodecyl benzene sulfonate solution, and uniformly stirring to obtain a uniformly dispersed mixed liquid A;
step two: adding a manganese sulfate solution into the mixed solution A obtained in the first step, and performing ultrasonic dispersion to obtain a uniformly dispersed mixed solution B;
step three: taking the mixed solution B in the step two as electrolyte, adopting foamed nickel as an anode and an equal-area graphite plate as a cathode, and carrying out electrochemical deposition on the anode to obtain PPy/GO/MnO 2 A nanocomposite electrode material.
In the first step, the preparation method of the graphene oxide dispersion liquid comprises the following steps:
in a 500mL flask, 3-6g NaNO was added 3 3-6g of graphite and concentrated 100-200mL of H 2 SO 4 Continuously stirring in ice water bath for reaction for 30-60min, and stirring continuously 9-18g KMnO 4 Slowly adding into a flask; continuously stirring the mixed solution at 35-40 ℃ for 1-1.5h, and then adding 100-200mL of double distilled water; maintaining the temperature of the mixed solution below 90 ℃, adding 80-120mLH 2 O 2 When no bubble is generated in the flask, the reaction is finished, and the color of the reaction product is changed from the initial dark brown to bright yellow to obtain a mixed solution C; carrying out centrifugal separation on the mixed solution C, wherein the centrifugal separation time is 4-10min, the rotating speed is 7000-9000r/min, adding 250-400ml of deionized water into a solid after carrying out solid-liquid separation, adding the obtained product into a dialysis bag, sealing the upper and lower seals of the dialysis bag, putting the dialysis bag into a water tank filled with deionized water for dialysis, testing by using a pH tester, and finishing the dialysis when the pH = 7; will be provided withAnd dispersing the dialyzed graphene oxide in 500-800ml of deionized water, and performing freeze drying treatment to prepare 1g/L GO dispersion liquid.
In the first step, the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution are stirred for 20-40min; the sodium dodecyl benzene sulfonate solution is formed by adding 32.6-75.2g of dodecyl benzene sulfonic acid into 1-2L of deionized water and then uniformly stirring.
In the second step, the manganese sulfate solution is formed by adding 75.5-151g of manganese sulfate into 1-2L of deionized water and then uniformly stirring.
In the second step, the ultrasonic power is 200-300W, and the ultrasonic time is 20-30min.
In the third step, the electrochemical deposition is carried out at room temperature, the voltage is 2-5V, the deposition time is 2.5-7.5min, and the electrolyte is magnetically stirred in the deposition process.
The pretreatment process of the dialysis bag comprises the following steps: processing dialysis bag into 20-30cm long unit, heating in hot water for 10-15min, and cooling.
The PPy/GO/MnO 2 Preparation method of nano composite electrode and prepared PPy/GO/MnO 2 The nano composite electrode material is used for adsorbing heavy metal ions in wastewater.
The heavy metal ion is Cd 2+ 、Cu 2+ Or Pb 2+ One or more of them.
Compared with the prior art, the invention has the beneficial effects that:
the invention selects graphene oxide dispersion liquid, pyrrole monomer, sodium dodecyl benzene sulfonate solution and manganese sulfate solution to prepare electrodeposition solution, the volume ratio of the graphene oxide dispersion liquid to the pyrrole monomer to the sodium dodecyl benzene sulfonate solution is (250-500): 7 (250-500), dodecyl benzene sulfonate (DBS-) can dope pure PPy to ensure that the PPy can show good conductivity and show cation exchange performance, simultaneously GO is better dispersed, a large amount of oxygen-containing functional groups exist to ensure that a carbon layer has negative charges, positive cations can easily enter interlamination, and favorable conditions can be provided for the load of polymer(ii) a The volume ratio of the mixed solution formed by the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution to the manganese sulfate solution is (1-2): 1, and nano MnO with uniform particle size can be electrodeposited 2 ，MnO 2 The specific capacitance of the composite electrode is improved, and the process of electric adsorption is facilitated.
The invention adopts an anode one-step electrochemical codeposition method to prepare PPy/GO/MnO 2 The nano composite material has the advantages of high deposition rate, simple operation, uniform electrode distribution, controllable thickness and the like; the electrodeposition method can directly electrodeposit the active substance on the current collector without using a binder, and the preparation process of the electrode is simple and green, has strong operability and repeatability and is suitable for batch production.
The invention is realized by adding MnO 2 Co-depositing with PPy and GO, controlling the morphology of the material by changing the ratio of the three materials and the electrodeposition time, and enabling Py to convert MnO in the electrochemical oxidation process in the electrochemical co-deposition process 2 Sandwiched between PPy film layers, mnO during co-deposition 2 Provide new nucleation centers for the deposition of Py, and thus, the encapsulation of MnO in spherical PPy 2 The structure of (1); and the layered GO is PPy and MnO 2 Provides larger specific surface area, uniformly disperses PPy, avoids the agglomeration and accumulation of PPy, and improves PPy/GO/MnO 2 Specific capacitance, adsorption capacity and adsorption cycle stability of the nanocomposite.
Drawings
FIG. 1 shows PPy/GO/MnO preparation of examples 1-3 of the present invention 2 TEM image of a nanocomposite electrode, wherein (a) is electrodeposition for 2.5min for example 1, (b) and (d) are electrodeposition for 5min for example 2, and (c) is electrodeposition for 7.5min for example 3.
FIG. 2 shows PPy/GO/MnO prepared according to examples 1-3 of the present invention 2 Nanocomposite electrode Cyclic Voltammetry (CV) test profiles.
FIG. 3 shows PPy/GO/MnO prepared in example 2 of the present invention 2 Nano composite electrode electric adsorption Cu 2+ In which (a) PPy/GO/MnO 2 The saturated adsorption curve of the nano composite electrode; (b) PPy/GO/MnO 2 Nanometer compositeThe cyclic adsorption capacity of the combined electrode.
FIG. 4 shows PPy/GO/MnO prepared in example 2 of the present invention 2 The adsorption capacity and the adsorption efficiency of the nano composite electrode under different initial concentrations.
FIG. 5 shows PPy/GO/MnO prepared in example 2 of the present invention 2 Nano composite electrode electric adsorption Cu 2+ The change curve of the adsorption quantity with time under different adsorption voltages.
FIG. 6 shows PPy/GO/MnO prepared in example 2 of the present invention 2 Nanocomposite electrode pair Cd 2+ 、Cu 2+ And Pb 2+ The adsorption performance of metal ions;
figure 7 is an X-ray diffraction pattern of GO dispersion prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings and examples.
Example 1A PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials: the preparation method comprises the following steps of (1) preparing a graphene oxide dispersion solution, a pyrrole monomer, a sodium dodecyl benzene sulfonate solution and a manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid to the pyrrole monomer to the sodium dodecyl benzene sulfonate solution is 500; the volume ratio of the graphene oxide dispersion liquid, the mixed solution of the pyrrole monomer and the sodium dodecyl benzene sulfonate solution to the manganese sulfate solution is 2:1.
The PPy/GO/MnO 2 The preparation method of the nano composite electrode material comprises the following steps:
the method comprises the following steps: fully mixing the graphene oxide dispersion liquid with the pyrrole monomer, adding the sodium dodecyl benzene sulfonate solution, and uniformly stirring for 20min; obtaining uniformly dispersed mixed liquor A;
in this example, a modified Hummers method was used to prepare graphene oxide dispersions, and 3g of NaNO was added to a 500mL round bottom flask 3 3g graphite and concentrated 100mL H 2 SO 4 The reaction was continued for 30min with stirring in an ice-water bath, and 9g of KMnO was added under continuous stirring 4 Slowly adding into a flask; continuously stirring the mixed solution at 35 ℃ for 1h, and then adding 100mL of double distilled water; temperature of the mixed solutionKeeping the temperature below 90 ℃, adding 80mLH 2 O 2 When no bubble is generated in the flask, the reaction is finished, and the color of the reaction product is changed from the initial dark brown to bright yellow to obtain a mixed solution C; carrying out centrifugal separation on the mixed solution C for 4min at the rotating speed of 7000r/min, adding 250ml of deionized water into the solid after carrying out solid-liquid separation, adding the obtained product into a dialysis bag (pretreatment of the dialysis bag, namely processing the dialysis bag into a unit with the length of 20cm, heating in hot water for 10min, cooling for standby), sealing the upper and lower seals of the dialysis bag, putting the dialysis bag into a water tank filled with deionized water for dialysis, testing by using a pH tester, and finishing the dialysis when the pH = 7; dispersing the dialyzed graphene oxide in 500ml of deionized water, and preparing 1g/L GO dispersion liquid after freeze drying treatment;
adding 1.4mL of pyrrole monomer into 100mL of GO dispersion liquid, stirring for 20min to obtain a uniform mixed solution, and adding 100mL of sodium dodecyl benzene sulfonate solution into the mixed solution; the sodium dodecyl benzene sulfonate solution is prepared by adding 32.6g of dodecyl benzene sulfonic acid into 1L of deionized water and then uniformly stirring; forming a mixed solution A;
step two: adding a manganese sulfate solution into the mixed solution A obtained in the first step, wherein the volume ratio of the mixed solution A to the manganese sulfate solution is 2:1; ultrasonically dispersing to a uniform state, wherein the ultrasonic power is 200W, and the ultrasonic time is 20min; obtaining a uniformly dispersed mixed solution B;
in this embodiment, 100mL of manganese sulfate solution is added into the mixed solution a, and the mixture is subjected to ultrasonic treatment for 20min to be uniformly dispersed; the manganese sulfate solution is formed by adding 75.5g of manganese sulfate into 1L of deionized water and then uniformly stirring;
step three: taking the mixed solution B as electrolyte, adopting foamed nickel as an anode and an equal-area graphite plate as a cathode, and carrying out electrochemical deposition on the anode to obtain PPy/GO/MnO 2 A nanocomposite electrode material;
the electrochemical deposition is carried out at room temperature, the voltage is 3.5V, the deposition time is 2.5min, and the electrolyte is magnetically stirred in the deposition process.
Example 2, the deposition time in the third step of example 1 was changed to 5min, and the other steps were not changed.
Example 3, the deposition time in step three of example 1 was changed to 7.5min, and the other steps were not changed.
Example 4 a PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials: graphene oxide dispersion liquid, pyrrole monomers, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid to the pyrrole monomer to the sodium dodecyl benzene sulfonate solution is 250; the volume ratio of the graphene oxide dispersion liquid, the mixed solution of the pyrrole monomer and the sodium dodecyl benzene sulfonate solution to the manganese sulfate solution is 1:1.
The PPy/GO/MnO 2 The preparation method of the nano composite electrode material comprises the following steps:
the method comprises the following steps: fully mixing the graphene oxide dispersion liquid with a pyrrole monomer, adding a sodium dodecyl benzene sulfonate solution, and uniformly stirring for 30min; obtaining uniformly dispersed mixed liquor A;
the preparation method of the graphene oxide dispersion liquid comprises the following steps:
in this example, a modified Hummers method was used to prepare graphene oxide dispersions, and 5g of NaNO was added to a 500mL flask 3 5g of graphite and 150mL of concentrated H 2 SO 4 The reaction was continued for 50min with stirring in an ice-water bath and 15g KMnO was added under continuous stirring 4 Slowly adding into a flask; the mixed solution is continuously stirred for 1.3h at the temperature of 38 ℃, and then 150mL of double distilled water is added; maintaining the temperature of the mixed solution below 90 ℃, adding 100mLH 2 O 2 Until no bubbles are generated in the flask, finishing the reaction, and changing the color of the reaction product from the initial dark brown color to bright yellow to obtain a mixed solution C; carrying out centrifugal separation on the mixed solution C, wherein the centrifugal separation time is 7min, the rotating speed is 8000r/min, after carrying out solid-liquid separation, adding 350ml of deionized water into a solid, adding the obtained product into a dialysis bag (pretreatment of the dialysis bag, namely processing the dialysis bag into a unit with the length of 30cm, heating in hot water for 15min, cooling for standby), sealing the upper and lower openings of the dialysis bag, putting the dialysis bag into a water tank filled with deionized water for dialysis, testing by using a pH tester, and finishing dialysis when the pH = 7; after dialysis is completedDispersing graphene oxide in 700ml of deionized water, and preparing 1g/L GO dispersion liquid after freeze drying treatment;
adding 1.4mL of pyrrole monomer into 100mL of GO dispersion liquid, stirring for 40min to obtain a uniform mixed solution, and adding 100mL of sodium dodecyl benzene sulfonate solution into the mixed solution; the sodium dodecyl benzene sulfonate solution is a sodium dodecyl benzene sulfonate solution formed by adding 75.2g of dodecyl benzene sulfonic acid into 1L of deionized water and then uniformly stirring; forming a mixed solution A;
step two: adding a manganese sulfate solution into the mixed solution A obtained in the first step, wherein the volume ratio of the mixed solution A to the manganese sulfate solution is 2:1; ultrasonically dispersing to a uniform state, wherein the ultrasonic power is 300W, and the ultrasonic time is 25min; obtaining a uniformly dispersed mixed solution B;
in this embodiment, 100mL of manganese sulfate solution is added into the mixed solution a, and the mixture is subjected to ultrasonic treatment for 25min to be uniformly dispersed; the manganese sulfate solution is formed by adding 100g of manganese sulfate into 2L of deionized water and then uniformly stirring;
step three: taking the mixed solution B as electrolyte, adopting foamed nickel as an anode and an equal-area graphite plate as a cathode, and carrying out electrochemical deposition on the anode to obtain PPy/GO/MnO 2 A nanocomposite electrode material;
the electrochemical deposition is carried out at room temperature under the voltage of 2V for 5min, and the electrolyte is magnetically stirred in the deposition process.
Example 5A PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials: the preparation method comprises the following steps of (1) preparing a graphene oxide dispersion solution, a pyrrole monomer, a sodium dodecyl benzene sulfonate solution and a manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid to the pyrrole monomer to the sodium dodecyl benzene sulfonate solution is 400; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer, the mixed solution of the sodium dodecyl benzene sulfonate solution and the manganese sulfate solution is 1.5.
The PPy/GO/MnO 2 The preparation method of the nano composite electrode material comprises the following steps:
the method comprises the following steps: fully mixing the graphene oxide dispersion liquid with the pyrrole monomer, adding the sodium dodecyl benzene sulfonate solution, and uniformly stirring for 40min; obtaining uniformly dispersed mixed liquor A;
the preparation method of the graphene oxide dispersion liquid comprises the following steps:
in this example, a modified Hummers method was used to prepare graphene oxide dispersions, and 6g of NaNO was added to a 500mL flask 3 6g of graphite and 200mL of concentrated H 2 SO 4 The reaction was continued for 60min with constant stirring in an ice-water bath and 18g KMnO was added under constant stirring 4 Slowly adding into a flask; the mixed solution is continuously stirred for 1.5h at the temperature of 40 ℃, and then 200mL of double distilled water is added; maintaining the temperature of the mixed solution below 90 ℃, adding 120mLH 2 O 2 When no bubble is generated in the flask, the reaction is finished, and the color of the reaction product is changed from the initial dark brown to bright yellow to obtain a mixed solution C; carrying out centrifugal separation on the mixed solution C for 10min at the rotating speed of 9000r/min, adding 400ml of deionized water into the solid after carrying out solid-liquid separation, adding the obtained product into a dialysis bag (pretreatment of the dialysis bag, namely processing the dialysis bag into a unit with the length of 25cm, heating in hot water for 13min, cooling for later use), sealing the upper and lower openings of the dialysis bag, putting the dialysis bag into a water tank filled with deionized water for dialysis, testing by using a pH tester, and finishing the dialysis when the pH = 7; dispersing the dialyzed graphene oxide in 800ml of deionized water, and preparing 1g/L GO dispersion liquid after freeze drying treatment;
adding 1.4mL of pyrrole monomer into 100mL of GO dispersion liquid, stirring for 40min to obtain a uniform mixed solution, and adding 100mL of sodium dodecyl benzene sulfonate solution into the mixed solution; the sodium dodecyl benzene sulfonate solution is prepared by adding 50.0g of dodecyl benzene sulfonic acid into 1L of deionized water and then uniformly stirring; forming a mixed solution A;
step two: adding a manganese sulfate solution into the mixed solution A in the first step, wherein the volume ratio of the mixed solution A to the manganese sulfate solution is 1.5; ultrasonically dispersing to a uniform state, wherein the ultrasonic power is 250W, and the ultrasonic time is 30min; obtaining a uniformly dispersed mixed solution B;
in this embodiment, 100mL of manganese sulfate solution is added into the mixed solution a, and the mixture is subjected to ultrasonic treatment for 30min to be uniformly dispersed; the manganese sulfate solution is formed by adding 151g of manganese sulfate into 1.5L of deionized water and then uniformly stirring;
step three: taking the mixed solution B as electrolyte, adopting foamed nickel as an anode and an equal-area graphite plate as a cathode, and carrying out electrochemical deposition on the anode to obtain PPy/GO/MnO 2 A nanocomposite electrode material;
the electrochemical deposition is carried out at room temperature under the voltage of 5V for 5min, and the electrolyte is magnetically stirred in the deposition process.
The following PPy/GO/MnO protocols prepared in examples 1-3 are illustrated with reference to the figures 2 And (5) characterizing the nano composite electrode.
As shown in FIG. 1, PPy/GO/MnO preparation for electrodeposition time of examples 1-3 of 2.5min, 5min and 7.5min, respectively 2 The shapes of the nano composite materials are respectively shown as (a), (b) and (d), (c); PPy/GO/MnO with increasing electrodeposition time 2 The color of the nano composite material becomes dark, which shows that the deposition amount of PPy on GO is gradually increased and plays a leading role in three materials; and from this it can be seen that PPy and MnO in the lamellar structure of GO at 2.5min of electrodeposition 2 The content of (A) is small; PPy and MnO when the electrodeposition time is increased to 5min 2 The dispersion in the GO sheet layer is relatively uniform; when the electrodeposition time was increased to 7.5min, PPy had significantly agglomerated on GO; in the electrochemical co-deposition process, py converts MnO in the electrochemical oxidation process 2 Sandwiched between PPy films, mnO during co-deposition 2 Provide new nucleation centers for the deposition of Py, and thus, the encapsulation of MnO in spherical PPy 2 The structure of (1); and the layered GO is PPy and MnO 2 Provides larger specific surface area, uniformly disperses PPy, avoids the agglomeration and accumulation of PPy, and improves PPy/GO/MnO 2 Specific capacitance, adsorption capacity and adsorption cycle stability of the nanocomposite.
PPy/GO/MnO 2 The process of the electric adsorption of the nano composite material on the heavy metal wastewater is as follows: the conductivity of the solution is measured by a conductivity meter, and the electrode is PPy/GO/MnO prepared by experiments 2 The nano composite material simulates heavy metal wastewater and is one or a mixture of copper, cadmium, lead and the like; are respectively equipped with200mL of Cd with initial concentration of 100mg/L 2+ 、Cu 2+ And Pb 2+ A solution; the operating (clamping) voltage was set to 1.2V; place PPy/GO/MnO 2 And magnetically stirring the nano composite material, and recording every 1min to ensure that the electrolyte reaches adsorption-desorption balance.
As shown in fig. 2, fig. 2 shows the specific capacitance value of the composite electrode tested by CV, which is tested by using a three-electrode system: the prepared composite electrode is a working electrode, the Pt electrode is a counter electrode, a Saturated Calomel Electrode (SCE) is a reference electrode, and 1mol/L CuSO is used 4 The solution acts as an electrolyte. PPy/GO/MnO prepared when the electrodeposition time of the embodiments 1-3 of the invention is 2.5min, 5min and 7.5min respectively is obtained 2 The CV curve of the nano composite electrode at the scanning speed of 5mV/s is that the curved surface area of the electrode with the deposition time of 5min is obviously larger than that of the other two electrodes, so that the specific capacitance is the highest. Obtained by a specific capacitance calculation formula, and PPy/GO/MnO under different electrodeposition time 2 The specific capacitance of the nano composite electrode is 107.42F/g (2.5 min), 376.58F/g (5 min) and 156.67F/g (7.5 min), respectively.
As shown in FIG. 3, (a) is the PPy/GO/MnO prepared in example 2 of the present invention 2 Nano composite electrode electric adsorption Cu 2+ The saturated adsorption curve of (2) is that after about 8min of adsorption, the adsorption saturation is reached, and the saturated adsorption capacity is 36.77mg/g; (b) Is PPy/GO/MnO 2 The cycle adsorption capacity of the nano composite electrode is changed into 99% after 5 times of cycle adsorption, and the adsorption capacity is changed into 97% after 10 times of cycle adsorption.
As shown in FIG. 4, FIG. 4 shows the PPy/GO/MnO prepared in example 2 of the present invention 2 The adsorption capacity and the adsorption efficiency of the nano composite electrode under different initial concentrations are increased along with the increase of the initial concentrations, and the adsorption efficiency is reduced along with the increase of the initial concentrations.
As shown in FIG. 5, FIG. 5 shows the PPy/GO/MnO content of example 2 of the present invention 2 Nano composite electrode electric adsorption Cu 2+ The adsorption capacity is the highest at 1.6V and is 38.92mg/g according to the change curve of the adsorption capacity with time under different adsorption voltages.
As shown in FIG. 6, FIG. 6 shows the results obtained in example 2 of the present inventionPPy/GO/MnO 2 Nanocomposite electrode pair Cd 2+ 、Cu 2+ And Pb 2+ As is clear from FIG. 6, the saturated adsorption capacity of the metal ions is Pb 2+ The slope of the curve is maximum, which indicates PPy/GO/MnO 2 Nanocomposite electrode pair Pb 2+ The adsorption rate of (2) is fastest; cu 2+ Next, cd 2+ Minimum; and at the later stage of adsorption, cd 2+ The adsorption saturation is achieved firstly, and the saturated adsorption capacity is 28.89mg/g; for Cu 2+ Has a saturated adsorption capacity of 36.77mg/g for Pb 2+ The saturated adsorption capacity of (a) was 42.17mg/g; the results show that PPy/GO/MnO 2 The adsorption capacity of the nano composite electrode to three metal ions is Cd 2+ <Cu 2+ <Pb 2+ 。
As shown in fig. 7, fig. 7 is an X-ray diffraction spectrum of GO prepared in example 1 of the present invention, and as can be seen from fig. 7, a characteristic peak of GO is at 11.02 °, a crystal plane is (001), and the X-ray diffraction spectrum is consistent with a report of a literature related to GO.
As can be seen from the above examples, the present invention utilizes an anodic one-step electrochemical co-deposition process to produce PPy/GO/MnO 2 MnO of the nano-composite electrode under the condition of electrochemical polymerization 2 Successfully wrapped by PPy and uniformly distributed PPy on GO sheets by incorporating MnO 2 Co-deposition with PPy and GO allows MnO to be incorporated 2 Nanocrystallization and improvement of PPy/GO/MnO 2 Capacitive characteristics of nanocomposite, PPy/GO/MnO 2 The good structure of the nano composite material is beneficial to the diffusion of ions, and PPy/GO/MnO is in an adsorption test 2 The nano composite electrode has higher adsorption capacity and good cyclic adsorption stability to metal ions, and the preparation process is simple, so that the long-term reliable use of the capacitive deionization composite electrode is realized.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. PPy/GO/MnO 2 The nano composite electrode material is characterized by comprising the following raw materials: graphene oxide dispersion liquid, pyrrole monomers, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid to the pyrrole monomer to the sodium dodecyl benzene sulfonate solution is (250-500) to (7) (250-500); the volume ratio of a mixed solution formed by the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution to the manganese sulfate solution is (1-2) to 1.
2. A PPy/GO/MnO as claimed in claim 1 2 The preparation method of the nano composite electrode material is characterized by comprising the following steps of:
the method comprises the following steps: fully mixing the graphene oxide dispersion liquid with a pyrrole monomer, adding a sodium dodecyl benzene sulfonate solution, and uniformly stirring to obtain a uniformly dispersed mixed liquid A;
step two: adding a manganese sulfate solution into the mixed solution A obtained in the first step, and performing ultrasonic dispersion to obtain a uniformly dispersed mixed solution B;
step three: taking the mixed solution B obtained in the step two as electrolyte, adopting foamed nickel as an anode and an equal-area graphite plate as a cathode, and carrying out electrochemical deposition on the anode to obtain PPy/GO/MnO 2 A nanocomposite electrode material.
3. The method of claim 2, wherein: the preparation method of the graphene oxide dispersion liquid in the first step comprises the following steps:
in a 500mL flask, 3-6g NaNO was added 3 3-6g of graphite and concentrated 100-200mL of H 2 SO 4 Continuously stirring in ice water bath for reaction for 30-60min, and stirring continuously 9-18g KMnO 4 Slowly adding into a flask; continuously stirring the mixed solution at 35-40 ℃ for 1-1.5h, and then adding 100-200mL of double distilled water; maintaining the temperature of the mixed solution below 90 ℃, adding 80-120mLH 2 O 2 When no bubble is generated in the flask, the reaction is finished, and the color of the reaction product is changed from the initial dark brown to bright yellow to obtain a mixed solution C; centrifuging the mixed solution CSeparating, centrifuging for 4-10min at 7000-9000r/min, adding 250-400ml deionized water into solid after solid-liquid separation, adding the obtained product into dialysis bag, sealing the upper and lower seals of dialysis bag, dialyzing in water tank filled with deionized water, testing with pH meter, and dialyzing when pH = 7; and dispersing the dialyzed graphene oxide in 500-800ml of deionized water, and performing freeze drying treatment to prepare 1g/L GO dispersion liquid.
4. The method of claim 2, wherein: stirring the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution in the first step for 20-40min; the sodium dodecyl benzene sulfonate solution is formed by adding 32.6-75.2g of dodecyl benzene sulfonic acid into 1-2L of deionized water and then uniformly stirring.
5. The production method according to claim 2, characterized in that: and the manganese sulfate solution in the second step is formed by adding 75.5-151g of manganese sulfate into 1-2L of deionized water and uniformly stirring.
6. The method of claim 2, wherein: in the second step, the ultrasonic power is 200-300W, and the ultrasonic time is 20-30min.
7. The method of claim 2, wherein: in the third step, the electrochemical deposition is carried out at room temperature, the voltage is 2-5V, the deposition time is 2.5-7.5min, and the electrolyte is magnetically stirred in the deposition process.
8. The production method according to claim 3, characterized in that: the pretreatment process of the dialysis bag comprises the following steps: processing dialysis bag into 20-30cm long unit, heating in hot water for 10-15min, and cooling.
9. PPy/GO/MnO prepared by the method of claim 2 2 Nanometer compositeThe application of the composite electrode material is characterized in that: used for adsorbing heavy metal ions in the wastewater.
10. Use according to claim 9, characterized in that: the heavy metal ion is Cd 2+ 、Cu 2+ Or Pb 2+ One or more of them.
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