CN115465924B - 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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- 238000002360 preparation method Methods 0.000 title claims abstract description 23
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- 239000011259 mixed solution Substances 0.000 claims abstract description 61
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 56
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 48
- 239000006185 dispersion Substances 0.000 claims abstract description 43
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 38
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 38
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 38
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 38
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 37
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims abstract description 33
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- 238000004070 electrodeposition Methods 0.000 claims abstract description 22
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 229910002804 graphite Inorganic materials 0.000 claims abstract description 11
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- 238000002156 mixing Methods 0.000 claims abstract description 10
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- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- 238000000502 dialysis Methods 0.000 claims description 35
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- 238000003756 stirring Methods 0.000 claims description 26
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- 230000008021 deposition Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- YRIUSKIDOIARQF-UHFFFAOYSA-N dodecyl benzenesulfonate Chemical compound CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 YRIUSKIDOIARQF-UHFFFAOYSA-N 0.000 claims description 6
- 229940071161 dodecylbenzenesulfonate Drugs 0.000 claims description 6
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- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 claims 1
- 229940077388 benzenesulfonate Drugs 0.000 claims 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 7
- 238000002242 deionisation method Methods 0.000 abstract description 6
- 238000007709 nanocrystallization Methods 0.000 abstract description 3
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
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- 238000009792 diffusion process Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
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Classifications
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
-
- 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
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/46104—Devices therefor; Their operating or servicing
- C02F1/46109—Electrodes
- C02F2001/46133—Electrodes characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
PPy/GO/MnO 2 The nanometer composite electrode material, the preparation method and the application thereof are that firstly, graphene oxide dispersion liquid and pyrrole monomer are fully mixed, and sodium dodecyl benzene sulfonate solution is added and stirred uniformly to obtain uniformly dispersed mixed liquid; then adding a manganese sulfate solution into the mixed solution, and performing ultrasonic dispersion until the solution is in a uniform state to obtain a uniformly dispersed mixed solution; finally, the mixed solution is used as electrolyte, foam nickel is used as anode, an equal-area graphite plate is used as 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 mixing MnO 2 Co-deposition with PPy and GO can result in MnO 2 Nanocrystallization to improve PPy/GO/MnO 2 Capacitance characteristics of the nanocomposite; PPy/GO/MnO 2 The nanocomposite can be used as a good capacitive deionization electrode material, and a one-step electrochemical deposition method is adopted, so that the electrode forming condition is simple, and the electrode material with high efficiency and uniformity can be prepared.
Description
Technical Field
The invention belongs to the technical field of capacitance deionization, and in particular relates to a PPy/GO/MnO 2 Nanocomposite electrode material, preparation method and application thereof.
Background
The Capacitive Deionization (CDI) technology is used as a novel technology which is simple and convenient to operate, environment-friendly and resource-recoverable, and becomes one of ways for solving the problems of heavy metal wastewater pollution and the like, and the research core of the CDI technology at present is still the preparation of high-performance electrode materials. 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 such as poor mechanical properties, stable circulation, poor processability and the like as a CDI electrode material.
The current common CDI electrode preparation process is to uniformly brush or press the mixture of conductive agent and adhesive on the electrode matrix by high pressure after mixing the conductive agent and the adhesive according to a certain mass ratio. The conductive agent and the binder can play an important role in the electrode manufacturing process (application number: 202011269215.5, named as preparation and application of a composite material for the electrode of the capacitive deionization technology), but also bring problems, such as complex preparation process, reduced hydrophilicity, narrowing of ion channels of the electrode material, blocking of pore channels and increase of resistance of the electrode. Furthermore, the electrodes are prone to deformation in solution, which will affect the lifetime of the electrodes.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide a PPy/GO/MnO 2 Nano composite electrode material, preparation method and application thereof by mixing MnO 2 Co-deposition with PPy and GO can result in MnO 2 Nanocrystallization to improve PPy/GO/MnO 2 Capacitance characteristics of the nanocomposite; PPy/GO/MnO 2 The nanocomposite can be used as a good capacitive deionization electrode material, and the electrode forming condition is simple and the electrode material with high efficiency and uniformity can be prepared by adopting a one-step electrochemical deposition method.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials in parts by weight: graphene oxide dispersion liquid, pyrrole monomer, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is (250-500): 7 (250-500); graphene oxide dispersion liquid and pyrroleThe volume ratio of the mixed solution formed by the 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:
step one: fully mixing graphene oxide dispersion liquid with pyrrole monomer, adding sodium dodecyl benzene sulfonate solution, and uniformly stirring to obtain uniformly dispersed mixed liquid A;
step two: adding a manganese sulfate solution into the mixed solution A in the step one, and performing ultrasonic dispersion until the manganese sulfate solution is in a uniform state to obtain a uniformly dispersed mixed solution B;
step three: taking the mixed solution B in the second step as electrolyte, taking foam nickel as an anode, taking an equal-area graphite plate as a cathode, and performing electrochemical deposition on the anode to obtain PPy/GO/MnO 2 Nanocomposite electrode materials.
In the first step, the preparation method of the graphene oxide dispersion liquid comprises the following steps:
3-6g NaNO was added to a 500mL flask 3 3-6g graphite and concentrated 100-200mL H 2 SO 4 Continuously stirring in ice-water bath for 30-60min, and continuously stirring 9-18g KMnO 4 Slowly adding into the flask; continuously stirring the mixed solution at 35-40 ℃ for 1-1.5h, and then adding 100-200mL of double distilled water; the temperature of the mixed solution is kept below 90 ℃, and 80-120mLH is added 2 O 2 No bubbles are generated in the flask, the reaction is finished, and the color of the reaction product is changed from the original dark brown to bright yellow, so as to obtain a mixed solution C; centrifuging the mixed solution C for 4-10min at 7000-9000r/min, adding 250-400ml deionized water into the solid after 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, checking by a pH meter, and finishing the dialysis when the pH=7; dispersing the dialyzed graphene oxide in 500-800ml deionized water, and preparing a GO dispersion liquid with the concentration of 1g/L after freeze drying treatment.
In the first step, the stirring time of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is 20-40min; the sodium dodecyl benzene sulfonate solution is formed by adding 32.6-75.2g of dodecyl benzene sulfonate into 1-2L of deionized water and stirring uniformly.
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 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 the dialysis bag into 20-30cm length unit, heating in hot water for 10-15min, and cooling.
The PPy/GO/MnO 2 Preparation method of nano composite electrode, 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 prepares the electrodeposition solution by using graphene oxide dispersion liquid, pyrrole monomer, sodium dodecyl benzene sulfonate solution and manganese sulfate solution, wherein the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is (250-500): 7 (250-500) can enable dodecyl benzene sulfonate (DBS-) to dope pure PPy so that the PPy can show good conductivity and cation exchange performance, and simultaneously better disperse GO, and a large amount of oxygen-containing functional groups exist to enable a carbon layer to have negative charges, positive charges of cations easily enter the layers, thus providing favorable conditions for loading of polymers; 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 Is added to improve the composite electricityThe specific capacitance of the pole is more favorable for the electro-adsorption process.
The invention adopts an anode one-step electrochemical codeposition method to prepare PPy/GO/MnO 2 The nanocomposite 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 on the basis of not 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 mixing MnO 2 Codeposition with PPy and GO, and control the morphology structure of the material by changing the ratio of the three materials and the electrodeposition time, wherein Py controls MnO in the electrochemical oxidation process in the electrochemical codeposition process 2 Sandwiched in PPy film, mnO during co-deposition 2 Provides new nucleation centers for Py deposition, thus, the inclusion of MnO in spherical PPy occurs 2 Is of a structure of (2); and, the layered GO is PPy and MnO 2 Provides a larger specific surface area, uniformly disperses the PPy, avoids the agglomeration and accumulation of the PPy, and improves the PPy/GO/MnO 2 Specific capacitance, adsorption capacity and adsorption cycle stability of the nanocomposite.
Drawings
FIG. 1 shows the PPy/GO/MnO prepared in examples 1-3 of the present invention 2 A nanocomposite electrode TEM image, wherein (a) was electrodeposited for 2.5min for example 1, (b) and (d) were electrodeposited for 5min for example 2, and (c) was electrodeposited for 7.5min for example 3.
FIG. 2 shows the PPy/GO/MnO prepared in examples 1-3 of the present invention 2 Nanocomposite electrode Cyclic Voltammetry (CV) test patterns.
FIG. 3 is a schematic illustration of PPy/GO/MnO prepared in example 2 of the present invention 2 Electric adsorption Cu of nano composite electrode 2+ Wherein (a) PPy/GO/MnO 2 Saturated adsorption curve of the nanocomposite electrode; (b) PPy/GO/MnO 2 The cyclic adsorption capacity of the nanocomposite electrode.
FIG. 4 shows the PPy/GO/MnO prepared in example 2 of the present invention 2 Adsorption capacity and adsorption efficiency of the nanocomposite electrode at different initial concentrations.
FIG. 5 shows the PPy/GO/MnO prepared in example 2 of the present invention 2 Electric adsorption Cu of nano composite electrode 2+ And the adsorption amount changes with time under different adsorption voltages.
FIG. 6 shows the PPy/GO/MnO prepared in example 2 of the present invention 2 Nanocomposite electrode pair Cd 2+ 、Cu 2+ And Pb 2+ Adsorption performance of metal ions;
FIG. 7 is an X-ray diffraction pattern of GO dispersion prepared in example 1 of the present invention.
Detailed Description
The invention will now be described in further detail with reference to the drawings and examples.
Example 1, a PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials in parts by weight: graphene oxide dispersion liquid, pyrrole monomer, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is 500:7:500; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution mixed liquid 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:
step one: fully mixing the graphene oxide dispersion liquid with pyrrole monomers, adding a sodium dodecyl benzene sulfonate solution, and uniformly stirring for 20min; obtaining a uniformly dispersed mixed solution A;
in this example, a modified Hummers method was used to prepare graphene oxide dispersion, 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 stirred continuously in an ice-water bath for 30min, and 9g KMnO was stirred continuously 4 Slowly adding into the flask; the mixed solution is continuously stirred for 1h at 35 ℃, and then 100mL of double distilled water is added; the temperature of the mixed solution is kept below 90 ℃, and 80mLH is added 2 O 2 No bubbles are generated in the flask, the reaction is finished, and the color of the reaction product is changed from the original dark brown to bright yellow, so as to obtain a mixed solution C; centrifuging the mixed solution C for 4min, performing solid-liquid separation at 7000r/min, adding 250ml deionized water into the solid, and adding the obtained product into a dialysis bag (dialysis bag pretreatment, namely processing the dialysis bag into a 20cm length unit, 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, checking by a pH tester, and finishing the dialysis when the pH=7; dispersing the dialyzed graphene oxide in 500ml of deionized water, and preparing a GO dispersion liquid with the concentration of 1g/L 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 formed by adding 32.6g of dodecyl benzene sulfonate 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 step one, wherein the volume ratio of the mixed solution A to the manganese sulfate solution is 2:1; dispersing ultrasound to a uniform state, wherein the ultrasound power is 200W, and the ultrasound time is 20min; obtaining a uniformly dispersed mixed solution B;
in the embodiment, 100mL of manganese sulfate solution is added into the mixed solution A, and the mixed solution A 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 uniformly stirring;
step three: taking the mixed solution B as electrolyte, taking foam nickel as an anode, taking an equal-area graphite plate as a cathode, and performing 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.
In example 2, the deposition time in step three of example 1 was changed to 5min, and the other steps were unchanged.
Example 3 the deposition time in step three of example 1 was changed to 7.5min, the other steps being unchanged.
Example 4, a PPy/GO/MnO 2 Nanocomposite electricThe electrode material comprises the following raw materials in parts by weight: graphene oxide dispersion liquid, pyrrole monomer, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is 250:7:250; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution mixed liquid 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:
step one: fully mixing the graphene oxide dispersion liquid with pyrrole monomers, adding a sodium dodecyl benzene sulfonate solution, and uniformly stirring for 30min; obtaining a uniformly dispersed mixed solution 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 dispersion, and 5g of NaNO was added to a 500mL flask 3 5g graphite and concentrated 150mL H 2 SO 4 The reaction was stirred continuously in an ice-water bath for 50min, and 15g KMnO was stirred continuously 4 Slowly adding into the flask; the mixed solution is continuously stirred for 1.3 hours at 38 ℃, and then 150mL of double distilled water is added; the temperature of the mixed solution is kept below 90 ℃, and 100mLH is added 2 O 2 No bubbles are generated in the flask, the reaction is finished, and the color of the reaction product is changed from the original dark brown to bright yellow, so as to obtain a mixed solution C; centrifuging the mixed solution C for 7min at a speed of 8000r/min, adding 350ml deionized water into the solid after solid-liquid separation, and adding the obtained product into a dialysis bag (dialysis bag pretreatment, namely processing the dialysis bag into a 30cm length unit, heating in hot water for 15min, 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, checking by a pH tester, and finishing the dialysis when the pH=7; dispersing the dialyzed graphene oxide in 700ml of deionized water, and preparing a GO dispersion liquid with the concentration of 1g/L 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 formed by adding 75.2g of dodecyl benzene sulfonate 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 step one, wherein the volume ratio of the mixed solution A to the manganese sulfate solution is 2:1; dispersing ultrasound to a uniform state, wherein the ultrasound power is 300W, and the ultrasound time is 25min; obtaining a uniformly dispersed mixed solution B;
in the embodiment, 100mL of manganese sulfate solution is added into the mixed solution A, and ultrasonic treatment is carried out for 25min, so that the manganese sulfate solution is uniformly dispersed; the manganese sulfate solution is formed by adding 100g of manganese sulfate into 2L of deionized water and uniformly stirring;
step three: taking the mixed solution B as electrolyte, taking foam nickel as an anode, taking an equal-area graphite plate as a cathode, and performing 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 2V, the deposition time is 5min, and the electrolyte is magnetically stirred in the deposition process.
Example 5, a PPy/GO/MnO 2 The nano composite electrode material comprises the following raw materials in parts by weight: graphene oxide dispersion liquid, pyrrole monomer, sodium dodecyl benzene sulfonate solution and manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is 400:7:400; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution mixed liquid to the manganese sulfate solution is 1.5:1.
The PPy/GO/MnO 2 The preparation method of the nano composite electrode material comprises the following steps:
step one: fully mixing the graphene oxide dispersion liquid with pyrrole monomers, adding a sodium dodecyl benzene sulfonate solution, and uniformly stirring for 40min; obtaining a uniformly dispersed mixed solution A;
the preparation method of the graphene oxide dispersion liquid comprises the following steps:
this example uses a modified Hummers method to prepare oxidationGraphene Dispersion 6g NaNO was added to a 500mL flask 3 6g graphite and concentrated 200mL H 2 SO 4 The reaction was stirred continuously in an ice-water bath for 60min, 18g KMnO was stirred continuously 4 Slowly adding into the flask; the mixed solution is continuously stirred for 1.5 hours at 40 ℃, and then 200mL of double distilled water is added; the temperature of the mixed solution is kept below 90 ℃, and 120mLH is added 2 O 2 No bubbles are generated in the flask, the reaction is finished, and the color of the reaction product is changed from the original dark brown to bright yellow, so as to obtain a mixed solution C; centrifuging the mixed solution C for 10min at 9000r/min, adding 400ml deionized water into the solid after solid-liquid separation, and adding the obtained product into a dialysis bag (dialysis bag pretreatment, namely processing the dialysis bag into a 25cm length unit, heating in hot water for 13min, 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, checking by a pH tester, and finishing the dialysis when the pH=7; dispersing the dialyzed graphene oxide in 800ml of deionized water, and preparing a GO dispersion liquid with the concentration of 1g/L 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 formed by adding 50.0g of dodecyl benzene sulfonate into 1L of deionized water and uniformly stirring; forming a mixed solution A;
step two: adding a manganese sulfate solution into the mixed solution A in the step one, wherein the volume ratio of the mixed solution A to the manganese sulfate solution is 1.5:1; dispersing ultrasound to a uniform state, wherein the ultrasound power is 250W, and the ultrasound time is 30min; obtaining a uniformly dispersed mixed solution B;
in the embodiment, 100mL of manganese sulfate solution is added into the mixed solution A, and ultrasonic treatment is carried out for 30min, so that the manganese sulfate solution is uniformly dispersed; the manganese sulfate solution is formed by adding 151g of manganese sulfate into 1.5L of deionized water and uniformly stirring;
step three: taking the mixed solution B as electrolyte, taking foam nickel as an anode, taking an equal-area graphite plate as a cathode, and carrying out electrochemical on the anodeObtaining PPy/GO/MnO by chemical deposition 2 A nanocomposite electrode material;
the electrochemical deposition is carried out at room temperature, the voltage is 5V, the deposition time is 5min, and the electrolyte is magnetically stirred in the deposition process.
The PPy/GO/MnO prepared in examples 1-3 are described below with reference to the accompanying drawings 2 The nanocomposite electrode was characterized.
As shown in FIG. 1, examples 1-3 were prepared with electrodeposition times of 2.5min, 5min and 7.5min, respectively, of PPy/GO/MnO 2 The morphology of the nanocomposite is as shown in (a), (b) and (d) and (c), respectively; PPy/GO/MnO with increasing electrodeposition time 2 The color of the nano composite material is deepened, which shows that the deposition amount of PPy on GO is gradually increased and plays a leading role in three materials; and it can be found therefrom that PPy and MnO in the lamellar structure of GO at electrodeposition for 2.5min 2 Is smaller in content; when the electrodeposition time was increased to 5min, PPy and MnO 2 The dispersion in the GO sheets is relatively uniform; when the electrodeposition time is increased to 7.5min, PPy is obviously agglomerated on GO; during electrochemical codeposition, py will oxidize MnO during electrochemical oxidation 2 Sandwiched in PPy film, mnO during co-deposition 2 Provides new nucleation centers for Py deposition, thus, the inclusion of MnO in spherical PPy occurs 2 Is of a structure of (2); and, the layered GO is PPy and MnO 2 Provides a larger specific surface area, uniformly disperses the PPy, avoids the agglomeration and accumulation of the PPy, and improves the PPy/GO/MnO 2 Specific capacitance, adsorption capacity and adsorption cycle stability of the nanocomposite.
PPy/GO/MnO 2 The electro-adsorption process of the nanocomposite material to 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 experiment 2 The nanometer composite material simulates heavy metal wastewater to be one or more mixed solutions of copper, cadmium, lead and the like; 200mL of Cd with initial concentration of 100mg/L is prepared respectively 2+ 、Cu 2+ And Pb 2+ A solution; the operating (adsorption) voltage was set to 1.2V; placement of PPy/GO/MnO 2 The nanocomposite is stirred magnetically, recorded every 1min, and electrolyzedThe liquid reaches adsorption-desorption equilibrium.
As shown in fig. 2, fig. 2 shows the specific capacitance of the composite electrode tested by CV test, using a three-electrode system: the prepared composite electrode is a working electrode, a Pt electrode is a counter electrode, a Saturated Calomel Electrode (SCE) is a reference electrode, and 1mol/L CuSO is used 4 The solution serves as an electrolyte. Obtaining the PPy/GO/MnO prepared in the examples 1-3 of the present invention at electrodeposition times of 2.5min, 5min and 7.5min, respectively 2 The nano composite electrode has a CV curve with a scanning rate of 5mV/s, wherein the area of the curved surface of the electrode with a deposition time of 5min is obviously larger than that of the other two electrodes, so that the specific capacitance is highest. Obtained by a specific capacitance calculation formula, PPy/GO/MnO under different electrodeposition time 2 The specific capacitance of the nanocomposite electrode was 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 PPy/GO/MnO prepared in example 2 of the present invention 2 Electric adsorption Cu of nano composite electrode 2+ After about 8min of adsorption, reaching adsorption saturation, and the saturated adsorption capacity is 36.77mg/g; (b) Is PPy/GO/MnO 2 The cyclic adsorption capacity of the nano composite electrode is changed to 99% of the initial adsorption capacity after 5 times of cyclic adsorption, and 97% of the initial adsorption capacity after 10 times of cyclic adsorption.
As shown in FIG. 4, FIG. 4 shows the PPy/GO/MnO according to example 2 of the present invention 2 The adsorption capacity and adsorption efficiency of the nano composite electrode under different initial concentrations are increased along with the increase of the initial concentration, and the adsorption efficiency is reduced along with the increase of the initial concentration.
As shown in FIG. 5, FIG. 5 shows the PPy/GO/MnO according to example 2 of the present invention 2 Electric adsorption Cu of nano composite electrode 2+ The adsorption capacity with time is the highest at 1.6V, which is 38.92mg/g.
As shown in FIG. 6, FIG. 6 shows the PPy/GO/MnO according to example 2 of the present invention 2 Nanocomposite electrode pair Cd 2+ 、Cu 2+ And Pb 2+ As can be seen from FIG. 6, pb 2+ The maximum slope of the curve is shown to indicate PPy/GO/MnO 2 Nanocomposite electrode pair Pb 2+ Is the fastest; cu (Cu) 2+ Next, cd 2+ Minimum; and in the later stage of adsorption, cd 2+ Firstly reaching adsorption saturation, wherein the saturated adsorption capacity is 28.89mg/g; for Cu 2+ The saturated adsorption capacity of (C) is 36.77mg/g, and the adsorption capacity of (C) is equal to that of Pb 2+ The saturated adsorption capacity of (2) is 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 shows the X-ray diffraction pattern of GO produced in example 1 of the present invention, and as can be seen from fig. 7, the characteristic peak of GO is at 11.02 °, the crystal plane is (001), and the results are consistent with the literature report related to GO.
As can be seen from the above examples, the present invention employs an anodic one-step electrochemical codeposition process to prepare PPy/GO/MnO 2 MnO of nano composite electrode under electrochemical polymerization condition 2 Successfully coated with PPy and uniformly distributed on the GO sheet by mixing MnO 2 Co-deposition with PPy and GO can result in MnO 2 Nanocrystallization to improve PPy/GO/MnO 2 Capacitance characteristics of nanocomposite, PPy/GO/MnO 2 The good structure of the nanocomposite is beneficial to the diffusion of ions, and PPy/GO/MnO is in adsorption test 2 The nano composite electrode has higher adsorption capacity and good cyclical adsorption stability to metal ions, and the preparation process is simple, so that the long-term reliable use of the capacitance deionization composite electrode is realized.
The above embodiments are only illustrative of the preferred embodiments of the present invention and are not intended to limit the scope of the present invention, and various modifications and improvements made by those skilled in the art to the technical solutions of the present invention should fall within the protection scope defined by the claims of the present invention without departing from the design spirit of the present invention.
Claims (8)
1. PPy/GO/MnO 2 The preparation method of the nano composite electrode material is characterized by comprising the steps of 2 The nano composite electrode material comprises the following raw materials in parts by weight: graphene oxide dispersion, pyrrole monomer, and dodecyl groupSodium benzenesulfonate solution, manganese sulfate solution; the volume ratio of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution is (250-500): 7 (250-500); 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;
the PPy/GO/MnO 2 The preparation method of the nano composite electrode material comprises the following steps:
step one: fully mixing graphene oxide dispersion liquid with pyrrole monomer, adding sodium dodecyl benzene sulfonate solution, and uniformly stirring to obtain uniformly dispersed mixed liquid A;
step two: adding a manganese sulfate solution into the mixed solution A in the step one, and performing ultrasonic dispersion until the manganese sulfate solution is in a uniform state to obtain a uniformly dispersed mixed solution B;
step three: taking the mixed solution B in the second step as electrolyte, taking foam nickel as an anode, taking an equal-area graphite plate as a cathode, and performing electrochemical deposition on the anode to obtain PPy/GO/MnO 2 A nanocomposite electrode material;
the preparation method of the graphene oxide dispersion liquid in the first step comprises the following steps:
3-6g NaNO was added to a 500mL flask 3 3-6g graphite and concentrated 100-200mL H 2 SO 4 Continuously stirring in ice-water bath for 30-60min, and continuously stirring 9-18g KMnO 4 Slowly adding into the flask; continuously stirring the mixed solution at 35-40 ℃ for 1-1.5h, and then adding 100-200mL of double distilled water; the temperature of the mixed solution is kept below 90 ℃, and 80-120mLH is added 2 O 2 No bubbles are generated in the flask, the reaction is finished, and the color of the reaction product is changed from the original dark brown to bright yellow, so as to obtain a mixed solution C; centrifuging the mixed solution C for 4-10min at 7000-9000r/min, adding 250-400ml deionized water into the solid after 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, checking by a pH meter, and finishing the dialysis when the pH=7; dispersing the dialyzed graphene oxide in 500-800ml deionized water,after freeze-drying treatment, a GO dispersion of 1g/L was prepared.
2. The method of manufacturing according to claim 1, characterized in that: the stirring time of the graphene oxide dispersion liquid, the pyrrole monomer and the sodium dodecyl benzene sulfonate solution in the first step is 20-40min; the sodium dodecyl benzene sulfonate solution is formed by adding 32.6-75.2g of dodecyl benzene sulfonate into 1-2L of deionized water and stirring uniformly.
3. The method of manufacturing according to claim 1, characterized in that: and 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 uniformly stirring.
4. The method of manufacturing according to claim 1, characterized in that: in the second step, the ultrasonic power is 200-300W, and the ultrasonic time is 20-30min.
5. The method of manufacturing according to claim 1, characterized in that: and 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.
6. The method of manufacturing according to claim 1, characterized in that: the pretreatment process of the dialysis bag comprises the following steps: processing the dialysis bag into 20-30cm length unit, heating in hot water for 10-15min, and cooling.
7. PPy/GO/MnO prepared by the preparation method according to claim 1 2 The application of the nano composite electrode material is characterized in that: is used for adsorbing heavy metal ions in wastewater.
8. The use according to claim 7, characterized in that: the heavy metal ion is Cd 2+ 、Cu 2+ Or Pb 2+ One or more of them.
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