CN114446671B - Preparation method of MOF-5/PPy/GO nano material and application of MOF-5/PPy/GO nano material in aspect of super capacitor - Google Patents
Preparation method of MOF-5/PPy/GO nano material and application of MOF-5/PPy/GO nano material in aspect of super capacitor Download PDFInfo
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- 239000013132 MOF-5 Substances 0.000 title claims abstract description 77
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000003990 capacitor Substances 0.000 title abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001291 vacuum drying Methods 0.000 claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 10
- 239000010935 stainless steel Substances 0.000 claims abstract description 10
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 7
- CQQSQBRPAJSTFB-UHFFFAOYSA-N 4-(bromomethyl)benzoic acid Chemical compound OC(=O)C1=CC=C(CBr)C=C1 CQQSQBRPAJSTFB-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000002135 nanosheet Substances 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 25
- 238000009210 therapy by ultrasound Methods 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 9
- 239000003607 modifier Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 6
- 239000006230 acetylene black Substances 0.000 claims description 5
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 235000011164 potassium chloride Nutrition 0.000 claims description 5
- 239000001103 potassium chloride Substances 0.000 claims description 5
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 238000011056 performance test Methods 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000005855 radiation Effects 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- -1 polytetrafluoroethylene Polymers 0.000 claims 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims 1
- 239000004810 polytetrafluoroethylene Substances 0.000 claims 1
- 229920000128 polypyrrole Polymers 0.000 abstract description 77
- 239000007772 electrode material Substances 0.000 abstract description 7
- 229910021389 graphene Inorganic materials 0.000 abstract description 7
- 238000004146 energy storage Methods 0.000 abstract description 6
- 239000003792 electrolyte Substances 0.000 abstract description 2
- 238000012983 electrochemical energy storage Methods 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 description 15
- 238000002484 cyclic voltammetry Methods 0.000 description 6
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- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229920001940 conductive polymer Polymers 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 238000002083 X-ray spectrum Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/48—Conductive polymers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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- 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
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Abstract
The invention discloses a preparation method of MOF-5/PPy/GO nano material and application thereof in super capacitor. The invention is to modify polypyrrole/graphene oxide and Zn with 4-bromomethyl benzoic acid 2+ And terephthalic acid is deposited and reacted for 48 hours at 80 ℃ to prepare MOF-5/PPy/GO nano material with a specific structure, and then the MOF-5/PPy/GO nano material after vacuum drying is smeared on a stainless steel sheet to prepare the modified electrode based on the MOF-5/PPy/GO nano material. The electrode material has the advantages that due to the unique composite structure, the specific surface area and the conductivity of the MOF are effectively increased by the carrier, and the multiplying power performance and the cycle life of the composite electrode material in the water-based electrolyte are also effectively improved. The substrate serving as the electrode current collector is applied to super capacitors, has good electrochemical energy storage performance such as high specific capacitance and the like, and has potential application prospect in the field of energy storage devices.
Description
Technical Field
The invention belongs to the field of supercapacitors, and particularly relates to a preparation method of MOF-5/PPy/GO nano material and application of the MOF-5/PPy/GO nano material in the aspect of supercapacitors.
Background
Supercapacitors exhibit excellent unique properties in many electrochemical storage systems due to the increasing demand for energy. The super capacitor, also called electrochemical capacitor, is a novel energy storage device, can store a large amount of charges, is transmitted under a high power rated value, has high power density and excellent safety coefficient, and has wide application prospect in the field of energy storage.
The super capacitor consists of a positive electrode, a negative electrode, a current collector, electrolyte and a diaphragm. The electrode material is a carrier for storing charges, which determines the main performance of the super capacitor, and the wide use of the super capacitor is limited due to low energy density, so the preparation of the electrode material with high capacity becomes one of effective methods for solving the problem of low energy density. In recent years, MOF-5 derived electrode materials attract attention of vast researchers in the energy storage field, the materials realize electric energy storage through an electrochemical double-layer capacitance principle, and a charge adsorption process occurs between micropore structures of the materials, so that the materials can store charges with high energy density, and a higher capacitance value is generated. The material has high capacitance value and high power density, but is used as a capacitor electrode material, has poor conductive efficiency and poor cycle stability, and the problems greatly limit the application of the MOF-5 derivative material in the field of super capacitor energy storage.
The composite material prepared by taking the polypyrrole/graphene oxide as the carrier of the MOF-5 has unique lamellar texture, and retains the original morphology of the MOF-5 and the polypyrrole/graphene. These composites have increased adsorption capacity compared to their original MOFs due to the creation of new steric spaces between the MOFs and polypyrrole/graphene oxide. The cyclic stability of the material is improved due to the enhancement of the space structure, and the material has great significance for optimizing the MOF-5 derivative material in the aspect of super capacitor.
Disclosure of Invention
The invention provides a preparation method of MOF-5/PPy/GO nano material and application of the MOF-5/PPy/GO nano material in super capacitor, which overcomes the defects of the prior art, and the composite has higher capacitance, cycle stability and good multiplying power performance.
The invention adopts the technical scheme that:
the preparation method of the MOF-5/PPy/GO nano material comprises the following steps:
1) In-situ chemical polymerization of pyrrole (Py) on the GO nano-sheet under the condition of ultrasonic radiation to obtain polypyrrole/graphene oxide (PPy/GO) nano-sheet;
2) Under the condition of heating in an oil bath, 4-bromomethylbenzoic acid is modified on the PPy/GO nano-sheet obtained in the step 1) to obtain a PBA/PPy/GO nano-sheet;
3) Dispersing the PBA/PPy/GO nano-sheets obtained in the step 2) and terephthalic acid in N, N-Dimethylformamide (DMF), then adding zinc nitrate, and loading the MOF-5 metal-organic framework onto the PBA/PPy/GO nano-sheets to obtain the MOF-5/polypyrrole/graphene oxide (MOF-5/PPy/GO) nano-material.
Preferably, the preparation method of the MOF-5/PPy/GO nano material comprises the following steps of: adding 0.2g of GO nano-sheets into 100mL of deionized water, performing ultrasonic dispersion, adding 0.2g of Py, performing ultrasonic dispersion, and adding 0.6g of FeCl 3 ·6H 2 And (3) continuing ultrasonic treatment for 0.5h, washing the obtained product with distilled water and ethanol in sequence, centrifuging, and carrying out vacuum drying at 50 ℃ to obtain the PPy/GO nano-sheet.
Preferably, the preparation method of the MOF-5/PPy/GO nano material comprises the following step 2): adding 0.03g of PPy/GO nano-sheets into 25mL of DMF, adding 0.14g of 4-bromomethylbenzoic acid, carrying out ultrasonic treatment for 5min, adding 0.05g of KOH powder, carrying out ultrasonic treatment for 5min, carrying out reflux reaction for 24h in an oil bath at 60 ℃, cooling, washing the obtained product with distilled water and ethanol in sequence, centrifuging, and carrying out vacuum drying at 50 ℃ to obtain the PBA/PPy/GO nano-sheets.
Preferably, the preparation method of the MOF-5/PPy/GO nano material comprises the following step 3): adding 0.02g of PBA/PPy/GO nano-sheets into 30mL of DMF, adding 0.058g of terephthalic acid, carrying out ultrasonic treatment for 5min, adding 0.11g of zinc nitrate, carrying out ultrasonic treatment for 5min, carrying out reflux reaction in an oil bath at 80 ℃ for 48h, cooling, washing the obtained product with distilled water and ethanol in sequence, centrifuging, and carrying out vacuum drying at 50 ℃ to obtain the MOF-5/PPy/GO nano-material.
Further, the preparation method of the MOF-5/PPy/GO nano material comprises the following steps: the rotation speed was 10000rpm and the time was 300s.
A modified electrode based on MOF-5/PPy/GO nano material is prepared by using a stainless steel sheet as a base electrode, and attaching the MOF-5/PPy/GO nano material prepared by the preparation method to the stainless steel sheet.
The preparation method of the modified electrode based on the MOF-5/PPy/GO nano material comprises the following steps:
1) Ultrasonically dispersing MOF-5/PPy/GO nano material, acetylene black and vinylidene fluoride in 1mL absolute ethyl alcohol to obtain a uniformly dispersed composite modifier;
2) And (3) dripping the uniformly dispersed composite modifier obtained in the step (1) on the surface of a clean stainless steel sheet, and drying at 60 ℃ for 12 hours to obtain the MOF-5/PPy/GO modified electrode.
Further, in the step 1), according to the mass ratio, the MOF-5/PPy/GO nano material comprises acetylene black and vinylidene fluoride=8:1:1.
An application of a modified electrode based on MOF-5/PPy/GO nano material in the field of super capacitors.
Further, the application method comprises the following steps: the modified electrode based on the MOF-5/PPy/GO nano material is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as an auxiliary electrode, a three-electrode system is formed, and the performance test of the supercapacitor is carried out in a 1M potassium chloride solution.
The beneficial effects of the invention are as follows:
1. the MOF-5/PPy/GO nano material prepared by the method has a uniform layered structure and a unique three-dimensional structure, the MOF-5/PPy/GO composite nano material has small change and stable molecular structure in the rapid charge and discharge process, and the conductive polymer improves the conductivity and electrochemical stability of the MOF-5 double-layer capacitive supercapacitor.
2. The modified electrode based on the MOF-5/PPy/GO nano material prepared by the invention has larger specific surface area and conductivity, and the zinc metal organic framework also has good conductivity, and the prepared MOF-5/PPy/GO material has the characteristics of high capacitance of the MOF, high conductivity and high cycling stability of the conductive polymer.
3. Compared with the prior art, the modified MOF-5 material designed and synthesized by the invention has higher conductivity and structural stability, and effectively improves the capacitance performance, the multiplying power performance and the cycling stability of the conductive polymer electrode material.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of MOF-5/PPy/GO nanomaterial.
FIG. 2 is an energy scattering X-ray spectroscopy (EDS) diagram of MOF-5/PPy/GO nanomaterials.
FIG. 3 is an X-ray diffraction (XRD) pattern of PPy/GO nanoplatelets and MOF-5/PPy/GO nanomaterials.
FIG. 4 is a graph of constant current charge-discharge (GCD) at different current densities for MOF-5/PPy/GO modified electrodes.
FIG. 5 is a graph of Cyclic Voltammetry (CV) curves for MOF-5/PPy/GO modified electrodes at different scan rates.
FIG. 6 is a graph of the stability of a MOF-5/PPy/GO modified electrode at a current density of 2A/g for 3000 cycles.
Detailed Description
Example 1MOF-5/PPy/GO nanomaterials
The preparation method comprises the following steps:
1) The Hummers method prepares GO nano-sheets: 67.5mL of concentrated sulfuric acid, 2.0g of high purity graphite and 1.6g of NaNO were sequentially added into a three-necked flask 3 Stirring uniformly, keeping the temperature of the system below 5 ℃, and slowly and continuously adding 9g KMnO into the mixed solution within 1h 4 Then placing in a water bath at 36 ℃ for reaction for 0.5H, standing for two weeks at room temperature, diluting with 560mL of 60 ℃ water, and dripping H 2 O 2 Until the solution is bright yellow, centrifuging (10000 rpm) while the solution is hot, washing to neutrality, and vacuum drying at 50 ℃ to obtain GO nano-sheets;
2) Preparing PPy/GO nano-sheets: adding 0.2g of GO nano-sheets into 100mL of deionized water, performing ultrasonic dispersion, adding 0.2g of pyrrole (Py), performing ultrasonic dispersion, and adding 0.6g of FeCl 3 ·6H 2 Continuously performing ultrasonic treatment for 0.5h, washing the obtained product with distilled water and ethanol in sequence, centrifuging at 10000rpm for 300s, and performing vacuum drying at 50 ℃ to obtain PPy/GO nano-sheets;
3) Preparing PBA/PPy/GO nano-sheets: adding 25mL of DMF (dimethyl formamide) into a 50mL round bottom flask, sequentially adding 0.03g of PPy/GO nano-sheets and 0.14g of 4-bromomethylbenzoic acid, carrying out ultrasonic treatment for 5min, adding 0.05g of KOH powder, carrying out ultrasonic treatment for 5min, carrying out reflux reaction in an oil bath at 60 ℃ for 24h, cooling, sequentially washing the obtained product with distilled water and ethanol, centrifuging at 10000rpm for 300s, and carrying out vacuum drying at 50 ℃ to obtain PBA/PPy/GO nano-sheets;
4) Preparing MOF-5/PPy/GO nano material: adding 30mL of DMF into a 50mL beaker, sequentially adding 0.02g of PBA/PPy/GO nano-sheet and 0.058g of terephthalic acid, carrying out ultrasonic treatment for 5min, then adding 0.11g of zinc nitrate, carrying out ultrasonic treatment for 5min, carrying out reflux reaction in an oil bath at 80 ℃ for 48h, cooling, sequentially washing the obtained product with distilled water and ethanol, centrifuging at 10000rpm for 300s, and carrying out vacuum drying at 50 ℃ to obtain the MOF-5/PPy/GO nano-material.
(II) detection
1. A Scanning Electron Microscope (SEM) image of the MOF-5/PPy/GO nano material is shown in figure 1, and the prepared material can be observed to have a unique three-dimensional structure and a lamellar structure.
2. The energy scattering X-ray spectrum (EDS) diagram of the MOF-5/PPy/GO nano material is shown in fig. 2, peaks of elements of C, N, O and Zn can be obviously observed, and the chemical composition of the composite material is shown as the elements.
3. The X-ray diffraction (XRD) patterns of the PPy/GO nano-sheet and the MOF-5/PPy/GO nano-material are shown in figure 3, and the XRD patterns of the two materials are obviously different, because the MOF-5 forms a typical metal organic network structure after being effectively coordinated and grown on the surface of polypyrrole/graphene oxide in situ through terephthalic acid.
Example 2 MOF-5/PPy/GO nanomaterial-based modified electrode
The preparation method comprises the following steps:
1) Preparation of the composite modifier: taking 8mg of the dried MOF-5/PPy/GO nano material prepared in the example 1, adding 1mg of acetylene black, 1mg of vinylidene fluoride and 1mL of absolute ethyl alcohol, and performing ultrasonic dispersion for 30min to obtain black suspension, namely the composite modifier for later use;
2) Electrode treatment: respectively ultrasonic washing stainless steel sheet with size of 1cm×1.5cm with acetone, anhydrous ethanol and water for 30min, and oven drying;
3) Preparation of modified electrode: and (3) transferring 0.125mL of the composite modifier prepared in the step (1) by using a pipette, dripping the composite modifier onto the surface of the stainless steel sheet treated in the step (2), and drying the stainless steel sheet at 60 ℃ for 12 hours to obtain the MOF-5/PPy/GO modified electrode.
(II) electrochemical Performance test
1. Charge and discharge performance research of modified electrode based on MOF-5/PPy/GO nano material
The MOF-5/PPy/GO modified electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, and the platinum sheet electrode is used as an auxiliary electrode; experiments were performed on the CHI760E electrochemical workstation, including acquisition and processing of experimental data; charge and discharge tests were performed in 1M KCl solution at current densities of 10A/g, 5A/g, 2A/g.
FIG. 4 is a graph of constant current charge and discharge (GCD) of MOF-5/PPy/GO modified electrodes at different current densities, showing that the maximum capacitance is 60F/g at a 2A/g sweep rate, and the charge and discharge curves have certain symmetry, indicating that the material has certain reversibility in the constant current charge and discharge process.
2. MOF-5/PPy/GO nanomaterial-based modified electrode cyclic voltammetry curve comparison
In an electrolytic cell of 1M KCl solution, a MOF-5/PPy/GO modified electrode is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, and a platinum sheet electrode is used as an auxiliary electrode; experiments were performed on the CHI760E electrochemical workstation with attached computer software for acquisition and processing of experimental data; the cyclic voltammogram test is carried out in the potential range of 0.9V to-0.1V (vs. Ag/AgCl), and a stable cyclic voltammogram is recorded.
As shown in FIG. 5, which is a graph comparing Cyclic Voltammetry (CV) curves of MOF-5/PPy/GO modified electrodes at different scanning rates, it can be seen from the CV curves that a rectangular curve with high symmetry order appears due to the double-layer capacitance characteristic, and a rapid charge and discharge rate is also shown.
3. Stability measurement of MOF-5/PPy/GO nanomaterial-based modified electrode
The MOF-5/PPy/GO modified electrode is used as a working electrode, the Ag/AgCl electrode is used as a reference electrode, and the platinum sheet electrode is used as an auxiliary electrode; experiments were performed on the CHI760E electrochemical workstation, including acquisition and processing of experimental data; in a 1M KCl solution, charge and discharge were carried out at a current density of 2A/g for 3000 cycles.
FIG. 6 is a graph showing the capacitance decay curve of a MOF-5/PPy/GO modified electrode cycled 3000 times at a current density of 2A/g, showing that the material tends to stabilize and the capacitance change is insignificant due to the slow increase trend in the initial phase of specific capacitance upon sufficient activation of the material under electrochemical conditions, and the capacitance remains at 133.5% after 3000 charges and discharges.
The foregoing description of the preferred embodiments of the present invention is merely illustrative, and not restrictive, of the invention. It will be appreciated by those skilled in the art that many changes, modifications and even equivalent changes may be made thereto without departing from the spirit and scope of the invention as defined in the appended claims, but are to be accorded the true scope of the invention.
Claims (10)
- The preparation method of the MOF-5/PPy/GO nano material is characterized by comprising the following steps:1) Under the condition of ultrasonic radiation, in-situ chemical polymerization of pyrrole on the GO nano-sheet to obtain PPy/GO nano-sheet;2) Under the condition of heating in an oil bath, 4-bromomethylbenzoic acid is modified on the PPy/GO nano-sheet obtained in the step 1) to obtain a PBA/PPy/GO nano-sheet;3) Dispersing the PBA/PPy/GO nano-sheets obtained in the step 2) and terephthalic acid in N, N-dimethylformamide, then adding zinc nitrate, and loading the MOF-5 metal-organic framework on the PBA/PPy/GO nano-sheets to obtain the MOF-5/PPy/GO nano-material.
- 2. The preparation method according to claim 1, wherein the step 1) specifically comprises: adding 0.2g of GO nano-sheets into 100mL of deionized water, performing ultrasonic dispersion, adding 0.2g of pyrrole, performing ultrasonic dispersion, and adding 0.6g of FeCl 3 ·6H 2 And (3) continuing ultrasonic treatment for 0.5h, washing the obtained product with distilled water and ethanol in sequence, centrifuging, and carrying out vacuum drying at 50 ℃ to obtain the PPy/GO nano-sheet.
- 3. The preparation method according to claim 1, wherein the step 2) comprises the following steps: adding 0.03g of PPy/GO nano-sheets into 25mL of N, N-dimethylformamide, adding 0.14g of 4-bromomethylbenzoic acid, carrying out ultrasonic treatment for 5min, adding 0.05g of KOH powder, carrying out ultrasonic treatment for 5min, carrying out reflux reaction for 24h in an oil bath at 60 ℃, cooling, washing the obtained product with distilled water and ethanol in sequence, centrifuging, and carrying out vacuum drying at 50 ℃ to obtain the PBA/PPy/GO nano-sheets.
- 4. The preparation method according to claim 1, wherein the step 3) specifically comprises: adding 0.02g of PBA/PPy/GO nano-sheets into 30mL of N, N-dimethylformamide, adding 0.058g of terephthalic acid, carrying out ultrasonic treatment for 5min, adding 0.11g of zinc nitrate, carrying out ultrasonic treatment for 5min, carrying out reflux reaction for 48h in an oil bath pot at 80 ℃, cooling, washing the obtained product with distilled water and ethanol in sequence, centrifuging, and carrying out vacuum drying at 50 ℃ to obtain the MOF-5/PPy/GO nano-material.
- 5. The method according to any one of claims 2 to 4, wherein the centrifugation conditions are: the rotation speed was 10000rpm and the time was 300s.
- 6. The MOF-5/PPy/GO nano material-based modified electrode is characterized in that a stainless steel sheet is used as a base electrode, and the MOF-5/PPy/GO nano material prepared by the preparation method of claim 1 is attached to the stainless steel sheet to prepare the MOF-5/PPy/GO modified electrode.
- 7. The method for preparing the modified electrode based on the MOF-5/PPy/GO nano material as set forth in claim 6, which is characterized by comprising the following steps:1) Ultrasonically dispersing MOF-5/PPy/GO nano material, acetylene black and vinylidene fluoride in 1mL absolute ethyl alcohol to obtain a uniformly dispersed composite modifier;2) And (3) dripping the uniformly dispersed composite modifier obtained in the step (1) on the surface of a clean stainless steel sheet, and drying at 60 ℃ for 12 hours to obtain the MOF-5/PPy/GO modified electrode.
- 8. The preparation method according to claim 7, wherein in the step 1), the MOF-5/PPy/GO nanomaterial comprises acetylene black and polytetrafluoroethylene=8:1:1 in mass ratio.
- 9. The use of a modified electrode based on MOF-5/PPy/GO nanomaterials as claimed in claim 6 in the field of supercapacitors.
- 10. The use according to claim 9, characterized in that the method is as follows: the modified electrode based on MOF-5/PPy/GO nano material as claimed in claim 6 is used as a working electrode, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as an auxiliary electrode, a three-electrode system is formed, and the performance test of the supercapacitor is carried out in 1M potassium chloride solution.
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