CN114976062B - Preparation method of nitrogen-doped rGO loaded MnO nanoparticle catalyst - Google Patents
Preparation method of nitrogen-doped rGO loaded MnO nanoparticle catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 131
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 55
- 239000000725 suspension Substances 0.000 claims abstract description 36
- 239000011259 mixed solution Substances 0.000 claims abstract description 34
- 238000010438 heat treatment Methods 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000012046 mixed solvent Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000008247 solid mixture Substances 0.000 claims abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 15
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000005406 washing Methods 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 125000001477 organic nitrogen group Chemical group 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims description 20
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 19
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical group NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 18
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 5
- 229940071125 manganese acetate Drugs 0.000 claims description 4
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical group [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 39
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 239000012298 atmosphere Substances 0.000 abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 239000002202 Polyethylene glycol Substances 0.000 description 20
- 229920001223 polyethylene glycol Polymers 0.000 description 20
- 239000002245 particle Substances 0.000 description 17
- 229910021642 ultra pure water Inorganic materials 0.000 description 15
- 239000012498 ultrapure water Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 238000002604 ultrasonography Methods 0.000 description 11
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 9
- 230000009467 reduction Effects 0.000 description 9
- 239000000446 fuel Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 238000001075 voltammogram Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 7
- 239000010431 corundum Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 6
- 239000002041 carbon nanotube Substances 0.000 description 6
- 238000000349 field-emission scanning electron micrograph Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004108 freeze drying Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 229940082328 manganese acetate tetrahydrate Drugs 0.000 description 5
- CESXSDZNZGSWSP-UHFFFAOYSA-L manganese(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O CESXSDZNZGSWSP-UHFFFAOYSA-L 0.000 description 5
- 229920006395 saturated elastomer Polymers 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 229910021389 graphene Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
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- 238000012360 testing method Methods 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 206010034133 Pathogen resistance Diseases 0.000 description 2
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- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical class [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
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Abstract
The invention relates to a preparation method of a nitrogen-doped rGO supported MnO nanoparticle catalyst, which comprises the following steps: dispersing GO in an alcohol-water mixed solvent to obtain GO suspension; secondly, adding PEG, water-soluble manganese salt and an organic nitrogen source into the GO suspension, and adjusting the pH value of the obtained mixed solution to be alkaline; placing the mixed solution in a high-pressure reaction kettle, performing hydrothermal reaction, and then cooling, washing and drying to obtain a solid mixture of a nanometer manganese oxide precursor and nitrogen-doped rGO; and fourthly, performing heat treatment on the solid mixture for a preset time in an inert atmosphere at 800-1200 ℃ to obtain the nitrogen-doped rGO supported small-size MnO nano particle catalyst. The MnO/N-rGO catalyst prepared by the preparation method has good catalytic activity, stability and methanol resistance.
Description
Technical Field
The invention relates to the field of non-noble metal nano catalysts; more particularly, relates to a preparation method of a non-noble metal nano catalyst.
Background
Fuel cells are energy conversion devices that directly convert chemical energy stored in fuels and oxidants into electrical energy. The fuel cell has the advantages of high energy conversion efficiency, no noise, no pollution and the like, and is becoming an ideal energy utilization mode because the chemical energy is directly converted into the electric energy without a heat engine process and is not limited by the Carnot cycle.
The main problems with current fuel cells are slow cathode side Oxygen Reduction Reaction (ORR) kinetics and high cost of catalyst. Pt and Pt-based alloys have traditionally been considered the best ORR catalysts because Pt (platinum) exhibits high catalytic activity for oxygen reduction. However, pt-based catalysts also have disadvantages such as high cost, scarcity, low durability, cross-over effects, and carbon monoxide (CO) poisoning effects. For example, pt costs in low temperature fuel cells are about 50% of the total stack cost, and the stability of the catalyst is also reduced during operation due to problems such as dissolution, agglomeration, etc. of Pt. In addition, CO generated during operation can clog Pt active sites, degrading catalyst performance, which severely hampers the large-scale commercialization of fuel cells.
Manganese oxides have received much attention due to their low cost, availability, and chemical and electrochemical stability. In particular, manganese oxide vs HO 2 - Conversion to O 2 And OH-has good ORR activity, and can effectively treat intermediate product H in ORR process 2 O 2 Conversion to H 2 O, thereby improving catalytic efficiency; however, pure manganese oxide has poor conductivity and needs to be bonded to a good conductive material (e.g., carbon nanotubes, graphene, etc.). Wherein Graphene Oxide (GO) is a material with a unique two-dimensional structure, which has sp 2 The hybridized honeycomb carbon, high surface area, good conductivity and excellent chemical stability make it an ideal ORR catalyst support. The doped hetero atoms (such as N, S, P, B and the like) in the GO have better oxygen reduction performance and durability, and the doped hetero atoms can change the electronic structure of the GO and regulate O 2 Thereby weakening the O-O bond such that the oxygen reduction potential is reduced.
Prior Art (Huang Junjie. Study of manganese oxide-based direct methanol Fuel cell cathode catalyst [ D ]]Instructions for the university, yan Shanda, 2014:15) discloses a method for preparing MnO/C-N/CNTs catalysts, comprising the steps of: (1) KMnO having a concentration of 0.03mol/L was first prepared 4 Adding CNTs and milk powder (for example, the ratio of CNTs to the carbonized carbon material (C-N) of milk powder is 2:1) into the solution under ultrasonic vibration, and then ultrasonically treating the mixed solutionOscillating for 30min to disperse uniformly; (2) Drying the beaker filled with the mixed solution in an oven, grinding to obtain uniform powder, and placing the powder into a small crucible; (3) Placing the small crucible into a vacuum reaction furnace chamber, starting a vacuum pump, and enabling the vacuum degree to reach 10 -1 Pa and then introducing N 2 Heating to 600-900 ℃ at 20 ℃/min, preserving heat for 2h, closing a heating valve, cooling to room temperature, taking out the container, and finally obtaining the MnO/C-N/CNTs catalyst.
The prior art adopts a one-step pyrolysis method to prepare MnO/C-N/CNTs catalyst, and the catalyst prepared by the one-step method has a certain ORR catalytic activity, but a plurality of improvements still remain: on one hand, the particle size of the formed MnO particles is larger, and the particles are easy to agglomerate; on the other hand, mnO particles bind poorly to the N active site. Accordingly, there is a need for improvements over existing methods of preparing MnO nanoparticle catalysts.
Disclosure of Invention
The embodiment of the invention provides a preparation method of a nitrogen-doped rGO supported MnO nanoparticle catalyst, which comprises the following steps:
dispersing GO in an alcohol-water mixed solvent to obtain GO suspension;
secondly, adding PEG, water-soluble manganese salt and an organic nitrogen source into the GO suspension, and adjusting the pH value of the obtained mixed solution to be alkaline;
placing the mixed solution into a high-pressure reaction kettle, performing hydrothermal reaction, and then cooling, washing and drying to obtain a solid mixture of a nanometer manganese oxide precursor and nitrogen-doped rGO;
and fourthly, performing heat treatment on the solid mixture for a preset time in an inert atmosphere at 800-1200 ℃ to obtain the nitrogen-doped rGO supported MnO nanoparticle catalyst.
In the preparation method embodiment of the invention, the reduction and nitrogen doping of GO are carried out by utilizing a hydrothermal reaction to obtain N-rGO, and nano manganese oxide precursor particles are loaded on the surface of the N-rGO. On one hand, a large number of active sites are formed on the N-rGO in the nitrogen doping process, and the active sites are beneficial to reducing the size of nano manganese oxide precursor particles; on the other hand, PEG (polyethylene glycol) is added into the mixed solution of the hydrothermal reaction and the pH of the mixed solution is adjusted to be alkaline, so that the nanometer manganese oxide precursor particles can be promoted to have smaller size and even distribution on N-rGO.
In this way, in the subsequent heat treatment step, N-rGO is continuously reduced to obtain the nitrogen-doped rGO carrier, and the nano manganese oxide precursor is converted into small-sized MnO nanoparticles, wherein the MnO nanoparticles are uniformly and firmly loaded on the nitrogen-doped rGO carrier, so that the specific surface area of the catalyst and the synergistic effect of the MnO nanoparticles and the nitrogen-doped rGO carrier are effectively improved, and the prepared nitrogen-doped rGO-loaded MnO nanoparticle catalyst has better durability and methanol cross-resistance effect than that of a commercial Pt/C catalyst.
According to one specific embodiment of the invention, the GO suspension is obtained by adding GO into an alcohol-water mixed solvent in a proportion of 0.5-5 mg/mL for ultrasonic dispersion. The GO is ultrasonically dispersed, and the multi-layer GO can be peeled off, so that the GO has a better environment when being doped with nitrogen and loaded with MnO crystal grains. Wherein the ultrasonic time can be controlled to be 3-5 h.
Preferably, the temperature of the GO suspension is controlled to be below 30 ℃ at the time of ultrasound to prevent GO curling.
According to an embodiment of the invention, the volume ratio of the alcohol to the water in the alcohol-water mixed solvent is 1-3:1, and the alcohol-water mixed solvent is preferably a mixed solvent of ethylene glycol and water so as to achieve a better GO dispersing effect.
According to one embodiment of the invention, in the step (a), the volume content of PEG in the mixed solution is controlled to be 5-30%, preferably 8-15%.
According to one embodiment of the invention, the mass percentage of Mn relative to (GO+Mn) is controlled in the step (a) to be 5-30 wt%, preferably 5-20 wt%, more preferably 8-12 wt%.
According to one embodiment of the invention, in step (ii), the pH of the resulting mixed solution is adjusted to 8-12, preferably 8-10.
According to a specific embodiment of the invention, the temperature of the hydrothermal reaction is controlled to be 100-200 ℃ in the step, and the reaction time is controlled to be 12-24 hours.
According to one embodiment of the invention, the solid mixture is heat treated in a step under nitrogen atmosphere at 1000-1200 ℃ for a period of 1-3 hours.
The manganese oxide gradually changes to low price along with the temperature rise, and the high temperature has a certain effect on the conversion of GO to rGO. The inventors have unexpectedly found that in the examples of the present invention, heat treatment at 1000-1200 ℃ under nitrogen atmosphere can obtain MnO nanoparticles with smaller size (the size of the crystal grain is 2-4 nm), which makes the prepared MnO/N-rGO catalyst have higher specific surface area, better conductivity and stability, and further, better oxygen reduction catalytic activity.
Preferably, the manganese salt is manganese acetate and the organic nitrogen source is dicyandiamide.
The melamine with high nitrogen content and easy decomposition is selected as a nitrogen source, so that N on GO is easy to be doped. And, the dicyandiamide generates NH during the decomposition process 3 The stirring effect is formed, so that GO sheets cannot be stacked together in the hydrothermal reaction process; residual dicyandiamide also generates NH during heat treatment 3 Acts as an "etch" for GO, forming more defect sites thereon.
The objects, technical solutions and advantages of the present invention will be more clearly described below, and the present invention will be further described in detail with reference to the accompanying drawings and the detailed description.
Drawings
FIG. 1 is a schematic flow chart of an embodiment of the preparation method of the present invention;
FIGS. 2a and b are FE-SEM and TEM images of MnO/N-rGO (10 wt% at 850 ℃) catalysts prepared in example 1, respectively;
FIGS. 3a and b are FE-SEM and TEM images of the MnO/N-rGO (10 wt% at 950 ℃ C.) catalyst prepared in example 2, respectively;
FIG. 4a is an FE-SEM image of a MnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst prepared in example 3;
FIGS. 4b and c are TEM images of the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3;
FIG. 4d is a HRTEM image of the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3;
FIG. 5 is an XRD pattern for the MnO/N-rGO (10 wt% at 850 ℃) catalyst prepared in example 1, the MnO/N-rGO (10 wt% at 950 ℃) catalyst prepared in example 2, and the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3;
FIG. 6 is a graph of Linear Sweep Voltammograms (LSV) for the MnO/N-rGO (10 wt% at 850 ℃) catalyst prepared in example 1, the MnO/N-rGO (10 wt% without PEG at 850 ℃) catalyst prepared in comparative example 1, and the MnO/N-rGO (10 wt% without NaOH at 850 ℃) catalyst prepared in comparative example 2;
FIG. 7 is a graph of Linear Sweep Voltammograms (LSV) versus the MnO/N-rGO (10 wt% at 950 ℃) catalyst prepared in example 2, as well as a commercial Pt/C catalyst;
FIG. 8 shows the MnO/N-rGO (10 wt% at 1050 ℃ C.) catalysts prepared in example 3 in N 2 And O 2 Electrochemical cyclic voltammogram (C-V) contrast plot under saturated conditions;
FIG. 9 is a graph comparing the chronoamperometric curves (i-t) for the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3 and a commercial Pt/C catalyst;
FIG. 10 is a graph comparing the chronoamperometric curves (i-t) of the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3 and the methanol crossover resistance of a commercial Pt/C catalyst;
FIG. 11 is a graph comparing Linear Sweep Voltammograms (LSVs) of the MnO/N-rGO (10wt% at 1050 ℃) catalyst made in example 3, the MnO/N-rGO (5wt% at 1050 ℃) catalyst made in example 5, the MnO/N-rGO (15wt% at 1050 ℃) catalyst made in example 6, and the commercial Pt/C catalyst;
FIG. 12 is a graph of Linear Sweep Voltammograms (LSV) versus the MnO/N-rGO (10wt% at 1150 ℃) catalyst made in example 4, as well as a commercial Pt/C catalyst.
Detailed Description
According to the embodiment of the invention, the small-size MnO nano particles are loaded on the nitrogen-doped rGO carrier and used as the active component of the oxygen reduction catalyst, so that the catalyst has good oxygen reduction catalytic activity, good stability and methanol cross resistance.
In the embodiment of the invention, the preparation method of the nitrogen-doped rGO supported MnO nanoparticle catalyst comprises the following steps:
dispersing GO in an alcohol-water mixed solvent to obtain GO suspension; wherein, the GO suspension liquid can be obtained by adding GO into an alcohol-water mixed solvent in a proportion of 0.5-5 mg/mL for ultrasonic dispersion, and the temperature of the GO suspension liquid is preferably controlled to be lower than 30 ℃ during ultrasonic treatment; the volume ratio of alcohol to water in the alcohol-water mixed solvent can be 1-3:1, and the alcohol-water mixed solvent is preferably a mixed solvent of ethylene glycol and water.
Secondly, adding PEG, water-soluble manganese salt and an organic nitrogen source into the GO suspension, and adjusting the pH value of the obtained mixed solution to be alkaline; wherein, the volume content of PEG in the mixed solution is preferably 5-30%; the organic nitrogen source can be dicyandiamide, the mass ratio of the dicyandiamide to GO can be 5-10:1, the manganese salt can be manganese acetate, and the mass percentage of Mn relative to (GO+Mn) can be 5-30wt%; the pH of the mixed solution is preferably 8 to 12, more preferably 8 to 10.
Placing the mixed solution into a high-pressure reaction kettle, performing hydrothermal reaction, cooling, washing and drying to obtain a solid mixture of a nanometer manganese oxide precursor and nitrogen-doped rGO (N-rGO); wherein the temperature of the hydrothermal reaction can be 100-200 ℃ and the reaction time is 12-24 h.
And fourthly, performing heat treatment on the solid mixture for a preset time in an inert atmosphere at 800-1200 ℃ to obtain the nitrogen-doped rGO supported MnO nanoparticle catalyst. Preferably, the solid mixture is heat treated for 1 to 3 hours in a nitrogen atmosphere at a temperature of between 1000 and 1200 ℃ to obtain the MnO/N-rGO catalyst.
Because the manganese element in the manganese oxide is easy to exist stably in a low valence state under the high temperature condition, the nanometer manganese oxide gradually changes from MnO in a high valence state with the increase of the heat treatment temperature in the heat treatment process 2 Gradually converted into MnO of lower valence (order: mnO) 2 →Mn 2 O 3 →Mn 3 O 4 MnO) and during the transformation process the manganese oxide particles will recrystallize to form nuclei. Therefore, the principle is skillfully utilized in the invention, and the nano manganese oxide after being subjected to the hydrothermal treatment is subjected to the pretreatmentThe mixture of the precursor and the N-rGO is subjected to heat treatment at high temperature to obtain small-size MnO nanoparticles, the MnO nanoparticles are uniformly distributed on the surface of the N-rGO carrier, and the catalyst with the small-size MnO nanoparticles supported on the N-rGO carrier and obtained under the induction of the temperature has obvious ORR catalytic activity, so that a new design idea is provided for the design and preparation of non-noble metal catalysts in the fields of fuel cells and metal-air cells.
In particular, mnO nanoparticles having smaller size and higher purity can be obtained by heat treatment in a nitrogen atmosphere at 1000 to 1200 ℃, such as Mn at 1050 DEG C 3 O 4 The particles are all converted into MnO nano particles with the particle diameter of only 2-4 nm, the ORR catalytic activity is obviously improved, and the performance is equivalent to that of a commercial Pt/C catalyst.
Hereinafter, the present invention will be described in more detail with reference to specific examples and comparative examples.
EXAMPLE 1 preparation of MnO/N-rGO (10 wt% at 850 ℃ C.) catalyst
90mg of GO is dispersed in a mixed solvent of 20mL of glycol and 10mL of ultrapure water, and after 4 hours of ultrasound, 3mg/mL of GO suspension is obtained, and the temperature of the GO suspension is controlled to be lower than 30 ℃ in the ultrasound process.
Dropwise adding 10mL of PEG into the GO suspension, and stirring for 10min after the addition is finished; 45mg of manganese acetate tetrahydrate (namely, about 10wt% of Mn relative to GO+Mn) is weighed and dissolved in 10mL of ultrapure water, then added into GO suspension dropwise, and stirred for 10min; 500mg of DCDA (dicyandiamide) was weighed into 15mL of ultrapure water, and the DCDA solution was added dropwise to the GO suspension, followed by stirring for 10min. Among them, the order of addition of PEG, manganese acetate and DCDA may not be limited.
Dropwise adding 0.1mol/L NaOH solution into the mixed solution, regulating the pH value of the mixed solution to 8.5, stirring for 30min, transferring into a 100mL high-pressure reaction kettle, and reacting for 12h at 160 ℃; after the reaction is finished, cooling to room temperature, suction filtering, washing and freeze drying.
Putting the solid mixture of the nanometer manganese oxide precursor and N-rGO obtained by drying into a square corundum crucible, and N-rGO at 850 DEG C 2 Heat treatment for 3h under atmosphere to finally obtain MnO/N-rGO (10 wt% at 850 ℃).
EXAMPLE 2 preparation of MnO/N-rGO (10 wt% at 950 ℃ C.) catalyst
Example 1 of example 2 differs only in the temperature of the heat treatment. Specifically, in example 2, a solid mixture of a nano manganese oxide precursor and N-rGO obtained by drying was subjected to N at 950 DEG C 2 And carrying out heat treatment for 3 hours in the atmosphere to finally obtain the MnO/N-rGO (10 wt percent at 950 ℃).
EXAMPLE 3 preparation of MnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst
Example 1 of example 3 differs only in the temperature of the heat treatment. Specifically, in example 3, a solid mixture of a nano manganese oxide precursor and N-rGO obtained by drying was subjected to a reaction at 1050℃and N 2 And carrying out heat treatment for 3 hours in the atmosphere to finally obtain the MnO/N-rGO (10 wt% at 1050 ℃).
EXAMPLE 4 preparation of MnO/N-rGO (10 wt% at 1150 ℃ C.) catalyst
Example 4 differs from example 1 only in the temperature of the heat treatment. Specifically, in example 4, the solid mixture of the nano manganese oxide precursor and N-rGO obtained by drying was subjected to N at 1150 ℃ 2 And carrying out heat treatment for 3 hours in the atmosphere to finally obtain the MnO/N-rGO (10 wt% at 1150 ℃).
EXAMPLE 5 preparation of MnO/N-rGO (5 wt% at 1050 ℃ C.) catalyst
90mg of GO is dispersed in a mixed solvent of 20mL of glycol and 10mL of ultrapure water, and after 4 hours of ultrasound, 3mg/mL of GO suspension is obtained, and the temperature of the GO suspension is controlled to be lower than 30 ℃ in the ultrasound process.
Dropwise adding 10mL of PEG into the GO suspension, and stirring for 10min after the addition is finished; 21mg of manganese acetate tetrahydrate (namely, mn is about 5wt% relative to GO+Mn) is weighed and dissolved in 10mL of ultrapure water, then added into the mixed solution dropwise, and stirred for 10min; 500mg of DCDA was weighed and dissolved in 15mL of ultrapure water, and the DCDA solution was added dropwise to the GO suspension, followed by stirring for 10min.
Dropwise adding 0.1mol/L NaOH solution into the mixed solution, regulating the pH value of the mixed solution to 8.5, stirring for 30min, transferring into a 100mL high-pressure reaction kettle, and reacting for 12h at 160 ℃; after the reaction is finished, cooling to room temperature, suction filtering, washing and freeze drying.
Putting the solid mixture of the nanometer manganese oxide precursor and N-rGO obtained by drying into a square corundum crucible, and N-corundum crucible at 1050 DEG C 2 And carrying out heat treatment for 3 hours in the atmosphere to finally obtain the MnO/N-rGO (5 wt% at 1050 ℃).
That is, example 5 differs from example 3 only in the content of Mn in the catalyst.
EXAMPLE 6 preparation of MnO/N-rGO (1050 ℃ C. 15 wt%) catalyst
90mg of GO is dispersed in a mixed solvent of 20mL of glycol and 10mL of ultrapure water, and after 4 hours of ultrasound, 3mg/mL of GO suspension is obtained, and the temperature of the GO suspension is controlled to be lower than 30 ℃ in the ultrasound process.
Dropwise adding 10mL of PEG into the GO suspension, and stirring for 10min after the addition is finished; 71mg of manganese acetate tetrahydrate (namely, the mass percentage of Mn relative to GO+Mn is about 15 wt%) is weighed and dissolved in 10mL of ultrapure water, then added into the mixed solution dropwise, and stirred for 10min; 500mg of DCDA was weighed and dissolved in 15mL of ultrapure water, and the DCDA solution was added dropwise to the GO suspension, followed by stirring for 10min.
Dropwise adding 0.1mol/L NaOH solution into the mixed solution, regulating the pH value of the mixed solution to 8.5, stirring for 30min, transferring into a 100mL high-pressure reaction kettle, and reacting for 12h at 160 ℃; after the reaction is finished, cooling to room temperature, suction filtering, washing and freeze drying.
Putting the solid mixture of the nanometer manganese oxide precursor and N-rGO obtained by drying into a square corundum crucible, and N-corundum crucible at 1050 DEG C 2 And carrying out heat treatment for 3 hours in the atmosphere to finally obtain the MnO/N-rGO (15 wt% at 1050 ℃).
That is, example 6 differs from example 3 only in the content of Mn in the catalyst.
Comparative example 1 preparation of MnO/N-rGO (10 wt% PEG free) catalyst at 850 ℃ C
Comparative example 1 differs from example 1 only in that no PEG was added to the mixed solution of the hydrothermal reaction. Specifically, the preparation method of comparative example 1 is as follows:
90mg of GO is dispersed in a mixed solvent of 20mL of glycol and 10mL of ultrapure water, and after 4 hours of ultrasound, 3mg/mL of GO suspension is obtained, and the temperature of the GO suspension is controlled to be lower than 30 ℃ in the ultrasound process.
45mg of manganese acetate tetrahydrate is weighed and dissolved in 10mL of ultrapure water, then added into the GO suspension drop by drop, and stirred for 10min; 500mg of DCDA was weighed and dissolved in 15mL of ultrapure water, and the DCDA solution was added dropwise to the GO suspension, followed by stirring for 10min.
Dropwise adding 0.1mol/L NaOH solution into the mixed solution, regulating the pH value of the mixed solution to 8.5, stirring for 30min, transferring into a 100mL high-pressure reaction kettle, and reacting for 12h at 160 ℃; after the reaction is finished, cooling to room temperature, suction filtering, washing and freeze drying.
Putting the solid mixture of the nanometer manganese oxide precursor and N-rGO obtained by drying into a square corundum crucible, and N-rGO at 850 DEG C 2 And carrying out heat treatment for 3 hours in the atmosphere to finally obtain the MnO/N-rGO (10 wt% without PEG at 850 ℃).
Comparative example 2 preparation of MnO/N-rGO (10 wt% NaOH-free 850 ℃ C.) catalyst
Comparative example 2 differs from example 1 only in that the pH of the mixed solution was not adjusted. Specifically, the preparation method of comparative example 2 is as follows:
90mg of GO is dispersed in a mixed solvent of 20mL of glycol and 10mL of ultrapure water, and after 4 hours of ultrasound, 3mg/mL of GO suspension is obtained, and the temperature of the GO suspension is controlled to be lower than 30 ℃ in the ultrasound process.
Dropwise adding 10mL of PEG into the GO suspension, and stirring for 10min after the addition is finished; 45mg of manganese acetate tetrahydrate is weighed and dissolved in 10mL of ultrapure water, then added into the GO suspension drop by drop, and stirred for 10min; 500mg of DCDA was weighed and dissolved in 15mL of ultrapure water, and the DCDA solution was added dropwise to the GO suspension, followed by stirring for 10min.
Transferring the mixed solution into a 100mL high-pressure reaction kettle, and reacting for 12 hours at 160 ℃; after the reaction is finished, cooling to room temperature, suction filtering, washing and freeze drying.
Putting the solid mixture of the nanometer manganese oxide precursor and N-rGO obtained by drying into a square corundum crucible, and N-rGO at 850 DEG C 2 Heat treatment for 3h under atmosphere to finally obtain MnO/N-rGO (10 wt% of non-NaOH at 850 ℃) catalyst。
Morphology, structure and composition analysis of N-rGO carrier and MnO nano particles
FIG. 2a is an FE-SEM image of the MnO/N-rGO (10 wt% at 850 ℃) catalyst prepared in example 1, and FIG. 2b is a TEM image of the catalyst. As can be seen from fig. 2a, the N-rGO carrier has a good shape, is not agglomerated and curled, indicating that the multi-layer graphene is well exfoliated during ultrasonic dispersion. As can be seen from FIG. 2b, in the MnO/N-rGO (10 wt% at 850 ℃) catalyst prepared in example 1, the particle size of MnO nanoparticles is 15-35 nm, and the MnO nanoparticles are uniformly distributed on the surface of the N-rGO carrier, so that the catalyst has a larger specific surface area, and is beneficial to improving the catalytic performance.
FIG. 3a is an FE-SEM image of the MnO/N-rGO (10 wt% at 950 ℃ C.) catalyst prepared in example 2, and FIG. 3b is a TEM image of the catalyst. As can be seen from fig. 3a and 3b, example 2 has a substantially similar morphology and size as the catalyst prepared in example 1.
FIG. 4a is an FE-SEM image of the MnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst prepared in example 3, and FIGS. 4b and 4c are TEM images of the catalyst. As can be seen from fig. 4a and 4b, the N-rGO carrier has a good shape, is not agglomerated and curled, and illustrates that the multi-layer graphene is well exfoliated during ultrasonic dispersion. From fig. 4c, it can be seen that after recrystallization at 1050 ℃, the grain size of MnO particles becomes smaller, the average size is 2-4 nm, and the MnO particles are uniformly dispersed on the N-rGO carrier, which makes the catalyst have a larger specific surface area, and is beneficial to further improving catalytic performance. The (200) plane of the MnO can be determined from the lattice fringes of the particles in fig. 4 d.
FIG. 5 is an XRD pattern for the MnO/N-rGO (10 wt% at 850 ℃) catalyst prepared in example 1, the MnO/N-rGO (10 wt% at 950 ℃) catalyst prepared in example 2, and the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3. As can be seen from FIG. 5, the XRD pattern of the MnO/N-rGO (10 wt% at 850 ℃ C.) catalyst has a relatively remarkable Mn 3 O 4 Diffraction peaks (i.e., those indicated by arrows in FIG. 5) indicate that the catalyst also contains a certain amount of Mn 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the Mn in XRD pattern of MnO/N-rGO (10 wt% at 950 ℃ C.) catalyst 3 O 4 The diffraction peak is obviously weakened, namely Mn 3 O 4 The content of (2) is obviously reduced; mn in XRD pattern of MnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst 3 O 4 The diffraction peak disappeared and only the diffraction peak of MnO, indicating that the nano manganese oxide precursor was completely converted to MnO upon heat treatment at 1050 ℃. The leftmost peak in each catalyst profile is the diffraction peak of the N-rGO support.
Catalytic performance test
Test conditions: at O 2 Testing in saturated 0.1mol/L KOH solution by using a three-electrode system; wherein the reference electrode is an Ag/AgCl electrode, and the counter electrode is a platinum electrode. The potentials in FIGS. 6-8 and 11-12 are both scaled standard hydrogen electrode potentials.
FIG. 6 is a graph comparing Linear Sweep Voltammograms (LSV) of the MnO/N-rGO (10 wt% at 850 ℃) catalyst prepared in example 1, the MnO/N-rGO (10 wt% without PEG at 850 ℃) catalyst prepared in comparative example 1, and the MnO/N-rGO (10 wt% without NaOH at 850 ℃) catalyst prepared in comparative example 2. As can be seen visually in FIG. 6, the starting potential, half-wave potential and limiting current of the MnO/N-rGO (10 wt% at 850 ℃) catalyst were all higher than those of the MnO/N-rGO (10 wt% without PEG at 850 ℃) catalyst and the MnO/N-rGO (10 wt% without NaOH at 850 ℃). It is explained that adding PEG and adjusting the pH of the mixed solution to alkaline during the hydrothermal reaction can significantly improve the ORR performance of the catalyst, which is attributable to the addition of PEG, adjusting the pH of the mixed solution to alkaline, and nitrogen doping while the hydrothermal reaction is performed, which is advantageous for finally obtaining MnO nanoparticles with smaller particle size and uniform distribution.
FIG. 7 is a graph comparing the Linear Sweep Voltammograms (LSV) of the MnO/N-rGO (10 wt% at 950 ℃) catalyst prepared in example 2 with a commercial Pt/C catalyst. As can be seen from FIG. 7, the MnO/N-rGO (10 wt% at 950 ℃ C.) catalyst prepared in example 2 has a better half-wave potential (0.81V) and limiting current density (3.30 mA cm) -2 ) Half-wave potential (0.87V) and limiting current density (4.59 mA cm) with commercial Pt/C catalyst -2 ) There is a certain gap compared with the prior art.
FIG. 8 shows the MnO/N-rGO (10 wt% at 1050 ℃ C.) catalysts prepared in example 3 in N 2 And O 2 Comparison of electrochemical cyclic voltammograms (C-V) under saturated conditions is evident from FIG. 8It was seen that the MnO/N-rGO (1050 ℃ C. 10 wt.%) catalyst was relative to N 2 Saturated with O 2 The particularly pronounced reduction peak (0.7V vs RHE) in saturated atmosphere suggests that the MnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst has very good ORR performance.
FIG. 9 is a graph comparing the current curve (i-t) of the MnO/N-rGO (10wt% at 1050 ℃) catalyst prepared in example 3 with that of a commercial Pt/C catalyst, it can be seen very intuitively from FIG. 9 that the current of the commercial Pt/C catalyst decays 19.2% after 30000s of the test, whereas the MnO/N-rGO (10wt% at 1050 ℃) catalyst decays only 11.9%, which indicates that the MnO/N-rGO (10wt% at 1050 ℃) catalyst has better durability than the commercial Pt/C catalyst.
FIG. 10 is a graph comparing the chronoamperometric curves (i-t) of the methanol resistance test of the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared in example 3 with a commercial Pt/C catalyst, wherein the methanol was added at 200 seconds and the catalyst was tested for methanol crossover resistance. As can be seen from FIG. 10, the commercial Pt/C catalyst is particularly fast responding to methanol and immediately converts to methanol oxidation, whereas the MnO/N-rGO (10wt% at 1050 ℃) catalyst is essentially ineffective for methanol oxidation and very effective against methanol crossover effects.
FIG. 11 is a graph of Linear Sweep Voltammograms (LSV) comparisons for the MnO/N-rGO (10wt% at 1050 ℃) catalyst of example 3, the MnO/N-rGO (5wt% at 1050 ℃) catalyst of example 5, the MnO/N-rGO (15wt% at 1050 ℃) catalyst of example 6, and the commercial Pt/C catalyst; as can be seen from FIG. 11, the MnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst has excellent ORR catalytic activity, half-wave potential (0.83V) and limiting current density (4.31 mA cm) -2 ) Has approached the half-wave potential (0.87V) and limiting current density (4.59 mA cm) of commercial Pt/C catalyst -2 ) And is superior to the MnO/N-rGO (1050 ℃ C. 5 wt%) catalyst of example 5 and the MnO/N-rGO (1050 ℃ C. 15 wt%) catalyst of example 6. That is, among them, mnO/N-rGO (10 wt% at 1050 ℃ C.) catalyst has the best ORR activity. Moreover, the catalysts obtained according to the invention have excellent ORR properties from the point of view of the non-noble metal catalysts in comparison with Pt catalysts.
FIG. 12 shows the MnO/N-rGO (10 wt% at 1150 ℃ C.) catalyst prepared in example 4 with commercial PLinear Sweep Voltammogram (LSV) versus t/C catalyst; as can be seen from the figure, the MnO/N-rGO (10wt% at 1150 ℃ C.) catalyst prepared in example 4 also has a better half-wave potential (0.75V) and limiting current density (3.53 mA cm) -2 ) Half-wave potential (0.87V) and limiting current density (4.59 mA cm) with commercial Pt/C catalyst -2 ) There is a certain gap compared with the prior art.
The commercial Pt/C catalyst of the present invention as a comparative object was purchased from Johnson Matthey.
In summary, in the embodiment of the invention, nitrogen doping and reduction are performed on GO through hydrothermal reaction to obtain N-rGO, and nano manganese oxide precursor particles are loaded on the surface of N-rGO; and PEG and pH are added into the mixed solution of the hydrothermal reaction to control the size of nano manganese oxide precursor particles, and finally small-size MnO nano particles uniformly loaded on an N-rGO carrier are obtained through high-temperature heat treatment, and the MnO nano particles can be firmly combined with the carrier, so that the specific surface area of the catalyst and the synergistic effect of MnO and N-rGO are effectively improved, and the prepared nitrogen-doped rGO loaded nano particle catalyst has better durability and methanol cross effect than commercial Pt/C catalyst. Wherein the MnO/N-rGO (10 wt% at 1050 ℃) catalyst prepared under multiple excellent conditions has ORR catalytic activity close to that of commercial Pt/C catalyst.
While the invention has been described with reference to specific embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention.
Claims (9)
1. The preparation method of the nitrogen-doped rGO supported MnO nanoparticle catalyst for the ORR reaction comprises the following steps:
dispersing GO in an alcohol-water mixed solvent to obtain GO suspension;
secondly, adding PEG, water-soluble manganese salt and an organic nitrogen source into the GO suspension, and adjusting the pH value of the obtained mixed solution to be alkaline;
placing the mixed solution into a high-pressure reaction kettle, performing hydrothermal reaction, and then cooling, washing and drying to obtain a solid mixture of a nanometer manganese oxide precursor and nitrogen-doped rGO;
fourthly, performing heat treatment on the solid mixture for 1-3 hours in a nitrogen atmosphere at 1000-1200 ℃ to obtain a nitrogen-doped rGO supported MnO nanoparticle catalyst;
wherein, in the step III, the temperature of the hydrothermal reaction is controlled to be 100-200 ℃ and the reaction time is controlled to be 12-24 hours;
wherein the manganese salt is manganese acetate, and the organic nitrogen source is dicyandiamide.
2. The preparation method of claim 1, wherein the GO suspension is obtained by adding GO to an alcohol-water mixed solvent in a ratio of 0.5-5 mg/mL for ultrasonic dispersion.
3. The method of claim 2, wherein the temperature of the GO suspension is controlled to be less than 30 ℃ when sonicated.
4. The preparation method according to claim 1, wherein the volume ratio of the alcohol to the water in the alcohol-water mixed solvent is 1-3:1.
5. The preparation method according to claim 4, wherein the alcohol-water mixed solvent is a mixed solvent of ethylene glycol and water.
6. The preparation method according to claim 1, wherein the volume content of PEG in the mixed solution is controlled to be 5-30% in the step.
7. The production method according to claim 1, wherein the mass percentage of Mn relative to (GO+Mn) is controlled to be 5 to 30wt%.
8. The preparation method according to claim 1, wherein the pH of the resulting mixed solution is adjusted to 8 to 12 in the step.
9. The preparation method according to claim 8, wherein the pH of the resulting mixed solution is adjusted to 8 to 10 in the step.
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