CN112331863A - Non-noble metal oxygen reduction electrocatalyst W/N/C and preparation method thereof - Google Patents
Non-noble metal oxygen reduction electrocatalyst W/N/C and preparation method thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 17
- 239000001301 oxygen Substances 0.000 title claims abstract description 17
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 17
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- QNRATNLHPGXHMA-XZHTYLCXSA-N (r)-(6-ethoxyquinolin-4-yl)-[(2s,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]methanol;hydrochloride Chemical compound Cl.C([C@H]([C@H](C1)CC)C2)CN1[C@@H]2[C@H](O)C1=CC=NC2=CC=C(OCC)C=C21 QNRATNLHPGXHMA-XZHTYLCXSA-N 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 4
- IVHJCRXBQPGLOV-UHFFFAOYSA-N azanylidynetungsten Chemical compound [W]#N IVHJCRXBQPGLOV-UHFFFAOYSA-N 0.000 claims abstract description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 3
- 239000010937 tungsten Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 153
- 239000000243 solution Substances 0.000 claims description 64
- 238000010438 heat treatment Methods 0.000 claims description 47
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 claims description 38
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 38
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 24
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 18
- 239000007983 Tris buffer Substances 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- 239000012046 mixed solvent Substances 0.000 claims description 9
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 9
- 150000003657 tungsten Chemical class 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 238000003763 carbonization Methods 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
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- 229910052757 nitrogen Inorganic materials 0.000 abstract description 5
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- 239000002184 metal Substances 0.000 abstract description 3
- 238000005530 etching Methods 0.000 abstract description 2
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- 239000000463 material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 10
- 230000010287 polarization Effects 0.000 description 9
- 239000007853 buffer solution Substances 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 8
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 7
- 102000020897 Formins Human genes 0.000 description 7
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- 229910003091 WCl6 Inorganic materials 0.000 description 7
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 101000993059 Homo sapiens Hereditary hemochromatosis protein Proteins 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
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Images
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- 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
Abstract
A non-noble metal oxygen reduction electrocatalyst W/N/C and a preparation method thereof relate to the field of electrochemical catalytic materials, the non-noble metal oxygen reduction electrocatalyst W/N/C is tungsten-nitrogen co-doped porous carbon with a rhombic dodecahedron shape, the particle size of the catalyst is 100-200 nm, and the mass percentage of tungsten elements is 2% -5%. MOFs is adopted as a precursor, and a hollow carbon shell with a rhombic dodecahedron shape is prepared after pyrolysis through the etching effect of an alkali solution. The electrocatalyst has a micro-meso-large hierarchical pore channel structure, high nitrogen content and rich active sites (WN of porphyrin-like structure)xAnd WN metalxPhase) and has higher ORR catalytic activity and stability, and has important significance for improving key performances such as energy conversion efficiency, rate capability, cycle life and the like of metal-air batteries and fuel cells.
Description
Technical Field
The invention relates to the field of electrochemical catalytic materials, in particular to a non-noble metal electro-catalyst W/N/C for oxygen reduction and a preparation method thereof.
Background
The development of new energy systems is promoted by the increasing depletion and severe environmental problems of fossil energy. The metal-air battery and the fuel battery have the advantages of high energy conversion efficiency, high energy density, small environmental pollution and the like, have wide application prospects in the fields of portable power supplies, fixed power stations and the like, and have important scientific significance and practical value for future large-scale energy storage and mobile storage in relevant research. Both fuel cells and metal-air cells involve Oxygen Reduction Reactions (ORR) that require a catalyst in order to accelerate the inherently slow kinetics of the oxygen reduction reaction. Currently, the most widely used, most catalytically active ORR catalyst is the noble metal platinum (Pt) -based catalyst. However, the disadvantages of high price, low reserves, easy poisoning, etc. of Pt limit its large-scale commercialization. In order to solve the problems, the development of a non-noble metal catalyst with high activity, high stability and low price is significant for improving energy and environmental problems. The non-noble metal catalyst has the advantages of more abundant resources, low price, adjustable appearance, flexible components, controllable active sites and the like. Non-noble metal-nitrogen-carbon catalysts (M/N/C, M ═ Fe, Co, etc.) were found to have good ORR activity, with high Fe/N/C activity and low cost, considered as the best replacement for Pt-based catalysts. However, the existing research results show that the stability of the Fe/N/C catalyst is far from the stability of the commercial Pt/C catalyst, and the practical popularization is difficult.
It is reported in the literature that oxidative corrosion of carbon in Fe/N/C catalysts is one of the main causes of its performance decay. Hydrogen peroxide is inevitably generated in the ORR process, and the hydrogen peroxide is easy to generate Fenton reaction with Fe ions in the catalyst to generate strong oxidizing free radicals, so that the active center and the whole structure of the catalyst are seriously corroded. Therefore, the development of a high-activity, high-stability non-Fe-based M/N/C catalyst is of great importance.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a non-noble metal oxygen reduction electrocatalyst W/N/C and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a non-noble metal oxygen reduction electrocatalyst W/N/C is tungsten-nitrogen co-doped porous carbon with a rhombic dodecahedron shape, the particle size of the catalyst is 100-200 nm, and the mass percent of tungsten elements is 2% -5%.
The preparation method of the non-noble metal oxygen reduction electrocatalyst W/N/C comprises the following steps:
1) adding tungsten salt into a mixed solvent of an organic solvent and an alkali solution, performing ultrasonic dispersion, adding ZIF-8, stirring for a certain time, adding methanol, centrifuging, and drying to obtain a primary product;
2) carbonizing the dried primary product;
3) adding the carbonized product into NH3And (4) keeping the temperature for a certain time under the-Ar mixed atmosphere to obtain the non-noble metal oxygen reduction electrocatalyst W/N/C.
The mass ratio of the ZIF-8 to the tungsten salt to the organic solvent to the aqueous alkali is 1: 0.02-0.4: 157-240: 0.48-0.73.
The tungsten salt comprises tungsten hexachloride, ammonium paratungstate and phosphotungstic acid; the organic solvent comprises methanol, ethanol and isopropanol.
The alkali solution comprises a Tris (Tris) buffer solution, sodium hydroxide and potassium hydroxide, and the pH value of the alkali solution is 9-11.
The stirring time in the step 1) is 12-14 h.
The carbonization method in the step 2) is as follows: placing the dried product in a tube furnace, carrying out heat treatment under the protection of inert gas, and heating at the rate of 5-10 ℃ for min-1Heating to 800-950 ℃ and keeping the temperature for 3-5 h.
The method for keeping the temperature for a certain time in the step 3) comprises the following steps: heating rate of 10-15 deg.C for min-1Heating to 800-950 ℃ and keeping the temperature for 10-30 min.
The ZIF-8 is prepared by the following steps:
1) adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A;
2) dissolving 2-methylimidazole in methanol to prepare a solution B;
3) and pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 20-24 h, centrifuging at 8000rpm for 4min, washing with methanol, repeatedly centrifuging and washing for 2-3 times, and drying the obtained white product in a vacuum drying oven at 80 ℃ to obtain ZIF-8.
The Zn (NO)3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 8.5-9.5.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1. the W/N/C catalyst is synthesized by using the tungsten salt as a metal source and the ZIF-8 as a carbon source and a nitrogen source, has high ORR catalytic activity and stability, and has important significance for improving the key performances such as energy conversion efficiency, rate capability, cycle life and the like of a metal-air battery and a fuel cell;
2. the W/N/C electrocatalyst adopts ZIF-8 as a precursor, and has the advantages of controllable morphology, pore structure and active sites; the porous nitrogen-rich carbon material is formed after calcination, the content of nitrogen in the carbon material is rich, the electronegativity of N is strong, electrons on C atoms in the carbon material are transferred to the N atoms, the positive charges of the carbon atoms are increased, and the carbon material shows good electropositivity, so that the adsorption capacity of the catalyst on oxygen atoms in the oxygen reduction reaction process is promoted, and the forward proceeding of the reaction is promoted;
3. by the etching action of the alkali solution, the electrocatalyst has a micro-meso-large hierarchical pore channel structure, high nitrogen content and rich active sites (WN of porphyrin-like structure)xAnd WN metalxPhase) advantage of concerted catalysis;
4. the catalyst has higher activity when being applied to oxygen reduction reaction under alkaline condition, wherein the half-wave potential reaches 0.914V and the half-wave potential reaches 0.9VThe mass activity reaches 6.54Ag-1The Tafel slope is 56mV dec-1(ii) a In the durability experiment, after 5000 circles of circulation, half-wave is only attenuated by 13mV, and after 10000 circles of circulation, half-wave is attenuated by 18mV, so that the stability is more excellent compared with commercial Pt/C;
5. the preparation method is simple and easy to implement, low in cost and suitable for mass production.
Drawings
FIG. 1 shows the results of the catalysts obtained in examples 1 to 7 and comparative example 1 at 10mV s-1Recording Linear Sweep Voltammetry (LSV) in a saturated 0.1M KOH solution at a scanning rate to obtain a polarization curve;
FIG. 2 shows the potential range of 0.6-1.0V and sweep rate of 50mV s for the catalyst obtained in example 1-1After 5000 and 10000 turns of rotation speed of 1600rpm scanning, recording Linear Sweep Voltammetry (LSV) in saturated 0.1M KOH solution to obtain a polarization curve;
FIG. 3 shows the potential range of 0.6 to 1.0V and sweep rate of 50mV s for the catalyst obtained in comparative example 1-1After 5000 and 10000 turns of rotation speed of 1600rpm scanning, recording Linear Sweep Voltammetry (LSV) in saturated 0.1M KOH solution to obtain a polarization curve;
FIG. 4 is a Scanning Electron Microscope (SEM) image of the catalyst obtained in example 1;
FIG. 5 is a Transmission Electron Microscope (TEM) image of the catalyst obtained in example 1.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects of the present invention clearer and clearer, the present invention is further described in detail below with reference to the accompanying drawings and embodiments.
Example 1
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:9.0: 184. Pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 22h, centrifuging at 8000rpm for 4min, washing with methanol, and repeatedly centrifuging and washing for 2-3 times to obtain white productAnd (4) drying the mixture in a vacuum drying oven at the temperature of 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 13 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.04:157: 0.48. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 5 deg.C for min-1Raising the temperature to 950 ℃ and keeping the temperature for 3 hours. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 15 deg.C for min under-Ar mixed atmosphere-1Heating to 950 ℃ and keeping the temperature for 15min to obtain the W/N/C catalyst.
Example 2
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:8.5: 137. And pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 20h, centrifuging at 8000rpm for 4min, washing with methanol, repeating centrifugation-washing for 2-3 times, and drying the obtained white product in a vacuum drying oven at 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 12 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.02:157: 0.48. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 5 deg.C for min-1Heating to 950 deg.C and keeping the temperatureThe time is 3 h. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 15 deg.C for min under-Ar mixed atmosphere-1Heating to 950 ℃ and keeping the temperature for 15min to obtain the W/N/C catalyst.
Example 3
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:9.5: 230. And pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 24h, centrifuging at 8000rpm for 4min, washing with methanol, repeating centrifugation-washing for 2-3 times, and drying the obtained white product in a vacuum drying oven at 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 14 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.4:240: 0.73. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 10 deg.C for min-1Raising the temperature to 950 ℃ and keeping the temperature for 5 hours. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 10 deg.C for min under-Ar mixed atmosphere-1Heating to 950 ℃ and keeping the temperature for 15min to obtain the W/N/C catalyst 3.
Example 4
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:9.0: 184. Pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 20h, centrifuging at 8000rpm for 4min, washing with methanol, and repeatedly centrifuging and washing for 2-3 times to obtain the final productAnd drying the obtained white product in a vacuum drying oven at the temperature of 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 13 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.04:157: 0.48. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 5 deg.C for min-1Raising the temperature to 900 ℃ and preserving the temperature for 3 h. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 15 deg.C for min under-Ar mixed atmosphere-1Heating to 900 ℃ and keeping the temperature for 15min to obtain the W/N/C catalyst.
Example 5
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:9.0: 184. And pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 24h, centrifuging at 8000rpm for 4min, washing with methanol, repeating centrifugation-washing for 2-3 times, and drying the obtained white product in a vacuum drying oven at 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 13 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.04:157: 0.48. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 5 deg.C for min-1Heating to 800 deg.C and holding for 3 h. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 10 deg.C for min under-Ar mixed atmosphere-1Heating to 800 ℃ and keeping the temperature for 30min to obtain the W/N/C catalyst.
Example 6
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2And dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:9.0: 184. And pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 24h, centrifuging at 8000rpm for 4min, washing with methanol, repeating centrifugation-washing for 2-3 times, and drying the obtained white product in a vacuum drying oven at 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 13 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.04:157: 0.48. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 10 deg.C for min-1Raising the temperature to 950 ℃ and keeping the temperature for 4 hours. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 15 deg.C for min under-Ar mixed atmosphere-1Heating to 950 ℃ and keeping the temperature for 10min to obtain the W/N/C catalyst.
Example 7
(1) Preparing ZIF-8: adding Zn (NO)3)2·6H2And dissolving O in methanol to prepare solution A. Dissolving 2-methylimidazole in methanol to obtain solution B containing Zn (NO)3)2·6H2The molar ratio of O, 2-methylimidazole and methanol is 1:9.0: 184. Pouring the solution B into the solution A, carrying out ultrasonic treatment for 2min, standing for 24h, centrifuging at 8000rpm for 4min, washing with methanol, and repeatedly centrifuging and washing for 2-3 timesAnd secondly, drying the obtained white product in a vacuum drying oven at the temperature of 80 ℃ to obtain ZIF-8.
(2) Preparation of W/N/C catalyst: WCl is added into a mixed solvent of ethanol and Tris (Tris (hydroxymethyl aminomethane)) buffer solution with the volume ratio of 1:16And adding ZIF-8 after ultrasonic dispersion, and magnetically stirring for 13 hours after ultrasonic treatment for 30 min. ZIF-8, WCl6Ethanol and tris (hydroxymethyl) aminomethane in a mass ratio of 1:0.04:157: 0.48. Methanol (v/v, methanol: solution 1:10) was added to the solution obtained after stirring, centrifuged at 8000rpm for 4min, and the product was dried in a vacuum oven at 80 ℃. Placing the dried product in a tube furnace, performing heat treatment under the protection of inert gas, and heating at a heating rate of 5 deg.C for min-1Raising the temperature to 950 ℃ and keeping the temperature for 3 hours. Finally, the carbonized product is placed in a tube furnace in NH3Heating rate of 15 deg.C for min under-Ar mixed atmosphere-1Heating to 950 ℃ and keeping the temperature for 30min to obtain the W/N/C catalyst.
The electrochemical performance test steps of the electrocatalyst prepared in the embodiments 1 to 7 are as follows:
(1) 4mg of the sample was dispersed in a mixed solution containing 600. mu.L of ethanol, 370. mu.L of ultrapure water and 30. mu.L of 5% Nafion solution, and sonicated for 1 hour to form a uniform slurry.
(2) 20ul of the slurry is loaded on a glassy carbon electrode with the diameter of 5mm to serve as a working electrode, electrocatalysis data are tested by adopting a three-electrode system, and a graphite rod and an Hg/HgO electrode are respectively a counter electrode and a reference electrode.
(3) Potential reference Reversible Hydrogen Electrode (RHE): ERHE＝EHg/HgO+0.098+0.059×pH(0.1M KOH)。
(4) ORR Performance test O at 30 ℃2/N2In saturated 0.1M KOH solution, with a catalyst loading of 400. mu.g cm-2The polarization curve test conditions are as follows: the potential range is 0.2-1.0V, and the sweep rate is 10mV s-11600rpm, iR compensation of 85%. The ORR polarization curves of the catalysts obtained in examples 1 to 7 are shown in FIG. 1.
The test conditions for durability of the catalyst prepared in example 1 were: the potential range is 0.6-1.0V, and the sweeping speed is 50mV s-1Rotational speed of the motor1600rpm, 5000 and 10000 cycles, and ORR polarization curve as shown in FIG. 2.
Morphology characterization of the catalyst prepared in example 1:
(1) a certain amount of the catalyst prepared in example 1 was weighed and tested for morphology by a Scanning Electron Microscope (SEM), as shown in FIG. 4, the catalyst was a rhombic dodecahedron and had a particle size of about 100 to 200 nm.
(2) Weighing a certain amount of the catalyst prepared in example 1, and testing the morphology and structural characteristics of the catalyst by a Transmission Electron Microscope (TEM), the catalyst shown in FIG. 5 contains abundant pore structures.
The morphology and structure characteristics of the catalyst prepared in the embodiments 2 to 7 of the invention are not much different from those of the catalyst 1.
Comparative example 1
The comparative example used in the present invention is a commercial Pt/C20% catalyst.
Comparative example 1 Pt/C20% catalyst electrochemical performance test:
(1) 2mg of the sample was dispersed in a mixed solution containing 600. mu.L of ethanol, 370. mu.L of ultrapure water and 30. mu.L of 5% Nafion solution, and sonicated for 1 hour to form a uniform slurry.
(2) 10ul of slurry is loaded on a glassy carbon electrode with the diameter of 5mm to serve as a working electrode, electrocatalysis data are tested by adopting a three-electrode system, and a graphite rod and an Hg/HgO electrode are respectively a counter electrode and a reference electrode.
(3) Potential reference Reversible Hydrogen Electrode (RHE): ERHE＝EHg/HgO+0.098+0.059×pH(0.1M KOH)。
(4) ORR test O at 30 ℃2/N2In saturated 0.1M KOH solution, with a catalyst loading of 200. mu.g cm-2The polarization curve test conditions are as follows: the potential range is 0.2-1.0V, and the sweep rate is 10mV s-11600rpm, iR compensation of 85%. The ORR polarization curve of comparative example 1 is shown in FIG. 1.
(5) Comparative example 1 the durability test conditions of the catalyst were: the potential range is 0.6-1.0V, and the sweeping speed is 50mV s-11600rpm, and 5000 and 10000 cycles of cycle. The ORR polarization curve is shown in fig. 3.
Claims (10)
1. A non-noble metal oxygen reduction electrocatalyst W/N/C is characterized in that: the non-noble metal oxygen reduction electrocatalyst W/N/C is tungsten-nitrogen co-doped porous carbon with a rhombic dodecahedron shape, the particle size of the catalyst is 100-200 nm, and the mass percentage of tungsten element is 2% -5%.
2. A method of making a non-noble metal oxygen reduction electrocatalyst W/N/C as claimed in claim 1, comprising the steps of:
1) adding tungsten salt into a mixed solvent of an organic solvent and an alkali solution, performing ultrasonic dispersion, adding ZIF-8, stirring for a certain time, adding methanol, centrifuging, and drying to obtain a primary product;
2) carbonizing the dried primary product;
3) adding the carbonized product into NH3And (4) keeping the temperature for a certain time under the-Ar mixed atmosphere to obtain the non-noble metal oxygen reduction electrocatalyst W/N/C.
3. The method of claim 2, wherein: the mass ratio of the ZIF-8 to the tungsten salt to the organic solvent to the aqueous alkali is 1: 0.02-0.4: 157-240: 0.48-0.73.
4. The method of claim 2, wherein: the tungsten salt comprises tungsten hexachloride, ammonium paratungstate and phosphotungstic acid; the organic solvent comprises methanol, ethanol and isopropanol.
5. The method of claim 2, wherein: the alkaline solution comprises a Tris buffer solution, sodium hydroxide and potassium hydroxide, and the pH value of the alkaline solution is 9-11.
6. The method according to claim 2, wherein the stirring time in step 1) is 12 to 14 hours.
7. The method of claim 2, wherein the method comprisesCharacterized in that the carbonization method in the step 2) is as follows: placing the dried product in a tube furnace, carrying out heat treatment under the protection of inert gas, and heating at the rate of 5-10 ℃ for min-1Heating to 800-950 ℃ and keeping the temperature for 3-5 h.
8. The method according to claim 2, wherein the step 3) of maintaining the mixture at a high temperature for a certain period of time comprises the following steps: heating rate of 10-15 deg.C for min-1Heating to 800-950 ℃ and keeping the temperature for 10-30 min.
9. The method of claim 2, wherein said ZIF-8 is prepared by the steps of:
1) adding Zn (NO)3)2·6H2Dissolving O in methanol to prepare solution A;
2) dissolving 2-methylimidazole in methanol to prepare a solution B;
3) and pouring the solution B into the solution A, standing after ultrasonic treatment, centrifuging and washing for multiple times, and drying the obtained product to obtain the ZIF-8.
10. The method of claim 9, wherein: the Zn (NO)3)2·6H2The molar ratio of O to 2-methylimidazole is 1: 8.5-9.5.
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