CN113285083A - Non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon and preparation method and application thereof - Google Patents
Non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon and preparation method and application thereof Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 70
- 239000001301 oxygen Substances 0.000 title claims abstract description 70
- 230000009467 reduction Effects 0.000 title claims abstract description 65
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 64
- YYXHRUSBEPGBCD-UHFFFAOYSA-N azanylidyneiron Chemical compound [N].[Fe] YYXHRUSBEPGBCD-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 51
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 67
- 238000001035 drying Methods 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims abstract description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000005303 weighing Methods 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 15
- 229930006000 Sucrose Natural products 0.000 claims abstract description 15
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 15
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 14
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001451 polypropylene glycol Polymers 0.000 claims abstract description 11
- 239000005720 sucrose Substances 0.000 claims abstract description 11
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 9
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000004132 cross linking Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000000446 fuel Substances 0.000 claims description 16
- 229960004793 sucrose Drugs 0.000 claims description 14
- 238000005530 etching Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 7
- 238000003763 carbonization Methods 0.000 claims description 5
- 238000009656 pre-carbonization Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 6
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 21
- 238000012360 testing method Methods 0.000 description 17
- 239000007787 solid Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229920000557 Nafion® Polymers 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000008151 electrolyte solution Substances 0.000 description 3
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- H01M4/96—Carbon-based electrodes
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
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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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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Abstract
The invention relates to a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon and a preparation method and application thereof, deionized water is used as a solvent, sucrose, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer and tetraethyl orthosilicate are used as solutes, concentrated hydrochloric acid is added as a catalyst at the same time, crosslinking the poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, fully reacting, filtering, drying to obtain a mixture, and weighing a certain amount of the mixture in deionized water, adding a proper amount of concentrated sulfuric acid, ferric nitrate nonahydrate and urea, fully stirring, drying, roasting in a nitrogen atmosphere, and removing silicon dioxide by using a hydrofluoric acid solution to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst. Compared with the prior art, the invention has the advantages of cheap and easily obtained raw materials, simple preparation method and little environmental pollution, and the prepared electrocatalyst has better oxygen reduction catalytic performance.
Description
Technical Field
The invention relates to an electrochemical energy technology and the related technical field thereof, in particular to a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon and a preparation method and application thereof.
Background
Fuel cells are used as a clean energy conversion system to convert the chemical energy of a fuel into electrical energy. The heat engine is limited to about 20% conversion efficiency by the carnot cycle, whereas the fuel cell is not limited by the carnot cycle, with energy conversion approaching 100%. Therefore, theoretically, the fuel cell can always output electric energy to the outside as long as the fuel cell is supplied with fuel from the outside without interruption. In recent years, the shipment of fuel cells has been increasing rapidly, for example, in 2018 the shipment of fuel cells is approaching 7 million stations (800 megawatts), with a corresponding total revenue approaching $ 23 million. Currently, fuel cells, such as Proton Exchange Membrane Fuel Cells (PEMFCs), are dominant in the market. However, what is needed is a fuel cell cathode catalyst. Of all the oxygen reduction catalysts, the platinum group catalyst is generally considered to be the best due to its characteristics of large current density, four electron transfer process in the reaction, and the like. However, the platinum-based catalyst is scarce in source and expensive, and is easily poisoned and deactivated by carbon monoxide, methanol and other substances, which is the biggest obstacle to the commercial application of the fuel cell. Therefore, the oxygen reduction electrode catalyst with high catalytic activity is developed, and has wide prospects in scientific research and practical production and application.
In recent years, in order to reduce the overpotential of oxygen reduction catalysts and simultaneously reduce the cost of the catalysts, research and research have been continued, and substitution for platinum-based catalysts, such as metal-free catalysts or non-noble metal catalysts, has been desired.
Disclosure of Invention
The invention aims to provide a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon, and a preparation method and application thereof.
The purpose of the invention can be realized by the following technical scheme: a process for preparing Fe-N codoped mesoporous carbon non-noble metal oxygen reduction electrocatalyst includes dissolving deionized water as solvent, cane sugar, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer and tetraethyl orthosilicate as solute in deionized water, adding concentrated hydrochloric acid as catalyst, crosslinking the poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, fully reacting, filtering, drying to obtain a mixture, and weighing a certain amount of the mixture in deionized water, adding a proper amount of concentrated sulfuric acid, ferric nitrate nonahydrate and urea, fully stirring, drying, roasting in a nitrogen atmosphere, and removing silicon dioxide by using hydrofluoric acid solution to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst.
At present, various metal and nitrogen co-doped carbon materials are applied to oxygen reduction catalysts, and the metal generally comprises iron, cobalt, nickel, copper or manganese and the like. The iron-nitrogen co-doped catalyst carbon material has good oxygen reduction performance in an alkaline medium, and the performance of the iron-nitrogen co-doped catalyst carbon material can be comparable to or even superior to that of a platinum-based catalyst.
In the invention, deionized water is used as a solvent, cheap and easily available cane sugar is used as a carbon source, a poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer (P123) is used as a carbon precursor, tetraethyl orthosilicate (TEOS) is used as a pore-forming agent, and concentrated hydrochloric acid is added as a catalyst to crosslink the P123. The cane sugar and other raw materials used in the invention have low price, the preparation process and the production method are relatively simple, and the large-scale production is easy.
Further, the preparation method specifically comprises the following steps:
(1) firstly, adding cheap and easily-obtained sucrose and poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer serving as a carbon source into deionized water, then dropwise adding concentrated hydrochloric acid with the mass fraction of 37% while stirring, finally weighing tetraethyl orthosilicate, adding the tetraethyl orthosilicate, and fully stirring at 40-50 ℃;
(2) heating to 90-110 ℃ after 22-26 h, reacting for 22-26 h, stopping heating, and performing suction filtration and drying to obtain a mixture;
(3) weighing the mixture obtained in the step (2), adding the mixture into deionized water, then dropwise adding a certain amount of concentrated sulfuric acid with the mass fraction of 98%, stirring, then adding urea and ferric nitrate nonahydrate, stirring at room temperature for 10-14 hours, and drying at 70-90 ℃;
(4) and (3) heating the product obtained in the step (3) to 150-170 ℃ in a nitrogen atmosphere for pre-carbonization, then heating to 750-850 ℃ for carbonization, and finally etching silicon in the carbonized product by using a hydrofluoric acid solution to form hollow holes so as to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst.
Preferably, the mass ratio of the sucrose, the poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, the tetraethyl orthosilicate and the deionized water in the step (1) is 1:1: 2.1-2.3: 10. Namely, under the condition of a certain proportion of other raw materials, the performance of the catalyst can be controlled by changing the amount of the tetraethyl orthosilicate added to control the pores after carbonization.
Preferably, the mass ratio of the deionized water to the concentrated hydrochloric acid in the step (1) is 1: 1.1-1.3, so that the acid concentration of the total solution is 5.5-6.5 mol/L.
Preferably, the mass ratio of the mixture added in the step (3), urea and ferric nitrate nonahydrate is 1:1: 0.008-0.015. In the invention, when the addition amount of the iron nitrate nonahydrate is in the range, the oxygen reduction catalyst can show the oxygen reduction performance superior to that of the catalyst without the addition of the iron nitrate nonahydrate, which shows that the content of the added iron nitrate nonahydrate has a large influence on the performance of the catalyst.
Preferably, the mass ratio of the mixture added in the step (3), concentrated sulfuric acid and deionized water is 1: 1.8-1.9: 20.
Preferably, the pre-carbonization time in the step (4) is 50-70 min, and the carbonization time is 100-140 min.
Preferably, the mass concentration of the hydrofluoric acid solution in the step (4) is 5-20%, and the etching stirring time is 6-12 hours.
A non-noble metal oxygen reduction electrocatalyst of iron and nitrogen co-doped mesoporous carbon is prepared by adopting the preparation method.
The application of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst is used for fuel cell cathode oxygen reduction.
Compared with the prior art, the invention has the following advantages:
1. the preparation process and the production method are simple: stirring by a simple one-pot method to obtain an intermediate, then stirring and drying by the one-pot method, calcining, and removing silicon dioxide to obtain iron-nitrogen co-doped mesoporous carbon;
2. the sucrose and other raw materials used in the invention are cheap and commercialized, and the preparation process and the production method are relatively simple and easy for large-scale production;
3. the catalyst prepared by the invention has excellent oxygen reduction activity of the cathode of the fuel cell under alkaline conditions, and has better long-time tolerance and methanol tolerance than commercial Pt \ C;
4. the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst prepared by the invention has an obvious oxygen reduction peak, the half-wave potential is more correct than that of a commercial Pt/C catalyst, the preparation cost is low, and the stability and methanol tolerance are good;
5. the catalyst can replace a platinum-based catalyst, avoids the problems that the platinum-based catalyst is scarce in source, expensive in price, easy to be poisoned and inactivated by substances such as carbon monoxide, methanol and the like, has wide prospect in scientific research and practical production application, and is beneficial to the commercial application of fuel cells;
6. the raw materials are cheap and easy to obtain, the preparation process and the production method are relatively simple, the environmental pollution is small, and the prepared iron-nitrogen co-doped mesoporous carbon electrocatalyst has good oxygen reduction catalytic performance.
Drawings
FIG. 1 is a cyclic voltammetry curve of a non-noble metal oxygen reduction electrocatalyst for preparing iron-nitrogen co-doped mesoporous carbon according to embodiment 3 of the present invention;
FIG. 2 is a scanning electron microscope image of a non-noble metal oxygen reduction electrocatalyst for iron-nitrogen co-doped mesoporous carbon prepared in embodiment 3 of the present invention;
FIG. 3 is a nitrogen adsorption diagram of a non-noble metal oxygen reduction electrocatalyst for iron-nitrogen co-doped mesoporous carbon prepared in example 3 of the present invention;
FIG. 4 is an X-ray photoelectron spectroscopy analysis chart of a non-noble metal oxygen reduction electrocatalyst for preparing iron-nitrogen co-doped mesoporous carbon according to embodiment 3 of the present invention;
FIG. 5 is a graph of the timing current curve of a non-noble metal oxygen reduction electrocatalyst with Fe-N co-doped mesoporous carbon prepared in example 3 of the present invention, which is the current density loss percentage of the Fe-N co-doped mesoporous carbon catalyst and commercial Pt-C after 10000s at a constant voltage of-0.35V and a rotation speed of 1600 rpm;
FIG. 6 is a graph of methanol tolerance of a non-noble metal oxygen reduction electrocatalyst with iron and nitrogen co-doped mesoporous carbon prepared in example 3 of the present invention, which is measured by the percentage loss of current density of the iron and nitrogen co-doped mesoporous carbon catalyst and commercial platinum carbon after 1000s at a constant voltage of-0.35V and a rotation speed of 1600 rpm;
FIG. 7 is a cyclic voltammogram of non-noble metal oxygen reduction electrocatalysts prepared from Fe-N co-doped mesoporous carbon in examples 1-5 of the present invention;
fig. 8 is a graph comparing the linear sweep voltammograms of non-noble metal oxygen reduction electrocatalysts prepared from iron-nitrogen co-doped mesoporous carbon in examples 1-5 with commercial platinum carbon at 1600 rpm.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The following examples are carried out on the premise of the technical scheme of the invention, and detailed embodiments and specific operation processes are given, but the scope of the invention is not limited to the following examples.
The methods described in the examples of the present invention are conventional methods unless otherwise specified. The raw materials can be purchased from publicly available commercial sources unless otherwise specified.
The model of the instrument or equipment used in the embodiment of the invention and the information of the manufacturer are as follows:
air-blast drying oven, model DHG-9920A, manufacturer: Shanghai-Hengchang scientific instruments, Inc.;
scanning Electron Microscope (SEM), model Phenom Pro X, manufacturer usa;
x-ray photoelectron spectrometer, model: AXIS UltraDLD, manufacturer: shimadzu, Japan;
electrochemical workstation, model: manufacturer of Autolab PGSTAT 302N: wantong Switzerland.
In the specific embodiment of the invention, the cyclic voltammetry curve of the prepared catalyst is tested in an Autolab PGSTAT302N electrochemical workstation, and the specific operating conditions are as follows: the test system is a three-electrode system, wherein the counter electrode is a platinum wire electrode, the working electrode is a glassy carbon electrode loaded with a sample catalyst, the reference electrode is a silver/silver chloride electrode, and the scanning test speed is 10 mV/s; the procedure for preparing the working electrode supporting the sample catalyst was as follows: dissolving 1mg of sample catalyst in a mixed solution of 200. mu.L of a hydroalcoholic solution (the volume ratio of the hydroalcoholic solution is 4: 1) and 10. mu.L of Nafion (5% solution purchased from Sigma-Aldrich platform), performing ultrasonic dissolution, dropwise adding 12. mu.L of the mixed solution of the sample catalyst to a working electrode for three times, and drying at30 ℃. When the cyclic voltammetry curve of the sample catalyst is tested, N is respectively introduced into 0.1M KOH solution2And O2Used for creating an inert gas atmosphere and an oxygen test gas atmosphere. Before the cyclic voltammogram was tested, the working electrode loaded with the sample catalyst was cycled 15 times in a 0.1M KOH solution under nitrogen to activate the electrode, and then the cyclic voltammogram test was performed again.
In the specific embodiment of the present invention, the linear sweep voltammetry of the sample is tested in an Autolab PGSTAT302N electrochemical workstation, and the specific operating conditions are as follows: the test system isA three-electrode system, wherein 0.1M KOH solution is electrolyte solution, a reference electrode is a silver/silver chloride electrode, a counter electrode is a platinum sheet electrode, a working electrode is a rotating disc working electrode loaded with a sample catalyst, and the scanning test speed is 10 mV/s; the procedure for preparing the sample catalyst-loaded rotating disk working electrode was as follows: dissolving 1mg of sample catalyst in a mixed solution of 200 mu L of hydroalcoholic solution (the volume ratio of the hydroalcoholic solution is 4: 1) and 10 mu L of Nafion (5% solution purchased from Sigma-Aldrich platform), performing ultrasonic dissolution, dropwise adding 12 mu L of the mixed solution of the sample catalyst on a rotating disc working electrode for three times, and drying at the temperature of 30 ℃ to obtain the catalyst. Before testing linear sweep voltammetry, N is respectively introduced into 0.1M KOH solution2And O2An inert gas atmosphere and an oxygen test gas atmosphere are formed. The rotating disk working electrode loaded with the sample catalyst was cycled 15 times in 0.1M KOH solution to activate the electrode before testing the linear cyclic voltammogram. When tested under oxygen conditions, the sample catalysts were tested for linear sweep voltammograms at different rotational speeds (400-.
In the specific embodiment of the invention, the prepared sample timing current curve is tested in an Autolab PGSTAT302N electrochemical workstation, and the specific operating conditions are as follows: the test system is a three-electrode system, wherein 0.1M KOH is an electrolyte solution, a reference electrode is a silver/silver chloride electrode, a counter electrode is a platinum sheet electrode, a working electrode is a rotating disc working electrode loaded with a sample catalyst, and the scanning test speed is 10 mV/s; the preparation process of the rotating disc working electrode loaded with the sample catalyst is as follows: dissolving 1mg of sample catalyst in a mixed solution of 200 mu L of hydroalcoholic solution (the volume ratio of the hydroalcoholic solution is 4: 1) and 10 mu L of Nafion (5% solution purchased from Sigma-Aldrich platform), performing ultrasonic dissolution, dropwise adding 12 mu L of the mixed solution of the sample catalyst on a rotating disc working electrode for three times, and drying at the temperature of 30 ℃ to obtain the catalyst. The test conditions for the chronoamperometric curve were: and testing the change of the current of the sample catalyst along with the test time within 10000s at a constant voltage of-0.35V and a rotating speed of 1600 rpm.
In the specific embodiment of the invention, the prepared methanol tolerance curve of the catalyst is tested in an Autolab PGSTAT302N electrochemical workstation, and the specific operating conditions are as follows: the test system is a three-electrode system, wherein 0.1M KOH is an electrolyte solution, a reference electrode is a silver/silver chloride electrode, a counter electrode is a platinum sheet electrode, a working electrode is a rotating disc working electrode loaded with a sample catalyst, and the scanning test speed is 10 mV/s; the procedure for preparing the sample catalyst-loaded rotating disk working electrode was as follows: dissolving 1mg of sample catalyst in a mixed solution of 200 mu L of hydroalcoholic solution (the volume ratio of the hydroalcoholic solution is 4: 1) and 10 mu L of Nafion (5% solution purchased from Sigma-Aldrich platform), performing ultrasonic dissolution, dropwise adding 12 mu L of the mixed solution of the sample catalyst on a rotating disc working electrode for three times, and drying at the temperature of 30 ℃ to obtain the catalyst. The test conditions for the methanol tolerance curve were: the sample catalyst was tested for 1000s at a constant voltage of-0.35V and a rotational speed of 1600rpm for the change in current and time as methanol was added.
Example 1
A preparation method of a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon comprises the steps of firstly adding 4g of sucrose and 40mL of P1234 g into deionized water, then dropwise adding 40mL of 37% HCl in stirring, finally weighing about 9g of TEOS, and reacting by magnetic stirring at 45 ℃. Heating to 100 ℃ after 24h, stopping heating after 24h, and performing suction filtration and drying to obtain a mixed solid. Weighing 1g of mixed solid, adding the mixed solid into 20mL of deionized water, then dropwise adding 1mL of 98% sulfuric acid, stirring for 10 minutes, then adding 1g of urea, stirring for 12 hours at room temperature, drying at 80 ℃, and drying in a nitrogen atmosphere. It was heated to 160 ℃ at a rate of 2 ℃/min for 1 hour under a nitrogen atmosphere and then to 800 ℃ at the same rate for 2 hours. And finally, etching by using 10% of HF by mass to remove silicon dioxide. Vacuum drying for 6 hours at 50 ℃ to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst. As can be seen from FIG. 7, the Fe-N co-doped mesoporous carbon of this case has a distinct oxygen reduction peak at-0.173V. As can be seen from FIG. 8, the initial potentials of the iron-nitrogen co-doped mesoporous carbon and the commercial Pt/C in the case are-0.046V and 0.012V respectively, which are only 0.034V different from the commercial Pt/C, and the half-wave potentials are-0.155V and-0.166V respectively, which are 0.011V more than the commercial Pt/C, which indicates that the catalyst has certain oxygen reduction performance.
Example 2
A preparation method of a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon comprises the steps of firstly adding 4g of sucrose and 40mL of P1234 g into deionized water, then dropwise adding 40mL of 37% HCl in stirring, finally weighing about 9g of TEOS, and reacting by magnetic stirring at 45 ℃. Heating to 100 ℃ after 24h, stopping heating after 24h, and performing suction filtration and drying to obtain a mixed solid. Weighing 1g of mixed solid, adding the mixed solid into 20mL of deionized water, then dropwise adding 1mL of 98% sulfuric acid, stirring for 10 minutes, then adding 1g of urea and 0.008g of ferric nitrate nonahydrate, stirring for 12 hours at room temperature, drying at 80 ℃, and drying in a nitrogen atmosphere. It was heated to 160 ℃ at a rate of 2 ℃/min for 1 hour under a nitrogen atmosphere and then to 800 ℃ at the same rate for 2 hours. And finally, etching by using 10% of HF by mass to remove silicon dioxide. Vacuum drying for 6 hours at 50 ℃ to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst. As can be seen from FIG. 7, the iron-nitrogen co-doped mesoporous carbon electrocatalyst of this case has a significant oxygen reduction peak at a voltage of-0.127V. As can be seen from FIG. 7, the initial potential and half-wave potential of the iron-nitrogen co-doped mesoporous carbon in this case are-0.024V and-0.139V, respectively, which indicates that the catalyst has certain oxygen reduction performance.
Example 3
A preparation method of a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon comprises the steps of firstly adding 4g of sucrose and 40mL of P1234 g into deionized water, then dropwise adding 40mL of 37% HCl in stirring, finally weighing about 9g of TEOS, and reacting by magnetic stirring at 45 ℃. Heating to 100 ℃ after 24h, stopping heating after 24h, and performing suction filtration and drying to obtain a mixed solid. Weighing 1g of mixed solid, adding the mixed solid into 20mL of deionized water, then dropwise adding 1mL of 98% sulfuric acid, stirring for 10 minutes, then adding 1g of urea and 0.01g of ferric nitrate nonahydrate, stirring for 12 hours at room temperature, drying at 80 ℃, and drying in a nitrogen atmosphere. It was heated to 160 ℃ at a rate of 2 ℃/min for 1 hour under a nitrogen atmosphere and then to 800 ℃ at the same rate for 2 hours. And finally, etching by using 10% of HF by mass to remove silicon dioxide. Vacuum drying for 6 hours at 50 ℃ to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst. Fig. 2 shows that the iron-nitrogen co-doped mesoporous carbon in the case is amorphous carbon, and an IV-type isothermal curve in fig. 3 shows that the iron-nitrogen co-doped mesoporous carbon in the case has a good mesoporous structure. As can be seen from fig. 4, the iron-nitrogen co-doped mesoporous carbon in this case contains four elements, namely carbon, nitrogen, oxygen, and iron, and the mass percentages of the four elements are 82.8%, 7.62%, 8.48%, and 1.10%, respectively. As can be seen from fig. 5, after 10000s, the current density of the case of the fe-n co-doped mesoporous carbon electrocatalyst is 86% and that of the commercial platinum-carbon catalyst is 78%, indicating that the case of the fe-n co-doped mesoporous carbon catalyst has better durability and stability than the commercial platinum-carbon catalyst. From fig. 6, it can be seen that the stability of commercial platinum-carbon decreases sharply when 3mL of 3M methanol is added at 500s, and after 1000s, the current density of the iron-nitrogen co-doped mesoporous carbon electrocatalyst of this case remains 92% and that of the commercial platinum-carbon catalyst is 63%, indicating that the iron-nitrogen co-doped mesoporous carbon catalyst of this case has better methanol tolerance than the commercial platinum-carbon catalyst. As can be seen from fig. 1 and 7, the iron-nitrogen co-doped mesoporous carbon electrocatalyst of this case has a significant oxygen reduction peak at a voltage of-0.120V. As can be seen from FIG. 8, the initial potential and half-wave potential of the Fe-N co-doped mesoporous carbon in this case are-0.01V and-0.123V, respectively, which indicates that the catalyst has a certain oxygen reduction performance.
Example 4
A preparation method of a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon comprises the steps of firstly adding 4g of sucrose and 40mL of P1234 g into deionized water, then dropwise adding 40mL of 37% HCl in stirring, finally weighing about 9g of TEOS, and reacting by magnetic stirring at 45 ℃. Heating to 100 ℃ after 24h, stopping heating after 24h, and performing suction filtration and drying to obtain a mixed solid. Weighing 1g of mixed solid, adding the mixed solid into 20mL of deionized water, then dropwise adding 1mL of 98% sulfuric acid, stirring for 10 minutes, then adding 1g of urea and 0.012g of ferric nitrate nonahydrate, stirring for 12 hours at room temperature, drying at 80 ℃, and drying in a nitrogen atmosphere. It was heated to 160 ℃ at a rate of 2 ℃/min for 1 hour under a nitrogen atmosphere and then to 800 ℃ at the same rate for 2 hours. And finally, etching by using 10% of HF by mass to remove silicon dioxide. Vacuum drying for 6 hours at 50 ℃ to obtain the iron-nitrogen co-doped mesoporous carbon nonmetal oxygen reduction electrocatalyst. As can be seen from FIG. 7, the iron-nitrogen co-doped mesoporous carbon electrocatalyst of this case has a significant oxygen reduction peak at a voltage of-0.143V. As can be seen from FIG. 8, the initial potential and half-wave potential of the Fe-N co-doped mesoporous carbon in this case are-0.028V and-0.141V, respectively, indicating that the catalyst has certain oxygen reduction performance.
Example 5
A preparation method of a non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon comprises the steps of firstly adding 4g of sucrose and 40mL of P1234 g into deionized water, then dropwise adding 40mL of 37% HCl in stirring, finally weighing about 9g of TEOS, and reacting by magnetic stirring at 45 ℃. Heating to 100 ℃ after 24h, stopping heating after 24h, and performing suction filtration and drying to obtain a mixed solid. Weighing 1g of mixed solid, adding the mixed solid into 20mL of deionized water, then dropwise adding 1mL of 98% sulfuric acid, stirring for 10 minutes, then adding 1g of urea and 0.015g of ferric nitrate nonahydrate, stirring for 12 hours at room temperature, drying at 80 ℃, and drying in a nitrogen atmosphere. It was heated to 160 ℃ at a rate of 2 ℃/min for 1 hour under a nitrogen atmosphere and then to 800 ℃ at the same rate for 2 hours. And finally, etching by using 10% of HF by mass to remove silicon dioxide. Vacuum drying for 6 hours at 50 ℃ to obtain the iron-nitrogen co-doped mesoporous carbon nonmetal oxygen reduction electrocatalyst. As can be seen from FIG. 7, the iron-nitrogen co-doped mesoporous carbon electrocatalyst of this case has a significant oxygen reduction peak at a voltage of-0.145V. As can be seen from FIG. 8, the initial potential and half-wave potential of the iron-nitrogen co-doped mesoporous carbon in this case are-0.043V and-0.159V, respectively, which indicates that the catalyst has certain oxygen reduction performance.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A process for preparing Fe-N codoped mesoporous carbon non-noble metal oxygen reduction electrocatalyst includes dissolving deionized water as solvent, cane sugar, poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer and tetraethyl orthosilicate as solute in deionized water, adding concentrated hydrochloric acid as catalyst, crosslinking the poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, fully reacting, filtering, drying to obtain a mixture, and weighing a certain amount of the mixture in deionized water, adding a proper amount of concentrated sulfuric acid, ferric nitrate nonahydrate and urea, fully stirring, drying, roasting in a nitrogen atmosphere, and removing silicon dioxide by using hydrofluoric acid solution to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst.
2. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 1, which is characterized by comprising the following steps:
(1) firstly, adding sucrose and poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer into deionized water, then dropwise adding concentrated hydrochloric acid with the mass fraction of 37% while stirring, finally weighing tetraethyl orthosilicate, adding the tetraethyl orthosilicate, and fully stirring at 40-50 ℃;
(2) heating to 90-110 ℃ after 22-26 h, reacting for 22-26 h, stopping heating, and performing suction filtration and drying to obtain a mixture;
(3) weighing the mixture obtained in the step (2), adding the mixture into deionized water, then dropwise adding a certain amount of concentrated sulfuric acid with the mass fraction of 98%, stirring, then adding urea and ferric nitrate nonahydrate, stirring at room temperature for 10-14 hours, and drying at 70-90 ℃;
(4) and (3) heating the product obtained in the step (3) to 150-170 ℃ in a nitrogen atmosphere for pre-carbonization, then heating to 750-850 ℃ for carbonization, and finally etching by using a hydrofluoric acid solution to obtain the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst.
3. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 2, wherein the mass ratio of the sucrose, the poly (ethylene oxide) -poly (propylene oxide) -poly (ethylene oxide) triblock copolymer, the tetraethyl orthosilicate, and the deionized water in the step (1) is 1:1: 2.1-2.3: 10.
4. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 2, wherein the mass ratio of the deionized water to the concentrated hydrochloric acid in the step (1) is 1: 1.1-1.3, so that the acid concentration of the total solution is 5.5-6.5 mol/L.
5. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 2, wherein the mass ratio of the mixture added in the step (3), urea and ferric nitrate nonahydrate is 1:1: 0.008-0.015.
6. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 2, wherein the mass ratio of the mixture added in the step (3), concentrated sulfuric acid and deionized water is 1: 1.8-1.9: 20.
7. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 2, wherein the pre-carbonization time in the step (4) is 50-70 min, and the carbonization time is 100-140 min.
8. The preparation method of the iron-nitrogen co-doped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 2, wherein the mass concentration percentage of the hydrofluoric acid solution in the step (4) is 5-20%, and the etching stirring time is 6-12 h.
9. A non-noble metal oxygen reduction electrocatalyst of iron-nitrogen co-doped mesoporous carbon, which is characterized by being prepared by the preparation method of any one of claims 1 to 8.
10. The use of the fe-n-codoped mesoporous carbon non-noble metal oxygen reduction electrocatalyst according to claim 9, wherein the fe-n-codoped mesoporous carbon non-noble metal oxygen reduction electrocatalyst is used for fuel cell cathode oxygen reduction.
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