CN116525846A - Nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 Nanoparticle composite catalyst and preparation method thereof - Google Patents
Nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 Nanoparticle composite catalyst and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 39
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- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 74
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 37
- 229910052717 sulfur Inorganic materials 0.000 title claims description 36
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims description 35
- 239000011593 sulfur Substances 0.000 title claims description 35
- 238000003756 stirring Methods 0.000 claims abstract description 28
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- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000001868 cobalt Chemical class 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000011347 resin Substances 0.000 claims abstract description 9
- 229920005989 resin Polymers 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 8
- 229960003638 dopamine Drugs 0.000 claims abstract description 8
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000008098 formaldehyde solution Substances 0.000 claims abstract description 6
- 229920001690 polydopamine Polymers 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 6
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 5
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims abstract description 4
- 239000010453 quartz Substances 0.000 claims abstract description 4
- 238000004321 preservation Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 23
- 239000002135 nanosheet Substances 0.000 claims description 13
- 239000002082 metal nanoparticle Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 208000021251 Methanol poisoning Diseases 0.000 abstract description 6
- 238000012360 testing method Methods 0.000 description 9
- 239000002064 nanoplatelet Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 2
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- 239000000725 suspension Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
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- 238000005260 corrosion Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
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- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- 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
-
- 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 & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a nitrogen-sulfur Co-doped porous nano carbon sheet supported Co9S8 nano particle composite catalyst for a fuel cell and a preparation method thereof, wherein the scheme comprises the steps of adding thiourea and cobalt salt into deionized water, and stirring to obtain a solution A; adding ethylenediamine and formaldehyde solution, and continuously stirring to obtain a solution B; adding the dopamine aqueous solution, and continuously stirring to obtain a solution C; adding tetraethoxysilane, continuously stirring, centrifugally cleaning and drying to obtain polydopamine coated Co 2+ Chelating thiourea-ethylenediamine-formaldehyde resins; placing the resin in a quartz tube furnace, introducing argon-hydrogen mixed gas, heating to a set temperature, and cooling after heat preservation reaction to obtain a composite material; immersing the composite material in ammonium bifluoride aqueous solution, and sequentially centrifugally cleaning and drying to obtain the catalyst. The composite catalyst prepared by the invention has large specific surface area, good catalytic performance, strong methanol poisoning resistance and durabilityThe performance is good, and stability is high, can be applied to the field of fuel cells.
Description
Technical Field
The invention relates to the technical field of catalysts, in particular to a nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for a fuel cell 9 S 8 Nanoparticle composite catalysts and methods of making the same.
Background
A Fuel Cell (Fuel Cell) is a power generation device that directly converts chemical energy of Fuel into electric energy. The high energy density, high conversion efficiency and environmentally friendly nature make fuel cells a powerful competitor for future mobile energy sources and large power plants. Although fuel cells have many applications in practice, they have not yet been commercialized on a large scale, mainly because of the high cost of the catalyst and poor stability of fuel cells. Recent studies have found that inexpensive nonmetallic cathode catalysts have the potential to solve the above problems. Among such cathode catalytic materials, electrochemical catalytic performance of porous carbon materials doped with nitrogen or Co-doped with nitrogen and other elements (P, S, fe, co, etc.) is particularly remarkable.
The transition metal composite catalyst made of the porous nanocarbon material has a high specific surface area, a hierarchical porous structure, and good corrosion resistance, and has been studied in a large amount as a cathode Oxygen Reduction Reaction (ORR) catalyst for fuel cells and metal-air cells in recent years to replace expensive noble metal-based catalysts. Direct pyrolysis of organometallic complexes has proven to be an efficient method for preparing porous carbon-based supported metal nanoparticles. However, conventional methods of directly pyrolyzing organometallic complexes tend to result in the loading of the synthesized carbon-based material with a variety of different metal nanoparticles, and the difficulty in removing poorly active metal species results in reduced overall catalyst performance and increased difficulty in determining the active sites.
Therefore, there is a need for a Co-doped porous nano carbon sheet loaded Co for fuel cells 9 S 8 The nanoparticle composite catalyst and the preparation method thereof overcome the defects existing in the prior art.
Disclosure of Invention
The invention aims at solving the problems existing in the prior art and provides a nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for a fuel cell 9 S 8 Nanoparticle composite catalysts and methods of making the same.
The core technology of the invention is that the porous carbon nano-sheet supported single metal nano-particle composite catalyst is prepared by directly carbonizing a precursor and simply selectively etching, so that the catalytic performance of the material is improved to the greatest extent.
In order to achieve the purpose of the application, the invention adopts the following technical scheme: nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 The nanoparticle composite catalyst comprises the following steps:
s00, adding thiourea and cobalt salt into deionized water, and stirring to obtain a solution A;
s10, adding ethylenediamine and formaldehyde solution into the solution A, and continuously stirring to obtain a solution B;
s20, adding a dopamine aqueous solution into the solution B, and continuously stirring to obtain a solution C;
s30, adding tetraethoxysilane into the solution C, continuously stirring, sequentially centrifuging, cleaning and drying to obtain polydopamine coated Co 2+ Chelating thiourea-ethylenediamine-formaldehyde resins;
s40, co 2+ Placing the chelated thiourea-ethylenediamine-formaldehyde resin in a quartz tube furnace, introducing argon-hydrogen mixed gas, heating to a set temperature, carrying out heat preservation reaction, and cooling to obtain a nitrogen-sulfur co-doped porous carbon nano sheet loaded multiple metal nano particle composite material;
s50, soaking the nitrogen and sulfur Co-doped porous carbon nano sheet loaded multi-metal nano particle composite material in an ammonium bifluoride aqueous solution, sequentially centrifuging, cleaning and drying to obtain the nitrogen and sulfur Co-doped porous carbon nano sheet loaded Co 9 S 8 Nanoparticle composite catalysts.
Further, in the S00 step, the mass ratio of thiourea to cobalt salt is (0.4-0.6 g): (0.1-0.3 g), and the dosage ratio of cobalt salt to deionized water is (0.1-0.3 g): 40mL. Preferably 0.5:0.2; the dosage ratio of cobalt salt to deionized water is (0.1-0.3 g) 40mL.
Further, in the step S10, the mass concentration of the formaldehyde solution is 35-40%, and the volume ratio of ethylenediamine to formaldehyde is (0.3-0.6 mL) (1.40-1.50 mL). Preferably 0.4:1.44.
Further, in the step S00 and the step S10, the stirring rotation speed is 800-1000 rpm, and the stirring time is 10-15 min; in the step S20, the stirring speed is 800-1000 rpm, and the stirring time is 1-3 h; in the step S30, the stirring speed is 800-1000 rpm, and the stirring time is 20-25 h.
Further, in the step S20, the concentration of the aqueous solution of dopamine is 40mg/mL, and the volume ratio of the aqueous solution of dopamine to deionized water is (3-6 mL): 40mL. Preferably 5:40.
Further, in the step S30, the volume ratio of the tetraethoxysilane to the deionized water is (0.15-0.25 mL): 40mL. Preferably 0.2:40.
Further, in the step S30 and the step S50, deionized water and absolute ethyl alcohol are adopted to clean filter residues until the filtrate is colorless. In the step S30, the drying temperature is 45-55 ℃, preferably 50 ℃; the drying time is 20 to 36 hours, preferably 24 hours. In the step S50, the drying temperature is 45-55 ℃, preferably 50 ℃; the drying time is 24 to 36 hours, preferably 24 hours.
Further, in the step S40, the volume ratio of the argon-hydrogen mixture is 95 percent to 5 percent; the flow rate of the introduced argon-hydrogen mixture is 300sccm; heating is started after argon-hydrogen mixture is introduced for 30min, and the heating rate is 5-8 ℃/min; the reaction time is 2-3 h, and the cooling rate is 5-8 ℃/min. The heating rate and the cooling rate are 5 ℃/min. The reaction time is 2-3 h, preferably 2h.
Further, in step S10, the cobalt salt is Co (NO 3 ) 2 ·6H 2 O。
Nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 Nanoparticle composite catalyst, co-doped porous nano carbon sheet loaded with Co by nitrogen and sulfur for fuel cell 9 S 8 The nanoparticle composite catalyst is prepared by a preparation method.
Compared with the prior art, the invention has the following beneficial effects:
1. the preparation method is simple, the porous carbon nano-sheet supported single metal nano-particle composite catalyst is prepared by directly carbonizing the precursor and subsequent simple selective etching inert components, the problem that a plurality of different nano-particles are simultaneously supported on a porous carbon material caused by the traditional method is avoided, and the catalytic performance of the material is improved to the greatest extent;
2. the preparation method is economical and suitable for large-scale production, can be expanded and modified to form a more general novel porous carbon preparation method, and has huge potential application prospect;
3. the nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co prepared by the invention 9 S 8 The nanoparticle composite catalyst has the advantages of large specific surface area, good catalytic performance, strong methanol poisoning resistance, good durability and high stability; such as: the specific surface area of the mesoporous part can reach 898.2m 2 Above/g, porous carbon avoids Co 9 S 8 The agglomeration among the nano particles fully exposes active sites, and in the catalytic test of ORR (electro-catalytic reduction), the performance of the nano particles is comparable with that of a commercial Pt/C catalyst, and the nano particles have higher electron transfer number, stronger methanol poisoning resistance and better durability under the condition of low overpotential.
Drawings
FIG. 1 shows a polydopamine coated Co prepared according to the invention 2+ SEM image of the chelated thiourea-ethylenediamine-formaldehyde resin;
FIG. 2 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nano-sheet prepared by the invention 9 S 8 SEM image of nanoparticle composite catalyst;
FIG. 3 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 Element distribution diagram of nano particle composite catalyst;
FIG. 4 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 BET specific surface area test curve of nanoparticle composite catalyst;
FIG. 5 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 Pore diameter test curve of nanoparticle composite catalyst;
FIG. 6 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 The nano-particle composite catalyst and the commercial catalyst are Pt/C oxygen reduction catalytic activity curves;
FIG. 7 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 Nanoparticle composite catalystsGraph of electron number transfer and hydrogen peroxide yield with commercial catalyst Pt/C;
FIG. 8 shows the Co-supported on the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 Durability graph of nanoparticle composite catalyst versus commercial catalyst Pt/C;
FIG. 9 shows the Co loading of the nitrogen and sulfur Co-doped porous carbon nanoplatelets prepared by the invention 9 S 8 Graph of methanol poisoning resistance of nanoparticle composite catalyst versus commercial catalyst Pt/C.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which are derived by a person skilled in the art based on the embodiments of the invention, fall within the scope of protection of the invention.
Example 1
As shown in figures 1-5, the nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for the fuel cell 9 S 8 The nanoparticle composite catalyst comprises the following steps:
(1) Adding 0.5g of thiourea and 0.2g of cobalt salt into 40.0mL of deionized water, and stirring to obtain a solution A;
(2) Slowly adding 0.40mL of ethylenediamine and 1.44mL of formaldehyde solution (38 wt.%) into the solution A in the step (1), and continuously stirring to obtain a solution B;
(3) Slowly adding 5.0mL of dopamine aqueous solution into the solution B in the step (2), and continuously stirring to obtain a solution C;
(4) Dropwise adding 0.2mL of ethyl orthosilicate into the solution C in the step (3), continuously stirring, centrifuging, cleaning and drying to obtain polydopamine coated Co 2+ Chelating thiourea-ethylenediamine-formaldehyde resin (silica-Co (II) -TEFR@PDA), the structural characterization of which is shown in figure 1;
(5) Co in the step (4) 2+ Placing the chelated thiourea-ethylenediamine-formaldehyde resin in a quartz tube furnace, introducing argon-hydrogen mixed gas, heating to 800 ℃, maintaining for 2h, and coolingObtaining the nitrogen and sulfur Co-doped porous carbon nano sheet loaded multiple metal nano particle composite material (silica-Co/Co) 9 S 8 @pnsc), the nitrogen and sulfur co-doped porous carbon nano sheet loaded with a plurality of metal nano particle composite materials contains a large number of silica nano particles;
(6) Soaking the nitrogen and sulfur Co-doped porous carbon nano sheet loaded multi-metal nano particle composite material in the step (5) in 4mol/L ammonium bifluoride aqueous solution, centrifuging, cleaning and drying to obtain the nitrogen and sulfur Co-doped porous carbon nano sheet loaded Co 9 S 8 Nanoparticle composite catalysts (Co) 9 S 8 @ PNSC). The structural representation is shown in figure 2; the elemental characterization is shown in fig. 4. The specific surface area test result of the catalyst prepared by the invention is shown in fig. 4, and the pore diameter test result is shown in fig. 5. As can be seen from FIGS. 4 and 5, the catalyst Co of the present invention 9 S 8 Surface area of @ PNSC is 898.2m 2 And/g, the pore size is mainly 3.5nm.
Example two
As shown in FIGS. 6-9, co is supported on a nitrogen-sulfur Co-doped porous nano-carbon sheet for a fuel cell according to an embodiment 9 S 8 The catalyst prepared by the nanoparticle composite catalyst preparation method.
In this example, the catalytic performance test is as follows:
electrochemical test characterization was performed on a CHI 750E electrochemical workstation manufactured by morning in the open sea in a test cell with a three electrode system, with a platinum wire as the counter electrode, an Ag/AgCl electrode as the reference electrode, and a catalyst-loaded glassy carbon electrode as the working electrode. Adding 2mg of catalyst into 980 mu L+20 mu LNafion solution, and ultrasonically oscillating for 30 minutes to obtain catalyst suspension with the concentration of 2mg/mL, uniformly coating 20 mu L of catalyst suspension on a glassy carbon electrode, and drying in air to obtain the glassy carbon electrode with the catalyst loading of 204 mu g/cm 2 The catalyst was tested for linear voltammetric scan curve (LSV) in an oxygen saturated aqueous 0.1M KOH solution at 1600rpm electrode speed. The test results are shown in FIGS. 6 to 9.
As can be seen from fig. 6, in the polarization curve of the ORR reaction (i.e., the catalyst oxygen reduction catalytic activity curve), the electrode half-wave potential on which the composite catalyst prepared in this example was supported was +0.845V with respect to the reversible hydrogen electrode, which is comparable to the commercial Pt/C (+0.847v); as can be seen from fig. 7, the number of electron transfer of the electrode carrying the composite catalyst prepared in this example in the voltage range of +0.2v to +0.8v was greater than 3.9, and the hydrogen peroxide yield was lower than 5%.
FIG. 8 is a graph of the durability of a composite catalyst under conditions such that the catalyst-supported electrode was continuously operated in an oxygen-saturated aqueous 0.1M KOH solution at an electrode speed of 1600rpm under constant voltage conditions of 0.50V. As can be seen from fig. 9, the composite catalyst prepared in this example was carried with a 16.2% decrease in current value at a constant voltage of 0.50V for 10 hours.
FIG. 9 is a graph showing the methanol poisoning resistance of a composite catalyst under the condition that the electrode carrying the catalyst is tested in an oxygen saturated aqueous solution of 0.1M KOH at an electrode rotation speed of 1600rpm under a constant voltage condition of 0.50 and V, and the catalyst is added into the aqueous solution of 1M methanol when the test is performed for 1000s, and then the test is continued, so that the graph showing the methanol poisoning resistance is obtained. As can be seen from fig. 9, the current value of the composite catalyst prepared in this example was increased by 1% after methanol was added thereto under a constant voltage of 0.50V.
The invention is not described in detail in the prior art, and therefore, the invention is not described in detail.
It will be understood that the terms "a" and "an" should be interpreted as referring to "at least one" or "one or more," i.e., in one embodiment, the number of elements may be one, while in another embodiment, the number of elements may be plural, and the term "a" should not be interpreted as limiting the number.
Although specific terms are used more herein, the use of other terms is not precluded. These terms are used merely for convenience in describing and explaining the nature of the invention; they are to be interpreted as any additional limitation that is not inconsistent with the spirit of the present invention.
The present invention is not limited to the above-mentioned preferred embodiments, and any person can obtain various other products without departing from the scope of the present invention, but any changes in shape or structure of the present invention, all having the same or similar technical solutions, fall within the scope of the present invention.
Claims (10)
1. Nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized by comprising the following steps:
s00, adding thiourea and cobalt salt into deionized water, and stirring to obtain a solution A;
s10, adding ethylenediamine and formaldehyde solution into the solution A, and continuously stirring to obtain a solution B;
s20, adding a dopamine aqueous solution into the solution B, and continuously stirring to obtain a solution C;
s30, adding tetraethoxysilane into the solution C, continuously stirring, sequentially centrifuging, cleaning and drying to obtain polydopamine coated Co 2+ Chelating thiourea-ethylenediamine-formaldehyde resins;
s40, mixing the Co 2+ Placing the chelated thiourea-ethylenediamine-formaldehyde resin in a quartz tube furnace, introducing argon-hydrogen mixed gas, heating to a set temperature, carrying out heat preservation reaction, and cooling to obtain a nitrogen-sulfur co-doped porous carbon nano sheet loaded multiple metal nano particle composite material;
s50, soaking the nitrogen and sulfur Co-doped porous carbon nano sheet loaded multi-metal nano particle composite material in an ammonium bifluoride aqueous solution, sequentially centrifuging, cleaning and drying to obtain the nitrogen and sulfur Co-doped porous carbon nano sheet loaded Co 9 S 8 Nanoparticle composite catalysts.
2. The Co-doped porous nano carbon sheet-supported nitrogen and sulfur for fuel cell according to claim 1 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the S00 step, the mass ratio of thiourea to cobalt salt is (0.4-0.6 g): (0.1-0.3 g), and the dosage ratio of cobalt salt to deionized water is (0.1-0.3 g): 40mL.
3. The Co-doped porous nano carbon sheet-supported nitrogen and sulfur for fuel cell according to claim 1 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the step S10, the mass concentration of the formaldehyde solution is 35-40%, and the volume ratio of the ethylenediamine to the formaldehyde is (0.3-0.6 mL) (1.40-1.50 mL).
4. The Co-doped porous nano carbon sheet-supported nitrogen and sulfur for fuel cell according to claim 1 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the S00 step and the S10 step, the stirring rotation speed is 800-1000 rpm, and the stirring time is 10-15 min; in the step S20, the stirring speed is 800-1000 rpm, and the stirring time is 1-3 h; in the step S30, the stirring speed is 800-1000 rpm, and the stirring time is 20-25 h.
5. The Co-doped porous nano carbon sheet-supported nitrogen and sulfur for fuel cell according to claim 1 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the step S20, the concentration of the aqueous dopamine solution is 40mg/mL, and the volume ratio of the aqueous dopamine solution to deionized water is (3-6 mL): 40mL.
6. The Co-doped porous nano carbon sheet-supported nitrogen and sulfur for fuel cell according to claim 1 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the step S30, the volume ratio of the ethyl orthosilicate to the deionized water is (0.15-0.25 mL) 40mL.
7. Co-doped porous nano carbon plate loaded with nitrogen and sulfur for fuel cell according to any one of claims 1-6 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the step S30 and the step S50, deionized water and absolute ethyl alcohol are adopted to clean filter residues until filtrate is colorless, and the drying temperature is 45-55 DEG CThe drying time is 24-36 h.
8. Co-doped porous nano carbon plate loaded with nitrogen and sulfur for fuel cell according to any one of claims 1-6 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the step S40, the volume ratio of the argon-hydrogen mixture is 95 percent to 5 percent; the flow rate of the introduced argon-hydrogen mixture is 300sccm; heating is started after argon-hydrogen mixture is introduced for 30min, and the heating rate is 5-8 ℃/min; the reaction time is 2-3 h, and the cooling rate is 5-8 ℃/min.
9. Co-doped porous nano carbon plate loaded with nitrogen and sulfur for fuel cell according to any one of claims 1-6 9 S 8 The preparation method of the nanoparticle composite catalyst is characterized in that in the step S10, the cobalt salt is Co (NO 3 ) 2 ·6H 2 O。
10. Nitrogen and sulfur Co-doped porous nano carbon sheet loaded Co for fuel cell 9 S 8 A nanoparticle composite catalyst comprising Co supported on the nitrogen-sulfur Co-doped porous nanocarbon sheet for a fuel cell according to any one of claims 1 to 9 9 S 8 The nanoparticle composite catalyst is prepared by a preparation method.
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