CN113871632B - Nitrogen-doped carbon-loaded Mo/Pd alloy catalyst and application thereof - Google Patents
Nitrogen-doped carbon-loaded Mo/Pd alloy catalyst and application thereof Download PDFInfo
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- CN113871632B CN113871632B CN202110969949.2A CN202110969949A CN113871632B CN 113871632 B CN113871632 B CN 113871632B CN 202110969949 A CN202110969949 A CN 202110969949A CN 113871632 B CN113871632 B CN 113871632B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- 229910001252 Pd alloy Inorganic materials 0.000 title claims abstract description 24
- 229910001182 Mo alloy Inorganic materials 0.000 title claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 54
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000001301 oxygen Substances 0.000 claims abstract description 23
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 23
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 239000011148 porous material Substances 0.000 claims abstract description 12
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 38
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 32
- 229910052751 metal Inorganic materials 0.000 claims description 25
- 239000002184 metal Substances 0.000 claims description 25
- 235000019260 propionic acid Nutrition 0.000 claims description 19
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 14
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000011068 loading method Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000000446 fuel Substances 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000002077 nanosphere Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229960000583 acetic acid Drugs 0.000 claims description 5
- 238000007598 dipping method Methods 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- QUKUNZDPKPLYGS-UHFFFAOYSA-N propanoic acid;1h-pyrrole Chemical compound CCC(O)=O.C=1C=CNC=1 QUKUNZDPKPLYGS-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 2
- 239000010411 electrocatalyst Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 25
- 238000006722 reduction reaction Methods 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 15
- 208000021251 Methanol poisoning Diseases 0.000 abstract description 6
- 239000002253 acid Substances 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 57
- 238000006243 chemical reaction Methods 0.000 description 24
- 229910015792 MoPd Inorganic materials 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 19
- 230000010287 polarization Effects 0.000 description 15
- 238000009826 distribution Methods 0.000 description 13
- 239000002082 metal nanoparticle Substances 0.000 description 12
- 238000001878 scanning electron micrograph Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 238000001000 micrograph Methods 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 230000000670 limiting effect Effects 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000000137 annealing Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 230000001788 irregular Effects 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 208000005374 Poisoning Diseases 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 2
- 229940010552 ammonium molybdate Drugs 0.000 description 2
- 235000018660 ammonium molybdate Nutrition 0.000 description 2
- 239000011609 ammonium molybdate Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 231100000572 poisoning Toxicity 0.000 description 2
- 230000000607 poisoning effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910001339 C alloy Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- ODOJGYBXTZYZCP-UHFFFAOYSA-N molybdenum palladium Chemical compound [Mo].[Pd].[Pd].[Pd] ODOJGYBXTZYZCP-UHFFFAOYSA-N 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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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
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention belongs to the technical field of electrochemical catalyst materials, and particularly relates to a nitrogen-doped carbon-supported Mo/Pd alloy catalyst and application thereof. The nitrogen-doped carbon-loaded Mo/Pd alloy catalyst is obtained by impregnating molybdate and chloropalladic acid into pore channels of nano spherical polypyrrole and calcining. The nitrogen-doped carbon-loaded Mo/Pd alloy catalyst provided by the invention has high activity, stability and methanol poisoning resistance to oxygen reduction reaction.
Description
Technical Field
The invention belongs to the technical field of electrochemical catalyst materials, and particularly relates to a nitrogen-doped carbon-supported Mo/Pd alloy catalyst and application thereof.
Background
The development of science and technology tends to increase the energy demand, especially the consumption of fossil fuels, which are non-renewable energy sources, which has forced people to search and produce ecologically friendly materials to replace non-renewable fuels. Currently, fuel cells are receiving extensive attention for their advantages of high energy conversion efficiency, low pollutant emission, etc., and the cathodic oxygen reduction (ORR) reaction is a critical step. However, there are still problems to be solved in the oxygen reduction reaction process, such as: the reaction kinetics is slower, and the ideal effect is not achieved; pt can promote the efficient progress of the oxygen reduction reaction, but its long-term cycle stability and poison resistance have a large room for improvement; pt is also economically unfriendly and accounts for approximately 20% of the cost of fuel cells. The commercial application of fuel cells is greatly limited by the problems of the Pt catalyst such as unfriendly economy, poor stability, weak poisoning resistance, and improved reaction kinetics. In summary, it is imperative to develop a fuel cell cathode catalyst with high catalytic activity, long-term use stability, strong poisoning resistance and low cost. The alloy formed by cheaper metals and noble metals is an effective way, on one hand, the addition of another metal can effectively reduce the consumption of noble metals, and on the other hand, the interaction between the two metals is expected to improve the catalytic performance and stability. However, the formation of the alloy often requires higher temperatures, the liquid phase reaction is suitable for the synthesis of only a small portion of the alloy, and the surfactant is required to stabilize the product against agglomeration, and the final residual surfactant can seriously affect the activity and stability of the catalyst.
Disclosure of Invention
The invention aims to overcome the defects and the shortcomings of the prior art and provide a nitrogen-doped carbon-supported Mo/Pd alloy catalyst and application thereof.
The technical scheme adopted by the invention is as follows: the preparation method of the nitrogen-doped carbon-supported Mo/Pd alloy catalyst comprises the following steps:
(1) Preparation of nanospheres polypyrrole: adding propionic acid into a container, heating to 130-160 ℃, mixing pyrrole with propionic acid to obtain pyrrole propionic acid solution, adding the pyrrole propionic acid solution into propionic acid in the container heated to 130-160 ℃ under stirring, and reacting for at least 1.5h by using oxygen as an oxidant to obtain black mixed solution; washing and separating the product with ethanol and water, and finally drying to obtain nano spherical polypyrrole;
(2) Preparation of nitrogen-doped carbon-supported Mo/Pd alloy catalyst: and (3) dipping molybdate and chloropalladate into the pore canal of the nano spherical polypyrrole prepared in the step (1), and calcining to obtain the nitrogen-doped carbon-loaded Mo-based alloy catalyst.
In some embodiments of the invention, in step (1), the pyrrole propionic acid solution is slowly added to propionic acid in a vessel heated to 130-160 ℃ and the step is added for 0-15min, preferably for 5-10 min.
In some embodiments of the invention, in step (1), the stirring speed is from 450 to 550 rpm.
In some embodiments of the invention, in step (1), the reaction time is 180 minutes.
In some embodiments of the invention, in step (1), the ratio of the total volume of propionic acid to the mass of pyrrole is 15:19-57, with a ratio of total volume of propionic acid to mass of pyrrole of 15:57 being most preferred.
In some embodiments of the present invention, in step (2), the nano-spherical polypyrrole prepared in step (1) is dispersed in water, then glacial acetic acid is added to the polypyrrole dispersion, molybdate and chloropalladate are added, stirring and impregnation are performed, so that molybdate and chloropalladate are impregnated into the pore canal of the nano-spherical polypyrrole, and calcination is performed after drying treatment.
In some embodiments of the invention, hydrogen is used as a reducing atmosphere and argon is used as a protective atmosphere during calcination.
In some embodiments of the invention, the calcination temperature is 620-820 ℃, with 720 ℃ being the most preferred calcination temperature.
In some embodiments of the invention, the calcination time is 1-3 hours, with a calcination time of 2 h being most preferred.
In some embodiments of the invention, the total metal loading is from 5 to 9 mg/25mg polypyrrole, with a total metal loading of 7 mg/25mg polypyrrole being most preferred.
In some embodiments of the invention, the molar ratio of Mo to Pd is 1:7-10, with a molar ratio of Mo to Pd of 1:9 being most preferred.
The use of a nitrogen-doped carbon-supported Mo/Pd alloy catalyst as described above as a redox electrocatalyst.
A fuel cell wherein the catalyst is a nitrogen doped carbon supported Mo/Pd alloy catalyst as described above.
The beneficial effects of the invention are as follows: the nitrogen-doped carbon-supported Mo/Pd alloy catalyst is prepared by directly carrying out solid-phase heat treatment after mixing raw materials, and the process is simple. The catalyst has high activity, stability and methanol poisoning resistance to oxygen reduction reaction.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions of the prior art, the drawings which are required in the description of the embodiments or the prior art will be briefly described, it being obvious that the drawings in the description below are only some embodiments of the invention, and that it is within the scope of the invention to one skilled in the art to obtain other drawings from these drawings without inventive faculty.
FIG. 1 is a scanning electron micrograph of polypyrrole prepared at various feed times: (a) 0 min; (b) 5min; (c) 10 min; (d) 15min;
FIG. 2 is a scanning electron micrograph of polypyrrole prepared at various stirring speeds (a) 300 rpm; (b) 400 rpm; (c) 500 rpm; (d) 600 rpm;
FIG. 3 is a scanning electron micrograph of polypyrrole prepared at various feed ratios, the amount of pyrrole (a) 190 mg; (b) 380 mg; (c) 570 mg; (d) 760 mg;
FIG. 4 is a scanning electron micrograph of polypyrrole prepared in comparative example 1;
FIG. 5 is Mo 0.14 Pd 0.86 SEM image of/N-C, (a), TEM image (b), high resolution transmission electron microscope image (C), and (d) is a white box magnified region of image (C);
FIG. 6 is Mo 0.14 Pd 0.86 N-C high-angle annular dark field transmission electron microscope pictures (a), pd, mo, C, N element signal superposition pictures (b), mo element distribution (C) and Pd element distribution (d);
FIG. 7 shows nitrogen adsorption-desorption isotherm (a), pore size distribution (b), mo for N-C materials 0.14 Pd 0.86 Nitrogen adsorption-desorption isotherms of N-C (inset)Pore size distribution) (c);
FIG. 8 shows PPY, mo 0.14 Pd 0.86 ORR polarization curve of the catalyst (a), tafel slope (b), of the catalyst/N-C, pt/C (20%), mo/N-C, pd/N-C; mo (Mo) 0.14 Pd 0.86 Kinetic current density of N-C and Pt/C (20%) (C), active area (d), mass specific activity (e), area specific activity (f);
in FIG. 9, (a) Mo 0.14 Pd 0.86 N-C cycle stability test; (b) Pt/C (20%) cycling stability test; (c) Mo (Mo) 0.14 Pd 0.86 Comparison of anti-methanol poisoning ability of N-C, pt/C (20%);
FIG. 10 is a scanning electron micrograph of a MoPd/N-C catalyst prepared at various reaction temperatures: (a) 670 ℃; (b) 720 ℃; (c) 770 ℃; (d) 820 ℃;
FIG. 11 is an ORR polarization curve of MoPd/N-C prepared at different reaction temperatures;
FIG. 12 is a scanning electron micrograph of MoPd/N-C samples prepared at various reaction times: (a) 1 h; (b) 1.5 h; (c) 2 h; (d) 2.5 h; (e) 3 h; and (f) ORR polarization curves of MoPd/N-C prepared at different reaction times;
FIG. 13 is a scanning electron micrograph of MoPd/N-C prepared at various loadings: (a) 5 mg; (b) 6 mg; (c) 7 mg; (d) 8 mg; (e) 9 mg; and (f) preparing ORR polarization curves of MoPd/N-C at different loads;
FIG. 14 is a scanning electron micrograph of MoPd/N-C prepared at various molar ratios: (a) 1/7; (b) 1/8; (c) 1/9; (d) 1/10; (e) 1/11; and (f) ORR polarization curves of MoPd/N-C prepared in different molar ratios.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings, for the purpose of making the objects, technical solutions and advantages of the present invention more apparent.
Example 1:
105 mL propionic acid was placed in a round bottom flask, a magnet was added, the rotation speed was set at 500rpm, and the temperature was raised to 145 ℃. Weighing 190 mg pyrrole solution by an electronic balance, dissolving in 45 mL propionic acid, dripping into a round bottom flask for about 10min, reacting 3h, and washing with ethanol and water after the reaction to obtain solid black powder, namely the nano spherical polypyrrole.
Examples 2 to 4
The addition time of the pyrrole solution in example 1 was changed to 0, 5 and 15min respectively, and the morphology of the obtained product was shown in fig. 1.
The morphology of polypyrrole prepared at different feeding times is studied, as shown in fig. 1 (a), pyrrole is directly added into propionic acid under the condition of 0min, and the polypyrrole is in a spherical structure as a whole, but a small part of polypyrrole has non-spherical irregular shapes; when the feeding time is slowed down to 5min, as shown in fig. 1 (b), the product is composed of balls, has uniform size, is distributed at about 250nm, and shows excellent dispersibility; when the feeding time is slowed down to 10min, as shown in fig. 1 (c), the uniformity and the dispersity of the product size distribution are still good, and the yield is more than 2 times of that obtained under the condition of 5min feeding time; when the charging time was 15min, as shown in FIG. 1 (d), the product size started to become uneven. In summary, the preferable feeding time is 5-10min, and the optimal feeding time is 10min.
Examples 5 to 7:
the stirring speeds in example 1 were changed to 300, 400 and 600 rpm, respectively, to obtain the product morphology as shown in FIG. 2.
The appearance of polypyrrole prepared at different stirring speeds is studied, and as shown in fig. 2 (a), under the condition of 300 rpm, the prepared polypyrrole is uneven in size, has other irregular shapes, but most of the polypyrrole maintains a spherical structure; when the stirring speed was increased to 400 rpm, as shown in FIG. 2 (b), the spherical structure was more and more uniform, and the dispersibility was improved; when the stirring speed is increased to 500rpm, as shown in fig. 2 (c), the irregular shape completely disappears, the product is polypyrrole nanospheres, the size distribution is narrow, and the dispersibility is good; when the stirring speed was increased to 600 rpm, as shown in FIG. 2 (d), the product exhibited a broad size distribution and some degree of blocking occurred. In summary, the optimal stirring speed was 500 rpm.
Examples 8 to 10:
the quality of pyrrole in example 1 was changed to 190, 380, 760 and mg respectively, and the morphology of the obtained product was as shown in fig. 3.
The morphology of the polypyrrole prepared by different feeding ratios is studied, and as shown in the figure 3 (a), the size distribution of the prepared polypyrrole is narrower under the condition that the ratio of the total volume of propionic acid to the mass of pyrrole is 15:19, and only slight adhesion occurs, but the yield is lower; under the condition that the ratio of the total volume of propionic acid to the mass of pyrrole is 15:38, as shown in fig. 3 (b), the appearance of the product is still in a spherical structure, but compared with (a), the product has relatively wide size distribution, partial spheres are adhered to form cucurbit polypyrrole, and the yield is low; when the ratio of the total volume of propionic acid to the mass of pyrrole is 15:57, as shown in fig. 3 (c), the size distribution and the dispersibility are good, and the yield is high; when the ratio of total propionic acid volume to pyrrole mass was 15:76, as shown in FIG. 3 (d), extremely uneven and severe blocking of nanosphere size occurred. In summary, the optimal feed ratio is that the ratio of the total volume of propionic acid to the mass of pyrrole is 15:57, and the ratio of the total volume of propionic acid to the mass of pyrrole is 15:57.
Comparative example 1:
placing 150 mL propionic acid and 190 mg pyrrole solution into a round bottom flask, adding magneton, heating to 145 ℃, reacting for 180min, and washing with ethanol and water after the reaction is finished to obtain solid black powder.
As shown in FIG. 4, the reaction gave spherical polypyrrole, but polypyrrole exhibited a broad adhesion and size distribution, and other irregular shapes occurred.
Example 11:
(1) The polypyrrole of 25mg is accurately weighed by an electronic balance and placed in a beaker, 15 mL of water and a magnet are added and stirred until the polypyrrole can be fully dispersed in the water. Then adding 0.2 mL glacial acetic acid into the dispersed polypyrrole solution after ultrasonic treatment, uniformly mixing, and adding ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O), finally adding chloropalladate (two)The total amount of the seed metal is 7mg, the mole ratio of Mo to Pd is 1/9), the ultrasonic treatment is continued, stirring and dipping are carried out for 12 h, and drying is carried out.
(2) The dried sample is placed in a quartz boat, and is subjected to heat treatment at a set temperature by using a tube furnace, hydrogen (0-10 SCCM) and argon (90-100 SCCM) are flowed in, and a sectional heating program is adopted in the preparation of MoPd/N-C, and the temperature is firstly raised to 550 ℃ from room temperature, then is kept at 1.5 and h, and is then directly raised to 720 ℃ from 550 ℃ and is kept at 2 h. After the reaction is finished, cooling to room temperature, and taking out the sample to obtain the MoPd/N-C catalyst.
Using Inductively Coupled Plasma (ICP) testing and calculation: the molar ratio of Mo to Pd in the sample prepared in this example was 1/6.2, and the MoPd/N-C catalyst prepared in this example was prepared from Mo 0.14 Pd 0.86 N-C.
Comparative example 2:
(1) The polypyrrole of 25mg is accurately weighed by an electronic balance and placed in a beaker, 15 mL of water and a magnet are added and stirred until the polypyrrole can be fully dispersed in the water. Then adding 0.2 mL glacial acetic acid into the dispersed polypyrrole solution after ultrasonic treatment, uniformly mixing, and adding ammonium molybdate ((NH) 4 ) 6 Mo 7 O 24 ·4H 2 O) (total amount of Mo 7 mg), continuing to ultrasonic, stirring and impregnating 12 h, and drying.
(2) The dried sample is placed in a quartz boat, and is subjected to heat treatment at a set temperature by using a tube furnace, hydrogen (0-10 SCCM) and argon (90-100 SCCM) are flowed in, and the Mo/N-C is prepared by adopting a sectional heating program, firstly, the temperature is raised to 550 ℃, the heat is preserved for 1.5h, and then the temperature is directly raised to 720 ℃ from 550 ℃ for 2 h. After the reaction, cooling to room temperature, taking out the sample to obtain the Mo/N-C catalyst.
Comparative example 3:
(1) The polypyrrole of 25mg is accurately weighed by an electronic balance and placed in a beaker, 15 mL of water and a magnet are added and stirred until the polypyrrole can be fully dispersed in the water. Then adding glacial acetic acid of 0.2 mL after ultrasonic treatment of the dispersed polypyrrole solution, uniformly mixing, adding chloropalladate (the total amount of palladium is 7 mg), continuing ultrasonic treatment, stirring, dipping 12 h, and drying.
(2) The dried sample is placed in a quartz boat, and is subjected to heat treatment at a set temperature by using a tube furnace, hydrogen (0-10 SCCM) and argon (90-100 SCCM) are flowed in, and a sectional heating program is adopted in the preparation of Pd/N-C, and the temperature is firstly increased to 550 ℃ from room temperature, then is kept at 1.5 and h, and is then directly increased to 720 ℃ from 550 ℃ and is kept at 2 h. After the reaction, cooling to room temperature, taking out the sample to obtain the Pd/N-C catalyst.
Comparative example 4:
and filling polypyrrole of 25mg into a quartz boat, and preserving heat at 720 ℃ for 2 h to obtain the N-C catalyst.
FIG. 5 (a) shows Mo 0.14 Pd 0.86 SEM image of N-C sample, and (b) transmission electron microscope image. The two graphs (a) and (b) are observed, the N-C material also maintains a spherical structure after high-temperature annealing, and the metal nano particles are obviously observed to be loaded in the nitrogen-carbon material, so that the metal is successfully impregnated into the polypyrrole. However, the N-C material has a few large-sized metal particles outside, which may not be impregnated with a small amount of Pd salt during impregnation, and at high temperature, pd metal agglomerates and grows due to the absence of nanosphere confinement, which is a side-on illustration of the extremely important role of carbon-nitrogen materials in limiting metal particle size. FIG. 5 (c) is Mo 0.14 Pd 0.86 The high resolution transmission electron microscope image of/N-C, (d) the white box enlarged part of the image (C), and (d) the related information of lattice fringes is given in the image, wherein the lattice intervals are respectively 0.256 nm and 0.222 nm which correspond to the (200) surface and the (111) surface of Mo-Pd alloy, after Mo element is introduced into the catalyst, the lattice interval of Pd is obviously compressed, and the compression is carried out from 0.257 nm of the pure Pd (200) surface to 0.245 nm, so that the adsorption energy between the catalyst and oxygen can be changed, which is probably one of reasons why the performance of the catalyst is superior to that of pure Pt.
Further use of P Mo 0.14 Pd 0.86 The N-C samples were subjected to elemental species and distribution tests, and FIGS. 6 (a) and (b) show that the samples contain four elements of Pd (Pd), mo (Mo), N (N), and C (C) (consistent with the elemental analysis test results)And Mo and Pd are uniformly distributed on each metal particle. The metal load reaches 77% through element analysis calculation, and is close to 79% of the calculated result of ICP, so that the ultrahigh metal load is proved.
And adopting a physical adsorption device nitrogen adsorption and desorption device to acquire data. As shown in FIG. 7 (c), the adsorption curve and desorption curve of nitrogen gas show that the total adsorption amount is 230 cm 3 g -1 The higher adsorption than the pure N-C material (fig. 7 (a)) may be attributed to the result of the carbon matrix being etched as a result of the nanoparticles formed breaking through the carbon shell after calcination of the supported metal salt at high temperature. The next 7 (c) plot also shows a pronounced hysteresis, which is characteristic of mesoporous solids. The data support is provided for the main distribution range of the pore diameter in the inset, the pore diameter is mainly distributed between 20 and 40 and nm, the pore diameter range is also larger than that of the pure N-C material, and the Mo is fully proved 0.14 Pd 0.86 the/N-C alloy is present inside the polypyrrole.
FIG. 8 is a schematic diagram of PPY, pt/C (20%), mo/N-C, pd/N-C, mo 0.14 Pd 0.86 LSV curves of N-C etc. catalysts. The analyzed LSV curve gives: first, the initial potential is compared, mo 0.14 Pd 0.86 The catalyst/N-C was 1.02V more nearly 1.23V than both 0.975V of Pt/C (20%) and 0.997V of Pd/N-C, indicating Mo 0.14 Pd 0.86 The N-C catalyst preferentially catalyzes the oxygen reduction reaction within the same overpotential range. Next, from half-wave potential analysis, mo 0.14 Pd 0.86 0.940/V of N-C, also the most positive of the catalysts tested, was 73 mV higher than Pt/C (20%), further indicating Mo 0.14 Pd 0.86 Preference of N-C. Finally from the limit current, mo 0.14 Pd 0.86 the/N-C catalyst was slightly lower than Pt/C (20%), but the other control Mo/N-C, pd/N-C catalyst was Mo 0.14 Pd 0.86 N-C has absolute advantages, indicating that alloy catalysts play an important role in the reaction. In summary, mo, from three basic oxygen reduction parameters 0.14 Pd 0.86 The N-C catalyst is a preferred oxygen reducing material. Tafel slope expresses currentSlope relationship between density and overpotential, as in FIG. 8 (b) Mo 0.14 Pd 0.86 N-C has the lowest slope of 50 mV dec -1 Below Pt/C (20%) (70 mV dec -1 ）、Pd/N-C（99 mV dec -1 ）、Mo/N-C（103 mV dec -1 ）、PPY（118 mV dec -1 ) (c) comparing the kinetic current densities more intuitively in the form of a histogram, when the overpotential is different, mo 0.14 Pd 0.86 The current density of the N-C kinetic control is higher than that of Pt/C (20%), which shows that the target catalyst has the fastest occurrence rate for promoting the oxygen reduction reaction and is controlled by the kinetics. For noble metal catalysts, mass specific activity (MA) and area Specific Activity (SA) are also one of the key points for evaluating the performance of one catalyst. The CV curve of fig. 8 (d) was tested in an electrolyte with continuous bubbling of argon. Mo, in terms of peak area of hydrogen adsorption 0.14 Pd 0.86 The ECSA of N-C is higher than Pt/C (20%), which can supply more active sites for the oxygen reduction reaction process to promote more efficient reaction. (e) And (f) the mass and area specific activities are better than those of Pt/C (20%) at different overpotential, for example, mo at an overpotential of 0.9V 0.14 Pd 0.86 The mass specific activity of N-C was 3.2 times that of Pt/C (20%), and the area specific activity was 3 times that of Pt/C (20%). Also, since Pd has a lower market price than Pt, mo, when the same catalytic activity is achieved 0.14 Pd 0.86 N-C is far lower in cost than Pt/C (20%) catalysts.
The ability to have long-term catalytic activity is one of factors to be considered in putting materials into practical use, and FIGS. 9 (a) and (b) are Mo respectively 0.14 Pd 0.86 Activity comparison curves of N-C and Pt/C (20%) before and after long-term cyclic testing using CV technique, cyclic voltammetry scanning was performed in a mixed area of kinetic and diffusion control, mo after 30000 testing 0.14 Pd 0.86 The two polarization curves of the N-C catalyst are completely coincident in this region and no attenuation occurs, which can be attributed to the in situ formation of polypyrroleThe carbon material plays a role in coating and protecting the MoPd alloy, so that the corrosion of alkaline solution can be reduced in the reaction process, and secondly, the doping of Mo element changes the electronic structure of Pd to a certain extent, so that the corrosion of harmful intermediates can be reduced. In contrast, pt/C (20%) decayed by 36 mV after only 20000 cycles of testing, indicating Mo 0.14 Pd 0.86 The N-C has better catalytic stability. (c) The graph shows Pt/C (20%) and Mo 0.14 Pd 0.86 The methanol poisoning resistance of N-C is also an important measure of the catalyst, since methanol poisoning resistance is critical in methanol-fueled cells, and 1M CH is added as the reaction proceeds to 300. 300 s 3 The current of Pt/C (20%) was rapidly decayed after addition of the OH solution to a final decay of 47.55%, in contrast to Mo 0.14 Pd 0.86 The progress of the N-C catalyst was slightly degraded, from which it can be seen that Mo 0.14 Pd 0.86 N-C has more excellent methanol poisoning resistance than Pt/C (20%).
Examples 12 to 14:
the 720 ℃ holding temperature of the step (2) in the example 11 is respectively changed to 620 ℃,770 and 820 ℃, and the morphology of the obtained product is shown in figure 10.
The morphology of the MoPd/N-C catalyst prepared by different reactions is studied, and as shown in figure 10, the higher the reaction temperature is, the more serious the carbon-nitrogen structure generated by polypyrrole in situ is destroyed. When the temperature is low, as shown in fig. 10 (a), the metal alloy nano particles are mostly encapsulated in the nitrogen-carbon material, so that the original shape of the nitrogen-carbon material is maintained as a whole; at moderate temperatures, as shown in fig. 10 (b), the confinement effect of the nitrogen-doped carbon material on the metal is similar to the growth of the metal, and the metal alloy can be just exposed and put in aggregation and migration.
As shown in FIG. 11, polarization curves of MoPd/N-C catalysts were obtained at different temperatures. 720. The LSV curve obtained by testing the obtained sample has the maximum limiting current density (-5.21 mA/cm) relative to the polarization curve of other samples 2 ) And the most positive half-wave potential (0.940V). Further analysis of polarization curveThe presented information is consistent with the morphological analysis of the electron microscope image, and the temperature can have larger influence on the mass transfer process of MoPd/N-C. At 670 ℃, the metal nano particles are completely encapsulated in the N-C material as seen from an electron microscope image, and the sample obtained at 670 ℃ has smaller limiting current and half-wave potential in the catalytic oxygen reduction reaction as seen from a polarization curve, which can be attributed to the relatively closed structure, so that the active sites are not fully contacted with reactants within a specified time. When the temperature is 820 ℃, the metal nano-particles are completely exposed to the outside and have larger size, and when the metal nano-particles are applied to the oxygen reduction reaction, the oxygen can completely cover the nano-particles, and the catalytic process is also problematic. At 770℃, the metal particles are mostly exposed, but some N-C material is present, so that samples obtained at 770℃ exhibit better catalytic performance than samples obtained at 670℃ and 820℃. Finally, when the temperature is 720 ℃, the nitrogen-doped carbon material and the metal nano particles are optimally combined, and the small-size metal nano particles can be just exposed from the nitrogen-carbon material and can be fully contacted with oxygen in the catalytic reaction, so that the optimal oxygen reduction catalytic activity is shown.
From the analysis, 720℃was confirmed as the optimal reaction temperature.
Examples 15 to 18:
the incubation times of 2 h of step (2) in example 11 were changed to 1h, 1.5h, 2.5 h, 3h, respectively, to give the product morphology as shown in fig. 12.
FIGS. 12 (a) - (e) are SEM images of MoPd/N-C prepared at different reaction times (1, 1.5, 2, 2.5, 3 h), and (a) are electron microscope images of samples of reaction 1h at 720 ℃, and it can be found that the N-C material can well maintain the original spherical structure, metal nano particles can be found on the surface of the sphere, which indicates that the metal is successfully poured into polypyrrole, but the whole sample obtained by 1h is in a relatively closed state, and the difference between the sample obtained by 1h and other four samples is large in combination with the polarization curve of the image (f), so that the structure is unfavorable for the oxygen reduction reaction, and mass transfer process of the reaction can be hindered to a certain extent. As the reaction time continued to be prolonged, it was found that when (b) the carbon nitrogen material supported molybdenum palladium metal closed structure began to exhibit a relatively open morphology when reacting 1.5 h. The electron microscope images (c) - (e) of reactions 2, 2.5 and 3h show that the degree of openness of the nanospheres increases with the extension of the reaction time, so that slight collapse occurs at 2.5 h, and the polarization curve of the image (f) shows that the difference of limiting current densities is not very large when the reactions are 1.5-3 h, and the result is consistent with the appearance presented by the electron microscope images. Careful examination can show that the sample can achieve the best degree of openness while maintaining the structure of the N-C material nanospheres when reacting 2 h, as shown in figure (C), so that figure (f) shows that the sample prepared at a reaction time of 2 h has the best catalytic capacity for the oxygen reduction reaction.
Examples 19 to 22:
the total amount of Mo and Pd in the step (1) in the example 11 is changed to 5mg, 6mg, 8mg and 9mg respectively, and the morphology of the obtained product is shown in FIG. 13.
Fig. 13 (a) - (e) are electron microscopy images of samples prepared at total metal loadings of 5, 6, 7, 8, 9, mg. (a) The figure shows that a catalyst prepared under the loading condition of 5mg has a small amount of metal nano particles outside an N-C material, but the morphology of the N-C material is almost the same as that of the N-C material without metal loading, and the reason for the situation is attributable to that a small amount of metal salt does not enter a pore canal of polypyrrole in the stirring and soaking process, so that after high-temperature annealing, no metal soaked into the polypyrrole is formed, and no limited area effect of the N-C material is generated, the nano particles with larger size are formed outside the N-C material, and after calcination and reduction at a specific temperature, almost fully-closed MoPd/N-C still appears, and the possible reason is that the metal input amount is small, so that the metal in the N-C material has enough gaps to grow, and the ideal state of swelling and breaking the shell of the N-C material is not reached. (d) Graph (e) is a relatively high load, and it is found that there are significantly more exposed metal nanoparticles than graph (a), which can be attributed to the fact that under high load, some of the impregnation problems do not enter the polypyrrole pores, and other of the impregnation problems are due to the fact that the metal load is large, and the metal and the carbon body are tightly connected during high-temperature annealing, so that the metal nanoparticles are increased, and part of the polypyrrole carrier is broken and overflowed. At a loading of 7mg (c), the ideal structure is just achieved, and an oxygen-reduced active interface is formed between the metal particles and the carbon matrix. (f) The graph shows the polarization curves of the MoPd/N-C catalyst prepared at different loading amounts of 5, 6, 7, 8 and 9 and mg, and when the optimal loading amount is determined to be 7mg according to the half-wave potential and the limiting current, the performance of the MoPd/N-C catalyst is optimal.
Examples 23 to 25:
the molar ratios of Mo to Pd in step (1) in example 11 were changed to 1/7, 1/8 and 1/10, respectively, to give the product morphology as shown in FIG. 14.
FIGS. 14 (a) - (e) are SEM images of MoPd/N-C catalysts prepared at molar ratios of 1/7, 1/8, 1/9, 1/10, 1/11 for both Mo and Pd. Overall, as the addition amount of Pd becomes larger, the number of metal nanoparticles outside the N-C material becomes larger, and the nanoparticles are likely to remain as a result of agglomeration of Pd outside the polypyrrole at high temperature. At high temperature annealing, the size is much larger than the particles inside the polypyrrole, since there is no coating and growth limiting effect of the polypyrrole, resulting in free growth, which further suggests that the carbon matrix plays an important role in metal size control. When the molar ratio of Mo to Pd reaches 1/11, as shown in the figure (d), it is evident that there are a large number of metal particles outside, corresponding to the polarization curve of the figure (f), indicating that the larger metal nanoparticles are not the main active sites and do not play a role in improving the oxygen reduction reaction activity. It was further observed that only the plot (c), the sample prepared when the molar ratio of Mo to Pd was 1/9, was more open to carbon nitrogen material and did not have more large size nanoparticles. This is also shown on the polarization curve of plot (f) and it can be found that the 1/7-MoPd/N-C sample shows the best catalytic performance for the oxygen reduction reaction.
The foregoing disclosure is illustrative of the present invention and is not to be construed as limiting the scope of the invention, which is defined by the appended claims.
Claims (9)
1. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst is characterized in that the preparation method comprises the following steps:
(1) Preparation of nanospheres polypyrrole: adding propionic acid into a container, heating to 130-160 ℃, mixing pyrrole with propionic acid to obtain pyrrole propionic acid solution, adding the pyrrole propionic acid solution into propionic acid in the container heated to 130-160 ℃ under stirring, and reacting for at least 1.5h by using oxygen as an oxidant to obtain black mixed solution; washing and separating the product with ethanol and water, and finally drying to obtain nano spherical polypyrrole;
(2) Preparation of nitrogen-doped carbon-supported Mo/Pd alloy catalyst: and (3) dipping molybdate and chloropalladate into the pore canal of the nano spherical polypyrrole prepared in the step (1), and calcining to obtain the nitrogen-doped carbon-loaded Mo/Pd alloy catalyst.
2. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to claim 1, wherein: in the step (2), the nano spherical polypyrrole prepared in the step (1) is dispersed in water, glacial acetic acid is added into the polypyrrole dispersion liquid, molybdate and chloropalladate are added, stirring and dipping are carried out, so that molybdate and chloropalladate are dipped into pore channels of the nano spherical polypyrrole, and calcination is carried out after drying treatment.
3. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to claim 1, wherein: during calcination, hydrogen is used as a reducing atmosphere, and argon is used as a protective atmosphere.
4. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to claim 1, wherein: the calcination temperature was 720 ℃.
5. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to claim 4, wherein: the calcination time was 2 h.
6. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to claim 1, wherein: the total metal loading was 7 mg/25mg polypyrrole.
7. The nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to claim 6, wherein: the molar ratio of Mo to Pd was 1:9.
8. Use of a nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to any one of claims 1-7 as a redox electrocatalyst.
9. A fuel cell, characterized in that: wherein the catalyst is a nitrogen-doped carbon-supported Mo/Pd alloy catalyst according to any one of claims 1 to 7.
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