CN113571713B - PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell - Google Patents
PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 95
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 29
- 239000000446 fuel Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052760 oxygen Inorganic materials 0.000 title description 38
- 239000001301 oxygen Substances 0.000 title description 36
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 31
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 229920000642 polymer Polymers 0.000 claims abstract description 26
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011592 zinc chloride Substances 0.000 claims abstract description 19
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000004202 carbamide Substances 0.000 claims abstract description 15
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical group [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 10
- 239000012528 membrane Substances 0.000 claims description 9
- 235000019270 ammonium chloride Nutrition 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 8
- 239000011609 ammonium molybdate Substances 0.000 claims description 8
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 8
- 229940010552 ammonium molybdate Drugs 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 99
- 239000011701 zinc Substances 0.000 description 46
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 32
- 238000012360 testing method Methods 0.000 description 27
- 238000006722 reduction reaction Methods 0.000 description 23
- 230000009467 reduction Effects 0.000 description 21
- 229910052697 platinum Inorganic materials 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 239000000956 alloy Substances 0.000 description 13
- 229910045601 alloy Inorganic materials 0.000 description 13
- 239000013078 crystal Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000000843 powder Substances 0.000 description 11
- 239000003575 carbonaceous material Substances 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 241000710013 Lily symptomless virus Species 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000004502 linear sweep voltammetry Methods 0.000 description 9
- 230000007547 defect Effects 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000002243 precursor Substances 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 238000003917 TEM image Methods 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000047 product Substances 0.000 description 6
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- -1 phthalocyanine macrocycle Chemical class 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
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- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
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- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
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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
-
- 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
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The invention provides a PtZn-loaded nitrogen-doped carbon catalyst, a preparation method thereof and an oxyhydrogen fuel cell. The preparation method of the PtZn supported nitrogen doped carbon catalyst provided by the invention comprises the following steps: a) Mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride to react to form PtZn phthalocyanine polymer; b) Carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate; c) And mixing the intermediate with acid liquor for reaction to obtain the PtZn loaded nitrogen-doped carbon catalyst. The PtZn loaded nitrogen-doped carbon catalyst prepared by the preparation method is efficient and stable, and has low cost and simple preparation process.
Description
Technical Field
The invention relates to the field of energy materials, in particular to a PtZn-loaded nitrogen-doped carbon catalyst, a preparation method thereof and an oxyhydrogen fuel cell.
Background
At present, along with the development of human society, the traditional fossil energy sources face the problems of resource failure, serious pollution and the like, and people are promoted to research and develop clean and efficient renewable energy source storage and conversion technologies. Among them, the oxyhydrogen fuel cell is focused by people because of the advantages of cleanness, environmental protection, no pollution, high energy density, light weight, portability and the like, and is expected to become a substitute for traditional fossil fuels. However, the occurrence of the Oxygen Reduction Reaction (ORR) at the cathode of a fuel cell is a key factor limiting its efficiency, and the selection of an appropriate oxygen reduction catalyst is an effective means to overcome this problem due to the slow kinetics of the oxygen reduction reaction itself.
At present, pt/C catalysts can be widely used commercially, but it is well known that Pt resources are scarce, which results in the price of Pt/C catalysts being high; meanwhile, the high-activity Pt/C catalyst needs to prepare nano-scale Pt nano-particles, which requires a complex and high-grade preparation process; finally, an important dilemma for Pt-based noble metal catalysts is that Pt is extremely poisoned by methanol or carbon monoxide and that unavoidable degradation problems occur during long-term testing, which can lead to instability in continuous operating environment testing, thereby causing significant activity decay.
Therefore, developing a Pt-based noble metal ORR catalyst with low cost, simple preparation process, stability and high efficiency is an important research topic of application significance, and is also considered as a feasible path for finally realizing large-scale application.
Disclosure of Invention
In view of the above, the present invention aims to provide a PtZn-supported nitrogen-doped carbon catalyst, a method for producing the same, and an oxyhydrogen fuel cell. The Pt-based noble metal ORR catalyst provided by the invention is efficient and stable, and has the advantages of low cost and simple preparation process.
The invention provides a preparation method of a PtZn supported nitrogen doped carbon catalyst, which comprises the following steps:
a) Mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride to react to form PtZn phthalocyanine polymer;
b) Carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate;
c) And mixing the intermediate with acid liquor for reaction to obtain the PtZn loaded nitrogen-doped carbon catalyst.
Preferably, in the step a), the reaction is performed under the action of a catalyst;
The catalyst is ammonium chloride and ammonium molybdate.
Preferably, in the step a), the molar ratio of the ammonium chloroplatinate to the zinc chloride is 1:15-25.
Preferably, in the step a), the molar ratio of the ammonium chloroplatinate to the urea is 1:0.06-0.07;
the molar ratio of the ammonium chloroplatinate to the pyromellitic anhydride is 1:10.
Preferably, the molar ratio of the ammonium chloroplatinate to the ammonium chloride to the ammonium molybdate is 1:0.02:0.7-0.8.
Preferably, in the step a), the reaction temperature is 215-225 ℃ and the reaction time is 1.5-2.5 h.
Preferably, in the step b), the pyrolysis treatment is performed at a temperature of 920 to 955 ℃ for a time of 2 to 2.5 hours.
Preferably, in the step c):
the concentration of the acid liquor is 2M;
The acid liquor is one or more selected from H 2SO4 solution, HCl solution and HNO 3 solution;
The temperature of the mixing reaction is 80 ℃ and the time is 12-15 h.
The invention also provides the PtZn-loaded nitrogen-doped carbon catalyst prepared by the preparation method.
The invention also provides an oxyhydrogen fuel cell, wherein the ORR catalyst on the membrane electrode in the oxyhydrogen fuel cell is the PtZn-loaded nitrogen-doped carbon catalyst in the technical scheme.
Firstly, mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride for reaction to form PtZn phthalocyanine polymer (PtZnPPc); then carrying out pyrolysis treatment on the polymer in a protective atmosphere to obtain an intermediate; finally, the intermediate is mixed with acid liquor for reaction to obtain the PtZn loaded nitrogen doped carbon catalyst. According to the invention, ammonium chloroplatinate which is low in price and easy to store is adopted as a Pt precursor, pt atoms and Zn are anchored by utilizing the capability of coordinating metals in the center of a phthalocyanine macrocycle, the size of the PtZn alloy is controlled by high-temperature evaporation of Zn, meanwhile, the electronic structure of Pt is changed by introducing zinc atoms, so that a (111) crystal face in PtZn is subjected to compressive strain compared with a Pt (111) crystal face, the fact that d band center moves downwards to reduce the adsorption capability of PtZn/NC to oxygen is explained, the Pt/NC has ORR catalytic activity exceeding that of Pt/C, finally, zn atoms have the same atomic radius as that of Pt, zn can be easily filled when the PtZn alloy is degraded to generate defects, and the PtZn/NC is crucial to improving the stability of a catalyst, so that the PtZn/NC also shows high activity and high stability exceeding that of commercial Pt/C.
Experimental results show that the catalyst material prepared by the invention not only has high-efficiency oxygen reduction catalytic activity (half-wave potential is 0.85V (vs. RHE), but also has excellent hydrogen precipitation performance, hydrogen evolution performance has extremely low over-potential of 5mV (vs. RHE) when the current density is 10mA/cm 2, and PtZn/NC is prepared into a membrane electrode assembly to be applied to an oxyhydrogen fuel cell for testing, and the peak power density is as high as 1W/cm 2, which exceeds the testing result of the oxyhydrogen fuel cell taking commercial Pt/C as MEA.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below, it being obvious that the drawings in the description below are only embodiments of the present invention, and that other drawings can be obtained from the provided drawings without inventive effort for a person skilled in the art.
FIG. 1 is a TEM image of the catalyst powder PtZn/NC obtained in example 1; wherein, FIG. 1a is a TEM image under a 50nm scale, and FIG. 1b is a TEM image under a 10nm scale;
FIG. 2 is an XRD pattern of PtZn/NC, pt/NC and NC of the samples obtained in example 1 and comparative examples 1 to 2;
FIG. 3 is a comparative graph of an oxygen reduction linear scan LSV for an oxygen reduction electrode based on the catalyst samples obtained in example 1 and comparative examples 1-2 and a commercial Pt/C catalyst; FIG. 3a is a graph showing LSV curves of PtZn/NC, pt/NC, NC and commercial Pt/C under oxygen reduction test conditions, and FIG. 3b is a graph showing LSV curves of PtZn/NC, pt/NC, NC and commercial Pt/C under hydrogen gas evolution reaction test conditions;
FIG. 4 is an ADT test chart of PtZn/NC sample obtained in example 1;
FIG. 5 is a graph showing stability test of PtZn/NC and commercial Pt-C catalyst obtained in example 1;
FIG. 6 is a graph showing a polarization curve test of an oxyhydrogen fuel cell based on the catalyst PtZn/NC obtained in example 1;
FIG. 7 is a graph showing a stability test of an oxyhydrogen fuel cell based on the catalyst PtZn/NC obtained in example 1;
FIG. 8 is a graph of LSV comparison of oxygen reduction based on 6 catalyst samples with different Pt/Zn ratios in example 4.
Detailed Description
The invention provides a preparation method of a PtZn supported nitrogen doped carbon catalyst, which comprises the following steps:
a) Mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride to react to form PtZn phthalocyanine polymer;
b) Carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate;
c) And mixing the intermediate with acid liquor for reaction to obtain the PtZn loaded nitrogen-doped carbon catalyst.
Firstly, mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride for reaction to form PtZn phthalocyanine polymer (PtZnPPc); then carrying out pyrolysis treatment on the polymer in a protective atmosphere to obtain an intermediate; finally, the intermediate is mixed with acid liquor for reaction to obtain the PtZn loaded nitrogen doped carbon catalyst. According to the invention, ammonium chloroplatinate which is low in price and easy to store is adopted as a Pt precursor, pt atoms and Zn are anchored by utilizing the capability of coordinating metals in the center of a phthalocyanine macrocycle, the size of the PtZn alloy is controlled by high-temperature evaporation of Zn, meanwhile, the electronic structure of Pt is changed by introducing zinc atoms, so that a (111) crystal face in PtZn is subjected to compressive strain compared with a Pt (111) crystal face, the fact that d band center moves downwards to reduce the adsorption capability of PtZn/NC to oxygen is explained, the Pt/NC has ORR catalytic activity exceeding that of Pt/C, finally, zn atoms have the same atomic radius as that of Pt, zn can be easily filled when the PtZn alloy is degraded to generate defects, and the PtZn/NC is crucial to improving the stability of a catalyst, so that the PtZn/NC also shows high activity and high stability exceeding that of commercial Pt/C.
Regarding step a): ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride are mixed and reacted to form PtZn phthalocyanine polymer.
In the invention, the synthetic route for forming PtZn phthalocyanine polymer PtZnPPc by reacting the above four raw materials is as follows:
in the invention, ammonium chloroplatinate is adopted as a Pt precursor, so that the preparation method is low in price and easy to store, the preparation cost can be effectively reduced, and the ammonium chloroplatinate can react with the other 3 raw materials to form PtZn phthalocyanine polymer with a certain structure.
In the invention, the zinc chloride is a Zn precursor. In some embodiments of the invention, the molar ratio of ammonium chloroplatinate to zinc chloride is 1:1, 1:5, 1:10, 1:20, 1:30, or 1:50. In the present invention, the molar ratio of the ammonium chloroplatinate to the zinc chloride is preferably 1: (15 to 25), more preferably 1:20. Through controlling above-mentioned proportion, can effectively disperse Pt metal, avoid it to take place to gather in the follow-up pyrolysis step, if zinc chloride duty cycle is too low, can not effectively separate Pt and Pt's distance in the product structure, causes Pt's gathering, makes the half-wave potential of product lower, and oxygen reduction activity is relatively poor, if zinc chloride duty cycle is too high, excessive Zn can cause the collapse of carbon material structure in pyrolysis evaporation step, has destroyed the carbon skeleton, makes material stability reduce.
In the present invention, the source of urea is not particularly limited, and is a general commercial product. The molar ratio of the ammonium chloroplatinate to the urea is preferably 1:0.06-0.07; in some embodiments of the invention, the molar ratio is 1:0.07.
In the present invention, the source of pyromellitic anhydride is not particularly limited, and is a general commercial product. In the present invention, the molar ratio of the ammonium chloroplatinate to pyromellitic anhydride is preferably 1:10.
In the present invention, the above four raw materials are preferably reacted under the action of a catalyst. In the present invention, the catalyst is preferably ammonium chloride or ammonium molybdate. In the invention, the mol ratio of the ammonium chloroplatinate to the ammonium chloride to the ammonium molybdate is 1:0.02:0.7-0.8; in some embodiments of the invention, the molar ratio is 1:0.02:0.74.
In the present invention, the temperature of the reaction is preferably 215 to 225 ℃, more preferably 220 ℃. The reaction time is preferably 1.5 to 2.5 hours, more preferably 2 hours. In the present invention, the above reaction is preferably carried out under an air atmosphere. According to the invention, ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride are used as raw materials, a specific phthalocyanine macrocycle is formed between the urea and the pyromellitic anhydride through the reaction, and metal Zn and Pt atoms are coordinated and anchored in the N4 center of the phthalocyanine macrocycle to form PtZn phthalocyanine polymer PtZnPPc; the introduction of Zn atoms changes the electronic structure of a metal crystal face, so that the (111) crystal face in PtZn is compressively strained compared with the Pt (111) crystal face, and the adsorption capacity of PtZn/NC to oxygen is reduced, so that the PtZn/NC has ORR catalytic activity exceeding Pt/C, and Zn atoms have the same atomic radius as Pt, and Zn can be easily filled when the PtZn alloy is degraded to generate defects, which is important for improving the stability of the catalyst, so that the PtZn/NC also shows high activity and high stability exceeding that of commercial Pt/C. In the invention, after the light green powder is obtained through the reaction, washing treatment is also carried out, and PtZn phthalocyanine polymer PtZnPPc is obtained after washing.
Regarding step b): and carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate.
In the present invention, the kind of the protective gas in the protective atmosphere is not particularly limited, and may be a conventional inert gas such as nitrogen or argon, etc., which are well known to those skilled in the art.
The PtZn phthalocyanine polymer obtained in the step a) is an organic high molecular polymer containing Pt, zn, C, N, H, O elements, the organic high molecular polymer is subjected to pyrolysis treatment in a protective atmosphere, C, N elements are carbonized, a polymer skeleton is still reserved, a graphite-like carbon nitride material is formed, H and O elements leave at a high temperature of pyrolysis, defects and metal oxides (such as zinc oxide) are generated at the same time, pt and Zn elements form PtZn alloy at a high temperature and are loaded at the defects of the carbon nitride material, and the PtZn-loaded nitrogen-doped carbon material is obtained. In addition, in the pyrolysis process, the evaporation of Zn can avoid the aggregation of Pt and create more holes, ptZn nano particles are effectively exposed to serve as active site, and the oxygen reduction performance of the material is improved.
In the present invention, the pyrolysis treatment temperature is preferably 920 to 955 ℃, more preferably 925 ℃. If the pyrolysis temperature is too low, the carbonization degree of the carbon nitride material is low, the conductivity is poor, and the mass-charge transmission is not facilitated; if the temperature is too high, the PtZn alloy aggregates, the particles become large, and the specific surface area utilization of the active species (PtZn alloy) decreases, resulting in a decrease in the activity of the product. In the present invention, the pyrolysis treatment time is preferably 2 to 2.5 hours, more preferably 2 hours; in the pyrolysis treatment link, the heating rate to the pyrolysis temperature is preferably 5 ℃/min.
Regarding step c): and mixing the intermediate with acid liquor for reaction to obtain the PtZn-loaded nitrogen-doped carbon catalyst.
In the invention, the acid liquid is preferably one or more of H 2SO4 solution, HCl solution and HNO 3 solution. In the present invention, the concentration of the acid solution is preferably 2M.
In the invention, the use amount of the intermediate and the acid solution is not particularly limited, and the intermediate can be immersed into the acid solution.
In the present invention, it is preferable to further wash with water and dry after the above-mentioned acid washing reaction. The drying is preferably vacuum drying. After the post-treatment, the PtZn-loaded nitrogen-doped carbon material is obtained.
In the invention, the reaction temperature of the intermediate and the acid liquor is preferably 80 ℃; the reaction time is preferably 12 to 15 hours. The step of heat treatment in acid liquor mainly comprises the step of carrying out double decomposition reaction on an acidic medium and metal oxide (such as zinc oxide) so as to remove zinc oxide species which have no catalytic activity in the PtZn load nitrogen-doped carbon material obtained in the step b), thereby obtaining the high-activity PtZn load nitrogen-doped carbon material.
The invention provides a method for preparing a catalyst PtZn/NC by a solid phase method, which adopts ammonium chloroplatinate which is low in price and easy to store as a Pt precursor, utilizes the capability of coordinating metals in the macrocyclic center of phthalocyanine to anchor Pt atoms and Zn to control the size of PtZn alloy by high-temperature evaporation, and simultaneously, the introduction of zinc atoms changes the electronic structure of Pt, so that the (111) crystal face in PtZn has compressive strain compared with the Pt (111) crystal face, which indicates that d band center moves downwards to reduce the adsorption capability of PtZn/NC to oxygen, thereby having ORR catalytic activity exceeding that of Pt/C, finally, zn atoms have the same atomic radius as that of Pt, and Zn can be easily filled when the PtZn alloy is degraded to generate defects, which is important for improving the stability of the catalyst, so that PtZn/NC also has high activity and high stability exceeding that of commercial Pt/C. The catalyst material prepared by the invention is applied to a hydrogen-oxygen fuel cell (particularly used as a catalyst of an air electrode in the hydrogen-oxygen fuel cell) to test, and shows a peak power density of up to 1W/cm 2, which means that the catalyst has remarkable practical application value and provides theoretical basis and experimental guidance for hydrogen energy storage and conversion technology.
The invention also provides the PtZn-loaded nitrogen-doped carbon catalyst prepared by the preparation method. In the invention, the granularity of the PtZn loaded nitrogen doped carbon catalyst is less than or equal to 10nm, and most of the particles are less than 10nm.
The invention also provides an MEA component, wherein the catalyst on the membrane electrode is the PtZn loaded nitrogen-doped carbon catalyst in the technical scheme.
The invention also provides an oxyhydrogen fuel cell, wherein the ORR catalyst on the membrane electrode is the PtZn-loaded nitrogen-doped carbon catalyst in the technical scheme.
Compared with the prior art, the PtZn-loaded nitrogen-doped carbon catalyst provided by the invention has the following beneficial effects:
1. The Pt atoms are anchored by utilizing the capability of coordinating metal in the center of the phthalocyanine ring, and meanwhile, excessive Zn atoms are introduced to increase the distance between Pt and Pt, so that aggregation of materials during pyrolysis is avoided, and therefore, the noble metal ORR catalyst with PtZn nanometer size smaller than 10nm is prepared, and the control of nanometer size is a key premise that PtZn/NC can surpass commercial Pt/C.
2. The introduction of Zn atoms changes the electronic structure of Pt, and XRD analysis of PtZn/NC shows that the (111) crystal face in PtZn has compressive strain compared with the Pt (111) crystal face, which indicates that d band center moves downwards, which means that the adsorption capacity of PtZn/NC to oxygen is weakened, so that the PtZn/NC has ORR catalytic activity exceeding that of Pt/C, and the regulation and control of the electronic structure can clearly explain the catalytic mechanism.
3. Zn atoms have the same atomic radius as Pt, and Zn can be easily filled when PtZn alloy is degraded to generate defects, which is important for improving the stability of the catalyst, so PtZn/C also shows excellent stability and durability.
4. The catalyst material prepared by the invention not only has high-efficiency oxygen reduction catalytic activity (half-wave potential is 0.85V (vs. RHE), which is better than that of a commercial platinum-carbon catalyst which is 0.83V (vs. RHE), but also has excellent hydrogen precipitation performance, hydrogen evolution has extremely low overvoltage of 5mV (vs. RHE) when the current density is 10mA/cm 2, and PtZn/NC is prepared into a film-forming electrode assembly to be applied to an oxyhydrogen fuel cell for testing, and the peak power density is as high as 1W/cm 2, which exceeds the testing result of the oxyhydrogen fuel cell taking commercial Pt/C as MEA.
For a further understanding of the present invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are merely intended to illustrate further features and advantages of the invention, and are not limiting of the claims of the invention.
Example 1
Preparation of S1, ptZn phthalocyanine Polymer (PtZnPPc):
0.5mmol of ammonium chloroplatinate, 10mmol of zinc chloride, 0.035mmol of urea, 0.01mmol of ammonium chloride, 0.37mmol of ammonium molybdate and 5mmol of pyromellitic anhydride are weighed, added into a mortar, fully ground and transferred into a magnetic boat, the magnetic boat is placed into a tube furnace, and heated at 220 ℃ for 2 hours in an air atmosphere to obtain light green powder. Sequentially washing with water, methanol and acetone, and suction filtering to obtain PtZn phthalocyanine polymer PtZnPPc.
S2, preparation of PtZn-loaded nitrogen-doped carbon material (PtZn/NC) catalyst:
200mg PtZnPPc of the powder was placed in a tube furnace and heated at 5℃per minute to 925℃for 2 hours under an N 2 atmosphere to obtain a black powder. The obtained powder was put into 80mL of a 2M H 2SO4 solution, refluxed at 80℃overnight with stirring, suction-filtered, washed with water, and then put into an oven to be dried at 60℃under vacuum for 24 hours, to obtain catalyst powder PtZn/NC.
The transmission electron microscope test results of the obtained product are shown in FIG. 1, and FIG. 1 is a TEM image of the catalyst powder PtZn/NC obtained in example 1; fig. 1a is a TEM image on a 50nm scale, and fig. 1b is a TEM image on a 10nm scale. It can be seen that the product obtained in example 1 has a particle size of 10nm or less and a majority of particles have a particle size of < 10nm.
Comparative example 1: preparation of Pt Supported Nitrogen doped carbon Material (Pt/NC)
S1, the process of the embodiment 1 is carried out, except that zinc chloride is not added.
S2, the same as in the embodiment 1.
Comparative example 2: preparation of Nitrogen-doped carbon Material NC
S1, the process of the example 1 is carried out, except that ammonium chloroplatinate and zinc chloride are not added.
S2, the same as in the embodiment 1.
Example 3
1. XRD testing
X-ray diffraction (XRD) tests were conducted on the samples PtZn/NC, pt/NC and NC obtained in example 1 and comparative examples 1 to 2, and as a result, see FIG. 2, FIG. 2 is an XRD pattern of the samples PtZn/NC, pt/NC and NC obtained in example 1 and comparative examples 1 to 2.
2. Electrochemical performance test
Preparation of oxygen reduction electrode material: ethanol and Nafion solution with the concentration of 5wt% are mixed according to the volume ratio of 20:1 to obtain a mixed solution, then a small amount of ultrapure water (the volume ratio of the ultrapure water to the precursor mixed solution is 0.2:1) is added for mixing, then 5mg of catalyst is weighed and dispersed in the obtained mixed solution, and ultrasonic dispersion is carried out for 1h to obtain the catalyst ink with uniform dispersion. And (3) dropwise adding 10mL of catalyst ink onto the glassy carbon electrode with the diameter of 5mm, and naturally drying at room temperature (the catalyst loading amount is 0.5mg/cm 2) to obtain the oxygen reduction electrode.
Constructing a three-electrode system: ag-AgCl (3M KCl solution) is used as a reference electrode, a carbon rod is used as a counter electrode, and the glassy carbon electrode coated with the catalyst is used as a working electrode. The working electrode mounted on the tester was run into a 0.5M H 2SO4 solution saturated with O 2 for testing at a scan rate of 50mV/s.
Results of testing the oxygen reduction and hydrogen evolution performance of the resulting samples referring to fig. 3, fig. 3 is a graph showing the comparison of LSV curves of the oxygen reduction linear scan based on the catalyst samples obtained in example 1 and comparative examples 1 to 2 and the oxygen reduction electrode of the commercial Pt/C catalyst, wherein fig. 3a is a graph showing the comparison of LSV curves of PtZn/NC, pt/NC, NC and commercial Pt/C under the oxygen reduction test conditions, and fig. 3b is a graph showing the comparison of LSV curves of PtZn/NC, pt/NC, NC and commercial Pt/C under the hydrogen evolution reaction test conditions. As can be seen from FIG. 3a, the catalyst PtZn/NC prepared in example 1 has a half-wave potential of 0.85V (vs. RHE) which is superior to the commercial 20wt% Pt/C catalyst (0.83V, vs. RHE), and the catalyst PtZn/NC prepared in the invention has high-efficiency oxygen reduction performance. As can be seen from FIG. 3b, the catalyst PtZn/NC prepared in example 1 has an overpotential of 5mV (vs. RHE) at 10mA/cm 2, which is superior to the commercial 20wt% Pt/C catalyst (35 mV, vs. RHE), and the catalyst PtZn/NC prepared in the invention has high-efficiency hydrogen gas precipitation performance, and can be used as a dual-functional electrocatalyst for oxygen gasification raw reaction (ORR) and hydrogen gas precipitation reaction (HER).
ADT and stability tests were performed on the above three-electrode system, and as a result, see FIGS. 4 and 5, FIG. 4 is an ADT test chart of the sample PtZn/NC obtained in example 1, and FIG. 5 is a stability test chart of the sample PtZn/NC obtained in example 1 and a commercial platinum carbon catalyst. As can be seen from FIGS. 4 to 5, the PtZn/NC obtained in example 1 was found to have a half-wave potential which was attenuated by only 35mV after 10000 cycles, and was able to maintain 92% of the original current density after 20000 seconds of operation, demonstrating that the catalyst PtZn/NC prepared in the present invention had excellent stability.
3. Preparation and testing of MEA Membrane electrode
The catalyst PtZn/NC prepared in example 1 was spray coated to prepare an MEA assembly: anode: 0.1mg Pt/cm2; and (3) cathode: 0.1mg Pt/cm2,5cm2; proton membrane: nafion211; hot pressing conditions: 0.2MPa,90s. Machine model: multi-range fuel CELL TEST SYSTEM (850e,Scribner Associates Inc.). Test conditions: 80 ℃,1.5bar (150 kPa), 100% RH (relative humidity).
Test results referring to fig. 6 and 7, fig. 6 is a polarization curve test chart of an oxyhydrogen fuel cell based on the catalyst PtZn/NC obtained in example 1, and fig. 7 is a stability test chart of an oxyhydrogen fuel cell based on the catalyst PtZn/NC obtained in example 1. As can be seen from fig. 6, the application of the PtZn/NC-prepared film electrode assembly to an oxyhydrogen fuel cell was tested, exhibiting a peak power density as high as 1W/cm 2, exceeding the oxyhydrogen fuel cell test result (0.7W/cm 2) of commercial Pt/C as MEA, demonstrating that the PtZn/NC-prepared film electrode has excellent oxyhydrogen fuel cell properties. As can be seen from fig. 7, in the oxyhydrogen fuel cell test, the peak power density of PtZn/NC after 30000 cycles was still maintained at 92% or more, demonstrating that the membrane electrode prepared by PtZn/NC has excellent cycle stability.
Example 4
Preparation of S1, ptZn phthalocyanine Polymer (PtZnPPc):
0.035mmol (2.1 g) of urea, 0.01mmol (0.5 g) of ammonium chloride, 0.37mmol (0.13 g) of ammonium molybdate and 5mmol (1.1 g) of pyromellitic anhydride were weighed into a mortar, and then ammonium chloroplatinate and zinc chloride (wherein the molar amount of ammonium chloroplatinate was fixed at 0.5 mmol) were added in the molar ratios of Pt to Zn of 1:1, 1:5, 1:10, 1:20 (i.e., corresponding example 1), 1:30 and 1:50, respectively, and after sufficient grinding, transferred to a magnetic boat, the magnetic boat was placed into a tube furnace and heat-treated at 220℃for 2 hours under an air atmosphere to obtain pale green powder. Sequentially washing with water, methanol and acetone, and suction filtering to obtain PtZn phthalocyanine polymer powder respectively named ：Pt1Zn1PPc、Pt1Zn5PPc、Pt1Zn10PPc、Pt1Zn20PPc、Pt1Zn30PPc、 Pt1Zn50PPc.
S2, preparing a PtZn supported nitrogen doped carbon material catalyst:
the procedure of example 1 was followed, and the obtained catalyst powder was designated ：Pt1Zn1/NC、 Pt1Zn5/NC、Pt1Zn10/NC、Pt1Zn20/NC( as example 1 product) and Pt 1Zn30/NC、Pt1Zn50/NC, respectively.
The above 6 catalyst samples were each prepared as oxygen reduction electrode materials according to example 3, and oxygen reduction linear scan LSV curves were tested according to example 3, and the results are shown in fig. 8, and fig. 8 is a graph showing comparison of oxygen reduction LSVs for the catalyst samples based on 6 different Pt/Zn ratios in example 4. The main comparative index of the oxygen reduction property of the catalyst is the half-wave potential, that is, the potential corresponding to the half value of the limiting current density (the current density J corresponding to the abscissa of 0.2V in the figure), and a larger (positive) value indicates a quicker oxygen reduction and a more excellent oxygen reduction property.
As can be seen from FIG. 8, the half-wave potential of Pt 1Zn5/NC was 0.71V, the half-wave potential of Pt 1Zn10/NC was 0.80V, the half-wave potential of Pt 1Zn20/NC was 0.85V, the half-wave potential of Pt 1Zn30/NC was 0.80V, and the half-wave potential of Pt 1Zn50/NC was 0.65V, wherein Pt 1Zn20/NC exhibited the most excellent oxygen reduction activity, i.e., the half-wave potential was 0.85V, which was significantly higher than the other molar ratio catalysts, and higher than the commercial platinum carbon catalysts (0.83V, vs. When the Pt/Zn ratio is 1:1, 1:5 and 1:10, the Zn ratio is too small, and the distance between Pt and Pt is not effectively separated, so that Pt is aggregated; when the Pt/Zn ratio is 1:30 or 1:50, excessive Zn is evaporated at the pyrolysis temperature to cause collapse of the carbon material structure, and the carbon skeleton is destroyed, so that the stability of the material is reduced.
As can be seen from the above examples, the present invention provides a method for preparing a catalyst PtZn/NC by a solid phase method, which uses cheap and easy-to-store ammonium chloroplatinate as a Pt precursor, and uses the capability of coordinating metals in the macrocyclic center of phthalocyanine to anchor Pt atoms and Zn to control the size of the PtZn alloy by high-temperature evaporation, and at the same time, the introduction of zinc atoms changes the electronic structure of Pt, so that the (111) crystal plane in PtZn is compressively strained compared with the Pt (111) crystal plane, which means that the d-band center moves down to weaken the adsorption capability of PtZn/NC to oxygen, thus having ORR catalytic activity exceeding that of Pt/C, and finally, zn atoms have the same atomic radius as Pt, and Zn can be easily filled when the PtZn alloy is degraded to generate defects, which is critical to promote the stability of the catalyst, so that Zn/NC also shows high activity and high stability of Pt than commercial Pt/C. The catalyst material prepared into the membrane electrode assembly is applied to an oxyhydrogen fuel cell for testing, and shows peak power density of up to 1W/cm 2, which means that the catalyst has remarkable practical application value and provides theoretical basis and experimental guidance for hydrogen energy storage and conversion technology.
The principles and embodiments of the present invention have been described herein with reference to specific examples, the description of which is intended only to aid in understanding the method of the invention and its core concept, including the best mode, and also to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that it will be apparent to those skilled in the art that the present invention may be modified and practiced without departing from the spirit of the invention, and that these modifications and adaptations are intended to be within the scope of the appended claims. The scope of the patent protection is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal language of the claims.
Claims (5)
1. The preparation method of the PtZn supported nitrogen doped carbon catalyst is characterized by comprising the following steps of:
a) Mixing ammonium chloroplatinate, zinc chloride, urea and pyromellitic anhydride to react to form PtZn phthalocyanine polymer; the molar ratio of the ammonium chloroplatinate to the zinc chloride is 1:15-25; the reaction is carried out under the action of a catalyst; the catalyst is ammonium chloride and ammonium molybdate; the mol ratio of the ammonium chloroplatinate to the ammonium chloride to the ammonium molybdate is 1:0.02:0.7-0.8; the molar ratio of the ammonium chloroplatinate to the urea is 1:0.06-0.07; the reaction temperature is 215-225 ℃ and the reaction time is 1.5-2.5 h;
b) Carrying out pyrolysis treatment on the PtZn phthalocyanine polymer in a protective atmosphere to obtain an intermediate; the pyrolysis treatment is carried out at a temperature of 920-955 ℃ for 2-2.5 hours;
c) And mixing the intermediate with acid liquor for reaction to obtain the PtZn loaded nitrogen-doped carbon catalyst.
2. The method according to claim 1, wherein in the step a),
The molar ratio of the ammonium chloroplatinate to the pyromellitic anhydride is 1:10.
3. The method according to claim 1, wherein in step c):
the concentration of the acid liquor is 2M;
The acid liquor is one or more selected from H 2SO4 solution, HCl solution and HNO 3 solution;
the temperature of the mixing reaction is 80 ℃ and the time is 12-15 h.
4. A PtZn-supported nitrogen-doped carbon catalyst produced by the production method of any one of claims 1 to 3.
5. An oxyhydrogen fuel cell, wherein the ORR catalyst on the membrane electrode in the oxyhydrogen fuel cell is the PtZn-supported nitrogen-doped carbon catalyst of claim 4.
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