CN117174924A - Non-noble metal catalyst, preparation method thereof, fuel cell and automobile - Google Patents
Non-noble metal catalyst, preparation method thereof, fuel cell and automobile Download PDFInfo
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- CN117174924A CN117174924A CN202311131594.5A CN202311131594A CN117174924A CN 117174924 A CN117174924 A CN 117174924A CN 202311131594 A CN202311131594 A CN 202311131594A CN 117174924 A CN117174924 A CN 117174924A
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 130
- 239000003054 catalyst Substances 0.000 title claims abstract description 77
- 239000000446 fuel Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 150000001923 cyclic compounds Chemical class 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 32
- 239000013522 chelant Substances 0.000 claims abstract description 25
- 125000003277 amino group Chemical group 0.000 claims abstract description 24
- 238000001354 calcination Methods 0.000 claims abstract description 22
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000002253 acid Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- DTXVKPOKPFWSFF-UHFFFAOYSA-N 3(S)-hydroxy-13-cis-eicosenoyl-CoA Chemical compound NC1=CC=C(Cl)N=N1 DTXVKPOKPFWSFF-UHFFFAOYSA-N 0.000 claims description 10
- 150000001491 aromatic compounds Chemical class 0.000 claims description 8
- 150000001334 alicyclic compounds Chemical class 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 125000006413 ring segment Chemical group 0.000 claims description 6
- WOXWUZCRWJWTRT-UHFFFAOYSA-N 1-amino-1-cyclohexanecarboxylic acid Chemical compound OC(=O)C1(N)CCCCC1 WOXWUZCRWJWTRT-UHFFFAOYSA-N 0.000 claims description 4
- KHUFHLFHOQVFGB-UHFFFAOYSA-N 1-aminoanthracene-9,10-dione Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2N KHUFHLFHOQVFGB-UHFFFAOYSA-N 0.000 claims description 4
- DRNGLYHKYPNTEA-UHFFFAOYSA-N 4-azaniumylcyclohexane-1-carboxylate Chemical compound NC1CCC(C(O)=O)CC1 DRNGLYHKYPNTEA-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- HWYHZTIRURJOHG-UHFFFAOYSA-N luminol Chemical compound O=C1NNC(=O)C2=C1C(N)=CC=C2 HWYHZTIRURJOHG-UHFFFAOYSA-N 0.000 claims description 3
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical compound C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 claims description 3
- LJXQPZWIHJMPQQ-UHFFFAOYSA-N pyrimidin-2-amine Chemical compound NC1=NC=CC=N1 LJXQPZWIHJMPQQ-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- -1 amino cyclic compound Chemical class 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 8
- 230000000536 complexating effect Effects 0.000 abstract description 5
- 125000004122 cyclic group Chemical group 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- 238000001035 drying Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000010668 complexation reaction Methods 0.000 description 13
- 239000012528 membrane Substances 0.000 description 13
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 239000010453 quartz Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 125000004429 atom Chemical group 0.000 description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000002791 soaking Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000956 alloy Substances 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 229910000365 copper sulfate Inorganic materials 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- 150000001717 carbocyclic compounds Chemical class 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- ZVIDMSBTYRSMAR-UHFFFAOYSA-N N-Methyl-4-aminobenzoate Chemical compound CNC1=CC=C(C(O)=O)C=C1 ZVIDMSBTYRSMAR-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 125000005595 acetylacetonate group Chemical group 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
Abstract
The application relates to a non-noble metal catalyst, a preparation method thereof, a fuel cell and an automobile. The preparation method of the non-noble metal catalyst comprises the following steps: mixing an amino-containing cyclic compound, a non-noble metal salt and an organic solvent, and then carrying out a complex reaction at 60-80 ℃ to obtain a non-noble metal chelate; and calcining the non-noble metal chelate to obtain the non-noble metal catalyst. The amino group on the amino cyclic compound and the non-noble metal ions in the non-noble metal salt undergo a complexing reaction to generate a non-noble metal chelate, and the non-noble metal chelate has a cyclic structure, so that the non-noble metal catalyst can be effectively prevented from being dissolved by acid after the non-noble metal chelate is further calcined, the stability of the non-noble metal catalyst is further effectively improved, and the obtained non-noble metal catalyst has higher quality activity and current density.
Description
Technical Field
The application relates to the field of batteries, in particular to a non-noble metal catalyst, a preparation method thereof, a fuel cell and an automobile.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs) are one of the important ways to achieve the "two-carbon strategy". While excessive cost is still an important factor limiting further commercialization of fuel cell automobiles. To date, commercial proton exchange membrane fuel cell products still rely heavily on Pt-based catalysts, such that catalyst costs account for over 40% of fuel cell costs. The low use, even no use, of Pt noble metals without affecting performance is a requisite path to facilitate large-scale application of fuel cells.
Conventional proton exchange membrane fuel cell catalysts include Pt/C catalysts, which are highly dispersed Pt nanoparticles supported on activated carbon, such Pt/C catalysts are disadvantageous for further reduction of Pt loading. At present, alloying is adopted to modify, such as adding elements such as cobalt, nickel, palladium and the like to prepare an alloy catalyst so as to reduce the dosage of Pt and obtain higher catalytic activity; however, the alloy element is easy to be dissolved by acid and lost, so that the alloy catalyst is degraded faster, and the stability is poor.
Disclosure of Invention
Based on the above, the application provides a non-noble metal catalyst with higher mass activity and higher stability, a preparation method thereof, a fuel cell and an automobile.
The technical scheme for solving the technical problems is as follows.
In one aspect, the application provides a method for preparing a non-noble metal catalyst, comprising the steps of:
mixing an amino-containing cyclic compound, a non-noble metal salt and an organic solvent, and then carrying out a complex reaction at 60-80 ℃ to obtain a non-noble metal chelate;
and calcining the non-noble metal chelate to obtain the non-noble metal catalyst.
In some embodiments, the non-noble metal catalyst may be prepared by a method wherein the cyclic compound comprises at least one of an alicyclic compound and an aromatic compound, the cyclic compound being substituted with the amino group.
In some embodiments, the non-noble metal catalyst is prepared by a method wherein the cycloaliphatic compound comprises at least one of cyclohexane and piperazine.
In some of these embodiments, the non-noble metal catalyst is prepared by a process wherein the aromatic compound comprises at least one of benzene, pyridazine, anthraquinone, and pyrimidine.
In some of these embodiments, the non-noble metal catalyst is prepared by a process wherein the amino group is directly attached to a ring atom in the cyclic compound.
In some of these embodiments, the non-noble metal catalyst is prepared by a process wherein the amino-containing cyclic compound comprises at least one of 3-aminophthalhydrazide, 3-amino-6-chloropyridazine, 1-aminocyclohexane carboxylic acid, 1-aminoanthraquinone, 4-aminocyclohexane carboxylic acid, 2-aminopyrimidine, and 1-amino-4-methylpiperazine.
In some embodiments, the non-noble metal salt comprises at least one of copper, iron, and cobalt.
In some embodiments, the non-noble metal salt comprises at least one of a nitrate, sulfate, chloride, and acetate of a non-noble metal.
In some of these embodiments, the non-noble metal catalyst is prepared by a process wherein the molar ratio of the non-noble metal salt to the amino-containing cyclic compound is 1 (3-10).
In some embodiments, the organic solvent comprises at least one of ethanol, cyclohexane, and acetone.
In some embodiments, the non-noble metal catalyst is prepared by the calcination treatment at a temperature of 600 ℃ to 1000 ℃ for a time of 1h to 4h.
In some of these embodiments, the non-noble metal catalyst is prepared by a method wherein the atmosphere of the calcination treatment comprises at least one of nitrogen, argon, and helium.
In some embodiments, the method for preparing a non-noble metal catalyst further comprises the step of removing impurities from the calcined product by using an acid solution after the calcining process is finished.
The second aspect of the application provides a non-noble metal catalyst prepared by the preparation method provided by the first aspect.
A third aspect of the application provides a fuel cell comprising the second aspect provides a non-noble metal catalyst.
A fourth aspect of the application provides an automobile comprising the fuel cell provided in the third aspect.
Compared with the prior art, the preparation method of the non-noble metal catalyst has the following beneficial effects:
according to the preparation method of the non-noble metal catalyst, the amino-containing cyclic compound, the non-noble metal salt and the organic solvent are mixed and then subjected to complexation reaction at a specific temperature, the amino on the cyclic compound and the non-noble metal ions in the non-noble metal salt are subjected to complexation reaction to generate the non-noble metal chelate, the non-noble metal chelate has a cyclic structure, so that when the non-noble metal chelate is further subjected to calcination treatment and subjected to carbonization reduction reaction, the amino-containing cyclic compound is used as a carbon source and a nitrogen source, the carbon element forms a uniform and stable pore structure, nitrogen atoms linked on a carbon skeleton and the non-noble metal atoms complexed with the nitrogen atoms are uniformly distributed in the pore structure of carbon, the acting force between the generated non-noble metal in the non-noble metal-N-C catalyst and the carbon skeleton is strong, and acid dissolution can be effectively avoided, and the stability of the non-noble metal catalyst is effectively improved; meanwhile, as no additional carbon source or nitrogen source is required to be introduced, the additional degradation caused by the non-uniform size of the catalyst is avoided; and the non-noble metal in the non-noble metal-N-C exists in a single atom form, so that the catalytic site of the catalyst is fully exposed, and the obtained non-noble metal catalyst has higher mass activity and current density.
The preparation method of the non-noble metal catalyst is simple, low in cost and good in development prospect.
Detailed Description
Reference now will be made in detail to embodiments of the application, one or more examples of which are described below. Each example is provided by way of explanation, not limitation, of the application. Indeed, it will be apparent to those skilled in the art that various modifications and variations can be made to the present application without departing from the scope or spirit of the application. For example, features illustrated or described as part of one embodiment can be used on another embodiment to yield still a further embodiment.
Accordingly, it is intended that the present application cover such modifications and variations as fall within the scope of the appended claims and their equivalents. Other objects, features and aspects of the present application will be disclosed in or be apparent from the following detailed description. It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present application.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.
The terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising one … …" does not exclude the presence of other like elements in a process, method, article, or apparatus that comprises the element. The indefinite articles "a" and "an" preceding an element or component of the application are not limited to the requirement (i.e. the number of occurrences) of the element or component. Thus, the use of "a" or "an" should be interpreted as including one or at least one, and the singular reference of an element or component includes the plural reference unless the amount clearly dictates otherwise. The meaning of "a plurality of" means at least two, e.g., two, three, etc., unless explicitly defined otherwise.
The weights of the relevant components mentioned in the description of the embodiments of the present application may refer not only to the specific contents of the components, but also to the proportional relationship between the weights of the components, so long as the contents of the relevant components in the description of the embodiments of the present application are scaled up or down within the scope of the disclosure of the embodiments of the present application. Specifically, the weight described in the specification of the embodiment of the present application may be mass units known in the chemical industry field such as μ g, mg, g, kg.
Except where shown or otherwise indicated in the operating examples, all numbers expressing quantities of ingredients, physical and chemical properties, and so forth, used in the specification and claims are to be understood as being modified in all instances by the term "about". For example, therefore, unless indicated to the contrary, the numerical parameters set forth in the foregoing specification and attached claims are approximations that can be varied appropriately by those skilled in the art utilizing the teachings disclosed herein seeking to obtain the desired properties. The use of numerical ranges by endpoints includes all numbers subsumed within that range and any range within that range, e.g., 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, 5, and the like.
An embodiment of the present application provides a method for preparing a non-noble metal catalyst, including:
step S10: mixing the cyclic compound containing amino, non-noble metal salt and organic solvent, and then carrying out complexation reaction at 60-80 ℃ to obtain the non-noble metal chelate.
It is understood that the temperature of the complexation reaction includes, but is not limited to, 60 ℃, 62 ℃, 65 ℃, 68 ℃, 70 ℃, 72 ℃, 75 ℃, 78 ℃, 80 ℃. The following holds true for the range that any two of these point values may be made up as end values in some examples.
By controlling the reaction temperature, the amino group in the amino group-containing cyclic compound and the non-noble metal ion in the non-noble metal salt undergo a complexing reaction to generate a non-noble metal chelate, and the non-noble metal chelate has a cyclic structure.
In some examples, in step S10, the temperature of the complexation reaction is 60 ℃ to 70 ℃.
Further, the temperature of the complexation reaction is 60-65 ℃.
In some examples, in step S10, the time of the complexation reaction is 1h to 4h.
It is understood that the time of the complexation reaction includes, but is not limited to, 1h, 2h, 3h, 4h.
It is understood that amino in an amino-containing cyclic compound means that the cyclic compound is substituted with at least one amino group; further, the atom of the cyclic compound substituted with an amino group may be located on the ring, i.e., the amino group is directly attached to a ring atom of the cyclic compound, e.g., the amino group replaces a hydrogen atom on a benzene ring, and the amino group is directly attached to a carbon atom on the benzene ring; the amino-substituted atom of the cyclic compound may also be absent from the ring, i.e., there may be other atoms between the amino group and the ring atom in the cyclic compound, such as methyl hydrogen on amino-substituted toluene; further, the cyclic compound may further contain other substituents such as carboxyl, hydroxyl, halogen, etc.; further, cyclic compounds are classified into alicyclic compounds and aromatic compounds, and may be classified into carbocyclic compounds and heterocyclic compounds according to ring atoms, and may be classified into monocyclic and polycyclic compounds according to the number of rings.
In some examples, in step S10, the cyclic compound includes at least one of an alicyclic compound and an aromatic compound, and the cyclic compound is substituted with an amino group.
It is understood that alicyclic compounds are a class of carbocyclic compounds that have similar properties to aliphatic compounds; the aromatic compound is a compound containing benzene ring or condensed benzene system in the molecule.
Further, the alicyclic compound includes at least one of cyclohexane and piperazine.
Further, the aromatic compound includes at least one of benzene, pyridazine, anthraquinone and pyrimidine.
In some examples, in step S10, the amino group is directly attached to a ring atom in the cyclic compound.
In some examples thereof, in step S10, the amino-containing cyclic compound includes amino-substituted cyclohexane, amino-substituted pyridazine, amino-substituted anthraquinone, amino-substituted pyrimidine, amino-substituted piperazine, and amino-substituted phthalhydrazide.
In some examples thereof, in step S10, the amino group-containing cyclic compound includes at least one of 3-aminophthalhydrazide, 3-amino-6-chloropyridazine, 1-aminocyclohexane carboxylic acid, 1-aminoanthraquinone, 4-aminocyclohexane carboxylic acid, 2-aminopyrimidine, and 1-amino-4-methylpiperazine.
In some of these examples, in step S10, the non-noble metal in the non-noble metal salt includes at least one of copper, iron, and cobalt.
In some of these examples, in step S10, the non-noble metal in the non-noble metal salt comprises copper.
In some examples, in step S10, the non-noble metal salt is a soluble metal salt.
It is understood that soluble metal salts include, but are not limited to, nitrates, sulfates, halides, acetates, carbonates, acetylacetonates, and the like.
In some examples, in step S10, the non-noble metal salt includes at least one of a nitrate, sulfate, halide, and acetate of the non-noble metal.
Further, the non-noble metal salt includes at least one of copper nitrate, copper sulfate, copper chloride, copper acetate, iron nitrate, iron sulfate, iron chloride, and iron acetate.
In some examples, in step S10, the non-noble metal salt includes at least one of copper nitrate, copper sulfate, copper chloride, copper acetate.
In some examples, in step S10, the molar ratio of the non-noble metal salt to the amino group-containing cyclic compound is 1 (3 to 10).
It is understood that the molar ratio of non-noble metal salt to amino-containing cyclic compound includes, but is not limited to, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10.
Alternatively, the molar ratio of the non-noble metal salt to the amino group-containing cyclic compound is 1 (3-7).
In some examples thereof, in step S10, the organic solvent includes at least one of ethanol, cyclohexane, and acetone.
Alternatively, the organic solvent comprises ethanol.
In some examples, in step S10, the volume ratio of the total mass of the amino group-containing cyclic compound and the non-noble metal salt to the organic solvent is (20 to 40) g/L.
It is understood that the volume ratio of the total mass of the amino group-containing cyclic compound and the non-noble metal salt to the organic solvent includes, but is not limited to, 20g/L, 22g/L, 25g/L, 28g/L, 30g/L, 32g/L, 35g/L, 38g/L, 40g/L.
In some examples, after the completion of the complexing reaction, step S10 further includes a step of removing the solvent from the reaction solution after the complexing reaction.
It is understood that the removal of the solvent means that the solvent in the reaction solution is removed, and the black powder is obtained after the solvent is removed, that is, the non-noble metal chelate.
In some examples, in step S10, the step of removing the solvent includes: and drying the reaction solution after the complexation reaction at 30-50 ℃ for 8-16 h.
It will be appreciated that in the solvent removal step, the drying temperature includes, but is not limited to, 30 ℃, 35 ℃, 40 ℃, 42 ℃, 46 ℃, 50 ℃ for a period of time including, but not limited to, 8 hours, 10 hours, 12 hours, 15 hours, 16 hours.
Step S20: and calcining the non-noble metal chelate to obtain the non-noble metal catalyst.
According to the preparation method of the non-noble metal catalyst, the amino-containing cyclic compound, the non-noble metal salt and the organic solvent are mixed and then subjected to complexation reaction at a specific temperature, the amino on the cyclic compound and the non-noble metal ions in the non-noble metal salt are subjected to complexation reaction to generate the non-noble metal chelate, the non-noble metal chelate has a cyclic structure, so that when the non-noble metal chelate is further subjected to calcination treatment and subjected to carbonization reduction reaction, the amino-containing cyclic compound is used as a carbon source and a nitrogen source, the carbon element forms a uniform and stable pore structure, nitrogen atoms linked on a carbon skeleton and the non-noble metal atoms complexed with the nitrogen atoms are uniformly distributed in the pore structure of carbon, the acting force between the generated non-noble metal in the non-noble metal-N-C catalyst and the carbon skeleton is strong, and acid dissolution can be effectively avoided, and the stability of the non-noble metal catalyst is effectively improved; meanwhile, as no additional carbon source or nitrogen source is required to be introduced, the additional degradation caused by the non-uniform size of the catalyst is avoided; and the non-noble metal in the non-noble metal-N-C exists in a single atom form, so that the catalytic site of the catalyst is fully exposed, and the obtained non-noble metal catalyst has higher mass activity and current density.
In some examples, in step S20, the calcination treatment is performed at 600 to 1000 ℃ for 1 to 4 hours.
It is understood that the temperature of the calcination treatment includes, but is not limited to 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃, 820 ℃, 850 ℃, 900 ℃, 950 ℃, 1000 ℃ for a period of time including, but not limited to, 1h, 2h, 3h, 3.5h, 4h.
Optionally, the temperature of the calcination treatment is 600 ℃ to 900 ℃.
Further, the temperature of the calcination treatment is 800-900 ℃.
In some of these examples, in step S20, the atmosphere of the calcination process includes at least one of nitrogen and an inert gas.
In some of these examples, in step S20, the atmosphere of the calcination process includes at least one of nitrogen, argon, and helium.
Optionally, the atmosphere of the calcination treatment is nitrogen.
In some of these examples, in step S20, a calcination process is performed in a quartz tube furnace.
In some examples, after the calcining step is finished in step S20, the method further includes a step of removing impurities from the calcined product with an acid solution.
And (3) removing impurities from the calcined product by adopting acid liquor, so that non-noble metal oxides and non-noble metal chelates which are not completely pyrolyzed and generated by oxidation of uncomplexed metal ions in the calcination treatment can be removed.
In some examples, the acid solution includes at least one of sulfuric acid and hydrochloric acid in the removing step.
In some examples, the concentration of the acid solution in the impurity removal step is 0.05mol/L to 0.15mol/L.
It is understood that the concentration of the acid solution includes, but is not limited to, 0.05mol/L, 0.08mol/L, 0.1mol/L, 0.12mol/L, 0.14mol/L, 0.15mol/L.
In some examples, the removing step comprises: and (3) placing the calcined product into acid liquor for soaking.
In some examples, the acid treatment time is 16-24 hours in the impurity removal step.
It is understood that the acid treatment time includes, but is not limited to, 16h, 18h, 20h, 22h, 24h.
The preparation method of the non-noble metal catalyst is simple, low in cost and good in development prospect.
The application provides a non-noble metal catalyst, which is prepared by the preparation method.
The non-noble metal catalyst provided by the application has a general formula of Me-N-C, wherein Me is a non-noble metal element.
An embodiment of the application provides an application of the non-noble metal catalyst in preparing fuel cells.
Another embodiment of the present application provides a fuel cell comprising the non-noble metal catalyst described above.
The non-noble metal catalyst can endow the fuel cell with larger electrochemical active area (ECSA), higher mass activity and current density and better stability.
It will be appreciated that the fuel cell comprises a membrane electrode and bipolar plates disposed on both sides of the membrane electrode, the membrane electrode comprising a proton exchange membrane, a catalyst layer and a gas diffusion layer, the catalyst layer being disposed on both sides of the proton exchange membrane, the gas diffusion layer being disposed on a side of the catalyst layer remote from the proton exchange membrane, the catalyst layer comprising the non-noble metal catalyst described above.
An embodiment of the present application provides an electric device including the above-described fuel cell.
It is understood that electrical devices include, but are not limited to, automobiles, airplanes, medical devices, household appliances, and the like.
An embodiment of the present application provides an automobile including the above fuel cell.
The present application will be described in further detail with reference to the following specific embodiments, but the embodiments of the present application are not limited thereto.
Example 1
1) Adding 2.0g of copper chloride and 8.0g of 3-amino-6 chloropyridazine into 200mL of ethanol, uniformly dispersing by ultrasonic, reacting for 5 hours at 60 ℃, placing the reaction solution into a drying box, and drying for 10 hours at 40 ℃ to remove the solvent to obtain black powder, namely a non-noble metal chelate; wherein, the mol ratio of the copper chloride to the 3-amino-6-chloropyridazine is 1:4.2;
2) Transferring the black powder into a quartz tube furnace, pyrolyzing the sample at 800 ℃ for 2 hours under the protection of nitrogen, cooling the sample to room temperature, soaking the sample in 0.1mol/L dilute sulfuric acid for 16 hours, filtering the solution, washing filter residues with deionized water for 3 times, and drying the sample at 60 ℃ for 12 hours to obtain the non-noble metal catalyst.
Example 2
1) Adding 2.4g of copper sulfate and 8.4g of 4-aminocyclohexylcarboxylic acid into 200mL of ethanol, uniformly dispersing by ultrasonic, reacting for 4 hours at 70 ℃, placing the reaction solution into a drying box, and drying at 40 ℃ for 12 hours to remove the solvent to obtain black powder, namely a non-noble metal chelate;
2) Transferring the black powder into a quartz tube furnace, pyrolyzing the sample at 700 ℃ for 2 hours under the protection of nitrogen, cooling the sample to room temperature, soaking the sample in 0.1mol/L dilute sulfuric acid for 24 hours, filtering and washing filter residues with deionized water for 3 times, and drying the sample at 50 ℃ for 16 hours to obtain the non-noble metal catalyst.
Example 3
1) Adding 3.0g of copper nitrate and 12.0g of 1-aminoanthraquinone into 300mL of ethanol, uniformly dispersing by ultrasonic, reacting for 5 hours at 80 ℃, placing the reaction solution into a drying box, and drying for 14 hours at 50 ℃ to remove the solvent to obtain black powder, namely a non-noble metal chelate;
2) Transferring the black powder into a quartz tube furnace, pyrolyzing the sample at 900 ℃ for 1 hour under the protection of nitrogen, cooling the sample to room temperature, soaking the sample in 0.1mol/L dilute sulfuric acid for 24 hours, filtering the solution, washing filter residues with deionized water for 3 times, and drying the sample at 50 ℃ for 14 hours to obtain the non-noble metal catalyst.
Example 4
1) Adding 2.0g of copper acetate and 8.4g of 1-aminocyclohexane carboxylic acid into 250mL of ethanol, uniformly dispersing by ultrasonic, reacting for 5 hours at 80 ℃, placing the reaction solution into a drying box, and drying at 40 ℃ for 12 hours to remove the solvent to obtain black powder, namely a non-noble metal chelate;
2) Transferring the black powder into a quartz tube furnace, pyrolyzing the sample at 600 ℃ for 4 hours under the protection of nitrogen, cooling the sample to room temperature, soaking the sample in 0.1mol/L dilute sulfuric acid for 24 hours, filtering and washing filter residues with deionized water for 3 times, and drying the sample at 50 ℃ for 16 hours to obtain the non-noble metal catalyst.
Example 5
Substantially the same as in example 1, except that in example 5, step 2), the black powder was transferred into a quartz tube furnace, and the sample was pyrolyzed at 700 ℃ for 4 hours under nitrogen protection.
Example 6
Substantially the same as in example 1, except that in example 6, step 1), the temperature of the complexation reaction was 70 ℃.
Example 7
Substantially the same as in example 1, except that in step 1) of example 7, the molar ratio of the non-noble metal salt to the amino group-containing cyclic compound was 1:7.
Example 8
Substantially the same as in example 1, except that in example 8, step 1), the molar ratio of the non-noble metal salt to the amino group-containing cyclic compound was 1:10.
Comparative example 1
Substantially the same as in example 1, except that comparative example 1 was changed to equimolar thiourea with 3-amino-6-chloropyridazine in step 1) of example 1.
Comparative example 2
Substantially the same as in example 1, except that comparative example 1 was changed to equimolar 2, 2-bipyridine with 3-amino-6-chloropyridazine in step 1) of example 1.
Comparative example 3
Substantially the same as in example 1, except that comparative example 1 was changed to equimolar 4- (methylamino) benzoic acid with 3-amino-6 chloropyridazine in step 1) of example 1.
Comparative example 4
Substantially the same as in example 1, except that in comparative example 4, step 1), the temperature of the complexation reaction was 30 ℃.
Comparative example 5
1) Adding 2.0g of copper chloride and 8.0g of 3-amino-6 chloropyridazine into 200mL of ethanol, uniformly dispersing by ultrasonic, reacting at 60 ℃ for 5 hours, adding 60g of activated carbon, stirring for 24 hours, placing the reaction solution into a drying oven, and drying at 40 ℃ for 10 hours to remove the solvent to obtain black powder, namely a non-noble metal chelate; wherein, the mol ratio of the copper chloride to the 3-amino-6-chloropyridazine is 1:4.2;
2) Transferring the black powder into a quartz tube furnace, pyrolyzing the sample at 800 ℃ for 2 hours under the protection of nitrogen, cooling the sample to room temperature, soaking the sample in 0.1mol/L dilute sulfuric acid for 16 hours, filtering the solution, washing filter residues with deionized water for 3 times, and drying the sample at 60 ℃ for 12 hours to obtain the non-noble metal catalyst.
The main parameters of each example and comparative example are shown in table 1.
TABLE 1
Wherein "m 1 ：m 2 "refers to the molar ratio of non-noble metal salt to amino group-containing cyclic compound.
The catalyst slurry is prepared and integrated into a membrane electrode for performance test according to the following steps, namely the prepared membrane electrode has different types of only the catalyst, and other materials and processes are the same:
the non-noble metal catalysts obtained in the examples and comparative examples were mixed with deionized water using a commercially available Pt/C catalyst (available from TKK), respectively, and then isopropanol and Nafion D520 were added to dissolveThe liquid, I/C, was 0.8 and sonicated until the catalyst slurry was mixed well. CCM is prepared by ultrasonic spraying, MEA is prepared by the CCM, a gas diffusion layer and a proton exchange membrane, and the CCM, the gas diffusion layer and the proton exchange membrane are assembled into a single cell to test the electrochemical activity area (ECSA), the mass activity, the polarization curve of the single cell and the performance attenuation rate after 1000 circles of Acceleration Stress Test (AST) of the catalyst of each embodiment. The single cell test conditions were: the effective area of the single cell is 5 multiplied by 5cm 2 The temperature was 80℃and the test results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the non-noble metal catalysts prepared in the examples of the present application have an electrochemical active area of more than 90m 2 /g Pt The mass activity is higher than 0.175A/g, and the two indexes are obviously higher than those of a commercial Pt/C catalyst. The non-noble metal catalysts and commercial Pt/C prepared in each example and comparative example were prepared into film-forming electrodes and assembled into single cells, which showed that the current density at 0.65V was higher than 800mA/cm in each example 2 The current density at 0.6V is higher than 940mA/cm 2 . The performance of each example was also better than the comparative example and commercial Pt/C at both 0.6V and 0.65V voltages. Meanwhile, compared with comparative examples and commercial Pt/C, the stability of the non-noble metal catalyst prepared by each example is also obviously improved, the performance attenuation after 1000 cycles of accelerated endurance test is lower than 4.6%, the attenuation of each comparative example is higher than 6%, wherein the attenuation rate of the non-noble metal catalyst prepared by complexing and pyrolyzing metal ions and amino cyclic compounds is higher and the stability is better as the carbon source is additionally added in comparative example 5, and the attenuation rate of the non-noble metal catalyst reaches 9.15%.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples merely represent a few embodiments of the present application, which facilitate a specific and detailed understanding of the technical solutions of the present application, but are not to be construed as limiting the scope of the application. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the application, which are all within the scope of the application. It should be understood that, based on the technical solutions provided by the present application, those skilled in the art may obtain technical solutions through logical analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent of the application should therefore be determined with reference to the appended claims, which are to be construed as in accordance with the doctrines of claim interpretation.
Claims (15)
1. A method for preparing a non-noble metal catalyst, comprising the steps of:
mixing an amino-containing cyclic compound, a non-noble metal salt and an organic solvent, and then carrying out a complex reaction at 60-80 ℃ to obtain a non-noble metal chelate;
and calcining the non-noble metal chelate to obtain the non-noble metal catalyst.
2. The method of claim 1, wherein the cyclic compound comprises at least one of an alicyclic compound and an aromatic compound, and wherein the cyclic compound is substituted with the amino group.
3. The method of preparing according to claim 2, wherein the alicyclic compound comprises at least one of cyclohexane and piperazine; the aromatic compound comprises at least one of benzene, pyridazine, anthraquinone and pyrimidine.
4. The method of claim 1, wherein the amino group is directly attached to a ring atom in the cyclic compound.
5. The method of claim 1, wherein the amino-containing cyclic compound comprises at least one of 3-aminophthalhydrazide, 3-amino-6-chloropyridazine, 1-aminocyclohexane carboxylic acid, 1-aminoanthraquinone, 4-aminocyclohexane carboxylic acid, 2-aminopyrimidine, and 1-amino-4-methylpiperazine.
6. The method of any one of claims 1 to 5, wherein the non-noble metal of the non-noble metal salt comprises at least one of copper, iron, and cobalt.
7. The method of any one of claims 1 to 5, wherein the non-noble metal salt comprises at least one of a nitrate, sulfate, chloride, and acetate of a non-noble metal.
8. The process according to any one of claims 1 to 5, wherein the molar ratio of the non-noble metal salt to the amino group-containing cyclic compound is 1 (3 to 10).
9. The method according to any one of claims 1 to 5, wherein the organic solvent comprises at least one of ethanol, cyclohexane and acetone.
10. The method according to any one of claims 1 to 5, wherein the calcination treatment is carried out at a temperature of 600 to 1000 ℃ for a time of 1 to 4 hours.
11. The production method according to any one of claims 1 to 5, wherein the atmosphere of the calcination treatment comprises at least one of nitrogen, argon and helium.
12. The method according to any one of claims 1 to 5, further comprising the step of removing impurities from the calcined product with an acid solution after the completion of the calcination treatment.
13. A non-noble metal catalyst prepared by the method of any one of claims 1 to 12.
14. A fuel cell comprising the non-noble metal catalyst of claim 13.
15. An automobile comprising the fuel cell according to claim 14.
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