CN103721748B - High-efficiency oxygen molecule reduction base metal catalyst and preparation thereof - Google Patents
High-efficiency oxygen molecule reduction base metal catalyst and preparation thereof Download PDFInfo
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- CN103721748B CN103721748B CN201310728017.4A CN201310728017A CN103721748B CN 103721748 B CN103721748 B CN 103721748B CN 201310728017 A CN201310728017 A CN 201310728017A CN 103721748 B CN103721748 B CN 103721748B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 105
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 230000009467 reduction Effects 0.000 title claims abstract description 13
- 239000010953 base metal Substances 0.000 title abstract description 16
- 238000002360 preparation method Methods 0.000 title description 9
- 239000000446 fuel Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 229910052799 carbon Inorganic materials 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 19
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 150000004696 coordination complex Chemical class 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 8
- -1 cyano, nitro, amino Chemical group 0.000 claims description 7
- 125000000623 heterocyclic group Chemical group 0.000 claims description 7
- 125000002883 imidazolyl group Chemical group 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 125000004070 6 membered heterocyclic group Chemical group 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 150000004032 porphyrins Chemical class 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000011159 matrix material Substances 0.000 claims description 3
- 125000004424 polypyridyl Polymers 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000005257 alkyl acyl group Chemical group 0.000 claims description 2
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 2
- 125000004185 ester group Chemical group 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 238000011065 in-situ storage Methods 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- 239000002109 single walled nanotube Substances 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 43
- 238000006722 reduction reaction Methods 0.000 abstract description 17
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract 4
- 125000005647 linker group Chemical group 0.000 description 26
- 239000007787 solid Substances 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000002041 carbon nanotube Substances 0.000 description 14
- 229910021393 carbon nanotube Inorganic materials 0.000 description 14
- 230000002378 acidificating effect Effects 0.000 description 13
- 239000010411 electrocatalyst Substances 0.000 description 12
- 229910017052 cobalt Inorganic materials 0.000 description 7
- 239000010941 cobalt Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 238000011160 research Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 4
- JQRLYSGCPHSLJI-UHFFFAOYSA-N [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Fe].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 JQRLYSGCPHSLJI-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910001868 water Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 125000001072 heteroaryl group Chemical group 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 description 2
- BVVNOTCYUKCLDL-UHFFFAOYSA-N 1-(4-azidophenyl)imidazole Chemical compound C1=CC(N=[N+]=[N-])=CC=C1N1C=NC=C1 BVVNOTCYUKCLDL-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-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 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 125000004442 acylamino group Chemical group 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 230000003592 biomimetic effect Effects 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 125000006165 cyclic alkyl group Chemical group 0.000 description 2
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 150000003278 haem Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000003837 high-temperature calcination Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011664 nicotinic acid Substances 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 2
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 description 2
- AYEKOFBPNLCAJY-UHFFFAOYSA-O thiamine pyrophosphate Chemical compound CC1=C(CCOP(O)(=O)OP(O)(O)=O)SC=[N+]1CC1=CN=C(C)N=C1N AYEKOFBPNLCAJY-UHFFFAOYSA-O 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 208000021251 Methanol poisoning Diseases 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- XJJWWOUJWDTXJC-UHFFFAOYSA-N [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Mn].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 XJJWWOUJWDTXJC-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- WUPRCGRRQUZFAB-DEGKJRJSSA-N corrin Chemical compound N1C2CC\C1=C\C(CC/1)=N\C\1=C/C(CC\1)=N/C/1=C\C1=NC2CC1 WUPRCGRRQUZFAB-DEGKJRJSSA-N 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 159000000014 iron salts Chemical class 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
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 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 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000005406 washing Methods 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 invention provides a method for preparing a high-efficiency oxygen molecule reduction base metal catalyst, and in particular provides a complex catalysis system with the following structure of formula I: Carrier-(Linker-Ligand-Metal complex)n, wherein the definitions of the structural constitutional parts are as shown in the specification. The complex catalysis system provided by the invention can be applied to catalysis on oxygen molecule reduction reaction, can be used as an oxygen molecule reduction electric catalyst, is excellent in catalysis property, can be used for replacing the conventional novel metal platinum catalyst, and has great potential application prospects and commercial values in fields such as fuel cell electric vehicles.
Description
Technical Field
The invention relates to the field of fuel cell catalysts, and particularly provides a high-efficiency oxygen molecule reduction base metal catalyst and a preparation method thereof.
Background
A fuel cell is a device for continuously converting chemical energy of fuel (e.g., hydrogen) and oxygen directly into electric energy through an electrode chemical reaction, the anode of which is a hydrogen electrode (hydrogen is oxidatively decomposed into protons and electrons: H)2→2H++2e-) The cathode is an oxygen electrode (oxygen reduced to water: 1/2O2+2H++2e-→H2O), the anode and cathode are loaded with a quantity of catalyst to accelerate the electrochemical reaction occurring at the electrodes. The Fuel cell, especially the Proton Exchange Membrane Fuel Cell (PEMFC), has the characteristics of low operation temperature, short start-up time, high conversion efficiency, clean discharge (the product is water), and the like, and has great potential in future vehicle applications. Although the development of fuel cells is well established, one "bottleneck" that plagues the large-scale commercial production of fuel cell electric vehicles is that the cells are too expensive (mainly due to the high cost of their electrode electrocatalysts). At present, the electrocatalyst of the fuel cell is mainly platinum group noble metal. The development of new base metal electrocatalysts is particularly important due to the high price of the precious metal platinum and the continuing supply of platinum in the future.
Non-platinum catalysts, i.e., base metal catalysts, have been the focus of research in molecular oxygen reduction electrocatalysts. Transition metal complexes of cobalt, iron, manganese, etc., including macrocyclic complexes thereof, etcWhen used as ORR catalyst, some catalysts have good activity. The base metal catalysts can show higher catalytic activity and stability only by high-temperature treatment (more than or equal to 500 ℃), but the metal (macrocyclic) complex initially added after the high-temperature heat treatment is decomposed, so that the species of the active center of the catalyst are unclear. In addition, the durability of the catalyst is not good. In recent years, the research on base metal catalysts has been further and widely regarded and broken through. Zelenay groups of America have used polypyrrole (PPY) coated carbon powders to which cobalt acetate was added followed by NaBH4The carbon supported catalyst Co-PPY-C with coordination of pyrrole and cobalt is obtained by a reduction mode, and the catalyst shows high ORR catalytic activity but has low continuous stability. The group subsequently further improved the catalyst preparation by mixing aniline, carbon powder, cobalt and iron containing salts first and then obtaining a base metal electrocatalyst with high catalytic activity and durability almost comparable to the platinum catalyst by oxidative polymerization → high temperature treatment in nitrogen and ammonia atmosphere → acid rinse. Recently, they prepared nitrogen-doped N-Fe-CNT/CNP composite catalysts by simply mixing and calcining carbon nanotubes, nitrogen-containing precursors, and metallic iron salts. The composite catalyst exhibits ORR catalytic activity similar to commercial platinum/carbon under alkaline conditions. The Dodelet research group in canada reports that a nitrogen-containing ligand (such as phenanthroline) and iron acetate are added into a microporous structure of microcrystalline carbon by a ball milling technology, and then high-temperature treatment is carried out under the atmosphere of argon and ammonia gas to obtain a high-activity ORR electrocatalyst, but the stability of the catalyst is still not high, and the catalyst cannot compete with a platinum catalyst. Recently, they wrapped iron salt and nitrogen containing precursors with MOFs framework structures and then prepared new ORR catalysts by high temperature calcination, which showed higher volumetric activity and mass transfer performance. In addition, a great deal of research is carried out on metal-free (metal-free) nitrogen and fluorine doped carbon material ORR catalysts, the catalysts generally have better ORR catalytic performance under alkaline conditions, the catalytic performance in an acidic environment is equivalent to that of a platinum/carbon catalyst, and the doping amount and doping process of nitrogen and fluorine in the carbon material are difficult to control.
In summary, with the increasing demand for new energy, the research on base metal ORR electrocatalysts has been vigorously developed in recent years. However, the preparation process of the base metal ORR catalyst usually needs high-temperature treatment, the structural characteristics of the initial complex are completely destroyed by the heat treatment process, and the reaction activity of the catalyst cannot be regulated and controlled by changing the structural performance of the catalyst. In addition, most of the base metal ORR electrocatalysts reported so far exhibit high catalytic activity only in an alkaline environment, and only a very small number of them are comparable to the platinum/carbon catalyst.
In summary, there is an urgent need in the art to develop a catalyst for molecular oxygen reduction reaction that is inexpensive, simple in preparation method, and easy to control the reaction, and exhibits high catalytic activity under both alkaline and acidic conditions.
Disclosure of Invention
The invention aims to provide an oxygen molecule reduction reaction catalyst which has simple preparation method, easy reaction control and higher catalytic activity under alkaline and acidic conditions.
In a first aspect of the present invention, there is provided a composite catalyst having the structure:
Carrier-(Linker-Ligand-Metal complex)nformula I
Wherein,
"-" represents a chemical bond, said chemical bond being a covalent bond or a coordinate bond;
carrier is carbon-based matrix Carrier;
ligand is a five-membered or six-membered heterocyclic coordination group containing nitrogen;
the Linker is a connecting molecule, and the connecting molecule is respectively connected with the carbon-based carrier and the nitrogen-containing five-membered or six-membered heterocyclic coordination group through a covalent bond;
the Metal complex is selected from the group consisting of: substituted or unsubstituted iron, cobalt, manganese porphyrin molecules; substituted or unsubstituted iron, cobalt, manganese phthalocyanine molecules; substituted or unsubstituted iron, cobalt, manganese corrin molecules; copper, iron, cobalt and manganese complexes coordinated by nitrogen-containing ligands; the Metal complex forms a coordination bond with a nitrogen atom on a five-membered or six-membered heterocyclic ring containing nitrogen;
n≥1。
in another preferred embodiment, the Carrier is selected from the group consisting of: single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene; preferably, the Carrier is a multi-walled carbon nanotube.
In another preferred embodiment, the Ligand is selected from the group consisting of: imidazolyl, pyridyl or polypyridyl.
In another preferred embodiment, the Linker is selected from the group consisting of: substituted or unsubstituted C1-C5 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted heterocyclic aryl.
In another preferred embodiment, the Linker is a substituted or unsubstituted heterocyclic aromatic group, wherein the heterocyclic aromatic group has 3 to 9 nitrogen atoms.
In another preferred embodiment, at least one aromatic cyclic structural unit is present in the Linker.
In another preferred example, the Linker has the following structure:
in another preferred embodiment, the Metal complex is an iron-based porphyrin having the following structure:
wherein Ar is selected from the group consisting of: substituted or unsubstituted aryl, substituted or unsubstituted azacyclo aryl.
In another preferred embodiment, the Metal complex is ferriporphyrin having the following structure:
wherein R is1、R2、R3、R4、R5、R6、R7Each independently selected from the group consisting of: H. halogen, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C1-C4 alkyl-oxy, carboxyl, amino, amido.
In another preferred embodiment, R1、R2、R3、R4、R5、R6、R7Each independently selected from the group consisting of: H. f, Cl, Br, CH3、CF3Carboxy, COOCH3。
In another preferred embodiment, R1、R2、R3、R4、R5、R6、R7Are all H.
In another preferred embodiment, R1、R2、R3、R4、R5、R6、R7Are all F.
In another preferred embodiment, R1、R3、R4、R6、R7Are all CH3And R is2、R5Are all H.
In another preferred embodiment, R1、R4、R7Are both F, and R2、R3、R5、R6Are all H.
In another preferred embodiment, R1、R2、R4、R5、R7Are all H, and R3、R6Are all CF3。
In another preferred embodiment, R1、R2、R3、R5、R6、R7Are all H, and R4Is COOH or COOCH3。
In another preferred embodiment, R1、R2、R3、R5、R6Are all H, and R4、R7Is COOH or COOCH3。
In another preferred embodiment, R1Is F, R2、R3、R5、R6、R7Are all H, and R4Is COOH or COOCH3。
In another preferred embodiment, R1Is F, R2、R3、R5、R6Are all H, and R4、R7Is COOH or COOCH3。
In another preferred embodiment, R1Is F, R2、R3、R5、R6Are all H, and R4、R7Is COOH or COOCH3。
In another preferred embodiment, R1、R2、R3、R5、R6、R7Are both F, and R4Is COOH or COOCH3。
In another preferred embodiment, R1、R2、R3、R5、R6Are both F, and R4、R7Is COOH or COOCH3。
In another preferred embodiment, R1、R2、R5、R6、R7Are all H, R3Is CF3And R is4Is COOH or COOCH3。
In another preferred embodiment, R1、R2、R5、R6Are all H, R3Is CF3And R is4、R7Is COOH or COOCH3。
In a second aspect of the present invention, there is provided a method for preparing a catalyst according to the first aspect of the present invention, the method comprising the steps of:
(i) providing a carbon-based Carrier (Linker-Ligand) with a connecting molecule and a nitrogen-containing five-membered or six-membered heterocyclic coordination group modified on the surface, as shown in formula IanWherein the Linker molecule Linker is connected to the surface of the carbon-based Carrier through a covalent chemical bond, and the nitrogen-containing five-or six-membered heterocyclic group Ligand is connected to the Linker molecule Linker through a covalent chemical bond;
Carrier-(Linker-Ligand)mformula Ia
(ii) With substituted or unsubstituted Metal complex with said Carrier- (Linker-Ligand)mCarrying out a reaction to form a compound shown as a formula I;
Carrier-(Linker-Ligand-Metal complex)nformula I
Wherein, Carrier, Linker, Ligand, Metal complex, n are defined as the first aspect of the invention; m is greater than or equal to 1, and m and n can be equal or unequal.
In another preferred embodiment, in the preparation method, both steps (i) and (ii) are carried out at 80 ℃ or lower.
In another preferred embodiment, m.gtoreq.n.
In another preferred embodiment, in the compound of formula I prepared in the step (ii), the surface of the carbon-based carrier contains a part of-Linker-Ligand surface modifying group which is not coordinated with Metal complex.
In another preferred embodiment, the compound of formula Ia is prepared by a process comprising the steps of:
providing a carbon-based Carrier;
carrying out surface modification on the carbon-based Carrier by using a coupling reagent to form a carbon-based Carrier with a connecting molecule La modification on the surface;
the five or six membered heterocyclic group containing nitrogen is formed in situ on the linker molecule to give the compound of formula Ia.
In another preferred example, the La is the same as or different from the Linker.
In another preferred embodiment, the compound of formula Ia is prepared by a process comprising the steps of:
(a) providing a carbon-based Carrier;
(b) surface modification is carried out on the carbon-based Carrier by using one or more coupling reagents to obtain the surface-modified carbon-based Carrier- (Linker-Ligand)m(ii) a Wherein, in the coupling reagent, at least one structure contains a five-membered or six-membered heterocyclic group containing nitrogen.
In another preferred embodiment, the compound of formula Ia is prepared by a process comprising the steps of:
(a) providing a carbon-based Carrier;
(b) carrying out surface modification on the carbon-based Carrier by using a coupling reagent Linker '-X to obtain the surface-modified carbon-based Carrier- (Linker')m；
(c) Mixing a reagent Ligand-Linker 'containing a five-membered or six-membered heterocyclic group containing nitrogen in the structure with the surface modified carbon-based Carrier- (Linker')mReacting to obtain the carbon-based Carrier- (Linker-Ligand) with the surface modified with the coordination groupm；
The Linker ' and the Linker ' ' are connecting molecules with all or part of the structure of the Linker, and the Linker ' ' can react to form the Linker;
x is a leaving group.
In another preferred embodiment, the Linker' is phenyl.
In another preferred example, the Linker' -X is triisopropylsilylpropargyl azofluoroborate.
In another preferred embodiment, said step (b) is carried out in the presence of a reducing agent, preferably said reducing agent is hydrazine hydrate.
In another preferred embodiment, the Linker is 4-azidophenyl.
In another preferred embodiment, the Ligand-Linker "is 1- (4-azidophenyl) imidazole.
In a third aspect of the invention there is provided the use of a catalyst as described in the first aspect of the invention as a catalyst for the reduction of molecular oxygen.
In another preferred embodiment, the oxygen molecule reduction reaction is performed in an alkaline or acidic environment. Preferably, the acidic environment means that the pH of the reaction system is less than or equal to 5; the alkaline environment means that the pH value of the reaction system is more than or equal to 13.
In a fourth aspect of the present invention, there is provided an molecular oxygen reduction catalyst comprising a catalyst according to the first aspect of the present invention.
In a fifth aspect of the present invention, there is provided a fuel cell, wherein the fuel cell comprises the catalyst according to the first aspect of the present invention.
In another preferred embodiment, the electrode catalyst of the fuel cell comprises the catalyst of the first aspect of the present invention
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 ORR polarization curves of catalysts in alkaline environment. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M KOH,@1600rpm;CNTImFeF2TPP corresponding to the 4 th compound in Table 1, i.e. R1=R4=R7=F，R2=R3=R5=R6=H)。
FIG. 2 Generation of H on the working electrode of the disk in alkaline Environment2O2Is plotted against potential. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M KOH,@1600rpm)。
Figure 3 stability of catalyst in alkaline environment. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M KOH,@0.7V vs RHE,900rpm)。
FIG. 4 ORR polarization curves of catalysts in acidic environment, solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M HClO4,@1600rpm)。
FIG. 5 Generation of H on the disk working electrode in acidic Environment2O2Is plotted against potential. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M HClO4,@1600rpm)。
Figure 6 stability of catalyst in acidic environment, solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M HClO4,@0.7V vs RHE,900rpm)。
Detailed Description
Term(s) for
As used herein, the term "linker molecule" or "linking group" refers to a modifying group that is attached to a carbon-based support by a covalent bond. The term "chemically bonded" includes both direct bonding to the surface of the carbon-based carrier and covalent bonding to the modifying group on the surface of the carbon-based carrier.
The term "alkyl" as used herein refers to a straight, branched or cyclic alkyl group having 1 to 30 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, or the like.
The term "C1-C4 alkyl" refers to a straight, branched or cyclic alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, cyclopropyl, or the like.
The term "aryl (aryl" refers to an aryl group having 6 to 30 carbon atoms, including monocyclic or bicyclic aryl groups, such as phenyl, naphthyl, or the like.
The term "heteroaryl (heterocyclic aromatic group)" refers to a heteroaryl group having 2 to 30 carbon atoms, such as a pyrrolyl group, a pyridyl group, a furyl group, or the like.
The term "acylamino" refers to an acylamino group having 2 to 8 carbon atoms, such as an acetamido group, or the like.
The term "azacyclic aryl" refers to an azacyclic aryl group having 2 to 30 carbon atoms, such as pyridine, pyrrole, or the like.
Unless otherwise specified, the term "substituted" means that one or more hydrogen atoms on a group are replaced with a substituent selected from the group consisting of: C1-C10 alkyl, C1-C10 alkyl-oxy, halogen, hydroxyl, carboxyl (-COOH), C1-C10 alkyl-aldehyde group, C1-C10 alkyl-acyl, C2-C10 ester group, cyano, nitro, amino and phenyl; the phenyl group includes an unsubstituted phenyl group or a substituted phenyl group having 1 to 3 substituents selected from: halogen, C1-C10 alkyl, cyano, OH, nitro, C1-C10 alkyl-oxy and amino.
The term "polypyridyl" refers to a group having more than two pyridine ring structures within the structure, such as bipyridine or bipyridine.
The terms "carbon-based matrix support" or "carbon-based support" are used interchangeably and refer to the support carrier of the present invention.
The names corresponding to the abbreviations for each letter are as follows:
catalyst for reduction reaction of oxygen molecule
The compound of the formula I can be used for catalyzing oxygen molecule reduction reaction and preparing a catalyst for the oxygen molecule reduction reaction.
A preferred base metal ORR catalyst of the invention consists of a carbon nano tube with functionalized surface imidazole groups and biomimetic heme model metalloporphyrin. The imidazole group on the surface of the carbon nano tube completes covalent loading of the biomimetic catalyst on the carbon nano tube through axial coordination with iron porphyrin. The invention realizes the functionalization of imidazole groups on the surface of the carbon nano tube, and is characterized in that the effective assembly of the bionic heme model catalyst on the carbon nano tube is realized after the functional modification of the monomolecular layer on the surface of the carbon nano tube, and the ORR active reaction sites on the surface of the carbon nano tube are greatly increased, thereby greatly improving the ORR catalytic performance.
One preferred type of carbon-based support is multi-walled carbon nanotubes.
One preferred class of Linker molecules and coordinating groups (Linker-Ligand) is:
a preferred class of iron porphyrins and their derivatives are:
wherein Ar is selected from the group consisting of: substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 heteroaryl. Preferably, the ferriporphyrin derivative moiety has the structure shown in table 1:
TABLE 1 iron-based porphyrins
The invention realizes the functional modification of imidazole groups on the surface of the carbon nano tube and the covalent loading of the bionic ORR catalyst on the surface of the carbon nano tube. The ORR base metal catalyst is prepared in a mode that the catalyst structure is controllable and high-temperature calcination is not carried out, and the prepared ORR catalytic activity of the catalyst in acid and alkaline environments is superior to that of a commercial platinum/carbon catalyst.
The main advantages of the invention include:
(1) the catalyst prepared by the invention has a controllable structure and a clear catalytic activity center.
(2) The catalysts prepared by the present invention performed better than all reported base metal ORR catalysts and commercial platinum/carbon catalysts. The ORR half-wave potential, the ORR initial potential, the ORR current density, the methanol poisoning resistance and the like of the electrocatalyst prepared by the invention are superior to those of a commercial 20% platinum/carbon catalyst in acid and alkali environments.
(3) Because the catalytic performance of the ORR electrocatalyst is superior to that of a commercial 20% platinum/carbon catalyst, the ORR electrocatalyst is likely to be used as a base metal ORR electrocatalyst to replace the existing noble metal platinum catalyst, and has great potential application prospect and commercial value in the fields of fuel cells, electric automobiles and the like. The new energy automobile production company may have a potential demand for the technology.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
Example 1 imidazole group functionalized modification of carbon nanotube surface
The multi-wall carbon nano-tube (MWCNT, length is 50 μm, OD8-15nm, ID3-5nm, Chengdu Organic Chemical Co. Ltd, Chinese Academy of Sciences) and the triisopropylsilylphenylazo fluoroborate which are subjected to purification treatment are ultrasonically dispersed uniformly in water, a certain amount of hydrazine hydrate solution is added, the mixture is heated to 80 ℃ and reacts overnight. The resulting filter cake was filtered and washed with DMF and ultrapure water, respectively.
Dispersing a certain amount of triisopropynyl silylethynyl phenyl MWCNT in DMF, adding tetrabutyl ammonium fluoride in an ice water bath, and reacting for 2h at room temperature under a nitrogen atmosphere. Then, a certain amount of copper sulfate pentahydrate, sodium ascorbate and 1- (4-azidophenyl) imidazole are respectively added into the mixture and reacted for 36 hours at 50 ℃ under the nitrogen atmosphere. And filtering the obtained filter cake, and washing the filter cake with DMF, 50mmol/LEDTA aqueous solution and ultrapure water respectively to obtain the imidazole functionalized carbon nano tube MWCNTim.
Example 2 coordination loading of iron-based porphyrins on carbon nanotube surface
4.0mg of the modified MWCNTIm and 1.0mg of the iron porphyrin compound were dispersed in 1.0mL of methanol, and stirred at room temperature for 15 hours under a nitrogen atmosphere. The complex was filtered, washed 3 times with a small amount of methanol, dried under vacuum for 3h and stored in the dark under nitrogen. The iron porphyrins were selected from the compounds listed in table 1 above.
Example 3 catalyst Performance testing
(a) Catalyst ink (catalyst ink)) The preparation of (1): ultrasonically mixing a proper amount of 5% Nafion solution (Aldrich, USA) and isopropanol (volume ratio is 1:9) for 5min, and then adding a proper amount of the catalyst (CNTImFeF) prepared by the invention2TPP, corresponding to Compound 4 in Table 1, R1=R4=R7=F，R2=R3=R5=R6= H), the ultrasonic dispersion is uniform. And (3) dripping 10-15 mu L of catalyst ink on the surface of the glassy carbon electrode, and volatilizing the solvent at room temperature to serve as a working electrode.
(b) ORR catalytic performance electrochemical test:
the testing of the electrocatalytic properties of the catalysts was carried out by means of a rotating electrode device (MSR, product of Pine, USA) and a CHI760D electrochemical workstation. The test was carried out in a three-electrode system (all products of Pine, USA), with a glassy carbon electrode as the working disk electrode (OD:5mm), a Pt ring as the working ring electrode (ID:6.5mm, OD:7.5mm), a Pt wire as the counter electrode, and Hg/HgO (under alkaline conditions) or Ag/AgCl (under acidic conditions) as the reference electrode. The alkaline test environment is 0.1mol/L KOH solution, and the acidic test environment is 0.1mol/L HClO4And (3) solution. ORR measurements of control Pt-based catalysts were performed under the same conditions using a 20% Pt/C catalyst (JMHiSPC 3000, Johnson Matthey Fuel Cells, USA). The final potentials have all been converted to potentials relative to the Reversible Hydrogen Electrode (RHE).
The amount of the catalyst loaded on the surface of the glassy carbon electrode is as follows: the catalyst of the invention: the total amount of carbon nano tubes is as follows: 1.0mg/cm2The iron porphyrin is as follows: 0.2mg/cm2. Pt/C catalyst: 1.0mg/cm2。
The ORR polarization curve of the catalyst in alkaline environment is shown in FIG. 1. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP (0.1M KOH @1600 rpm). The experimental results show that the catalyst CNTImFeF of the invention is compared with the commercial 20% Pt/C catalyst2The ORR half-wave potential of TPP is shifted 50mV to the positive potential, and the ORR current density is increased by about 20%.
H generation on disk working electrode in alkaline environment2O2The percentage of (A) is plotted according to the potential variation curve2, respectively. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP (0.1M KOH @1600 rpm). The experimental result shows that the catalyst CNTImFeF of the invention2H generated by TPP2O2The amount of the catalyst is only about half of that of a commercial 20% Pt/C catalyst, which shows that the catalyst of the invention has higher four-electron reduction selectivity on ORR, thereby showing higher catalytic activity.
The stability of the catalyst in alkaline environment is shown in figure 3. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP (0.1M KOH, @0.7V vs RHE,900 rpm). The experimental result shows that after 25 hours, the catalyst CNTImFeF of the invention2TPP still retains about 96% of its catalytic activity, whereas the commercial 20% Pt/C catalyst only retains about 55%.
The ORR polarization curve of the catalyst in acidic environment is shown in fig. 4, solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M HClO4@1600 rpm). The experimental results show that the catalyst CNTImFeF of the invention is compared with the commercial 20% Pt/C catalyst2The ORR half-wave potential of TPP is shifted 36mV to positive potential, and the ORR current density is increased by about 20%.
H generation on disk working electrode in acidic environment2O2The percentage of (c) is plotted against potential as shown in fig. 5. Solid black line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M HClO4@1600 rpm). The experimental result shows that the catalyst CNTImFeF of the invention2H generated by TPP2O2The amount of the catalyst is less than that of a commercial 20% Pt/C catalyst, which shows that the catalyst of the invention has higher four-electron reduction selectivity on ORR, thereby showing higher catalytic activity.
The results of the stability experiment of the catalyst in an acidic environment are shown in fig. 6, with a black solid line: 20% Pt/C; solid red line: CNTImFeF2TPP(0.1M HClO4@0.7V vs RHE,900 rpm). The experimental result shows that the catalyst CNTImFeF of the invention is 12.5 hours later2TPP still retains about 91% of its catalytic activity, whereas the commercial 20% Pt/C catalyst only retains about 57%.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (9)
1. A composite catalyst having the structure:
Carrier-(Linker-Ligand-Metal complex)nformula I
Wherein,
"-" represents a chemical bond, said chemical bond being a covalent bond or a coordinate bond;
carrier is carbon-based matrix Carrier;
ligand is a five-membered or six-membered heterocyclic coordination group containing nitrogen;
the Linker is a connecting molecule, and the connecting molecule is respectively connected with the carbon-based carrier and the nitrogen-containing five-membered or six-membered heterocyclic coordination group through a covalent bond; and the Linker has the following structure:
the Metal complex has iron-based porphyrin with the following structure:
wherein Ar is selected from the group consisting of: substituted or unsubstituted aryl, substituted or unsubstituted azacyclo aryl;
n≥1；
wherein said substitution means that one or more hydrogen atoms on the group are substituted with a substituent selected from the group consisting of: C1-C10 alkyl, C1-C10 alkyl-oxy, halogen, hydroxyl, carboxyl (-COOH), C1-C10 alkyl-aldehyde group, C1-C10 alkyl-acyl, C2-C10 ester group, cyano, nitro, amino and phenyl; the phenyl group includes an unsubstituted phenyl group or a substituted phenyl group having 1 to 3 substituents selected from: halogen, C1-C10 alkyl, cyano, OH, nitro, C1-C10 alkyl-oxy and amino.
2. The catalyst of claim 1, wherein the Carrier is selected from the group consisting of: single-walled carbon nanotubes, multi-walled carbon nanotubes, graphene.
3. The catalyst of claim 1, wherein the Carrier is a multi-walled carbon nanotube.
4. The catalyst of claim 1, wherein Ligand is selected from the group consisting of: imidazolyl, pyridyl or polypyridyl.
5. The method of preparing a catalyst according to claim 1, comprising the steps of:
(i) providing a carbon-based Carrier with a connecting molecule and a nitrogen-containing five-membered or six-membered heterocyclic coordination group modified on the surface, wherein the connecting molecule Linker is connected to the surface of the carbon-based Carrier through a covalent chemical bond, and the nitrogen-containing five-membered or six-membered heterocyclic group Ligand is connected with the connecting molecule Linker through a covalent chemical bond;
Carrier-(Linker-Ligand)mformula Ia
(ii) With substituted or unsubstituted Metal complex with said Carrier- (Linker-Ligand)mCarrying out a reaction to form a compound shown as a formula I;
Carrier-(Linker-Ligand-Metal complex)nformula I
Wherein, Carrier, Linker, Ligand, Metal complex, n are defined as the claim 1; m is greater than or equal to 1, and m and n can be equal or unequal.
6. The process of claim 5, wherein the compound of formula Ia is prepared by a process comprising the steps of:
providing a carbon-based Carrier;
carrying out surface modification on the carbon-based Carrier by using a coupling reagent to form a carbon-based Carrier with a connecting molecule modification on the surface;
the five or six membered heterocyclic group containing nitrogen is formed in situ on the linker molecule to give the compound of formula Ia.
7. Use of a catalyst according to any of claims 1 to 4 as a catalyst for the reduction of molecular oxygen.
8. An oxygen molecule reduction catalyst, wherein the catalyst comprises a catalyst according to any one of claims 1 to 4.
9. A fuel cell comprising a catalyst according to any one of claims 1 to 4.
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