CN103611575B - Containing the preparation method of the catalyst of imidazole and its derivants - Google Patents
Containing the preparation method of the catalyst of imidazole and its derivants Download PDFInfo
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- CN103611575B CN103611575B CN201310639407.4A CN201310639407A CN103611575B CN 103611575 B CN103611575 B CN 103611575B CN 201310639407 A CN201310639407 A CN 201310639407A CN 103611575 B CN103611575 B CN 103611575B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 47
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 22
- 239000000463 material Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000003624 transition metals Chemical class 0.000 claims abstract description 17
- 239000002245 particle Substances 0.000 claims abstract description 10
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 9
- 150000002460 imidazoles Chemical class 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 21
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 12
- 239000008103 glucose Substances 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 10
- 238000003763 carbonization Methods 0.000 claims description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 235000010216 calcium carbonate Nutrition 0.000 claims description 6
- -1 transition metal salt Chemical class 0.000 claims description 6
- 229910052763 palladium Inorganic materials 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 51
- 238000005516 engineering process Methods 0.000 abstract description 13
- 239000010970 precious metal Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 43
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000000047 product Substances 0.000 description 8
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000000839 emulsion Substances 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 4
- 125000004433 nitrogen atom Chemical group N* 0.000 description 4
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229940015043 glyoxal Drugs 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- OPXLLQIJSORQAM-UHFFFAOYSA-N mebendazole Chemical compound C=1C=C2NC(NC(=O)OC)=NC2=CC=1C(=O)C1=CC=CC=C1 OPXLLQIJSORQAM-UHFFFAOYSA-N 0.000 description 3
- 229960003439 mebendazole Drugs 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 125000002883 imidazolyl group Chemical group 0.000 description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 2
- 229940099596 manganese sulfate Drugs 0.000 description 2
- 239000011702 manganese sulphate Substances 0.000 description 2
- 235000007079 manganese sulphate Nutrition 0.000 description 2
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 150000003460 sulfonic acids Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical compound OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 description 1
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052728 basic metal Inorganic materials 0.000 description 1
- 150000003818 basic metals Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 150000002390 heteroarenes Chemical class 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 125000002632 imidazolidinyl group Chemical group 0.000 description 1
- 150000002475 indoles Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- PCLURTMBFDTLSK-UHFFFAOYSA-N nickel platinum Chemical compound [Ni].[Pt] PCLURTMBFDTLSK-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000004355 nitrogen functional group Chemical group 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 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
- 238000005554 pickling Methods 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000010148 water-pollination Effects 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 present invention relates to the preparation of non-precious metal catalyst in fuel cell, aim to provide the preparation method of the catalyst containing imidazole and its derivants.Containing the preparation method of the catalyst of imidazole and its derivants, step should be comprised: prepare nitrogenous macropore material with carbon element, and the carbon-supported transition-metal catalyst of nitrogenous macropore that last obtained imidazole and its derivants is modified.The present invention adopts water heat transfer, the catalyst particle not only can obtain consistent size, being evenly distributed, and also can greatly shorten catalyst generated time; Calcine stage by stage under different temperatures, the through hole of macropore carbon is more unobstructed, and pore-size distribution is more balanced, and specific area is larger; Catalyst good conductivity, imidazole and its derivants decorative layer increases activity and the stability of catalyst, is specially adapted to big current working condition; The non-precious metal catalyst of synthesis can be used for the cathod catalyst of fuel cell or air cell, with low cost, is conducive to the universal of fuel cell and air cell technology.
Description
Technical field
The invention relates to the preparation of non-precious metal catalyst in fuel cell, particularly containing the preparation method of the catalyst of imidazole and its derivants.
Background technology
In recent years, because the technology of fuel cell (Fuel Cell) obtains strategic structural, add the multiple pressure such as environmental issue and energy deficiency in succession to arrive, the industries such as national governments and automobile, electric power, the energy pay attention to the development of fuel cell technology gradually.Fuel cell is the new generation technology of high efficiency, low stain, the diversification energy, and the electricity generation system of fuel cell, not only low than traditional fossil fuel cost, and have cleaning, high efficiency benefit, more in conjunction with generation technologies such as nuclear energy, biological energy source, solar energy, wind energies, the energy can be used diversification, renewableization and continue to use.Fuel cell uses the fuel reburning such as alcohols, natural gas, hydrogen, sodium borohydride, hydrazine to become electric current, and the fuel by external world's input is energy source, can continue to produce electric power, not need the charge-discharge procedures of secondary cell.During charging, as long as empty the container being full of byproduct water, and then put into fuel (fuel such as alcohol).Fuel cell is exactly briefly a generator.Fuel cell is firepower, waterpower, the outer 4th kind of electricity-generating method of nuclear energy.
Along with the development of nanosecond science and technology, fuel cell has had great breakthrough technically, particularly the appearance of the proton exchange model of low-temperature operation makes fuel cell be able to be entered by unattainable space technological applications field the category of people's livelihood application, and PEMFC is extensively taken seriously and forms one of focus development technology.Fuel cell power generation performance (power efficiency) depends primarily on electrode reaction and various ohmage.Compared with the oxidation reaction of fuel, the reduction reaction of oxygen carries out difficulty.Usual low-temperature fuel cell all needs to take precious metal material as catalyst.Although traditional catalyst platinum excellent performance, scarcity of resources, selling at exorbitant prices, cause the universal difficulty of fuel cell technology.The non-precious metal catalyst research and development substituting platinum have become focus and the key of fuel cell technology, and wherein, reducing oxygen reduction reaction (ORR) overpotential on negative electrode is one of fuel cell key technology.
In non-precious metal catalyst research, nitrogen-doped carbon material has good catalytic activity to ORR, and the existence of hetero atom N or O on carbocyclic ring, significantly improves the reaction speed of ORR.CNT, micropore and mesoporous carbon form graphite nitrogen (graphitic-N) and pyridine nitrogen (pyridinic-N) after carrying out N surface doping, to the catalytic activity of ORR, its performance is equivalent to the carbon supported platinum catalyst of city dealer.Some nitrogen-containing compounds such as phthalocyanine (Pc), porphyrin not only form graphite nitrogen and pyridine nitrogen with the carbon supported catalyst of Co or Fe compound on atomic scale or nanoscale, and also forming M-Nx(M is transition metal), there is remarkable catalytic action to ORR.Above result shows, forms nitrogen functional group on the carbon material and can obtain higher ORR catalytic activity.At present to the research of low cost catalyst mainly concentrates on Transition Metal Cluster Compounds mixture catalyst, center contains transition metal macrocyclic compound catalyst and metal carbide catalyst; Nitride, sulfide, boride and silicide etc. are used as Low-Temperature Fuel Cell Catalysts in addition also report, but the Performance Ratio of these catalyst is poor, studies also fewer.Great and the wide market of Research Significance for low cost catalyst.
Summary of the invention
Main purpose of the present invention meets the development of non-precious metal catalyst, provides imidazole and its derivants to modify the preparation method of the carbon-supported transition-metal catalyst of nitrogenous macropore.For solving the problems of the technologies described above, solution of the present invention is:
The preparation method of the catalyst containing imidazole and its derivants is provided, modifies the carbon-supported transition-metal catalyst of nitrogenous macropore for the preparation of imidazole and its derivants, comprise the following steps:
Steps A: get hydrophilic nano CaCO
3, urea, glucose is added in deionized water, then ultrasonic vibration mixes 30 minutes, urea and glucose is dissolved, Nano-meter CaCO3
3be uniformly dispersed formation suspension, solidify at 106 DEG C and form cured product in 6 hours, cured product is warming up to 500 DEG C, constant temperature carbonization 2 hours under nitrogen atmosphere protection, then at 900 DEG C, constant temperature carbonization 2 hours, form carbonized product, at 80 DEG C, carbonized product is washed by the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration and deionized water successively, filter, at 120 DEG C, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element again;
Described hydrophilic nano CaCO
3, urea, glucose and deionized water mass ratio be 8:8:8:100;
Step B: it is 100 ~ 400 orders that the nitrogenous macropore material with carbon element obtained in steps A is crushed to particle diameter, get the nitrogenous macropore material with carbon element after pulverizing and be placed in hydrothermal reaction kettle, imidazole and its derivants is added again in hydrothermal reaction kettle, add the aqueous solution containing transition metal salt, then after ultrasonic vibration mixes 20 minutes, sealed reactor, and be placed in oil bath, oil bath temperature is raised to 100 ~ 300 DEG C of reactions 12 hours, filter, again with after washed with de-ionized water, vacuum drying at 90 DEG C, obtain the carbon-supported transition-metal catalyst of nitrogenous macropore that imidazole and its derivants is modified,
The ratio of nitrogenous macropore material with carbon element, imidazole and its derivants, transition metal salt and water after described pulverizing is 2g:0.02 ~ 0.4g:1.2 ~ 6mmol:100mL; Described transition metal salt comprises the nitrate of transition metal, sulfate or chloride, and described transition metal is at least one in Pt, Pd, Ag, Mn, Fe, Co, Ni, Cu.
As further improvement, the hydrophilic nano CaCO in described steps A
3particle diameter be 15 ~ 40nm.
As further improvement, the hydrothermal reaction kettle in described step B adopts volume to be the hydrothermal reaction kettle of 150mL.
As further improvement, imdazole derivatives in described step B is that (methylimidazole is as glyoxal ethyline, 4-methylimidazole for the imdazole derivatives that obtains through alkylation or carboxylated of imidazoles, and mebendazole is the representative plain imidazole derivative obtained after imidazolidinyl, imidazolyl carboxylic acid such as imidazoles-2-carboxylic acid, imidazoles-4-carboxylic acid are the imdazole derivatives obtained after carboxylated).
The formation basic theory of nitrogenous macropore material with carbon element in the present invention:
Due to mixture azeotropic 106 DEG C time of glucose and urea and water, at 106 DEG C, glucose and urea generation polycondensation, solidify and be coated on Nano particles of calcium carbonate, and the polycondensation product of glucose and urea forms continuous phase.Be heated to 500 DEG C of polycondensation product generation carbonizations, form primary carbides, form fine and close solid content with nano-calcium carbonate.Be warming up to 900 DEG C of nano-calcium carbonates to decompose, CO
2in solid content, form unobstructed air flue in air release process, form one-level through hole.Meanwhile, there is further carbonization in primary carbides, forms micropore, forms secondary through holes.In pickling subsequently and alkaline cleaning procedure, nano-calcium carbonate occurs to decompose the rear calcium oxide formed and dissolves, and leaves three grades of through holes in material with carbon element.Due to CO
2originate from nano-calcium carbonate, therefore three grades of through holes must be connected with one-level through hole.By detecting, even if through 900 DEG C of calcinings, still containing nitrogen element in macropore carbon, this is because the nitrogen fixation of glucose and urea polycondensation product causes.
The present invention utilizes the characteristic of nitrogenous macropore carbon surface Nitrogen element, forms coordinate bond, form M-Nx catalytic center by the nitrogen of hydro-thermal method on macropore carbon surfaces externally and internally on nitrogen and imidazole ring and transition metal M.With pyrroles or indoles containing pyrrole ring single nitrogen element compared with, imidazoles contains two nitrogen, more easily forms M-Nx catalytic center with the nitrogen on macropore carbon surfaces externally and internally and transition metal.Good electric conductivity is possessed while there is high-specific surface area.
Compared with prior art, the invention has the beneficial effects as follows:
1, adopt water heat transfer, the catalyst particle not only can obtain consistent size, being evenly distributed, also can shorten catalyst generated time greatly.
2, glucose and urea admixture can obtain the nitrogenous macropore material with carbon element in surface as the presoma of macropore material with carbon element.
3, calcine stage by stage under different temperatures, the through hole of macropore carbon is more unobstructed, and pore-size distribution is more balanced, and specific area is larger.
4, catalyst good conductivity, imidazole and its derivants decorative layer increases activity and the stability of catalyst, is specially adapted to big current working condition.
5, the non-precious metal catalyst of synthesis can be used for the cathod catalyst of fuel cell or air cell, with low cost, be conducive to the universal of fuel cell and air cell technology, the catalyst containing imidazole and its derivants is the electrokinetic cell that the fuel cell of cathod catalyst or air cell can be applicable to electric automobile.
Accompanying drawing explanation
Fig. 1 is the performance comparison figure of fuel cell prepared by the fuel cell prepared in embodiment and commercially available platinum C catalyst.
Detailed description of the invention
Below in conjunction with accompanying drawing and detailed description of the invention, the present invention is described in further detail:
Imidazoles is the five-membered heteroaromatic compounds containing position nitrogen-atoms between two in molecular structure, and the non-share electron pair of the 1-position nitrogen-atoms in imidazole ring participates in cyclic conjugated, and the electron density of nitrogen-atoms reduces, and the hydrogen on this nitrogen-atoms is easily left away with hydrogen ion form.Thus imidazoles has faintly acid, can form salt with highly basic, and transition metal forms coordinate bond.
Nano-calcium carbonate is also known as super fine calcium carbonate.The title of standard and calcium carbonate superfine powder.The most ripe industry of nano-calcium carbonate application is that plastics industry is mainly used in high-grade plastic products.The rheological characteristic of plastic matrix can be improved, improve its mouldability.As plastic filler, there is toughened and reinforced effect, improve bending strength and the modulus of elasticity in static bending of plastics, heat distortion temperature and dimensional stability, also give plastics stagnant hot simultaneously.The industrial production process of nano-calcium carbonate is at certain density Ca (OH)
2suspension in pass into carbon dioxide and carry out carbonization.By to Ca (OH)
2the nucleation rate of the temperature of suspension, the flow-control calcium carbonate nucleus of carbon dioxide; In carbonization to after forming certain nucleus number, be converted into crystal growth by nucleus formation control and control, now add the growth rate that morphology regulation additives controls each crystal face, thus reach morphology controllable; By containing the hydrophily that can significantly improve nano-calcium carbonate after surfactant process.
Containing the preparation method of the catalyst of imidazole and its derivants, modify the carbon-supported transition-metal catalyst of nitrogenous macropore for the preparation of imidazole and its derivants, comprise the following steps:
Steps A: get the hydrophilic nano CaCO that particle diameter is 15 ~ 40nm
3, urea, glucose is added in deionized water, and hydrophilic nano CaCO
3, urea, glucose and deionized water mass ratio be 8:8:8:100, then ultrasonic vibration mixes 30 minutes, and urea and glucose are dissolved and and Nano-meter CaCO3
3be uniformly dispersed; solidify at 106 DEG C and form cured product in 6 hours; cured product is warming up to 500 DEG C, constant temperature carbonization 2 hours under nitrogen atmosphere protection, then at 900 DEG C; constant temperature carbonization 2 hours; form carbonized product, at 80 DEG C, carbonized product is washed by the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration and deionized water successively, filtered at room temperature; at 120 DEG C, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element again.
Step B: it is 100 ~ 400 orders that the nitrogenous macropore material with carbon element obtained in steps A is crushed to particle diameter, get the nitrogenous macropore material with carbon element after pulverizing and be placed in the hydrothermal reaction kettle that volume is 150mL, imidazole and its derivants is added again in hydrothermal reaction kettle, add the nitrate containing transition metal, sulfate or the muriatic aqueous solution, transition metal is Pt, Pd, Ag, Mn, Fe, Co, Ni, at least one in Cu, and make the nitrogenous macropore material with carbon element after pulverizing, imidazole and its derivants, the ratio of transition metal salt and water is 2g:0.02 ~ 0.4g:1.2 ~ 6mmol:100mL.Then after ultrasonic vibration mixes 20 minutes, sealed reactor, and be placed in oil bath, oil bath temperature is raised to 100 ~ 300 DEG C of reactions 12 hours, filters, then with after washed with de-ionized water, vacuum drying at 90 DEG C, obtains the carbon-supported transition-metal catalyst of nitrogenous macropore that imidazole and its derivants is modified.
Imdazole derivatives is wherein the imdazole derivatives that imidazoles obtains through alkylation or carboxylated.Imidazoles is easy to generate derivative, and the approach of generation has alkyl substitution, quaternary ammonium reaction, halogenating reaction, carboxylation reaction and salinization etc.Conventional imdazole derivatives is the product after alkyl metalepsis.In addition, also has pyridine series, cyamelide series, hydroxy methylimidazole series, imidazoline series etc.There are methylimidazole, methylimidazole, diethyl tetramethyl imidazoles, 4-methylimidazole and mebendazole etc. by imidazoles through the imdazole derivatives that alkylation obtains, have imidazolyl carboxylic acid, imidazoles-2-carboxylic acid, imidazoles-4-carboxylic acid etc. by imidazoles through the imdazole derivatives that carboxylated obtains.
The following examples can make professional and technical personnel's comprehend the present invention of this specialty, but do not limit the present invention in any way.
Embodiment one: prepared by macropore carbon
Get the hydrophilic nano CaCO that particle diameter is 15 ~ 40nm
3with urea and each 8g of glucose, be added in 100mL deionized water, ultrasonic vibration mixes 30 minutes makes urea and glucose dissolve and and Nano-meter CaCO3
3be uniformly dispersed; Then solidify 6 hours at 106 DEG C; Cured product is warming up to 500 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again at 900 DEG C, constant temperature carbonization 2 hours; At 80 DEG C, carbonized product is used successively the sodium hydroxide solution of the hydrochloric acid of 5wt% concentration, 30wt% concentration, deionized water washing, at 120 DEG C, freeze-day with constant temperature is after 4 hours, obtains nitrogenous macropore material with carbon element.
Embodiment two: imidazoles modifies the preparation of the carbon-supported noble metal catalyst of macropore
Get the hydrophilic nano CaCO that particle diameter is 15 ~ 40nm
3with urea and each 8g of glucose, be added in 100mL deionized water, ultrasonic vibration mixes 30 minutes makes urea and glucose dissolve and and Nano-meter CaCO3
3be uniformly dispersed; Then solidify 6 hours at 106 DEG C; Cured product is warming up to 500 DEG C under nitrogen atmosphere protection, constant temperature carbonization 2 hours; Again at 900 DEG C, constant temperature carbonization 2 hours; At 80 DEG C, carbonized product is successively with the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration, deionized water washing, and at 120 DEG C, freeze-day with constant temperature is after 4 hours, obtains nitrogenous macropore material with carbon element.
It is 100 ~ 400 orders that nitrogenous macropore material with carbon element is crushed to particle diameter, get the nitrogenous macropore carbon of 2g and be placed in hydrothermal reaction kettle, reactor volume is 150mL, add imidazoles 0.02g as material modified, add platinum chloride respectively, palladium bichloride or liquor argenti nitratis ophthalmicus 100mL, include platinum chloride respectively, palladium bichloride or silver nitrate 3 mMs, then after ultrasonic vibration mixes 20 minutes, sealed reactor, be placed in oil bath, oil bath temperature is raised to 100 DEG C of reactions 12 hours, filter, after washed with de-ionized water, imidazoles can be obtained after 90 DEG C of vacuum drying respectively and modify the carbon-supported platinum of nitrogenous macropore, palladium or silver catalyst.
Embodiment three: imidazoles modifies the preparation of the carbon-supported non-precious metal catalyst of nitrogenous macropore
It is 100 ~ 400 orders that the nitrogenous macropore material with carbon element that Example one obtains is crushed to particle diameter, get 2g and be placed in hydrothermal reaction kettle, reactor volume is 150mL, add imidazoles 0.1g as material modified, add copper chloride respectively, nickelous sulfate, cobalt nitrate, iron chloride or manganese sulfate solution 100mL, containing copper chloride respectively, nickelous sulfate, cobalt nitrate, iron chloride or manganese sulfate 1.2 mMs, after ultrasonic vibration mixes 20 minutes, sealed reactor, be placed in oil bath, oil bath temperature is raised to 200 DEG C of reactions 12 hours, filter, after washed with de-ionized water, imidazoles can be obtained after 90 DEG C of vacuum drying respectively and modify the carbon-supported copper of nitrogenous macropore, nickel, cobalt, iron or Mn catalyst.
Embodiment four: imdazole derivatives modifies the preparation of the carbon-supported platinum-nickel alloy catalyst of nitrogenous macropore
It is 100 ~ 400 orders that nitrogenous macropore material with carbon element obtained for embodiment one is crushed to particle diameter, get the nitrogenous macropore carbon of 2g and be placed in hydrothermal reaction kettle, reactor volume is 150mL, add 0.4g imidazoles-2-carboxylic acid respectively, imidazoles-4-carboxylic acid, glyoxal ethyline, 4-methylimidazole or mebendazole are as material modified, add platinum chloride and nickelous sulfate mixed solution 100mL, include platinum chloride and nickelous sulfate totally 6 mMs, after ultrasonic vibration mixes 20 minutes, sealed reactor, be placed in oil bath, oil bath temperature is raised to 300 DEG C of reactions 12 hours, filter, after washed with de-ionized water, imidazoles-2-carboxylic acid can be obtained respectively after 90 DEG C of vacuum drying, imidazoles-4-carboxylic acid, glyoxal ethyline, 4-methylimidazole, mebendazole modifies the carbon-supported platinum Raney nickel of nitrogenous macropore.
Embodiment five: prepared by fuel cell electrode
Imidazoles obtained in embodiment two is modified the carbon-supported platinum catalyst of nitrogenous macropore, with the Nafion solution of 5wt% for binding agent, modify nitrogenous macropore carbon-supported platinum catalyst mass ratio 3:7 by Nafion solution and imidazoles and be modulated into slurry, be coated to and hate on water-treated carbon paper, after one hour in Muffle furnace 150 DEG C calcining, naturally cool to room temperature and obtain anode of fuel cell after drying.
The carbon-supported platinum catalyst of nitrogenous macropore is modified through hating water-treated imidazoles, with the ptfe emulsion of 5wt% for binding agent, modify the carbon-supported platinum catalyst mass ratio 3: 7 of nitrogenous macropore by ptfe emulsion and imidazoles and be modulated into slurry, be coated to and hate on water-treated carbon paper, after one hour in Muffle furnace 350 DEG C calcining, naturally cool to room temperature and obtain negative electrode after drying.Then immerse the perfluorinated sulfonic acid base resin solution of 5wt%, dry the hydrophobicity negative electrode that rear formation has proton conduction.
Here the carbon-supported transition-metal catalyst of nitrogenous macropore adopting all the other imidazole and its derivants prepared in above-described embodiment to modify substitutes imidazoles and modifies the carbon-supported platinum catalyst of nitrogenous macropore, can obtain the electrode of fuel cell equally.
Embodiment six: imidazoles modifies the fuel cell of the carbon-supported catalyst preparing of nitrogenous macropore
Imidazoles obtained in embodiment three is modified the carbon-supported Co catalysts of nitrogenous macropore, with the Nafion solution of 5wt% for binding agent, modify nitrogenous macropore carbon-supported platinum catalyst mass ratio 3:7 by Nafion solution and imidazoles and be modulated into slurry, be coated to and hate on water-treated carbon paper, after one hour in Muffle furnace 150 DEG C calcining, naturally cool to room temperature and obtain anode of fuel cell after drying.
The carbon-supported Co catalysts of nitrogenous macropore is modified through hating water-treated imidazoles, with the ptfe emulsion of 5wt% for binding agent, modify the carbon-supported Co catalysts mass ratio 3: 7 of nitrogenous macropore by ptfe emulsion and imidazoles and be modulated into slurry, be coated to and hate on water-treated carbon paper, after one hour in Muffle furnace 350 DEG C calcining, naturally cool to room temperature and obtain negative electrode after drying.Then immerse the perfluorinated sulfonic acid base resin solution of 5wt%, dry the hydrophobicity negative electrode that rear formation has proton conduction.Prepare negative electrode and anode, select perfluorinated sulfonic resin (Nafion112) to be dielectric film, the catalyst layer of negative electrode and anode in opposite directions, forms sandwich structure with dielectric film, and hot-forming rear formation membrane electrode, is assembled into Proton Exchange Membrane Fuel Cells.
By negative electrode obtained in embodiment five and anode, perfluorinated sulfonic resin (Nafion112) is selected to be dielectric film, the catalyst layer of negative electrode and anode in opposite directions, sandwich structure is formed with dielectric film, hot-forming rear formation membrane electrode, be assembled into fuel cell, obtain modifying Proton Exchange Membrane Fuel Cells prepared by the carbon-supported platinum catalyst of nitrogenous macropore by imidazoles.
Fig. 1 is the fuel battery performance comparison diagram that imidazoles is modified the fuel cell of the carbon-supported catalyst preparing of nitrogenous macropore and commercially available platinum C catalyst and prepared.Wherein, in 1-embodiment five, the imidazoles of preparation modifies the power density curve of the hydrogen-oxygen fuel cell of the carbon-supported platinum catalyst electrode assembling of nitrogenous macropore, in 2-embodiment five, the imidazoles of preparation modifies the voltage polarization curve of the hydrogen-oxygen fuel cell of the carbon-supported platinum catalyst electrode assembling of nitrogenous macropore, imidazoles obtained in 3-embodiment three modifies the power density curve of the hydrogen-oxygen fuel cell of the carbon-supported Co catalysts electrode assembling of nitrogenous macropore, imidazoles obtained in 4-embodiment three modifies the voltage polarization curve of the hydrogen-oxygen fuel cell of the carbon-supported Co catalysts electrode assembling of nitrogenous macropore, the power density curve of the hydrogen-oxygen fuel cell of 5-commercially available platinum C catalyst electrode assembling, the voltage polarization curve of the hydrogen-oxygen fuel cell of 6-commercially available platinum C catalyst electrode assembling.Operating temperature: 80 DEG C, hydrogen and oxygen carry out 80 DEG C of humidifications respectively, and pressure is an atmospheric pressure.The negative electrode of three kinds of fuel cells and the transition metal loading of anode are 0.5mg/cm
2.
As seen from the figure, it is suitable with fuel battery performance prepared by commercially available platinum C catalyst that imidazoles modifies fuel cell prepared by the carbon-supported Co catalysts of nitrogenous macropore, and imidazoles is modified fuel cell prepared by the carbon-supported platinum catalyst of nitrogenous macropore and is better than fuel battery performance prepared by commercially available platinum C catalyst.
Finally, it should be noted that above what enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above embodiment, a lot of distortion can also be had.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.
Claims (3)
1., containing the preparation method of the catalyst of imidazole and its derivants, modify the carbon-supported transition-metal catalyst of nitrogenous macropore for the preparation of imidazole and its derivants, it is characterized in that, comprise the following steps:
Steps A: get hydrophilic nano CaCO
3, urea, glucose is added in deionized water, then ultrasonic vibration mixes 30 minutes, urea and glucose is dissolved, Nano-meter CaCO3
3be uniformly dispersed formation suspension, solidify at 106 DEG C and form cured product in 6 hours, cured product is warming up to 500 DEG C, constant temperature carbonization 2 hours under nitrogen atmosphere protection, then at 900 DEG C, constant temperature carbonization 2 hours, form carbonized product, at 80 DEG C, carbonized product is washed by the hydrochloric acid of 5wt% concentration, the sodium hydroxide solution of 30wt% concentration and deionized water successively, filter, at 120 DEG C, freeze-day with constant temperature, after 4 hours, obtains nitrogenous macropore material with carbon element again;
Described hydrophilic nano CaCO
3, urea, glucose and deionized water mass ratio be 8:8:8:100;
Step B: it is 100 ~ 400 orders that the nitrogenous macropore material with carbon element obtained in steps A is crushed to particle diameter, get the nitrogenous macropore material with carbon element after pulverizing and be placed in hydrothermal reaction kettle, imidazole and its derivants is added again in hydrothermal reaction kettle, add the aqueous solution containing transition metal salt, then after ultrasonic vibration mixes 20 minutes, sealed reactor, and be placed in oil bath, oil bath temperature is raised to 100 ~ 300 DEG C of reactions 12 hours, filter, again with after washed with de-ionized water, vacuum drying at 90 DEG C, obtain the carbon-supported transition-metal catalyst of nitrogenous macropore that imidazole and its derivants is modified,
The ratio of nitrogenous macropore material with carbon element, imidazole and its derivants, transition metal salt and water after described pulverizing is 2g:0.02 ~ 0.4g:1.2 ~ 6mmol:100mL; Described transition metal salt comprises the nitrate of transition metal, sulfate or chloride, and described transition metal is at least one in Pt, Pd, Ag, Mn, Fe, Co, Ni, Cu; Described imdazole derivatives is the imdazole derivatives that imidazoles obtains through alkylation or carboxylated.
2. the preparation method of the catalyst containing imidazole and its derivants according to claim 1, is characterized in that, the hydrophilic nano CaCO in described steps A
3particle diameter be 15 ~ 40nm.
3. the preparation method of the catalyst containing imidazole and its derivants according to claim 1, is characterized in that, the hydrothermal reaction kettle in described step B adopts volume to be the hydrothermal reaction kettle of 150mL.
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