JP2019099386A - Method for producing carbon alloy supporting transition metal - Google Patents
Method for producing carbon alloy supporting transition metal Download PDFInfo
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- JP2019099386A JP2019099386A JP2017227835A JP2017227835A JP2019099386A JP 2019099386 A JP2019099386 A JP 2019099386A JP 2017227835 A JP2017227835 A JP 2017227835A JP 2017227835 A JP2017227835 A JP 2017227835A JP 2019099386 A JP2019099386 A JP 2019099386A
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- 229910001339 C alloy Inorganic materials 0.000 title claims abstract description 104
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 102
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 98
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 36
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000011701 zinc Substances 0.000 claims abstract description 64
- 239000002798 polar solvent Substances 0.000 claims abstract description 56
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 56
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000002156 mixing Methods 0.000 claims abstract description 52
- 239000002243 precursor Substances 0.000 claims abstract description 50
- -1 imidazole compound Chemical class 0.000 claims abstract description 34
- 239000011246 composite particle Substances 0.000 claims abstract description 28
- 238000003763 carbonization Methods 0.000 claims abstract description 19
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000000725 suspension Substances 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 31
- 230000007704 transition Effects 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000010941 cobalt Substances 0.000 claims description 22
- 229910017052 cobalt Inorganic materials 0.000 claims description 22
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 22
- 239000003054 catalyst Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 238000010000 carbonizing Methods 0.000 claims description 8
- 239000000446 fuel Substances 0.000 claims description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 125000003158 alcohol group Chemical group 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 19
- 239000001301 oxygen Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 19
- 238000006722 reduction reaction Methods 0.000 abstract description 18
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000000052 comparative effect Effects 0.000 description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 239000002245 particle Substances 0.000 description 21
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 12
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 12
- 150000004687 hexahydrates Chemical class 0.000 description 12
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 10
- 238000005406 washing Methods 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 150000002460 imidazoles Chemical class 0.000 description 4
- 238000009616 inductively coupled plasma Methods 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000004993 emission spectroscopy Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229910052665 sodalite Inorganic materials 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 150000004292 cyclic ethers Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229940079865 intestinal antiinfectives imidazole derivative Drugs 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 238000000691 measurement method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 description 1
- HHIMNFJHTNVXBJ-UHFFFAOYSA-L zinc;dinitrite Chemical compound [Zn+2].[O-]N=O.[O-]N=O HHIMNFJHTNVXBJ-UHFFFAOYSA-L 0.000 description 1
- HSYFJDYGOJKZCL-UHFFFAOYSA-L zinc;sulfite Chemical compound [Zn+2].[O-]S([O-])=O HSYFJDYGOJKZCL-UHFFFAOYSA-L 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
Abstract
Description
本発明は、遷移金属担持カーボンアロイの製造方法に関する。 The present invention relates to a method of producing a transition metal-supported carbon alloy.
白金等を用いる貴金属系触媒は、高い酸素還元反応活性を有する触媒として、例えば固体高分子形燃料電池に用いられている。しかし、貴金属系触媒は高コストであるため、白金を含まない触媒の技術開発が進められている。 Noble metal catalysts using platinum or the like are used, for example, in solid polymer fuel cells as catalysts having high oxygen reduction reaction activity. However, since noble metal catalysts are expensive, technological development of platinum-free catalysts is in progress.
白金を含まない触媒としては、カーボンアロイが知られている。例えば、特許文献１には、燃料電池の電極用触媒として、窒素含有ポリマーで被覆されたカーボンナノチューブを焼成して得られるカーボンアロイが開示されている。 A carbon alloy is known as a catalyst not containing platinum. For example, Patent Document 1 discloses a carbon alloy obtained by firing a carbon nanotube coated with a nitrogen-containing polymer as a catalyst for a fuel cell electrode.
しかしながら、特許文献１に記載の方法で得られたカーボンアロイでは、酸素還元反応の触媒活性を向上させるのは困難である。 However, in the carbon alloy obtained by the method described in Patent Document 1, it is difficult to improve the catalytic activity of the oxygen reduction reaction.
本発明は上記の課題に鑑みてなされたものであり、その目的は、酸素還元反応の触媒活性を向上させることができる遷移金属担持カーボンアロイの製造方法を提供することである。 This invention is made in view of said subject, The objective is to provide the manufacturing method of the transition metal carrying | support carbon alloy which can improve the catalytic activity of oxygen reduction reaction.
本発明に係る遷移金属担持カーボンアロイの製造方法は、窒素を含むカーボンアロイと、前記カーボンアロイに担持された遷移金属とを含む遷移金属担持カーボンアロイの製造方法である。本発明に係る遷移金属担持カーボンアロイの製造方法は、混合工程と、乾燥工程と、炭化工程とを備える。前記混合工程では、遷移金属源、亜鉛源及びイミダゾール化合物を極性溶媒中で混合することにより複合体粒子の懸濁液を得る。前記混合工程において、前記遷移金属源中の遷移金属及び前記亜鉛源中の亜鉛の合計に対する、前記遷移金属源中の遷移金属のモル比が０．０５以上０．６０以下となるように、前記遷移金属源及び前記亜鉛源を使用する。前記乾燥工程では、前記複合体粒子を乾燥することにより前駆体を得る。前記炭化工程では、前記前駆体を不活性雰囲気下で炭化する。 The method for producing a transition metal supported carbon alloy according to the present invention is a method for producing a transition metal supported carbon alloy including a carbon alloy containing nitrogen and a transition metal supported by the carbon alloy. The method for producing a transition metal-supported carbon alloy according to the present invention comprises a mixing step, a drying step, and a carbonization step. In the mixing step, a transition metal source, a zinc source and an imidazole compound are mixed in a polar solvent to obtain a suspension of composite particles. In the mixing step, the molar ratio of the transition metal in the transition metal source to the total of the transition metal in the transition metal source and the zinc in the zinc source is 0.05 or more and 0.60 or less. Use a transition metal source and said zinc source. In the drying step, the composite particles are dried to obtain a precursor. In the carbonizing step, the precursor is carbonized under an inert atmosphere.
ある実施形態では、前記前駆体は、ゼオライト型イミダゾール骨格材料である。 In one embodiment, the precursor is a zeolitic imidazole framework.
ある実施形態では、前記遷移金属源は、鉄源、コバルト源、ニッケル源及び銅源からなる群から選択される一種以上である。 In one embodiment, the transition metal source is one or more selected from the group consisting of an iron source, a cobalt source, a nickel source and a copper source.
ある実施形態では、前記イミダゾール化合物は、２−メチルイミダゾールである。 In one embodiment, the imidazole compound is 2-methylimidazole.
ある実施形態では、前記乾燥工程における前記複合体粒子の加熱温度は、５０℃以上１００℃以下である。 In one embodiment, the heating temperature of the composite particles in the drying step is 50 ° C. or more and 100 ° C. or less.
ある実施形態では、前記炭化工程における前記前駆体の加熱温度は、７００℃以上９００℃以下である。 In one embodiment, the heating temperature of the precursor in the carbonizing step is 700 ° C. or more and 900 ° C. or less.
ある実施形態では、前記不活性雰囲気は、窒素雰囲気である。 In one embodiment, the inert atmosphere is a nitrogen atmosphere.
ある実施形態では、前記混合工程の前に、前記遷移金属源及び前記亜鉛源を第１極性溶媒中で混合することにより第１混合液を調製する予備混合工程を更に備える。この実施形態では、前記混合工程において、前記イミダゾール化合物を第２極性溶媒中に溶解させた第２混合液と、前記第１混合液とを混合する。 In one embodiment, the method further includes a pre-mixing step of preparing a first mixed solution by mixing the transition metal source and the zinc source in a first polar solvent before the mixing step. In this embodiment, in the mixing step, a second mixed solution in which the imidazole compound is dissolved in a second polar solvent is mixed with the first mixed solution.
ある実施形態では、前記第１極性溶媒及び前記第２極性溶媒は、何れも炭素原子数１以上３以下のアルコールである。 In one embodiment, each of the first polar solvent and the second polar solvent is an alcohol having 1 to 3 carbon atoms.
ある実施形態では、前記遷移金属担持カーボンアロイは、燃料電池の電極用触媒である。 In one embodiment, the transition metal-supported carbon alloy is a catalyst for an electrode of a fuel cell.
本発明の遷移金属担持カーボンアロイの製造方法によれば、酸素還元反応の触媒活性を向上させることができる遷移金属担持カーボンアロイを製造できる。 According to the method for producing a transition metal-supported carbon alloy of the present invention, it is possible to produce a transition metal-supported carbon alloy which can improve the catalytic activity of the oxygen reduction reaction.
以下、本発明の好適な実施形態について説明する。なお、「遷移金属」とは、周期表で第３族から第１１族までに存在する金属元素である。「遷移金属源」とは、遷移金属担持カーボンアロイの遷移金属成分の原料となる化合物、塩又は組成物であり、かつ極性溶媒に可溶な原料である。「亜鉛源」とは、遷移金属担持カーボンアロイの前駆体の亜鉛成分の原料となる化合物、塩又は組成物であり、かつ極性溶媒に可溶な原料である。「イミダゾール化合物」とは、イミダゾール環を有する化合物であり、かつ極性溶媒に可溶な化合物である。 Hereinafter, preferred embodiments of the present invention will be described. The “transition metal” is a metal element present in Groups 3 to 11 of the periodic table. The “transition metal source” is a compound, salt or composition as a raw material of the transition metal component of the transition metal-supported carbon alloy, and is a raw material soluble in a polar solvent. The “zinc source” is a compound, a salt or a composition serving as a raw material of a zinc component of a precursor of a transition metal-supported carbon alloy, and is a raw material soluble in a polar solvent. An "imidazole compound" is a compound which has an imidazole ring and is a compound which is soluble in a polar solvent.
「炭化」とは、有機物を含む材料が、不活性雰囲気下で加熱されることにより、炭素分に富んだ物質になることを意味する。 The term "carbonization" means that a material containing an organic matter becomes a carbon-rich material by being heated under an inert atmosphere.
「ゼオライト型イミダゾール骨格材料」とは、金属同士を架橋する有機架橋配位子としてイミダゾールを用いた、ゼオライト様トポロジーを有する構造体を骨格とする材料である。ゼオライト型イミダゾール骨格材料に使用される金属としては、例えば亜鉛、コバルト、及びこれらの組み合わせが挙げられる。以下、ゼオライト型イミダゾール骨格材料を、ＺＩＦと記載することがある。 The “zeolite type imidazole framework material” is a material having a framework having a zeolite-like topology, using imidazole as an organic bridging ligand which bridges metals. Metals used for the zeolite-type imidazole framework include, for example, zinc, cobalt, and combinations thereof. Hereinafter, the zeolite-type imidazole framework material may be described as ZIF.
本実施形態の製造方法の概要を説明する。本実施形態の製造方法によれば、窒素を含むカーボンアロイと、このカーボンアロイに担持された遷移金属とを含む遷移金属担持カーボンアロイが得られる。図１は、本実施形態に係る遷移金属担持カーボンアロイの製造方法を示すフローチャートである。図１に示すように、本実施形態に係る遷移金属担持カーボンアロイの製造方法は、混合工程Ｓ１と、乾燥工程Ｓ２と、炭化工程Ｓ３とを備える。 The outline of the manufacturing method of the present embodiment will be described. According to the manufacturing method of this embodiment, a transition metal-supported carbon alloy containing a carbon alloy containing nitrogen and a transition metal supported by the carbon alloy can be obtained. FIG. 1 is a flowchart showing a method of manufacturing a transition metal-supported carbon alloy according to the present embodiment. As shown in FIG. 1, the method for producing a transition metal-supported carbon alloy according to the present embodiment includes a mixing step S1, a drying step S2, and a carbonization step S3.
混合工程Ｓ１では、遷移金属源、亜鉛源及びイミダゾール化合物を極性溶媒中で混合することにより複合体粒子の懸濁液を得る。混合工程Ｓ１において、遷移金属源中の遷移金属及び亜鉛源中の亜鉛（Ｚｎ）の合計に対する、遷移金属源中の遷移金属のモル比が０．０５以上０．６０以下となるように、遷移金属源及び亜鉛源を使用する。上記モル比は、例えば遷移金属源としてコバルト（Ｃｏ）源を用いる場合、Ｃｏ／（Ｃｏ＋Ｚｎ）となる。乾燥工程Ｓ２では、複合体粒子を乾燥することにより前駆体を得る。炭化工程Ｓ３では、前駆体を不活性雰囲気下で炭化する。 In the mixing step S1, a suspension of composite particles is obtained by mixing a transition metal source, a zinc source and an imidazole compound in a polar solvent. Transition in the mixing step S1 such that the molar ratio of the transition metal in the transition metal source is 0.05 or more and 0.60 or less with respect to the total of the transition metal in the transition metal source and zinc (Zn) in the zinc source Use a metal source and a zinc source. The molar ratio is, for example, Co / (Co + Zn) when a cobalt (Co) source is used as a transition metal source. In the drying step S2, the composite particles are dried to obtain a precursor. In the carbonization step S3, the precursor is carbonized under an inert atmosphere.
酸素還元反応の触媒活性をより向上させるためには、遷移金属源中の遷移金属及び亜鉛源中の亜鉛の合計に対する、遷移金属源中の遷移金属のモル比が０．１０以上０．５０以下となるように、遷移金属源及び亜鉛源を使用することが好ましい。 In order to further improve the catalytic activity of the oxygen reduction reaction, the molar ratio of the transition metal in the transition metal source to the total of the transition metal in the transition metal source and the zinc in the zinc source is 0.10 or more and 0.50 or less Preferably, a transition metal source and a zinc source are used.
また、本実施形態に係る遷移金属担持カーボンアロイの製造方法は、混合工程Ｓ１の前に予備混合工程を更に備えてもよい。予備混合工程では、遷移金属源及び亜鉛源を第１極性溶媒中で混合することにより第１混合液を調製する。また、混合工程Ｓ１と乾燥工程Ｓ２との間に、複合体粒子を洗浄する洗浄工程を更に備えてもよい。以下、各工程についてそれぞれ説明する。なお、重複する構成要素については、説明を省略する場合がある。 Moreover, the manufacturing method of the transition metal carrying | support carbon alloy which concerns on this embodiment may further be equipped with the pre-mixing process before mixing process S1. In the pre-mixing step, the first mixture is prepared by mixing the transition metal source and the zinc source in a first polar solvent. Moreover, you may further comprise the washing process which wash | cleans composite particle | grains between mixing process S1 and drying process S2. Each of the steps will be described below. In addition, about the component which overlaps, description may be abbreviate | omitted.
［予備混合工程］
任意工程である予備混合工程では、遷移金属源及び亜鉛源を第１極性溶媒中で混合することにより第１混合液を調製する。
[Pre-mixing process]
In the optional premixing step, the first mixture is prepared by mixing the transition metal source and the zinc source in a first polar solvent.
（遷移金属源）
遷移金属源としては、特に限定されないが、製造コスト低減の観点からクロム源、マンガン源、鉄源、コバルト源、ニッケル源及び銅源からなる群から選択される一種以上が好ましい。このうち、酸素還元反応の触媒活性をより向上させるためには、遷移金属源としては、鉄源、コバルト源、ニッケル源及び銅源からなる群から選択される一種以上がより好ましく、コバルト源が更に好ましい。
(Transition metal source)
The transition metal source is not particularly limited, but is preferably one or more selected from the group consisting of a chromium source, a manganese source, an iron source, a cobalt source, a nickel source, and a copper source from the viewpoint of reducing manufacturing costs. Among them, in order to further improve the catalytic activity of the oxygen reduction reaction, as the transition metal source, one or more selected from the group consisting of an iron source, a cobalt source, a nickel source and a copper source is more preferable. More preferable.
遷移金属源の具体例としては、極性溶媒への溶解性を向上させる観点から、遷移金属の塩が好ましく、クロム、マンガン、鉄、コバルト、ニッケル及び銅から選択される一種以上の遷移金属の塩がより好ましい。遷移金属の塩としては、例えば、遷移金属の硝酸化物、遷移金属の亜硝酸化物、遷移金属のスルホン化物、遷移金属の亜硫酸化物、遷移金属の水酸化物及び遷移金属のハロゲン化物が挙げられる。このうち、極性溶媒への溶解性を向上させる観点から、遷移金属の硝酸化物が好ましい。 As a specific example of the transition metal source, from the viewpoint of improving solubility in polar solvents, salts of transition metals are preferable, and salts of one or more transition metals selected from chromium, manganese, iron, cobalt, nickel and copper Is more preferred. Examples of the transition metal salt include transition metal nitrates, transition metal nitrites, transition metal sulfonates, transition metal sulfites, transition metal hydroxides and transition metal halides. Among these, nitrates of transition metals are preferable from the viewpoint of improving the solubility in polar solvents.
また、遷移金属源は、結晶水を含んでもよい。結晶水を含む遷移金属源としては、例えば、硝酸コバルト（ＩＩ）六水和物及び塩化コバルト（ＩＩ）六水和物が挙げられる。 The transition metal source may also include water of crystallization. Examples of transition metal sources including water of crystallization include cobalt (II) nitrate hexahydrate and cobalt (II) chloride hexahydrate.
（亜鉛源）
亜鉛源としては、特に限定されないが、例えば、硝酸亜鉛、亜硝酸亜鉛、硫酸亜鉛、亜硫酸亜鉛、水酸化亜鉛及びハロゲン化亜鉛が挙げられる。このうち、極性溶媒への溶解性を向上させる観点から、硝酸亜鉛が好ましい。
(Zinc source)
The zinc source is not particularly limited, and examples thereof include zinc nitrate, zinc nitrite, zinc sulfate, zinc sulfite, zinc hydroxide and zinc halide. Among these, zinc nitrate is preferred from the viewpoint of improving the solubility in polar solvents.
また、亜鉛源は、結晶水を含んでもよい。結晶水を含む亜鉛源としては、例えば、硝酸亜鉛六水和物及び硫酸亜鉛七水和物が挙げられる。 The zinc source may also include water of crystallization. As a zinc source containing crystal water, for example, zinc nitrate hexahydrate and zinc sulfate heptahydrate can be mentioned.
（第１極性溶媒）
第１極性溶媒としては、水；アルコール；アセトン、メチルエチルケトン等のケトン；テトラヒドロフラン、テトラヒドロピラン、ジオキサン等の環状エーテル；ギ酸、酢酸等の有機酸；トリエチルアミン等のアミンが挙げられる。このうち、遷移金属源及び亜鉛源の溶解性を向上させる観点から、アルコールが好ましく、炭素原子数１以上３以下のアルコールがより好ましい。炭素原子数１以上３以下のアルコールとしては、メタノール、エタノール、１−プロパノール及び２−プロパノールが挙げられ、遷移金属源及び亜鉛源の溶解性を向上させる観点から、メタノールが好ましい。第１極性溶媒は、一種のみを使用してもよく、二種以上を併用してもよい。
(First polar solvent)
Examples of the first polar solvent include water; alcohols; ketones such as acetone and methyl ethyl ketone; cyclic ethers such as tetrahydrofuran, tetrahydropyran and dioxane; organic acids such as formic acid and acetic acid; and amines such as triethylamine. Among these, from the viewpoint of improving the solubility of the transition metal source and the zinc source, alcohols are preferable, and alcohols having 1 or more and 3 or less carbon atoms are more preferable. Examples of the alcohol having 1 to 3 carbon atoms include methanol, ethanol, 1-propanol and 2-propanol. From the viewpoint of improving the solubility of the transition metal source and the zinc source, methanol is preferable. The first polar solvent may be used alone or in combination of two or more.
（第１混合液の調製方法）
第１混合液を調製する方法としては、例えば容器に遷移金属源と亜鉛源と第１極性溶媒とを入れた後、スターラー等を用いてこれらを攪拌する方法が挙げられる。攪拌することにより、遷移金属源と亜鉛源と第１極性溶媒とが均一に混合された第１混合液が得られる。この第１混合液中の遷移金属及び亜鉛の含有量は、例えば１０ミリモル／Ｌ以上１００ミリモル／Ｌ以下である。遷移金属源及び亜鉛源のそれぞれの使用量は、遷移金属源中の遷移金属及び亜鉛源中の亜鉛の合計に対する、遷移金属源中の遷移金属のモル比が０．０５以上０．６０以下となるように調整する。攪拌時間としては、例えば１分以上６０分以下である。なお、遷移金属源と亜鉛源と第１極性溶媒とを容器に入れる際、入れる順番は特に限定されない。
(Preparation method of the first mixture)
As a method of preparing a 1st liquid mixture, for example, after putting a transition metal source, a zinc source, and the 1st polar solvent in a container, the method of stirring these using a stirrer etc. is mentioned. By stirring, a first mixed solution in which the transition metal source, the zinc source and the first polar solvent are uniformly mixed is obtained. The content of transition metal and zinc in the first mixture is, for example, 10 mmol / L or more and 100 mmol / L or less. The amounts of each of the transition metal source and the zinc source used are such that the molar ratio of the transition metal in the transition metal source is 0.05 or more and 0.60 or less to the total of the transition metal in the transition metal source and zinc in the zinc source Adjust to become The stirring time is, for example, 1 minute or more and 60 minutes or less. In addition, when putting a transition metal source, a zinc source, and a 1st polar solvent in a container, the order put in is not specifically limited.
［混合工程］
上述した予備混合工程を実施した場合、混合工程Ｓ１では、第１混合液と、第２混合液とを混合する。第２混合液は、イミダゾール化合物を第２極性溶媒中に溶解させることにより得られる。
[Mixing process]
When the above-mentioned pre-mixing step is performed, in the mixing step S1, the first mixed solution and the second mixed solution are mixed. The second mixture is obtained by dissolving the imidazole compound in a second polar solvent.
（イミダゾール化合物）
イミダゾール化合物としては、例えば無置換のイミダゾール、及びイミダゾール環の２位、４位及び５位の少なくとも１つに置換基を有するイミダゾール誘導体が挙げられる。イミダゾール誘導体の置換基としては、炭素原子数１以上６以下のアルキル基、ハロゲン原子及びニトロ基から選択される一種以上が好ましい。また、イミダゾール環の４位及び５位に有する置換基が互いに結合して環（脂肪族環又は芳香族環）を形成していてもよい。イミダゾール環の４位及び５位に有する置換基が互いに結合して環を形成する場合、環を形成する原子数は、例えば５以上７以下である。
(Imidazole compound)
Examples of the imidazole compound include unsubstituted imidazole and imidazole derivatives having a substituent at at least one of the 2-, 4- and 5-positions of the imidazole ring. The substituent of the imidazole derivative is preferably one or more selected from an alkyl group having 1 to 6 carbon atoms, a halogen atom and a nitro group. Further, the substituents at the 4- and 5-positions of the imidazole ring may be bonded to each other to form a ring (aliphatic ring or aromatic ring). When the substituents present at the 4- and 5-positions of the imidazole ring bond together to form a ring, the number of atoms forming the ring is, for example, 5 or more and 7 or less.
炭素原子数１以上６以下のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ｎ−ブチル基、ｓ−ブチル基、ｔ−ブチル基、ペンチル基、イソペンチル基、ネオペンチル基、及びヘキシル基が挙げられる。ハロゲン原子としては、例えば、フッ素原子、塩素原子、臭素原子及びヨウ素原子が挙げられる。 As an alkyl group having 1 to 6 carbon atoms, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, neopentyl group And hexyl groups. As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, for example.
イミダゾール化合物の中では、２−メチルイミダゾールが好ましい。２−メチルイミダゾールを用いると、後述する前駆体として、安定な構造であるソーダライト構造を持つＺＩＦ（ＺＩＦ−８）が得られる。 Among the imidazole compounds, 2-methylimidazole is preferred. When 2-methylimidazole is used, ZIF (ZIF-8) having a sodalite structure, which is a stable structure, is obtained as a precursor described later.
（第２極性溶媒）
第２極性溶媒は、上述した第１極性溶媒と同様の極性溶媒が使用できる。第２極性溶媒としては、イミダゾール化合物の溶解性を向上させる観点から、アルコールが好ましく、炭素原子数１以上３以下のアルコールがより好ましく、メタノールが更に好ましい。第２極性溶媒と第１極性溶媒とは相違していてもよいが、第１混合液と第２混合液とを混合する際の相溶性を向上させる観点から、第２極性溶媒は、上述した第１極性溶媒と同じ極性溶媒であることが好ましい。同様の観点から、第２極性溶媒の使用量は、第１極性溶媒の使用量と同じ量であることが好ましい。
(2nd polar solvent)
As the second polar solvent, the same polar solvent as the first polar solvent described above can be used. The second polar solvent is preferably an alcohol, more preferably an alcohol having 1 or more and 3 or less carbon atoms, and still more preferably methanol, from the viewpoint of improving the solubility of the imidazole compound. The second polar solvent may be different from the first polar solvent, but from the viewpoint of improving the compatibility when mixing the first mixture and the second mixture, the second polar solvent is the same as described above. The same polar solvent as the first polar solvent is preferred. From the same viewpoint, the amount of the second polar solvent used is preferably the same as the amount of the first polar solvent used.
（第２混合液の調製方法）
第２混合液を調製する方法としては、例えば容器にイミダゾール化合物と第２極性溶媒とを入れた後、スターラー等を用いてこれらを攪拌する方法が挙げられる。攪拌することにより、イミダゾール化合物と第２極性溶媒とが均一に混合された第２混合液が得られる。この第２混合液中のイミダゾール化合物の含有量は、例えば１００ミリモル／Ｌ以上２００ミリモル／Ｌ以下である。攪拌時間としては、例えば１分以上６０分以下である。なお、イミダゾール化合物と第２極性溶媒とを容器に入れる際、入れる順番は特に限定されない。
(Method of preparing the second mixture)
As a method of preparing a 2nd liquid mixture, for example, after putting an imidazole compound and a 2nd polar solvent in a container, the method of stirring these using a stirrer etc. is mentioned. By stirring, a second mixed solution in which the imidazole compound and the second polar solvent are uniformly mixed is obtained. The content of the imidazole compound in the second mixture liquid is, for example, 100 mmol / L or more and 200 mmol / L or less. The stirring time is, for example, 1 minute or more and 60 minutes or less. In addition, when putting an imidazole compound and a 2nd polar solvent in a container, the order put in is not specifically limited.
（混合方法）
第１混合液と第２混合液とを混合する方法としては、例えば容器に第１混合液及び第２混合液の何れか一方を入れた後、スターラー等を用いて容器内の混合液を攪拌しながら他方の混合液を滴下する方法が挙げられる。他方の混合液の滴下が完了した後、更に所定時間（例えば１２時間以上３６時間以下）、混合液を攪拌し続けることが好ましい。混合液を攪拌する際の雰囲気温度は、例えば１５℃以上３０℃以下である。第１混合液と第２混合液とを混合することにより、複合体粒子の懸濁液が得られる。複合体粒子としては、例えば遷移金属と亜鉛とがイミダゾール化合物で架橋されたＺＩＦからなる粒子が挙げられる。
(Mixing method)
As a method of mixing the first liquid mixture and the second liquid mixture, for example, after either of the first liquid mixture and the second liquid mixture is put in a container, the liquid mixture in the container is stirred using a stirrer or the like. While the other mixed solution is dropped. After the addition of the other mixture is completed, it is preferable to continue stirring the mixture for a predetermined time (for example, 12 hours or more and 36 hours or less). The atmosphere temperature at the time of stirring the liquid mixture is, for example, 15 ° C. or more and 30 ° C. or less. By mixing the first mixture and the second mixture, a suspension of composite particles is obtained. Examples of composite particles include particles composed of ZIF in which a transition metal and zinc are crosslinked by an imidazole compound.
なお、予備混合工程を実施しない場合、遷移金属源、亜鉛源及びイミダゾール化合物を極性溶媒中で混合する方法としては、例えば容器に遷移金属源と亜鉛源とイミダゾール化合物と極性溶媒とを入れた後、スターラー等を用いてこれらを攪拌する方法が挙げられる。この場合の極性溶媒としては、上述した第１極性溶媒及び第２極性溶媒と同様の極性溶媒が使用できる。攪拌する際の雰囲気温度は、例えば１５℃以上３０℃以下である。攪拌時間は、例えば１２時間以上３６時間以下である。遷移金属源、亜鉛源、イミダゾール化合物及び極性溶媒のそれぞれの使用量は、上述した予備混合工程を実施する場合と同様である。また、遷移金属源と亜鉛源とイミダゾール化合物と極性溶媒とを容器に入れる際、入れる順番は特に限定されない。この方法によっても、複合体粒子の懸濁液が得られる。複合体粒子としては、例えば遷移金属と亜鉛とがイミダゾール化合物で架橋されたＺＩＦからなる粒子が挙げられる。 In addition, as a method of mixing a transition metal source, a zinc source, and an imidazole compound in a polar solvent when not performing a pre-mixing process, for example, after putting a transition metal source, a zinc source, an imidazole compound, and a polar solvent in a container And a method of stirring them using a stirrer or the like. As a polar solvent in this case, the same polar solvent as the 1st polar solvent mentioned above and the 2nd polar solvent can be used. The atmosphere temperature at the time of stirring is, for example, 15 ° C. or more and 30 ° C. or less. The stirring time is, for example, 12 hours or more and 36 hours or less. The amounts of each of the transition metal source, the zinc source, the imidazole compound and the polar solvent used are the same as in the case of carrying out the above-mentioned premixing step. Moreover, when putting a transition metal source, a zinc source, an imidazole compound, and a polar solvent in a container, the order to put in is not specifically limited. Also by this method, a suspension of composite particles can be obtained. Examples of composite particles include particles composed of ZIF in which a transition metal and zinc are crosslinked by an imidazole compound.
遷移金属源、亜鉛源及びイミダゾール化合物を均一に混合するためには、予備混合工程を実施した後、第１混合液と第２混合液とを混合することが好ましい。 In order to uniformly mix the transition metal source, the zinc source and the imidazole compound, it is preferable to carry out the pre-mixing step and then to mix the first mixture and the second mixture.
［洗浄工程］
任意工程である洗浄工程では、複合体粒子を洗浄する。洗浄方法としては、例えば混合工程Ｓ１で使用した極性溶媒と同様の極性溶媒を使用して、複合体粒子を洗浄する方法が挙げられる。より具体的には、まず、混合工程Ｓ１で得られた複合体粒子の懸濁液から複合体粒子を濾取した後、再度、極性溶媒に加えて、複合体粒子を含む極性溶媒の懸濁液を得る。次いで、この懸濁液を遠心分離した後、懸濁液から複合体粒子を濾取する。この操作を複数回繰り返してもよい。この洗浄により、複合体粒子表面に付着した不純物が除去されるため、純度の高い前駆体を得ることができる。
[Washing process]
In the washing step which is an optional step, the complex particles are washed. Examples of the washing method include a method of washing the composite particles using a polar solvent similar to the polar solvent used in the mixing step S1. More specifically, after first filtering out the composite particles from the suspension of composite particles obtained in the mixing step S 1, the composite particles are again added to the polar solvent to suspend the polar solvent containing the composite particles. Get the liquid. The suspension is then centrifuged and the complex particles are filtered off from the suspension. This operation may be repeated multiple times. By this washing, the impurities attached to the surface of the composite particle are removed, so that a highly pure precursor can be obtained.
［乾燥工程］
乾燥工程Ｓ２では、複合体粒子を乾燥することにより前駆体を得る。乾燥させる複合体粒子は、例えば混合工程Ｓ１で得られた複合体粒子の懸濁液から濾取することができる。乾燥条件は、例えば加熱温度が４０℃以上１００℃以下であり、加熱時間が１０時間以上２４時間以下である。複合体粒子表面に存在する極性溶媒を充分に揮発させるためには、加熱温度が５０℃以上であることが好ましい。乾燥工程Ｓ２により、遷移金属担持カーボンアロイの前駆体が得られる。前駆体としては、例えば遷移金属と亜鉛とがイミダゾール化合物で架橋されたＺＩＦが挙げられる。
[Drying process]
In the drying step S2, the composite particles are dried to obtain a precursor. The composite particles to be dried can be filtered, for example, from the suspension of composite particles obtained in the mixing step S1. The drying conditions are, for example, a heating temperature of 40 ° C. or more and 100 ° C. or less, and a heating time of 10 hours or more and 24 hours or less. In order to sufficiently volatilize the polar solvent present on the surface of the composite particles, the heating temperature is preferably 50 ° C. or higher. By the drying step S2, a precursor of a transition metal-supported carbon alloy is obtained. Examples of the precursor include ZIF in which a transition metal and zinc are crosslinked by an imidazole compound.
［炭化工程］
炭化工程Ｓ３では、乾燥工程Ｓ２で得られた前駆体を不活性雰囲気下で炭化する。不活性雰囲気としては、製造コスト低減の観点から窒素雰囲気が好ましい。炭化工程Ｓ３における前駆体の加熱温度（炭化温度）は、例えば６５０℃以上９５０℃以下である。炭化工程Ｓ３において、前駆体中の亜鉛粒子が昇華するため、得られる炭化物（遷移金属担持カーボンアロイ）に細孔が形成される。燃料電池の電極用触媒として適用可能な電気抵抗値に調整するためには、炭化温度は７００℃以上であることが好ましい。酸素還元反応の触媒活性をより向上させるためには、炭化温度は９００℃以下であることが好ましい。炭化温度での加熱時間は、例えば２時間以上４時間以下である。炭化温度に到達するまでの昇温速度は、例えば０．５℃／分以上３℃／分以下である。
[Carbonization process]
In the carbonization step S3, the precursor obtained in the drying step S2 is carbonized under an inert atmosphere. As an inert atmosphere, a nitrogen atmosphere is preferable from the viewpoint of reducing the manufacturing cost. The heating temperature (carbonization temperature) of the precursor in carbonization process S3 is 650 degreeC or more and 950 degrees C or less, for example. In the carbonization step S3, since the zinc particles in the precursor are sublimated, pores are formed in the obtained carbide (transition metal supporting carbon alloy). The carbonization temperature is preferably 700 ° C. or higher in order to adjust the electric resistance value applicable to the electrode catalyst of the fuel cell. In order to further improve the catalytic activity of the oxygen reduction reaction, the carbonization temperature is preferably 900 ° C. or less. The heating time at the carbonization temperature is, for example, 2 hours or more and 4 hours or less. The temperature rising rate until reaching the carbonization temperature is, for example, 0.5 ° C./min or more and 3 ° C./min or less.
炭化工程Ｓ３により得られる遷移金属担持カーボンアロイ中の遷移金属の含有量は、酸素還元反応の触媒活性をより向上させるためには、０．１質量％以上２質量％以下であることが好ましい。遷移金属担持カーボンアロイ中の遷移金属の含有量は、上述した混合工程Ｓ１において、遷移金属源中の遷移金属及び亜鉛源中の亜鉛の合計に対する、遷移金属源中の遷移金属のモル比を変更することにより調整できる。 The content of the transition metal in the transition metal-supported carbon alloy obtained by the carbonizing step S3 is preferably 0.1% by mass or more and 2% by mass or less in order to further improve the catalytic activity of the oxygen reduction reaction. The transition metal content in the transition metal-supported carbon alloy changes the molar ratio of the transition metal in the transition metal source to the total of the transition metal in the transition metal source and the zinc in the zinc source in the above-mentioned mixing step S1 It can adjust by doing.
本実施形態の製造方法によれば、遷移金属源及び亜鉛源を特定比率で含む材料を極性溶媒中で混合させた後、乾燥することで、粒径の小さい遷移金属粒子、及び粒径の小さい亜鉛粒子が均一に配置された前駆体（例えばＺＩＦ）が得られる。この前駆体を炭化することで、粒径の小さい遷移金属粒子がカーボンアロイに均一に分散された状態で担持されると共に、粒径の小さい亜鉛粒子が昇華するため、例えば孔径１ｎｍ以下の細孔が均一に形成される。よって、本実施形態の製造方法で得られた遷移金属担持カーボンアロイによれば、触媒反応の活性点となる小粒径の遷移金属粒子が均一に分散されると共に、触媒反応の反応場となる細孔（例えば孔径１ｎｍ以下の細孔）が均一に形成されるため、酸素還元反応の触媒活性を向上させることができると考えられる。 According to the manufacturing method of the present embodiment, transition metal particles having a small particle size and particles having a small particle size can be obtained by mixing a material containing a transition metal source and a zinc source in a specific ratio in a polar solvent and drying it. A precursor (eg, ZIF) in which zinc particles are uniformly disposed is obtained. By carbonizing this precursor, transition metal particles having a small particle size are supported in a uniformly dispersed state in a carbon alloy, and zinc particles having a small particle size are sublimated, for example, pores having a pore diameter of 1 nm or less Are formed uniformly. Therefore, according to the transition metal-supporting carbon alloy obtained by the manufacturing method of the present embodiment, transition metal particles having a small particle diameter, which is the active point of the catalytic reaction, are uniformly dispersed and become the reaction site of the catalytic reaction. Since pores (for example, pores having a pore diameter of 1 nm or less) are uniformly formed, it is considered that the catalytic activity of the oxygen reduction reaction can be improved.
［遷移金属担持カーボンアロイの用途］
本実施形態の製造方法によって得られる遷移金属担持カーボンアロイ（以下、本遷移金属担持カーボンアロイと記載することがある。）は、例えば、構造材料、電極材料、ろ過材料、触媒材料等に適用可能である。特に、本遷移金属担持カーボンアロイは、酸素還元反応の触媒活性を向上させることができるため、燃料電池の電極用触媒に適用することが好ましい。
[Uses of transition metal-supported carbon alloy]
The transition metal supported carbon alloy obtained by the manufacturing method of the present embodiment (hereinafter sometimes referred to as the present transition metal supported carbon alloy) can be applied to, for example, structural materials, electrode materials, filtration materials, catalyst materials, etc. It is. In particular, since the present transition metal-supported carbon alloy can improve the catalytic activity of the oxygen reduction reaction, it is preferably applied to a catalyst for an electrode of a fuel cell.
本遷移金属担持カーボンアロイを好適に使用できる燃料電池としては、固体高分子形燃料電池（ＰＥＦＣ）が挙げられる。本遷移金属担持カーボンアロイは、酸素還元反応の触媒活性を向上させることができるため、例えばＰＥＦＣのカソード（空気極）用の触媒として用いることが好ましい。 As a fuel cell which can use this transition metal carrying | support carbon alloy suitably, a polymer electrolyte fuel cell (PEFC) is mentioned. The present transition metal-supported carbon alloy can improve the catalytic activity of the oxygen reduction reaction, and therefore, is preferably used as a catalyst for the cathode (air electrode) of PEFC, for example.
以下、実施例を用いて本発明を更に具体的に説明する。なお、本発明は実施例の範囲に何ら限定されるものではない。 Hereinafter, the present invention will be more specifically described using examples. The present invention is not limited to the scope of the examples.
［実施例１］
容器に、２５０ｍＬのメタノールと、硝酸コバルト（ＩＩ）六水和物と、硝酸亜鉛六水和物とを入れた後、これらの混合物を５分間攪拌し、第１混合液を得た（予備混合工程）。硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物のそれぞれの使用量は、硝酸コバルト（ＩＩ）六水和物中のコバルト（Ｃｏ）及び硝酸亜鉛六水和物中の亜鉛（Ｚｎ）の合計に対する、硝酸コバルト（ＩＩ）六水和物中のＣｏのモル比が０．１０となるように調整した。具体的には、１．７ミリモルの硝酸コバルト（ＩＩ）六水和物と、１５．３ミリモルの硝酸亜鉛六水和物とを使用した。以下、硝酸コバルト（ＩＩ）六水和物中のＣｏ及び硝酸亜鉛六水和物中のＺｎの合計に対する、硝酸コバルト（ＩＩ）六水和物中のＣｏのモル比を、Ｃｏ／（Ｃｏ＋Ｚｎ）と記載する。
Example 1
In a container, 250 mL of methanol, cobalt nitrate (II) hexahydrate, and zinc nitrate hexahydrate were placed, and the mixture was stirred for 5 minutes to obtain a first mixture (premixing) Process). The amounts of each of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate used are the same as cobalt (Co) in cobalt nitrate (II) hexahydrate and zinc (Zn in zinc nitrate hexahydrate) It adjusted so that the molar ratio of Co in cobalt nitrate (II) hexahydrate could be set to 0.10 with respect to the sum total of. Specifically, 1.7 millimoles of cobalt (II) nitrate hexahydrate and 15.3 millimoles of zinc nitrate hexahydrate were used. The molar ratio of Co in cobalt (II) hexahydrate to the total of Co in cobalt nitrate (II) hexahydrate and zinc in zinc nitrate hexahydrate is represented by Co / (Co + Zn). And write.
次いで、別の容器に、２５０ｍＬのメタノールと、４０．０ミリモルの２−メチルイミダゾールとを入れた後、これらの混合物を５分間攪拌し、第２混合液を得た。 Then, after putting 250 mL of methanol and 40.0 mmol of 2-methylimidazole in another container, these mixtures were stirred for 5 minutes to obtain a second mixture.
次いで、第１混合液を攪拌しながら第２混合液を第１混合液に滴下し、全ての第２混合液の滴下が終了した後、更に２４時間攪拌し続けた（混合工程）。攪拌の際、雰囲気温度は２５℃に維持した。この混合工程により、複合体粒子の懸濁液が得られた。 Then, while the first mixed solution was being stirred, the second mixed solution was dropped into the first mixed solution, and after dropping of all the second mixed solutions was completed, the stirring was continued for further 24 hours (mixing step). During the stirring, the ambient temperature was maintained at 25 ° C. This mixing step yielded a suspension of composite particles.
得られた複合体粒子の懸濁液から複合体粒子を濾取し、再度、５０ｍＬのメタノールに加えて懸濁液を得た後、この懸濁液を回転速度１１０００ｒｐｍで１０分間遠心分離し、複合体粒子を濾取した。このメタノールによる洗浄操作を３回繰り返して、複合体粒子の洗浄物（粉体）を得た。 The complex particles are collected by filtration from the resulting suspension of complex particles, added again to 50 mL of methanol to obtain a suspension, and this suspension is centrifuged at a rotational speed of 11,000 rpm for 10 minutes, The complex particles were filtered off. The washing operation with methanol was repeated three times to obtain a washed product (powder) of composite particles.
得られた複合体粒子の洗浄物を温度６０℃のオーブン中で１２時間乾燥し、実施例１のコバルト担持カーボンアロイの前駆体を得た（収量０．５ｇ）。次いで、得られた前駆体を管状炉内で炭化させた。炭化の際、管状炉内に窒素を６０ｍＬ／分の流量で通流させて管状炉内を窒素雰囲気にした。炭化条件は、昇温速度２℃／分で４００℃まで昇温させた後、４００℃で４時間保持し、更に１．３℃／分で８００℃まで昇温させた後、８００℃（炭化温度）で３時間保持する条件とした。この炭化工程により、前駆体中の亜鉛粒子を昇華させ、実施例１のコバルト担持カーボンアロイを得た（収量０．２５ｇ）。実施例１のコバルト担持カーボンアロイをエネルギー分散型Ｘ線分析（ＥＤＸ）により分析し、炭素、窒素及びコバルトが含まれていることを確認した。また、実施例１のコバルト担持カーボンアロイを高周波誘導結合プラズマ発光分光分析法（ＩＣＰ発光分光分析法）により分析し、コバルトの含有量が０．５質量％であることを確認した。なお、ＥＤＸ分析には、走査型電子顕微鏡（株式会社日立製作所製「Ｓ−４８００」）に装着されたＥＤＸ装置を用いた。また、ＩＣＰ発光分光分析には、ＩＣＰ発光分光分析装置（株式会社日立製作所製「ＳＰＳ３５００ＤＤ」）を用いた。 The washed composite particles were dried in an oven at a temperature of 60 ° C. for 12 hours to obtain a precursor of a cobalt-supported carbon alloy of Example 1 (yield: 0.5 g). The resulting precursor was then carbonized in a tubular furnace. During carbonization, nitrogen was allowed to flow through the tubular furnace at a flow rate of 60 mL / min to make the inside of the tubular furnace a nitrogen atmosphere. The carbonization conditions are such that the temperature is raised to 400 ° C. at a heating rate of 2 ° C./min, held at 400 ° C. for 4 hours, and further raised to 800 ° C. at 1.3 ° C / min, then 800 ° C. It was set as the conditions hold | maintained by temperature for 3 hours. By this carbonization step, the zinc particles in the precursor were sublimed to obtain a cobalt-supported carbon alloy of Example 1 (yield: 0.25 g). The cobalt-supported carbon alloy of Example 1 was analyzed by energy dispersive X-ray analysis (EDX), and it was confirmed that carbon, nitrogen and cobalt were contained. Further, the cobalt-supported carbon alloy of Example 1 was analyzed by high-frequency inductively coupled plasma emission spectrometry (ICP emission spectrometry), and it was confirmed that the content of cobalt was 0.5% by mass. In addition, EDX apparatus with which the scanning electron microscope ("S-4800" by Hitachi Ltd. make) was mounted | worn was used for EDX analysis. In addition, for ICP emission spectrometry, an ICP emission spectrometer ("SPS3500DD" manufactured by Hitachi, Ltd.) was used.
［実施例２］
予備混合工程において、Ｃｏ／（Ｃｏ＋Ｚｎ）が０．２０となるように硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物のそれぞれの使用量を調整したこと以外は、実施例１と同様の手順により、実施例２のコバルト担持カーボンアロイの前駆体を得た。なお、硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物の合計使用量は、実施例１と同じ量（１７．０ミリモル）とした。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより実施例２のコバルト担持カーボンアロイを得た。得られた実施例２のコバルト担持カーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素、窒素及びコバルトが含まれていることを確認した。
Example 2
Example 1 was repeated except that in the pre-mixing step, the amounts of cobalt (II) nitrate hexahydrate and zinc nitrate hexahydrate were adjusted so that Co / (Co + Zn) would be 0.20. The precursor of the cobalt-supported carbon alloy of Example 2 was obtained by the same procedure. The total amount used of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate was the same as in Example 1 (17.0 millimoles). The obtained precursor was carbonized in the same manner as in Example 1 to obtain a cobalt-supported carbon alloy of Example 2. The obtained cobalt-supporting carbon alloy of Example 2 was analyzed by EDX in the same manner as in Example 1, and it was confirmed that carbon, nitrogen and cobalt were contained.
［実施例３］
予備混合工程において、Ｃｏ／（Ｃｏ＋Ｚｎ）が０．３０となるように硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物のそれぞれの使用量を調整したこと以外は、実施例１と同様の手順により、実施例３のコバルト担持カーボンアロイの前駆体を得た。なお、硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物の合計使用量は、実施例１と同じ量（１７．０ミリモル）とした。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより実施例３のコバルト担持カーボンアロイを得た。得られた実施例３のコバルト担持カーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素、窒素及びコバルトが含まれていることを確認した。
[Example 3]
Example 1 was repeated except that in the pre-mixing step, the amounts of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate were adjusted such that Co / (Co + Zn) was 0.30. The precursor of the cobalt-supported carbon alloy of Example 3 was obtained by the same procedure. The total amount used of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate was the same as in Example 1 (17.0 millimoles). The obtained precursor was carbonized in the same procedure as in Example 1 to obtain a cobalt-supported carbon alloy of Example 3. The obtained cobalt-supporting carbon alloy of Example 3 was analyzed by EDX in the same manner as Example 1, and it was confirmed that carbon, nitrogen and cobalt were contained.
［実施例４］
予備混合工程において、Ｃｏ／（Ｃｏ＋Ｚｎ）が０．４０となるように硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物のそれぞれの使用量を調整したこと以外は、実施例１と同様の手順により、実施例４のコバルト担持カーボンアロイの前駆体を得た。なお、硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物の合計使用量は、実施例１と同じ量（１７．０ミリモル）とした。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより実施例４のコバルト担持カーボンアロイを得た。得られた実施例４のコバルト担持カーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素、窒素及びコバルトが含まれていることを確認した。
Example 4
Example 1 was repeated except that in the pre-mixing step, the amounts of cobalt (II) hexahydrate and zinc nitrate hexahydrate were adjusted so that Co / (Co + Zn) would be 0.40. The precursor of the cobalt-supported carbon alloy of Example 4 was obtained by the same procedure. The total amount used of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate was the same as in Example 1 (17.0 millimoles). The obtained precursor was carbonized in the same procedure as in Example 1 to obtain a cobalt-supported carbon alloy of Example 4. The obtained cobalt-supporting carbon alloy of Example 4 was analyzed by EDX in the same manner as in Example 1, and it was confirmed that carbon, nitrogen and cobalt were contained.
［実施例５］
予備混合工程において、Ｃｏ／（Ｃｏ＋Ｚｎ）が０．５０となるように硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物のそれぞれの使用量を調整したこと以外は、実施例１と同様の手順により、実施例５のコバルト担持カーボンアロイの前駆体を得た。なお、硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物の合計使用量は、実施例１と同じ量（１７．０ミリモル）とした。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより実施例５のコバルト担持カーボンアロイを得た。得られた実施例５のコバルト担持カーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素、窒素及びコバルトが含まれていることを確認した。
[Example 5]
Example 1 was repeated except that in the pre-mixing step, the amounts of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate were adjusted such that Co / (Co + Zn) was 0.50. The precursor of the cobalt-supported carbon alloy of Example 5 was obtained by the same procedure. The total amount used of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate was the same as in Example 1 (17.0 millimoles). The obtained precursor was carbonized in the same procedure as in Example 1 to obtain a cobalt-supported carbon alloy of Example 5. The obtained cobalt-supported carbon alloy of Example 5 was analyzed by EDX in the same manner as Example 1, and it was confirmed that carbon, nitrogen and cobalt were contained.
［比較例１］
予備混合工程において、硝酸コバルト（ＩＩ）六水和物を使用しなかったことと、１７．０ミリモルの硝酸亜鉛六水和物を使用したこと以外は、実施例１と同様の手順により、比較例１のカーボンアロイの前駆体を得た。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより比較例１のカーボンアロイを得た。得られた比較例１のカーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素及び窒素が含まれていることを確認した。
Comparative Example 1
The procedure of Example 1 is repeated except that cobalt (II) nitrate hexahydrate is not used and 17.0 millimoles of zinc nitrate hexahydrate is used in the pre-mixing step. The precursor of the carbon alloy of Example 1 was obtained. A carbon alloy of Comparative Example 1 was obtained by carbonizing the obtained precursor in the same procedure as in Example 1. The obtained carbon alloy of Comparative Example 1 was analyzed by EDX in the same manner as Example 1, and it was confirmed that carbon and nitrogen were contained.
［比較例２］
予備混合工程において、Ｃｏ／（Ｃｏ＋Ｚｎ）が０．７５となるように硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物のそれぞれの使用量を調整したこと以外は、実施例１と同様の手順により、比較例２のカーボンアロイの前駆体を得た。なお、硝酸コバルト（ＩＩ）六水和物及び硝酸亜鉛六水和物の合計使用量は、実施例１と同じ量（１７．０ミリモル）とした。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより比較例２のカーボンアロイを得た。得られた比較例２のカーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素、窒素及びコバルトが含まれていることを確認した。
Comparative Example 2
Example 1 was repeated except that in the pre-mixing step, the amounts of cobalt (II) nitrate hexahydrate and zinc nitrate hexahydrate were adjusted so that Co / (Co + Zn) would be 0.75. The precursor of the carbon alloy of Comparative Example 2 was obtained by the same procedure. The total amount used of cobalt nitrate (II) hexahydrate and zinc nitrate hexahydrate was the same as in Example 1 (17.0 millimoles). A carbon alloy of Comparative Example 2 was obtained by carbonizing the obtained precursor in the same procedure as in Example 1. The obtained carbon alloy of Comparative Example 2 was analyzed by EDX in the same manner as Example 1, and it was confirmed that carbon, nitrogen and cobalt were contained.
［比較例３］
予備混合工程において、硝酸亜鉛六水和物を使用しなかったことと、１７．０ミリモルの硝酸コバルト（ＩＩ）六水和物を使用したこと以外は、実施例１と同様の手順により、比較例３のカーボンアロイの前駆体を得た。得られた前駆体を用いて、実施例１と同様の手順で炭化させることにより比較例３のカーボンアロイを得た。得られた比較例３のカーボンアロイを、実施例１と同様にＥＤＸにより分析し、炭素、窒素及びコバルトが含まれていることを確認した。
Comparative Example 3
The procedure of Example 1 was repeated except that zinc nitrate hexahydrate was not used and 17.0 millimoles of cobalt (II) hexahydrate were used in the pre-mixing step. The precursor of the carbon alloy of Example 3 was obtained. A carbon alloy of Comparative Example 3 was obtained by carbonizing the obtained precursor according to the same procedure as in Example 1. The obtained carbon alloy of Comparative Example 3 was analyzed by EDX in the same manner as Example 1, and it was confirmed that carbon, nitrogen and cobalt were contained.
［分析及び評価］
（前駆体のＸ線回折測定による分析）
実施例１〜５のコバルト担持カーボンアロイの前駆体、及び比較例１〜３のカーボンアロイの前駆体について、それぞれＸ線回折測定装置（ＰＡＮａｌｙｔｉｃａｌ社製「Ｘ’ＰｅｒｔＰＲＯ ｄｉｆｆｒａｃｔｏｍｅｔｅｒ」）を用いてＸ線回折を測定した。測定したそれぞれの回折パターンを図２のグラフに示す。図２中、回折パターンＰＢ、ＰＣ、ＰＤ、ＰＥ及びＰＦは、それぞれ実施例１、２、３、４及び５のコバルト担持カーボンアロイの前駆体の回折パターンを示す。図２中、回折パターンＰＡ、ＰＧ及びＰＨは、それぞれ比較例１、２及び３のカーボンアロイの前駆体の回折パターンを示す。
[Analysis and evaluation]
(Analysis of precursor by X-ray diffraction measurement)
About the precursor of the cobalt carrying carbon alloy of Examples 1-5, and the precursor of the carbon alloy of Comparative Examples 1-3, X ray using X-ray-diffraction measuring apparatus ("X'PertPRO diffractometer" by PANalytical, respectively) The diffraction was measured. The respective diffraction patterns measured are shown in the graph of FIG. In FIG. 2, diffraction patterns PB, PC, PD, PE and PF show the diffraction patterns of the precursors of the cobalt-supporting carbon alloys of Examples 1, 2, 3, 4 and 5, respectively. In FIG. 2, the diffraction patterns PA, PG and PH show the diffraction patterns of the precursors of the carbon alloys of Comparative Examples 1, 2 and 3, respectively.
図２に示すように、実施例１〜５のコバルト担持カーボンアロイの前駆体、及び比較例１〜３のカーボンアロイの前駆体の回折パターンには、何れもソーダライト構造由来のピークのみが存在していた。よって、何れの前駆体においても、ＺＩＦ−８の結晶構造を有していることが確認された。 As shown in FIG. 2, only the peaks derived from the sodalite structure are present in the diffraction patterns of the cobalt-supported carbon alloy precursors of Examples 1 to 5 and the carbon alloy precursors of Comparative Examples 1 to 3, respectively. Was. Therefore, it was confirmed that each precursor has the crystal structure of ZIF-8.
（カーボンアロイの透過型電子顕微鏡（ＴＥＭ）による分析）
実施例１〜５のコバルト担持カーボンアロイ、及び比較例１〜３のカーボンアロイを、それぞれ透過型電子顕微鏡（株式会社日立製作所製「Ｈ８００」）を用いて観察した。図３（ｂ）、（ｃ）、（ｄ）、（ｅ）及び（ｆ）は、それぞれ実施例１、２、３、４及び５のコバルト担持カーボンアロイの電子顕微鏡写真（ＴＥＭ像）を示す。また、図３（ａ）、（ｇ）及び（ｈ）は、それぞれ比較例１、２及び３のカーボンアロイのＴＥＭ像を示す。図３（ｂ）〜（ｆ）に示すように、実施例１〜５のコバルト担持カーボンアロイ１では、コバルト粒子が確認できなかった。実施例１〜５のコバルト担持カーボンアロイ１には、ＴＥＭでは観察できない小粒径のコバルト粒子が均一に分散されているものと考えられる。なお、図３（ａ）に示すように、比較例１のカーボンアロイ１０についても、粒子状の物質は確認できなかった。一方、図３（ｇ）及び（ｈ）に示すように、比較例２及び３のカーボンアロイでは、コバルト粒子１１が確認できた。
(Analysis of carbon alloy by transmission electron microscope (TEM))
The cobalt-supported carbon alloys of Examples 1 to 5 and the carbon alloys of Comparative Examples 1 to 3 were observed using a transmission electron microscope ("H800" manufactured by Hitachi, Ltd.). 3 (b), (c), (d), (e) and (f) show electron micrographs (TEM images) of the cobalt-supported carbon alloys of Examples 1, 2, 3, 4 and 5, respectively. . Moreover, FIG. 3 (a), (g) and (h) shows the TEM image of the carbon alloy of Comparative Example 1, 2 and 3, respectively. As shown to FIG.3 (b)-(f), cobalt particle | grains were not able to be confirmed in cobalt carrying | support carbon alloy 1 of Examples 1-5. It is considered that cobalt particles of small particle diameter, which can not be observed by TEM, are uniformly dispersed in the cobalt-supporting carbon alloy 1 of Examples 1 to 5. In addition, as shown to Fig.3 (a), also about the carbon alloy 10 of the comparative example 1, the particulate-form substance was not able to be confirmed. On the other hand, as shown in FIGS. 3 (g) and (h), cobalt particles 11 were confirmed in the carbon alloys of Comparative Examples 2 and 3.
（酸素還元反応の触媒活性の評価）
実施例２のコバルト担持カーボンアロイ、比較例１のカーボンアロイ、及び参考例として白金担持カーボン（ＢＡＳＦ社製、カーボン：ＶＵＬＣＡＮ（登録商標）、白金の含有量：２０質量％）を、それぞれ触媒として用いてリニアスイープボルタンメトリーの測定を行い、酸素還元反応の触媒活性の評価を行った。リニアスイープボルタンメトリーの測定には、回転ディスク電極装置（ビー・エー・エス株式会社製「ＲＲＤＥ−３Ａ」）を用いた。以下、測定方法について説明する。
(Evaluation of catalytic activity of oxygen reduction reaction)
The cobalt-supported carbon alloy of Example 2 and the carbon alloy of Comparative Example 1 and, as a reference example, platinum-supported carbon (manufactured by BASF, carbon: VULCAN (registered trademark), content of platinum: 20% by mass), respectively as catalysts The measurement of linear sweep voltammetry was performed to evaluate the catalytic activity of the oxygen reduction reaction. For measurement of linear sweep voltammetry, a rotating disk electrode device ("RRDE-3A" manufactured by BAS Co., Ltd.) was used. The measurement method will be described below.
まず、０．８ｍＬの蒸留水、０．１ｍＬの２−プロパノール、及び０．１ｍＬのパーフルオロカーボン（Ａｌｄｒｉｃｈ社製「ＮＡＦＩＯＮ（登録商標）」）を含む溶液に、各触媒１ｍｇを加えた後、超音波処理により分散させて、各インクを作製した。回転ディスク電極装置の回転ディスク電極上へ各インクを塗付し、９０℃で５分間乾燥させる操作を繰り返すことにより、回転ディスク電極上の付着量が４００μｇ／ｃｍ2となるように各触媒を付着させた。各触媒が付着した回転ディスク電極を作用極とし、可逆水素電極（ＲＨＥ）を参照極とし、炭素電極を対極とし、酸素が飽和した０．１Ｍの水酸化カリウム水溶液を電解液としてリニアスイープボルタンメトリーの測定を行った。測定条件は、雰囲気温度を２５℃とし、回転ディスク電極の回転速度を１６００ｒｐｍとし、掃引速度を５ｍＶ／秒とした。 First, 1 mg of each catalyst was added to a solution containing 0.8 mL of distilled water, 0.1 mL of 2-propanol, and 0.1 mL of a perfluorocarbon (“NAFION®” manufactured by Aldrich). Each ink was prepared by dispersing by sonication. Each ink is applied onto the rotating disk electrode of the rotating disk electrode device and dried for 5 minutes at 90 ° C. By repeating the operation, each catalyst is adhered so that the adhesion amount on the rotating disk electrode becomes 400 μg / cm 2 I did. A rotary disk electrode with each catalyst attached is used as a working electrode, a reversible hydrogen electrode (RHE) is used as a reference electrode, a carbon electrode is used as a counter electrode, and a 0.1 M potassium hydroxide aqueous solution saturated with oxygen is used as an electrolyte. It measured. As measurement conditions, the ambient temperature was 25 ° C., the rotation speed of the rotating disk electrode was 1600 rpm, and the sweep speed was 5 mV / sec.
図４に、リニアスイープボルタンメトリーの測定結果を示す。図４中、電流密度−電位曲線Ｃ１は、白金担持カーボンを触媒として用いた際の電流密度−電位曲線である。電流密度−電位曲線Ｃ２は、実施例２のコバルト担持カーボンアロイを触媒として用いた際の電流密度−電位曲線である。電流密度−電位曲線Ｃ３は、比較例１のカーボンアロイを触媒として用いた際の電流密度−電位曲線である。電流密度−電位曲線が、白金担持カーボンを触媒として用いた際の電流密度−電位曲線Ｃ１の位置に近づくほど、酸素還元反応の触媒活性を向上させることができると評価した。図４に示すように、電流密度−電位曲線Ｃ２は、電流密度−電位曲線Ｃ３よりも、電流密度−電位曲線Ｃ１に近い曲線となった。この結果から、本発明に係る製造方法で得られた遷移金属担持カーボンアロイによれば、酸素還元反応の触媒活性を向上できることが示された。 The measurement result of linear sweep voltammetry is shown in FIG. In FIG. 4, a current density-potential curve C1 is a current density-potential curve when platinum-supported carbon is used as a catalyst. The current density-potential curve C2 is a current density-potential curve when the cobalt-supported carbon alloy of Example 2 is used as a catalyst. A current density-potential curve C3 is a current density-potential curve when the carbon alloy of Comparative Example 1 is used as a catalyst. It was evaluated that the catalytic activity of the oxygen reduction reaction can be improved as the current density-potential curve approaches the position of the current density-potential curve C1 when platinum-supported carbon is used as a catalyst. As shown in FIG. 4, the current density-potential curve C2 was closer to the current density-potential curve C1 than the current density-potential curve C3. From these results, it was shown that the transition metal-supported carbon alloy obtained by the production method according to the present invention can improve the catalytic activity of the oxygen reduction reaction.
本発明に係る遷移金属担持カーボンアロイの製造方法は、酸素還元反応の触媒活性を向上させることができる遷移金属担持カーボンアロイの製造方法として有用である。 The method for producing a transition metal-supported carbon alloy according to the present invention is useful as a method for producing a transition metal-supported carbon alloy that can improve the catalytic activity of the oxygen reduction reaction.
１ 遷移金属担持カーボンアロイ 1 Transition metal supported carbon alloy
Claims (10)
遷移金属源、亜鉛源及びイミダゾール化合物を極性溶媒中で混合することにより複合体粒子の懸濁液を得る混合工程と、
前記複合体粒子を乾燥することにより前駆体を得る乾燥工程と、
前記前駆体を不活性雰囲気下で炭化する炭化工程と
を備え、
前記混合工程において、前記遷移金属源中の遷移金属及び前記亜鉛源中の亜鉛の合計に対する、前記遷移金属源中の遷移金属のモル比が０．０５以上０．６０以下となるように、前記遷移金属源及び前記亜鉛源を使用する、遷移金属担持カーボンアロイの製造方法。 What is claimed is: 1. A method for producing a transition metal-supported carbon alloy comprising: a carbon alloy containing nitrogen; and a transition metal supported by the carbon alloy,
Mixing a transition metal source, a zinc source and an imidazole compound in a polar solvent to obtain a suspension of composite particles;
Drying the composite particles to obtain a precursor by drying;
Carbonizing the precursor under an inert atmosphere;
In the mixing step, the molar ratio of the transition metal in the transition metal source to the total of the transition metal in the transition metal source and the zinc in the zinc source is 0.05 or more and 0.60 or less. A transition metal source and a method of producing a transition metal supported carbon alloy using the zinc source.
前記混合工程において、前記イミダゾール化合物を第２極性溶媒中に溶解させた第２混合液と、前記第１混合液とを混合する、請求項１〜７の何れか一項に記載の遷移金属担持カーボンアロイの製造方法。 Before the mixing step, the method further comprises a pre-mixing step of preparing a first mixture by mixing the transition metal source and the zinc source in a first polar solvent,
The transition metal supported according to any one of claims 1 to 7, wherein in the mixing step, a second mixed solution in which the imidazole compound is dissolved in a second polar solvent, and the first mixed solution are mixed. Method of producing carbon alloy.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002909A (en) * | 2020-08-24 | 2020-11-27 | 广西师范大学 | Preparation method of Zn-Cu-N-based co-doped carbon composite material |
| CN114188557A (en) * | 2021-10-29 | 2022-03-15 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
| CN114367298A (en) * | 2021-12-23 | 2022-04-19 | 首都师范大学 | Double-enzyme active cobalt monoatomic nano enzyme and preparation method and application thereof |
| CN114843529A (en) * | 2022-06-09 | 2022-08-02 | 福州大学 | Water system ZIF (zero-valent iron) derivative-based porous carbon spheres as well as preparation method and application thereof |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112002909A (en) * | 2020-08-24 | 2020-11-27 | 广西师范大学 | Preparation method of Zn-Cu-N-based co-doped carbon composite material |
| CN114188557A (en) * | 2021-10-29 | 2022-03-15 | 陕西师范大学 | Preparation method and application of multi-mesoporous transition metal-nitrogen-carbon catalyst |
| CN114367298A (en) * | 2021-12-23 | 2022-04-19 | 首都师范大学 | Double-enzyme active cobalt monoatomic nano enzyme and preparation method and application thereof |
| CN114843529A (en) * | 2022-06-09 | 2022-08-02 | 福州大学 | Water system ZIF (zero-valent iron) derivative-based porous carbon spheres as well as preparation method and application thereof |
| CN114843529B (en) * | 2022-06-09 | 2024-01-05 | 福州大学 | Porous carbon sphere derived based on water system ZIF, and preparation method and application thereof |
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