JP6315532B1 - Electrocatalyst production method and hydrogen production method - Google Patents
Electrocatalyst production method and hydrogen production method Download PDFInfo
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- JP6315532B1 JP6315532B1 JP2017568315A JP2017568315A JP6315532B1 JP 6315532 B1 JP6315532 B1 JP 6315532B1 JP 2017568315 A JP2017568315 A JP 2017568315A JP 2017568315 A JP2017568315 A JP 2017568315A JP 6315532 B1 JP6315532 B1 JP 6315532B1
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims description 23
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 21
- 239000010411 electrocatalyst Substances 0.000 title description 2
- 239000002243 precursor Substances 0.000 claims abstract description 70
- 239000003054 catalyst Substances 0.000 claims abstract description 61
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 41
- 150000003624 transition metals Chemical class 0.000 claims abstract description 38
- 239000003960 organic solvent Substances 0.000 claims abstract description 34
- 239000000758 substrate Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 11
- -1 amide compound Chemical class 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000000463 material Substances 0.000 description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 238000005987 sulfurization reaction Methods 0.000 description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 15
- 229910052799 carbon Inorganic materials 0.000 description 15
- 239000002585 base Substances 0.000 description 14
- 229910052717 sulfur Inorganic materials 0.000 description 14
- 239000000203 mixture Substances 0.000 description 13
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- 239000011593 sulfur Substances 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000011261 inert gas Substances 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000005486 sulfidation Methods 0.000 description 6
- 239000010949 copper Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
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- 230000008859 change Effects 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
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- 239000010936 titanium Substances 0.000 description 3
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- 239000013065 commercial product Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000004683 dihydrates Chemical class 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000004687 hexahydrates Chemical class 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229910052740 iodine Inorganic materials 0.000 description 2
- 239000011630 iodine Substances 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- VZSRBBMJRBPUNF-UHFFFAOYSA-N 2-(2,3-dihydro-1H-inden-2-ylamino)-N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]pyrimidine-5-carboxamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)C(=O)NCCC(N1CC2=C(CC1)NN=N2)=O VZSRBBMJRBPUNF-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910001080 W alloy Inorganic materials 0.000 description 1
- KURZCZMGELAPSV-UHFFFAOYSA-N [Br].[I] Chemical compound [Br].[I] KURZCZMGELAPSV-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000014509 gene expression Effects 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- QFWPJPIVLCBXFJ-UHFFFAOYSA-N glymidine Chemical compound N1=CC(OCCOC)=CN=C1NS(=O)(=O)C1=CC=CC=C1 QFWPJPIVLCBXFJ-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- MOWMLACGTDMJRV-UHFFFAOYSA-N nickel tungsten Chemical compound [Ni].[W] MOWMLACGTDMJRV-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
簡便な方法によって、遷移金属を含有する硫化物を備えた電極を製造することができ、さらに、得られる硫化物のサイズの制御も容易に行うことができる電極触媒を製造する方法を提供する。本発明の電極の製造方法は、有機溶剤を含む溶媒、Ｍｏを含有する化合物、及び、Ｍｏ以外の遷移金属Ｍを含有する化合物を混合して酸化物前駆体を得る第１工程と、前記前駆体を電極基材に被覆させる第２工程と、前記電極基材に被覆した前記前駆体を硫化処理して該前駆体の硫化物を有する電極触媒を得る第３工程とを備える。Provided is a method for producing an electrode catalyst that can produce an electrode including a sulfide containing a transition metal by a simple method and that can easily control the size of the obtained sulfide. The electrode manufacturing method of the present invention includes a first step of obtaining an oxide precursor by mixing a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M other than Mo, and the precursor A second step of covering the body with an electrode substrate, and a third step of obtaining an electrode catalyst having a sulfide of the precursor by sulfiding the precursor coated on the electrode substrate.
Description
本発明は、電極触媒の製造方法及び水素の製造方法に関する。 The present invention relates to a method for producing an electrode catalyst and a method for producing hydrogen.
水素は燃焼時にＣＯ２排出がゼロであり、化石燃料に代わるクリーンなエネルギー源として期待されている。特に、太陽光、風力、水力等の再生可能なエネルギーを電力とする水の電気分解法による水素製造方法は一切ＣＯ２を排出しないことから、クリーンな水素の製造方法として大きな期待が寄せられている。Hydrogen emits zero CO 2 during combustion and is expected as a clean energy source to replace fossil fuels. In particular, the hydrogen production method based on water electrolysis using renewable energy such as sunlight, wind power, and hydropower does not emit any CO 2 , so there is great expectation as a clean hydrogen production method. Yes.
一般に、水の電気分解用の電極としては、炭素基材上に白金粒子触媒を固定したものが用いられている。しかしながら、白金は価格が高く、資源量にも限りがあるため、白金の使用量を低減する技術や白金代替触媒及び／又は電極の開発が求められている。 In general, as an electrode for water electrolysis, a platinum particle catalyst fixed on a carbon substrate is used. However, since platinum is expensive and has a limited amount of resources, development of a technique for reducing the amount of platinum used and a platinum alternative catalyst and / or electrode is required.
水の電気分解用の電極として、ナノサイズの微細化構造を有する遷移金属（例えば、Ｃｏ、Ｎｉ、Ｍｎ等）の硫化物又は酸化物等の新規な材料が最近では注目されており、盛んにその研究が進められている（例えば、特許文献１）。これらの材料は良好な活性を示す反面、ナノ化するためのコストが高くなり、また、繰り返し使用によってナノ構造が崩壊していくことも多いため、電極の長期安定性という点に改善の余地が残されている。 As materials for electrolysis of water, novel materials such as sulfides or oxides of transition metals (for example, Co, Ni, Mn, etc.) having a nano-sized refined structure have recently attracted attention and are actively being used. The research is underway (for example, Patent Document 1). Although these materials exhibit good activity, the cost for nano-fabrication is high, and the nanostructure often collapses due to repeated use, so there is room for improvement in terms of long-term stability of the electrode. It is left.
遷移金属の硫化物を合成する方法としては、例えば、還流電流を使用してＣｏＭｏＯ４前駆体を得た後に、異なる硫化温度下においてＣｏＭｏＳを合成する技術（例えば、非特許文献１）、水熱合成法によってＮｉＭｏＯ４前駆体を得た後に、３００℃でＮｉＳ２−ＭｏＳ２を合成する技術（例えば、非特許文献２）等が知られている。As a method for synthesizing a transition metal sulfide, for example, a technique of synthesizing CoMoS under different sulfidation temperatures after obtaining a CoMoO 4 precursor using a reflux current (for example, Non-Patent Document 1), hydrothermal A technique for synthesizing NiS 2 —MoS 2 at 300 ° C. after obtaining a NiMoO 4 precursor by a synthesis method (for example, Non-Patent Document 2) is known.
しかしながら、従来の遷移金属の硫化物を製造する方法は、合成手順が複雑であって製造に長時間要するものであり、設備コストも高いという問題があり、さらに、得られる硫化物の粒子サイズ等の制御も難しいものであった。 However, the conventional method of producing a transition metal sulfide has a problem that the synthesis procedure is complicated and requires a long time for production, and the equipment cost is high, and further, the particle size of the obtained sulfide, etc. It was also difficult to control.
本発明は、上記に鑑みてなされたものであり、簡便な方法によって、遷移金属を含有する硫化物を備えた電極を製造することができ、さらに、得られる硫化物のサイズの制御も容易に行うことができる電極触媒を製造する方法及び該方法で得られた電極触媒を使用する水素の製造方法を提供することを目的とする。 The present invention has been made in view of the above, and an electrode including a sulfide containing a transition metal can be produced by a simple method, and the size of the obtained sulfide can be easily controlled. It is an object of the present invention to provide a method for producing an electrode catalyst that can be performed and a method for producing hydrogen using the electrode catalyst obtained by the method.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、有機溶剤の存在下でＭｏを含有する化合物、及び、Ｍｏ以外の遷移金属Ｍを含有する化合物を反応させて得られる酸化物前駆体を硫化処理することで、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained an oxidation obtained by reacting a compound containing Mo and a compound containing a transition metal M other than Mo in the presence of an organic solvent. The present inventors have found that the above object can be achieved by subjecting the precursor of the product to sulfuration, and the present invention has been completed.
すなわち、本発明は、例えば、以下の項に記載の発明を包含する。
項１
有機溶剤を含む溶媒、Ｍｏを含有する化合物、及び、Ｍｏ以外の遷移金属Ｍを含有する化合物を混合して酸化物前駆体を得る第１工程と、
前記前駆体を電極基材に被覆させる第２工程と、
前記電極基材に被覆した前記前駆体を硫化処理して該前駆体の硫化物を有する電極触媒を得る第３工程と、
を備える電極触媒の製造方法。
項２
前記遷移金属Ｍは、Ｎｉ、Ｃｕ、Ｃｏ、Ｆｅ、Ｚｎ、Ｍｎ、Ｗ、Ｖ、Ｔｉ及びＣｒからなる群より選ばれる１種以上である、項１に記載の製造方法。
項３
前記有機溶剤は、アミド化合物、ケトン化合物、エステル化合物及びアルコール化合物からなる群より選ばれる１種以上である、項１又は２に記載の製造方法。
項４
前記前駆体はＭＭｏＯ４である、項１〜３のいずれか１項に記載の製造方法。
項５
項１〜４のいずれか１項に記載の製造方法で得られた電極触媒を使用して、水溶液中で電解処理を行う工程を含む、水素の製造方法。That is, the present invention includes, for example, the inventions described in the following sections.
A first step of obtaining an oxide precursor by mixing a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M other than Mo;
A second step of coating the precursor on the electrode substrate;
A third step of obtaining an electrode catalyst having a sulfide of the precursor by sulfiding the precursor coated on the electrode substrate;
A method for producing an electrode catalyst.
Item 3
Item 3. The method according to
Item 4
Item 4. The manufacturing method according to any one of
Item 5
Item 5. A method for producing hydrogen, comprising a step of performing an electrolytic treatment in an aqueous solution using the electrode catalyst obtained by the production method according to any one of
本発明の電極触媒の製造方法によれば、簡便な方法によって、遷移金属を含有する硫化物を備えた電極を製造することができ、さらに、得られる硫化物のサイズの制御も容易に行うことができる。また、この方法では、生成する硫化物のサイズの制御も容易であり、電極触媒のナノ構造が高度に制御されているので、得られる電極触媒は優れた触媒性能を示し、安定性も高い。 According to the method for producing an electrocatalyst of the present invention, an electrode having a sulfide containing a transition metal can be produced by a simple method, and the size of the obtained sulfide can be easily controlled. Can do. In addition, in this method, the size of the sulfide to be generated can be easily controlled, and the nanostructure of the electrode catalyst is highly controlled, so that the obtained electrode catalyst exhibits excellent catalytic performance and high stability.
以下、本発明の実施形態について詳細に説明する。なお、本明細書中において、「含有」及び「含む」なる表現については、「含有」、「含む」、「実質的にからなる」及び「のみからなる」という概念を含む。 Hereinafter, embodiments of the present invention will be described in detail. In the present specification, the expressions “containing” and “including” include the concepts of “containing”, “including”, “consisting essentially of”, and “consisting only of”.
本発明の電極触媒の製造方法は、下記の第１工程、第２工程及び第３工程を備える。
第１工程：有機溶剤を含む溶媒、Ｍｏを含有する化合物、及び、Ｍｏ以外の遷移金属Ｍを含有する化合物を混合して酸化物前駆体を得る工程。
第２工程：前記前駆体を電極基材に被覆させる工程。
第３工程：前記電極基材に被覆した前記前駆体を硫化処理して該前駆体の硫化物を有する電極触媒を得る工程。The method for producing an electrode catalyst of the present invention comprises the following first step, second step and third step.
First step: a step of obtaining an oxide precursor by mixing a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M other than Mo.
2nd process: The process of coat | covering the said precursor to an electrode base material.
Third step: A step of obtaining an electrode catalyst having a sulfide of the precursor by sulfiding the precursor coated on the electrode base material.
図１は、本発明に係る電極触媒の製造方法の一例を示すフロー図である。なお、図１中、Ｍｏ源は、Ｍｏを含有する化合物を意味し、Ｍ源は、Ｍｏ以外の遷移金属Ｍを含有する化合物を意味し、Ｓ源は、Ｓ（硫黄）を含有する化合物を意味する。 FIG. 1 is a flowchart showing an example of a method for producing an electrode catalyst according to the present invention. In FIG. 1, Mo source means a compound containing Mo, M source means a compound containing transition metal M other than Mo, and S source means a compound containing S (sulfur). means.
第１工程では、有機溶剤を含む溶媒と、Ｍｏを含有する化合物と、Ｍｏ以外の遷移金属Ｍを含有する化合物とを混合して酸化物前駆体（以下、単に「前駆体」と表記する）を得る。具体的にはＭｏを含有する化合物と、Ｍｏ以外の遷移金属Ｍを含有する化合物とが反応して、前駆体が生成する。 In the first step, a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M other than Mo are mixed to form an oxide precursor (hereinafter simply referred to as “precursor”). Get. Specifically, a compound containing Mo reacts with a compound containing a transition metal M other than Mo to produce a precursor.
有機溶剤の種類は特に限定されず、公知の有機溶剤を広く採用することができる。有機溶剤としては、例えば、アミド化合物、ケトン化合物、エステル化合物及びアルコール化合物からなる群より選ばれる１種以上を挙げることができ、この場合、前駆体をより低温で合成することができる。 The kind of organic solvent is not specifically limited, A well-known organic solvent can be employ | adopted widely. Examples of the organic solvent include one or more selected from the group consisting of amide compounds, ketone compounds, ester compounds, and alcohol compounds. In this case, the precursor can be synthesized at a lower temperature.
アミド化合物としては、Ｎ，Ｎ−ジメチルホルムアミド、ジメチルアセトアミド等が例示される。ケトン化合物としては、アセトン、メチルエチルケトン等が例示される。エステル化合物としては、酢酸エチル等が例示される。アルコール化合物としては、グリコール、メタノール、エタノール、イソプロピルアルコール等が例示される。 Examples of the amide compound include N, N-dimethylformamide, dimethylacetamide and the like. Examples of the ketone compound include acetone and methyl ethyl ketone. Examples of the ester compound include ethyl acetate. Examples of the alcohol compound include glycol, methanol, ethanol, isopropyl alcohol and the like.
有機溶剤は、極性が強い程使用量が多くなり、極性が弱い程使用量が少なくなる。極性が強い有機溶剤としては、エタノール、グリコール、メタノールが挙げられ、極性が弱い有機溶剤としては、アセトン、メチルエチルケトンが挙げられる。 The amount of the organic solvent used increases as the polarity increases, and the amount used decreases as the polarity decreases. Examples of the organic solvent having strong polarity include ethanol, glycol, and methanol, and examples of the organic solvent having weak polarity include acetone and methyl ethyl ketone.
有機溶剤は１種のみを使用してもよいし、２種以上を混合して使用することもできる。 Only one organic solvent may be used, or two or more organic solvents may be mixed and used.
溶媒が有機溶剤を含むことで、例えば、前駆体を得るための反応を常温（例えば、２５℃）及び常圧（例えば、大気圧下）で行うことができる。 When the solvent contains an organic solvent, for example, the reaction for obtaining the precursor can be performed at normal temperature (for example, 25 ° C.) and normal pressure (for example, under atmospheric pressure).
有機溶剤を含む溶媒はさらに水を含むことができる。この場合、Ｍｏを含有する化合物及び遷移金属Ｍを含有する化合物の溶解性が高まり、また、反応性も向上しやすい。 The solvent containing the organic solvent can further contain water. In this case, the solubility of the compound containing Mo and the compound containing the transition metal M is increased, and the reactivity is easily improved.
水の種類に制限は無く、純水、蒸留水、精製水、電解水等の各種の水を挙げることができる。 There is no restriction | limiting in the kind of water, Various waters, such as a pure water, distilled water, purified water, electrolyzed water, can be mentioned.
有機溶剤を含む溶媒が水を含む場合、原料の溶解性及び反応性の観点から、有機溶剤と水の全体積に対して有機溶剤が１０体積％以上であることが好ましく、２０体積％以上であることがより好ましく、３０体積％以上であることが特に好ましい。また、有機溶剤と水の全体積に対して有機溶剤の上限は、９０体積％とすることができ、７０体積％であることが好ましく、６０体積％であることがさらに好ましく、５０体積％であることが特に好ましい。 When the solvent containing the organic solvent contains water, the organic solvent is preferably 10% by volume or more based on the total volume of the organic solvent and water from the viewpoint of solubility and reactivity of the raw material, and is 20% by volume or more. More preferably, it is more preferably 30% by volume or more. The upper limit of the organic solvent relative to the total volume of the organic solvent and water can be 90% by volume, preferably 70% by volume, more preferably 60% by volume, and 50% by volume. It is particularly preferred.
Ｍｏを含有する化合物は特に限定されず、例えば、公知の化合物を広く使用することができる。Ｍｏを含有する化合物は、例えば、Ｍｏの酸化物、水酸化物、塩化物、硝酸塩、硫酸塩、オキシ硝酸塩、オキシ塩化物、有機酸等を挙げることができる。また、Ｍｏを含有する化合物としては、モリブデン酸の金属塩も例示することができ、この金属としては、例えばアルカリ金属を挙げることができる。Ｍｏを含有する化合物を含有する化合物は、水和物であってもよい。Ｍｏを含有する化合物は、１種単独又は２種以上を使用することができる。 The compound containing Mo is not particularly limited, and for example, known compounds can be widely used. Examples of the compound containing Mo include Mo oxide, hydroxide, chloride, nitrate, sulfate, oxynitrate, oxychloride, and organic acid. Moreover, as a compound containing Mo, the metal salt of molybdic acid can also be illustrated, As this metal, an alkali metal can be mentioned, for example. Hydrate may be sufficient as the compound containing the compound containing Mo. The compound containing Mo can use 1 type individually or 2 types or more.
Ｍｏを含有する化合物の代表例としては、モリブデン酸ナトリウム（Ｎａ２ＭｏＯ４）、モリブデン酸カリウム（Ｋ２ＭｏＯ４）、モリブデン酸アンモニア（（ＮＨ４）２ＭｏＯ４）を挙げることができる。Typical examples of the compound containing Mo include sodium molybdate (Na 2 MoO 4 ), potassium molybdate (K 2 MoO 4 ), and ammonia molybdate ((NH 4 ) 2 MoO 4 ).
Ｍｏを含有する化合物は、例えば、公知の方法で製造して得ることができ、あるいは、市販品から入手することもできる。 The compound containing Mo can be obtained, for example, by a known method, or can be obtained from a commercial product.
遷移金属Ｍを含有する化合物において、遷移金属Ｍは特に限定されない。遷移金属Ｍの具体例として、Ｎｉ、Ｃｕ、Ｃｏ、Ｆｅ、Ｚｎ、Ｍｎ、Ｗ、Ｖ、Ｔｉ及びＣｒからなる群より選ばれる１種以上が挙げられる。遷移金属Ｍは、第１工程における反応性の観点から、Ｎｉ、Ｃｕ、Ｃｏ、Ｆｅ、Ｚｎ及びＭｎからなる群より選ばれる１種以上であることが好ましく、Ｎｉ及びＣｏからなる群より選ばれる１種以上であることが特に好ましい。 In the compound containing the transition metal M, the transition metal M is not particularly limited. Specific examples of the transition metal M include one or more selected from the group consisting of Ni, Cu, Co, Fe, Zn, Mn, W, V, Ti, and Cr. The transition metal M is preferably at least one selected from the group consisting of Ni, Cu, Co, Fe, Zn and Mn from the viewpoint of reactivity in the first step, and is selected from the group consisting of Ni and Co. One or more types are particularly preferred.
遷移金属Ｍを含有する化合物は特に限定されず、例えば、公知の化合物を広く使用することができる。遷移金属Ｍを含有する化合物は、例えば、遷移金属Ｍの酸化物、水酸化物、塩化物、硝酸塩、硫酸塩、オキシ硝酸塩、オキシ塩化物、有機酸等を挙げることができる。遷移金属Ｍを含有する化合物は、水和物であってもよい。遷移金属Ｍを含有する化合物は、１種単独又は２種以上を使用することができる。 The compound containing the transition metal M is not specifically limited, For example, a well-known compound can be used widely. Examples of the compound containing the transition metal M include oxides, hydroxides, chlorides, nitrates, sulfates, oxynitrates, oxychlorides, and organic acids of the transition metals M. The compound containing the transition metal M may be a hydrate. The compound containing the transition metal M can be used alone or in combination of two or more.
遷移金属Ｍを含有する化合物の代表例としては、遷移金属Ｍの硝酸塩化合物、例えば、硝酸コバルト（Ｎｉ（ＮＯ３）２）、硝酸ニッケル（Ｃｏ（ＮＯ３）２）及び硝酸銅（Ｃｕ（ＮＯ３）２）、並びに遷移金属Ｍの塩化物、例えば、塩化ニッケル（ＮｉＣｌ２）を挙げることができる。Typical examples of the compound containing the transition metal M include nitrate compounds of the transition metal M, such as cobalt nitrate (Ni (NO 3 ) 2 ), nickel nitrate (Co (NO 3 ) 2 ), and copper nitrate (Cu (NO 3 ) 2 ), as well as chlorides of transition metals M, such as nickel chloride (NiCl 2 ).
遷移金属Ｍを含有する化合物は、例えば、公知の方法で製造して得ることができ、あるいは、市販品から入手することもできる。 The compound containing the transition metal M can be obtained, for example, by a known method, or can be obtained from a commercial product.
第１工程では、有機溶剤を含む溶媒、Ｍｏを含有する化合物、及び、Ｍｏ以外の遷移金属Ｍを含有する化合物を混合することで、Ｍｏを含有する化合物及び遷移金属Ｍを含有する化合物が反応し、前駆体が得られる。 In the first step, a compound containing Mo and a compound containing transition metal M react by mixing a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M other than Mo. Thus, a precursor is obtained.
第１工程で得られる前駆体は、例えば、ＭＭｏＯ４である。The precursor obtained in the first step is, for example, MMoO 4 .
有機溶剤を含む溶媒、Ｍｏを含有する化合物、及び、遷移金属Ｍを含有する化合物を混合する手順は特に限定されない。例えば、有機溶剤を含む溶媒に、Ｍｏを含有する化合物及び遷移金属Ｍを含有する化合物を添加する方法が挙げられる。また、Ｍｏを含有する化合物を含む溶媒と、遷移金属Ｍを含有する化合物を含む溶媒とをそれぞれあらかじめ準備して、これらを混合する方法が挙げられ、この場合、いずれか一方を他方に滴下してもよい。 The procedure for mixing the solvent containing the organic solvent, the compound containing Mo, and the compound containing the transition metal M is not particularly limited. For example, the method of adding the compound containing Mo and the compound containing the transition metal M to the solvent containing an organic solvent is mentioned. In addition, there is a method in which a solvent containing a compound containing Mo and a solvent containing a compound containing a transition metal M are prepared in advance and mixed together. In this case, either one is dropped onto the other. May be.
有機溶剤を含む溶媒、Ｍｏを含有する化合物、及び、遷移金属Ｍを含有する化合物を混合する方法は、適宜の混合手段を採用することができ、例えば、磁気撹拌機、ボールミル、ニーダー、ディスパー等の公知の混合機又は分散機を使用することができる。 As a method of mixing a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M, an appropriate mixing means can be adopted, for example, a magnetic stirrer, a ball mill, a kneader, a disper, etc. Any known mixer or disperser may be used.
Ｍｏを含有する化合物及び遷移金属Ｍを含有する化合物の混合割合は、第１工程で目的とする前駆体が得られる限りは特に限定されない。例えば、Ｍｏを含有する化合物と遷移金属Ｍを含有する化合物とモル比は、両者の反応が十分に進行するという点で１：０．０１〜１：１００が好ましく、１：０．１〜１：５０がより好ましく、１：０．８〜１：１０がさらに好ましい。Ｍｏを含有する化合物と遷移金属Ｍを含有する化合物とモル比は、１：１であることが最も好ましい。 The mixing ratio of the compound containing Mo and the compound containing the transition metal M is not particularly limited as long as the target precursor is obtained in the first step. For example, the molar ratio of the compound containing Mo and the compound containing the transition metal M is preferably 1: 0.01 to 1: 100 in that the reaction of both proceeds sufficiently, and 1: 0.1 to 1 : 50 is more preferable, and 1: 0.8 to 1:10 is more preferable. Most preferably, the molar ratio of the compound containing Mo and the compound containing the transition metal M is 1: 1.
また、溶媒の使用量も第１工程で目的とする前駆体が得られる限りは特に限定されない。 Further, the amount of the solvent used is not particularly limited as long as the target precursor is obtained in the first step.
上記混合後、有機溶剤を含む溶媒中でＭｏを含有する化合物と、遷移金属Ｍを含有する化合物との反応が進行する。この反応は、前述のように有機溶剤が存在することで、常温、常圧で進行し得る。 After the mixing, the reaction between the compound containing Mo and the compound containing the transition metal M proceeds in a solvent containing an organic solvent. This reaction can proceed at normal temperature and normal pressure in the presence of the organic solvent as described above.
前記反応の温度は、使用する原料及び有機溶剤の種類によって適宜設定することができる。前記反応は、好ましくは２０〜８０℃、より好ましくは、２５〜５５℃、特に好ましくは３０〜４０℃で行うことができる。 The temperature of the reaction can be appropriately set depending on the raw materials used and the type of organic solvent. The reaction is preferably performed at 20 to 80 ° C, more preferably 25 to 55 ° C, and particularly preferably 30 to 40 ° C.
前記反応の圧力は、使用する原料及び有機溶剤の種類によって適宜設定することができる。前記反応は、大気圧下で行うことが好ましい。なお、前記反応は、加圧下又は減圧下で行ってもよい。 The pressure of the reaction can be appropriately set depending on the raw materials used and the type of organic solvent. The reaction is preferably performed under atmospheric pressure. The reaction may be performed under pressure or under reduced pressure.
前記反応は、例えば、磁気撹拌機等で撹拌しながら行うことができる。また、磁気撹拌機に代えて又はこれと組み合わせて超音波を照射して前記反応を行うこともできる。 The said reaction can be performed, for example, stirring with a magnetic stirrer etc. Moreover, it can replace with a magnetic stirrer or it can also carry out the said reaction by irradiating an ultrasonic wave in combination.
前駆体は、有機溶剤に分散又は溶解した状態で得ることができ、これをそのまま次の第２工程で使用することができる。また、第１工程で得られた前駆体は、例えば、精製するなどして固形分として取り出してもよい。 The precursor can be obtained in a state of being dispersed or dissolved in an organic solvent, and can be used as it is in the next second step. In addition, the precursor obtained in the first step may be taken out as a solid content by, for example, purification.
第２工程では、第１工程で得た前記前駆体を電極基材に被覆させる。 In the second step, the electrode substrate is coated with the precursor obtained in the first step.
電極基材としては、炭素、ニッケル、ニッケル−リン合金、ニッケル−タングステン合金、ステンレス、チタン、鉄、銅、導電ガラス等を挙げることができる。電極基材には、本発明の効果が得られる範囲内で、他の成分が含まれていてもよい。 Examples of the electrode substrate include carbon, nickel, nickel-phosphorus alloy, nickel-tungsten alloy, stainless steel, titanium, iron, copper, and conductive glass. The electrode base material may contain other components within the range where the effects of the present invention can be obtained.
電極基材の形状は、使用目的や要求される性能により適宜選択することができる。電極基材の形状は、例えば、箔状、シート状、板状、棒状、メッシュ状等である。 The shape of the electrode substrate can be appropriately selected depending on the purpose of use and the required performance. The shape of the electrode substrate is, for example, a foil shape, a sheet shape, a plate shape, a rod shape, a mesh shape, or the like.
電極基材の具体例としては、チタン箔、炭素棒、炭素繊維布、炭素紙、グラフェンシート、グラッシーカーボン電極、伝導性ガラス、ガラス炭素電極等である。 Specific examples of the electrode substrate include titanium foil, carbon rod, carbon fiber cloth, carbon paper, graphene sheet, glassy carbon electrode, conductive glass, and glass carbon electrode.
前駆体を電極基材に被覆させる方法は特に限定されない。例えば、第１工程によって得られた、溶媒に分散又は溶解している前駆体、及び、電極基材を、容器に移して両者を接触させることで、前駆体を電極基材に被覆させることができる。もしくは、第１工程によって得られた、溶媒に分散又は溶解している前駆体に直接電極基材を浸漬させてもよい。 The method for coating the precursor on the electrode substrate is not particularly limited. For example, the precursor dispersed in or dissolved in the solvent obtained in the first step, and the electrode substrate can be transferred to a container and brought into contact with each other, whereby the precursor can be coated on the electrode substrate. it can. Or you may immerse an electrode base material directly in the precursor disperse | distributed or melt | dissolved in the solvent obtained by the 1st process.
前駆体と電極基材との接触時間は特に限定されず、例えば、０．５〜６時間とすることができる。また、前駆体と電極基材とを接触させるときの温度も特に限定されず、２５〜１４０℃とすることができる。 The contact time between the precursor and the electrode substrate is not particularly limited, and can be, for example, 0.5 to 6 hours. Moreover, the temperature at the time of making a precursor and an electrode base material contact is also not specifically limited, It can be set as 25-140 degreeC.
第２工程で前駆体と電極基材とを接触させることで、電極基材に前駆体（ＭＭｏＯ４）が被覆される。The precursor (MMoO 4 ) is coated on the electrode substrate by bringing the precursor and the electrode substrate into contact with each other in the second step.
電極基材に被覆される前駆体の形状は、例えば、棒状、針状、粒子状等であり、特に、本発明では、有機溶剤を含む溶媒の存在下で前駆体が生成することから、ナノサイズの棒状に形成されやすい。電極基材に被覆される前駆体は、例えば、直径が２０〜６００ｎｍの棒状となり、好ましくは２０〜１００ｎｍである。 The shape of the precursor coated on the electrode substrate is, for example, a rod shape, a needle shape, a particle shape, and the like. In particular, in the present invention, the precursor is generated in the presence of a solvent containing an organic solvent. It is easy to form in the size of a rod. The precursor coated on the electrode substrate is, for example, a rod having a diameter of 20 to 600 nm, preferably 20 to 100 nm.
第３工程では、第２工程にて電極基材に被覆した前駆体を硫化処理して該前駆体の硫化物を得る。これにより、前駆体の硫化物有する電極触媒を得ることができる。 In the third step, the precursor coated on the electrode base material in the second step is sulfurized to obtain a sulfide of the precursor. Thus, an electrode catalyst having a precursor sulfide can be obtained.
硫化処理の方法は特に限定されない。例えば、硫黄源（Ｓ源）となる原料と、前駆体が被覆された電極基材とを反応させることで、前駆体が硫化処理され、これにより前駆体が硫化物へと変化する。 The method of sulfuration treatment is not particularly limited. For example, by reacting a raw material to be a sulfur source (S source) with an electrode base material coated with the precursor, the precursor is subjected to sulfurization treatment, whereby the precursor is changed to sulfide.
硫黄源となる原料は特に限定されず、公知の原料を広く使用することができる。硫黄源となる原料は例えば、硫黄、硫化水素等を挙げることができる。硫黄源は、１種単独又は２種以上を使用することができる。 The raw material used as a sulfur source is not specifically limited, A well-known raw material can be used widely. Examples of the raw material to be a sulfur source include sulfur and hydrogen sulfide. The sulfur source can be used alone or in combination of two or more.
工程３における硫化処理は、例えば、不活性ガス雰囲気下で行うことができる。不活性ガスとしては、窒素、アルゴン、ヘリウム等の公知のガスを広く使用できる。例えば、不活性ガスを連続的に流入しながら硫化処理を行うこともできる。不活性ガスの流速は、例えば、１０〜１００ｃｍ３／ｍｉｎとすることができる。The sulfurization treatment in step 3 can be performed, for example, in an inert gas atmosphere. As the inert gas, known gases such as nitrogen, argon and helium can be widely used. For example, the sulfiding treatment can be performed while continuously flowing an inert gas. The flow rate of the inert gas can be set to, for example, 10 to 100 cm 3 / min.
硫化処理は、例えば、化学気相反応により行うことができる。つまり、硫黄源を加温するなどによって気化させ、気体状態で電極基材に被覆する前駆体と接触させることで、前駆体の硫化を進行させることができる。 The sulfurization treatment can be performed, for example, by a chemical vapor reaction. In other words, the sulfur source can be vaporized by, for example, heating, and brought into contact with the precursor that covers the electrode substrate in a gaseous state, whereby the sulfurization of the precursor can proceed.
硫化処理の温度は、例えば、３００〜６５０℃とすることができる。この場合、硫化処理が速やかに進行し、硫化率も高くなりやすい。硫化処理の温度は、４００〜５５０℃であることが好ましい。硫化処理の温度を所望の範囲にするまでの昇温速度は特に限定されず、例えば、２〜１０℃／ｍｉｎとすることができる。 The temperature of the sulfiding treatment can be set to 300 to 650 ° C., for example. In this case, the sulfidation process proceeds quickly and the sulfidation rate tends to increase. The temperature of the sulfiding treatment is preferably 400 to 550 ° C. The rate of temperature increase until the temperature of the sulfiding treatment is set to a desired range is not particularly limited, and can be set to 2 to 10 ° C./min, for example.
硫化処理の時間は、硫化処理の温度及び仕込み量に応じて適宜設定することができ、例えば、０．１〜５時間とすることができる。 The duration of the sulfiding treatment can be appropriately set according to the temperature of the sulfiding treatment and the amount charged, and can be set to 0.1 to 5 hours, for example.
硫化処理で使用する反応装置は特に限定されず、公知の反応装置を広く使用することができる。 The reaction apparatus used in the sulfiding treatment is not particularly limited, and a wide variety of known reaction apparatuses can be used.
図２（ａ）には、硫化処理で使用できる装置の一例の模式図を示している。この反応装置では、管状炉に設置された筒状の反応管が不活性ガスボンベ（ここではアルゴンボンベ）と連結しており、不活性ガスを供給しながら硫化処理を行うことができる。不活性ガスは、反応管の一端側から連続的に供給され、他端側から排出される。 FIG. 2A shows a schematic diagram of an example of an apparatus that can be used in the sulfidation treatment. In this reaction apparatus, a cylindrical reaction tube installed in a tubular furnace is connected to an inert gas cylinder (in this case, an argon cylinder), and a sulfiding treatment can be performed while supplying an inert gas. The inert gas is continuously supplied from one end side of the reaction tube and discharged from the other end side.
図２（ｂ）は、（ａ）における反応部を拡大した図である。反応管中において、例えば、不活性ガスの流入方向の上流側に硫黄源となる原料を、下流側に前駆体が被覆された電極基材を配置することができる。硫黄源となる原料及び電極基材は、例えば、磁性ボート等の容器に収容した状態で、反応管内に設置できる。硫化処理の後、電極基材を反応管から取り出し、必要に応じて洗浄等を行うことで、電極触媒を得ることができる。 FIG.2 (b) is the figure which expanded the reaction part in (a). In the reaction tube, for example, an electrode base material coated with a raw material serving as a sulfur source on the upstream side in the inflow direction of the inert gas and a precursor on the downstream side can be disposed. The raw material used as the sulfur source and the electrode base material can be installed in the reaction tube in a state accommodated in a container such as a magnetic boat, for example. After the sulfidation treatment, the electrode substrate can be taken out of the reaction tube and washed as necessary to obtain an electrode catalyst.
第３工程で得られる電極触媒は、電極基材が前駆体の硫化物で被覆された構造を有する。硫化物は、具体的にＭＭｏＳ（Ｍは前記遷移金属元素）で表される化合物である。 The electrode catalyst obtained in the third step has a structure in which an electrode base material is coated with a precursor sulfide. The sulfide is a compound specifically represented by MMoS (M is the transition metal element).
硫化物は、前記前駆体と同じく、例えば、棒状、針状、粒子状等であり、特に、本発明では、有機溶剤を含む溶媒の存在下で得られた前駆体を使用することから、硫化物は、ナノサイズの棒状に形成されやすい。電極基材に被覆される硫化物は、例えば、直径が２０〜６００ｎｍの棒状となり、好ましくは２０〜１００ｎｍである。 Like the precursor, the sulfide is, for example, rod-shaped, needle-shaped, particle-shaped, etc. In particular, the present invention uses a precursor obtained in the presence of a solvent containing an organic solvent. Objects are easily formed into nano-sized rods. The sulfide coated on the electrode substrate is, for example, a rod shape having a diameter of 20 to 600 nm, and preferably 20 to 100 nm.
本発明の製造方法で得られる電極触媒は、例えば、水の電気分解用の電極として使用することができる。この場合、電極触媒は、ナノ構造に制御されたＭＭｏＳを備えることで、優れた水素発生反応活性を示すことができる。また、本発明の製造方法で得られる電極触媒は、電極の安定性にも優れ、例えば、時間が経過しても電流密度の値が一定となりやすい。 The electrode catalyst obtained by the production method of the present invention can be used, for example, as an electrode for water electrolysis. In this case, the electrode catalyst can exhibit excellent hydrogen generation reaction activity by including MMoS controlled to have a nanostructure. The electrode catalyst obtained by the production method of the present invention is also excellent in electrode stability, and for example, the value of current density tends to be constant over time.
本発明の製造方法で得られる電極触媒は、水の電気分解用の電極の他、各種の用途に使用することができる。 The electrode catalyst obtained by the production method of the present invention can be used for various applications in addition to an electrode for water electrolysis.
本発明の製造方法で得られる電極触媒を使用した水素の製造方法の一例を説明する。 An example of a method for producing hydrogen using the electrode catalyst obtained by the production method of the present invention will be described.
水素の製造方法は、本発明の製造方法で得られる電極を例えば、アノードとして使用して、水溶液中で電解処理を行う工程を含むことができる。 The method for producing hydrogen can include a step of performing an electrolytic treatment in an aqueous solution using the electrode obtained by the production method of the present invention as an anode, for example.
カソードとしては、一般に水の電気分解においてカソードとして用いられる電極を使用することができる。例えば、炭素、白金、金などの貴金属などを素材とする電極をカソードとして用いることができる。 As the cathode, an electrode generally used as a cathode in water electrolysis can be used. For example, an electrode made of a noble metal such as carbon, platinum, or gold can be used as the cathode.
水溶液としては、一般に水の電気分解において用いられる成分を含む水溶液を使用することができる。水溶液は、ヨウ素臭素などのハロゲン、硫酸イオンなどを含むこともできる。なお、ヨウ素を含む水溶液を用いる場合、アノードにおいてヨウ素酸イオンが生成される。 As the aqueous solution, an aqueous solution containing components generally used in electrolysis of water can be used. The aqueous solution can also contain halogens such as iodine bromine, sulfate ions, and the like. When an aqueous solution containing iodine is used, iodate ions are generated at the anode.
水素の製造方法の具体的な例を挙げると、本発明の製造方法で得られた電極触媒をアノード、白金板をカソードとし、ヨウ素粉末を溶解した水溶液を電解液として、アノードに１Ｖ以上の電圧を印加する。これにより、アノード及びカソードにおいて下記（１）及び（２）の反応が起こり、カソードにおいて水素を生成させることができる。また、アノードへの印加電圧を増加させることにより、水素の生成速度を上昇させることができる。さらに、アノードにおいては、ヨウ素酸イオン（ＩＯ３ −）が生成されることから、ヨウ素酸（ＨＩＯ３）の製造方法としても有用である。As a specific example of the method for producing hydrogen, an electrode catalyst obtained by the production method of the present invention is used as an anode, a platinum plate is used as a cathode, an aqueous solution in which iodine powder is dissolved is used as an electrolyte, and a voltage of 1 V or more is applied to the anode. Apply. Thereby, the following reactions (1) and (2) occur at the anode and the cathode, and hydrogen can be generated at the cathode. In addition, the rate of hydrogen generation can be increased by increasing the voltage applied to the anode. Furthermore, since iodate ions (IO 3 − ) are produced at the anode, it is also useful as a method for producing iodic acid (HIO 3 ).
（アノード反応）
６Ｈ２Ｏ＋Ｉ２→１２Ｈ＋＋２ＩＯ３ −＋１０ｅ− （１）
（カソード反応）
２Ｈ＋＋２ｅ−→Ｈ２ （２）
上記水素の製造方法により製造された水素は、燃料電池や水素エンジンなどの燃料として好ましく使用することができる。(Anode reaction)
6H 2 O + I 2 → 12H + + 2IO 3 − + 10e − (1)
(Cathode reaction)
2H + + 2e − → H 2 (2)
Hydrogen produced by the above method for producing hydrogen can be preferably used as fuel for fuel cells, hydrogen engines and the like.
以下、実施例により本発明をより具体的に説明するが、本発明はこれら実施例の態様に限定されるものではない。 EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not limited to the aspect of these Examples.
（実施例１）
１ｍｍｏｌのＮａ２ＭｏＯ４の二水和物と、蒸留水及びＮ，Ｎ−ジメチルホルムアミドの混合溶媒（ｖ／ｖ＝２：１）１５ｍｌとを混合し、磁気攪拌機で約３０分攪拌することで、第１の混合液を調製した。また、１ｍｍｏｌのＣｏ（ＮＯ３）２の六水和物と、蒸留水及びＮ，Ｎ−ジメチルホルムアミドの混合溶媒（ｖ／ｖ＝２：１）１５ｍｌとを混合し、磁気攪拌機で約３０分攪拌することで、第２の混合液を調製した。次いで、第２の混合液を第１の混合液に少量ずつ滴下しながら全量を添加して第１の混合液と第２の混合液の混合物を、磁気攪拌機で約２０分攪拌した。これにより、前駆体（ＣｏＭｏＯ４）を含有する反応液を得た（工程１）。Example 1
1 mmol of Na 2 MoO 4 dihydrate was mixed with 15 ml of a mixed solvent of distilled water and N, N-dimethylformamide (v / v = 2: 1), and the mixture was stirred with a magnetic stirrer for about 30 minutes. A first mixed solution was prepared. Further, 1 mmol of Co (NO 3 ) 2 hexahydrate and 15 ml of a mixed solvent of distilled water and N, N-dimethylformamide (v / v = 2: 1) were mixed, and about 30 minutes with a magnetic stirrer. A second mixed solution was prepared by stirring. Next, the second mixture was added dropwise to the first mixture little by little, and the whole amount was added, and the mixture of the first mixture and the second mixture was stirred with a magnetic stirrer for about 20 minutes. Thus, to obtain a reaction solution containing a precursor (CoMoO 4) (Step 1).
その後、前駆体を含有する反応液及び電極基材である炭素棒を、４０ｍｌ容量のオートクレーブに収容した。次いで、オートクレーブを３０℃に保持して、チタン箔を、前駆体を含有する反応液に２時間浸漬させ、炭素棒に前駆体を被覆させた（工程２）。その後、前駆体が被覆された電極基材を取りだして洗浄した後、硫化処理を行った。 Thereafter, the reaction solution containing the precursor and the carbon rod as the electrode substrate were accommodated in a 40 ml autoclave. Next, the autoclave was kept at 30 ° C., and the titanium foil was immersed in a reaction solution containing the precursor for 2 hours to coat the precursor on the carbon rod (step 2). Thereafter, the electrode substrate coated with the precursor was taken out and washed, and then subjected to sulfurization treatment.
硫化処理は、前述の図２に示す反応装置を用いて行った。硫化処理で使用した硫黄源は硫黄粉末を１ｇ使用し、不活性ガスはアルゴンとした。硫化処理を行う前にあらかじめアルゴンを４０ｃｍ３／ｍｉｎの流速で１時間連続的に反応管内に供給した。その後、反応管内に硫黄源及び前駆体が被覆された電極基材を収容し、反応管を５℃／ｍｉｎの昇温速度で加熱して４００℃とした後、２時間にわたって硫化処理を行った（工程３）。硫化処理は、アルゴンガスを４０ｃｍ３／ｍｉｎの流速で供給しながら行った。硫化処理の後、反応管を冷却し、電極基材が硫化物で被覆されてなる電極触媒を得た。The sulfurization treatment was performed using the reaction apparatus shown in FIG. The sulfur source used in the sulfiding treatment was 1 g of sulfur powder, and the inert gas was argon. Prior to the sulfurization treatment, argon was continuously supplied into the reaction tube at a flow rate of 40 cm 3 / min for 1 hour in advance. Thereafter, an electrode base material coated with a sulfur source and a precursor was accommodated in the reaction tube, and the reaction tube was heated to 400 ° C. at a temperature increase rate of 5 ° C./min, and then subjected to sulfiding treatment for 2 hours. (Step 3). The sulfurization treatment was performed while supplying argon gas at a flow rate of 40 cm 3 / min. After the sulfurization treatment, the reaction tube was cooled to obtain an electrode catalyst in which the electrode base material was coated with sulfide.
（実施例２）
第１の混合液及び第２の混合液の調製に使用する溶媒を蒸留水及びＮ，Ｎ−ジメチルアセトアミドの混合溶媒（ｖ／ｖ＝２：１）に変更し、実施例１と同様の方法で電極基材が硫化物で被覆されてなる電極触媒を得た。(Example 2)
The same method as in Example 1 except that the solvent used for the preparation of the first mixed solution and the second mixed solution was changed to a mixed solvent of distilled water and N, N-dimethylacetamide (v / v = 2: 1). Thus, an electrode catalyst in which the electrode substrate was coated with sulfide was obtained.
（実施例３）
１ｍｍｏｌのＮａ２ＭｏＯ４の二水和物と、蒸留水及びメタノールの混合溶媒（ｖ／ｖ＝３：１）１５ｍｌとを混合し、磁気攪拌機で約３０分攪拌することで、第３の混合液を調製した。また、１ｍｍｏｌのＮｉ（ＮＯ３）２の六水和物と、蒸留水及びメタノールの混合溶媒（ｖ／ｖ＝３：１）１５ｍｌとを混合し、磁気攪拌機で約３０分攪拌することで、第４の混合液を調製した。次いで、第４の混合液を第３の混合液に少量ずつ滴下しながら全量を添加して第３の混合液と第４の混合液の混合物を、磁気攪拌機で約２０分攪拌した。これにより、前駆体（ＮｉＭｏＯ４）を含有する反応液を得た（工程１）。(Example 3)
A third mixture was prepared by mixing 1 mmol of Na 2 MoO 4 dihydrate and 15 ml of a mixed solvent of distilled water and methanol (v / v = 3: 1) and stirring with a magnetic stirrer for about 30 minutes. A liquid was prepared. Further, 1 mmol of Ni (NO 3 ) 2 hexahydrate and 15 ml of a mixed solvent of distilled water and methanol (v / v = 3: 1) are mixed and stirred with a magnetic stirrer for about 30 minutes. A fourth mixture was prepared. Next, the fourth mixture was added dropwise to the third mixture little by little, and the whole amount was added, and the mixture of the third mixture and the fourth mixture was stirred with a magnetic stirrer for about 20 minutes. Thus, to obtain a reaction solution containing a precursor (NiMoO 4) (Step 1).
その後、前駆体を含有する反応液及び電極基材である炭素棒を、４０ｍｌ容量のオートクレーブに収容した。次いで、オートクレーブを８０℃に保持して、炭素棒を、前駆体を含有する反応液に２時間浸漬させ、炭素棒に前駆体を被覆させた（工程２）。その後、前駆体が被覆された電極基材を取りだして洗浄した後、硫化処理を行った。 Thereafter, the reaction solution containing the precursor and the carbon rod as the electrode substrate were accommodated in a 40 ml autoclave. Next, the autoclave was kept at 80 ° C., and the carbon rod was immersed in the reaction solution containing the precursor for 2 hours to coat the precursor on the carbon rod (step 2). Thereafter, the electrode substrate coated with the precursor was taken out and washed, and then subjected to sulfurization treatment.
硫化処理は、前述の図２に示す反応装置を用いて行った。硫化処理で使用した硫黄源は硫黄粉末１ｇを使用し、不活性ガスはアルゴンとした。硫化処理を行う前にあらかじめアルゴンを４０ｃｍ３／ｍｉｎの流速で１時間連続的に反応管内に供給した。その後、反応管内に硫黄源及び前駆体が被覆された電極基材を収容し、反応管を５℃／ｍｉｎの昇温速度で加熱して５００℃とした後、２時間にわたって硫化処理を行った（工程３）。硫化処理は、アルゴンガスを４０ｃｍ３／ｍｉｎの流速で供給しながら行った。硫化処理の後、反応管を冷却し、電極基材が硫化物で被覆されてなる電極触媒を得た。The sulfurization treatment was performed using the reaction apparatus shown in FIG. The sulfur source used in the sulfiding treatment was 1 g of sulfur powder, and the inert gas was argon. Prior to the sulfurization treatment, argon was continuously supplied into the reaction tube at a flow rate of 40 cm 3 / min for 1 hour in advance. Thereafter, an electrode base material coated with a sulfur source and a precursor was accommodated in the reaction tube, and the reaction tube was heated at a heating rate of 5 ° C./min to 500 ° C., and then subjected to sulfiding treatment for 2 hours. (Step 3). The sulfurization treatment was performed while supplying argon gas at a flow rate of 40 cm 3 / min. After the sulfurization treatment, the reaction tube was cooled to obtain an electrode catalyst in which the electrode base material was coated with sulfide.
（実施例４）
第３の混合液及び第４の混合液の調製に使用する溶媒を蒸留水及びアセトンの混合溶媒（ｖ／ｖ＝３：１）に変更したこと以外は実施例３と同様の方法で電極基材が硫化物で被覆されてなる電極触媒を得た。Example 4
The electrode group was prepared in the same manner as in Example 3 except that the solvent used for the preparation of the third mixed solution and the fourth mixed solution was changed to a mixed solvent of distilled water and acetone (v / v = 3: 1). An electrode catalyst in which the material was coated with sulfide was obtained.
図３は、実施例１〜４で得られた電極触媒のＳＥＭ画像である。図３（ａ）から、実施例１で得られた電極触媒は、炭素棒表面に直径５０ｎｍに成長した硫化物が形成されていることがわかる。図３（ｂ）から、実施例２で得られた電極触媒は、炭素棒表面に直径１００ｎｍに成長した硫化物が形成されていることがわかる。図３（ｃ）から、実施例３で得られた電極触媒は、炭素棒表面に直径２５０ｎｍに成長した硫化物が形成されていることがわかる。図３（ｄ）から、実施例４で得られた電極触媒は、炭素棒表面に直径３００ｎｍに成長した硫化物が形成されていることがわかる。 FIG. 3 is an SEM image of the electrode catalyst obtained in Examples 1-4. FIG. 3A shows that the electrode catalyst obtained in Example 1 has sulfides grown to a diameter of 50 nm formed on the carbon rod surface. FIG. 3B shows that the electrode catalyst obtained in Example 2 has sulfides grown to a diameter of 100 nm formed on the carbon rod surface. From FIG. 3C, it can be seen that the electrode catalyst obtained in Example 3 has sulfides grown to a diameter of 250 nm formed on the surface of the carbon rod. FIG. 3 (d) shows that the electrode catalyst obtained in Example 4 has sulfides grown to a diameter of 300 nm on the surface of the carbon rod.
図４は、実施例１で得られた電極触媒のＸＲＤ測定結果である。この図４には、実施例１の工程１で得られた前駆体（ＣｏＭｏＯ４）と、工程３で得られた硫化物（ＣｏＭｏＳ）のＸＲＤチャートを示している。この結果は、前駆体が硫化処理により硫化物に変化したこと、つまり、ＣｏＭｏＯ４がＣｏＭｏＳに変化していることを示している。4 is an XRD measurement result of the electrode catalyst obtained in Example 1. FIG. FIG. 4 shows an XRD chart of the precursor (CoMoO 4 ) obtained in
図５（ａ）は、実施例１で得られた電極触媒（ＣｏＭｏＳ−１）、及び、実施例２で得られた電極触媒（ＣｏＭｏＳ−２）の電位−電流密度の関係を示すグラフである。なお、比較としてＰｔ電極の結果も併せて示している。電位−電流密度の関係を示すグラフは、三電極電気化学測定装置を使用して作成した。測定は、電位を一方向へ掃引するリニアスイープボルタンメトリー（ｌｉｎｅａｒ ｓｗｅｅｐ ｖｏｌｔａｍｍｅｔｒｙ、ＬＳＶ ０〜−０．６Ｖ ｖｓ Ａｇ／ＡｇＣｌ）法により、２ｍＶ／ｓの掃引速度にて１ＭのＫＯＨ溶液中で行った。
FIG. 5A is a graph showing the potential-current density relationship between the electrode catalyst (CoMoS-1) obtained in Example 1 and the electrode catalyst (CoMoS-2) obtained in Example 2. . For comparison, the result of the Pt electrode is also shown. A graph showing the relationship between potential and current density was prepared using a three-electrode electrochemical measurement apparatus. The measurement was performed in a 1 M KOH solution at a sweep rate of 2 mV / s by a linear sweep voltammetry (
図５（ｂ）は、実施例１で得られた電極触媒（ＣｏＭｏＳ−１）、及び、実施例２で得られた電極触媒（ＣｏＭｏＳ−２）のターフェル勾配を示している。ターフェル勾配は、図５（ａ）に示す水素発生反応の結果に基づいて算出した。 FIG.5 (b) has shown the Tafel gradient of the electrode catalyst (CoMoS-1) obtained in Example 1, and the electrode catalyst (CoMoS-2) obtained in Example 2. FIG. The Tafel slope was calculated based on the result of the hydrogen generation reaction shown in FIG.
図５（ａ）及び（ｂ）の結果から、ＣｏＭｏＳ−１（実施例１）及びＣｏＭｏＳ−２（実施例２）は良好な水素発生反応活性を示すことがわかる。ＣｏＭｏＳ−１の触媒活性はＣｏＭｏＳ−２より良い結果であり、この差は主に電極基材と硫化物のナノ構造（棒状の直径）等の違いによるものと推察される。 From the results of FIGS. 5A and 5B, it can be seen that CoMoS-1 (Example 1) and CoMoS-2 (Example 2) exhibit good hydrogen generation reaction activity. The catalytic activity of CoMoS-1 is better than that of CoMoS-2, and this difference is presumed to be mainly due to differences in the electrode substrate and sulfide nanostructure (rod-like diameter).
図６は、実施例１で得られた電極触媒（ＣｏＭｏＳ−１）、及び、実施例２で得られた電極触媒（ＣｏＭｏＳ−２）の安定性を評価した結果を示す。具体的に図６は、実施例１で得られた電極触媒（ＣｏＭｏＳ−１）、及び、実施例２で得られた電極触媒（ＣｏＭｏＳ−２）の時間変化に伴う電流密度の変化を示す。いずれの電極触媒も優れた安定性を示すことがわかる。 FIG. 6 shows the results of evaluating the stability of the electrode catalyst (CoMoS-1) obtained in Example 1 and the electrode catalyst (CoMoS-2) obtained in Example 2. Specifically, FIG. 6 shows a change in current density with time change of the electrode catalyst (CoMoS-1) obtained in Example 1 and the electrode catalyst (CoMoS-2) obtained in Example 2. It can be seen that both electrode catalysts exhibit excellent stability.
図７（ａ）は、実施例３で得られた電極触媒（ＮｉＭｏＳ−１）、及び、実施例４で得られた電極触媒（ＮｉＭｏＳ−２）の電位−電流密度の関係を示すグラフである。電位−電流密度の関係を示すグラフは、図５と同様の方法で得た。 FIG. 7A is a graph showing the potential-current density relationship between the electrode catalyst (NiMoS-1) obtained in Example 3 and the electrode catalyst (NiMoS-2) obtained in Example 4. . A graph showing the relationship between potential and current density was obtained in the same manner as in FIG.
図７（ｂ）は、実施例３で得られた電極触媒（ＮｉＭｏＳ−１）、及び、実施例４で得られた電極触媒（ＮｉＭｏＳ−２）のターフェル勾配を示している。ターフェル勾配は、図７（ａ）に示す水素発生反応の結果に基づいて算出した。 FIG.7 (b) has shown the Tafel gradient of the electrode catalyst (NiMoS-1) obtained in Example 3, and the electrode catalyst (NiMoS-2) obtained in Example 4. FIG. The Tafel slope was calculated based on the result of the hydrogen generation reaction shown in FIG.
図７（ａ）及び（ｂ）の結果から、ＮｉＭｏＳ−１（実施例３）及びＮｉＭｏＳ−２（実施例４）は良好な水素発生反応活性を示すことがわかる。ＮｉＭｏＳ−１では，１１５ｍＶにおいて電流密度が１０ｍＡ／ｃｍ２を示した。From the results of FIGS. 7A and 7B, it can be seen that NiMoS-1 (Example 3) and NiMoS-2 (Example 4) exhibit good hydrogen generation reaction activity. NiMoS-1 showed a current density of 10 mA / cm 2 at 115 mV.
Claims (5)
前記前駆体を電極基材に被覆させる第２工程と、
前記電極基材に被覆した前記前駆体を硫化処理して該前駆体の硫化物を有する電極触媒を得る第３工程と、
を備える電極触媒の製造方法。A first step of obtaining an oxide precursor by mixing a solvent containing an organic solvent, a compound containing Mo, and a compound containing a transition metal M other than Mo;
A second step of coating the precursor on the electrode substrate;
A third step of obtaining an electrode catalyst having a sulfide of the precursor by sulfiding the precursor coated on the electrode substrate;
A method for producing an electrode catalyst.
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