JP6761998B2 - Method for manufacturing polymer protective material-free supported catalyst - Google Patents
Method for manufacturing polymer protective material-free supported catalyst Download PDFInfo
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- JP6761998B2 JP6761998B2 JP2015039661A JP2015039661A JP6761998B2 JP 6761998 B2 JP6761998 B2 JP 6761998B2 JP 2015039661 A JP2015039661 A JP 2015039661A JP 2015039661 A JP2015039661 A JP 2015039661A JP 6761998 B2 JP6761998 B2 JP 6761998B2
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- protective material
- polymer protective
- supported catalyst
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- 239000003054 catalyst Substances 0.000 title claims description 64
- 229920000642 polymer Polymers 0.000 title claims description 53
- 230000001681 protective effect Effects 0.000 title claims description 53
- 238000004519 manufacturing process Methods 0.000 title claims description 32
- 238000000034 method Methods 0.000 title claims description 8
- 239000002245 particle Substances 0.000 claims description 45
- 239000002105 nanoparticle Substances 0.000 claims description 43
- 239000000463 material Substances 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 239000003960 organic solvent Substances 0.000 claims description 20
- 150000001875 compounds Chemical class 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 14
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 14
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 14
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 13
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002894 organic compounds Chemical class 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 7
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 150000005846 sugar alcohols Polymers 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 125000004432 carbon atom Chemical group C* 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009835 boiling Methods 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
- 230000001603 reducing effect Effects 0.000 claims description 4
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 3
- ONRCPNSLHJCYOL-UHFFFAOYSA-N 1-methyl-2-pyrrolidin-1-yl-2H-pyridine Chemical compound CN1C(C=CC=C1)N1CCCC1 ONRCPNSLHJCYOL-UHFFFAOYSA-N 0.000 claims description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 claims description 3
- VATRWWPJWVCZTA-UHFFFAOYSA-N 3-oxo-n-[2-(trifluoromethyl)phenyl]butanamide Chemical compound CC(=O)CC(=O)NC1=CC=CC=C1C(F)(F)F VATRWWPJWVCZTA-UHFFFAOYSA-N 0.000 claims description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910000323 aluminium silicate Inorganic materials 0.000 claims description 3
- 239000000292 calcium oxide Substances 0.000 claims description 3
- 235000012255 calcium oxide Nutrition 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- DSWNRHCOGVRDOE-UHFFFAOYSA-N n,n-dimethylmethanimidamide Chemical compound CN(C)C=N DSWNRHCOGVRDOE-UHFFFAOYSA-N 0.000 claims description 3
- 229960005323 phenoxyethanol Drugs 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 2
- IYWJIYWFPADQAN-LNTINUHCSA-N (z)-4-hydroxypent-3-en-2-one;ruthenium Chemical compound [Ru].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O IYWJIYWFPADQAN-LNTINUHCSA-N 0.000 claims 1
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims 1
- 239000011259 mixed solution Substances 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- RTZYCRSRNSTRGC-LNTINUHCSA-K (z)-4-oxopent-2-en-2-olate;ruthenium(3+) Chemical compound [Ru+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O RTZYCRSRNSTRGC-LNTINUHCSA-K 0.000 description 7
- OCKGFTQIICXDQW-ZEQRLZLVSA-N 5-[(1r)-1-hydroxy-2-[4-[(2r)-2-hydroxy-2-(4-methyl-1-oxo-3h-2-benzofuran-5-yl)ethyl]piperazin-1-yl]ethyl]-4-methyl-3h-2-benzofuran-1-one Chemical compound C1=C2C(=O)OCC2=C(C)C([C@@H](O)CN2CCN(CC2)C[C@H](O)C2=CC=C3C(=O)OCC3=C2C)=C1 OCKGFTQIICXDQW-ZEQRLZLVSA-N 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006230 acetylene black Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 description 2
- 229960001545 hydrotalcite Drugs 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- -1 mulite Chemical compound 0.000 description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 description 1
- BPEVHDGLPIIAGH-UHFFFAOYSA-N ruthenium(3+) Chemical compound [Ru+3] BPEVHDGLPIIAGH-UHFFFAOYSA-N 0.000 description 1
- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
-
- 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
Description
本発明は、ナノ粒子が担持体に担持され、高分子保護材を含有しない高分子保護材フリー担持触媒の製造方法に関する。 The present invention relates to a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material.
従来、化学反応触媒又は燃料電池などでは、カーボン系の担体にナノ粒子を担持した不均一系触媒が用いられている。また、ボイラー又は排ガスの浄化などでは、セラミックス系の担体にナノ粒子を担持した不均一系触媒が用いられている。不均一系触媒に用いるナノ粒子として（ｆｃｃ）Ｒｕナノ粒子が開示されている（例えば、特許文献１、又は非特許文献１を参照。）。非特許文献１では、（ｆｃｃ）Ｒｕナノ粒子を担体に担持して不均一系触媒として使用する場合、ポリビニルピロリドンなどの高分子保護材を用いてナノ粒子を合成・精製した後に、得られたナノ粒子を担体に担持している。 Conventionally, in a chemical reaction catalyst, a fuel cell, or the like, a heterogeneous catalyst in which nanoparticles are supported on a carbon-based carrier has been used. Further, in the purification of boilers or exhaust gas, a heterogeneous catalyst in which nanoparticles are supported on a ceramic-based carrier is used. (Fcc) Ru nanoparticles are disclosed as nanoparticles used in a heterogeneous catalyst (see, for example, Patent Document 1 or Non-Patent Document 1). In Non-Patent Document 1, when (fcc) Ru nanoparticles are supported on a carrier and used as a heterogeneous catalyst, the nanoparticles are obtained after synthesizing and purifying the nanoparticles using a polymer protective material such as polyvinylpyrrolidone. Nanoparticles are supported on a carrier.
しかし、ナノ粒子の合成時に用いた高分子保護材が触媒中に残っていると、触媒の効果が十分に発揮されない場合がある。高分子保護材の除去を目的としてナノ粒子の精製を繰り返すと、精製回数が増加するにつれて得られるナノ粒子の収量が少なくなるという問題である。 However, if the polymer protective material used in the synthesis of nanoparticles remains in the catalyst, the effect of the catalyst may not be fully exhibited. When the purification of nanoparticles is repeated for the purpose of removing the polymer protective material, there is a problem that the yield of the obtained nanoparticles decreases as the number of purifications increases.
本発明の目的は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる高分子保護材フリー担持触媒を、従来の方法よりも効率的に得ることができる製造方法を提供することである。 An object of the present invention is to produce a polymer protective material-free supported catalyst capable of fully exerting the effect of the catalyst without using a polymer protective material that deteriorates the performance of the catalyst, more efficiently than the conventional method. To provide a method.
本発明に係る高分子保護材フリー担持触媒の製造方法は、ナノ粒子が担持体に担持され、高分子保護材を含有しない高分子保護材フリー担持触媒の製造方法であって、前記ナノ粒子の合成原料となる化合物と、前記担持体と、炭素数が２以上の還元性をもつ有機溶媒と、を含有し、かつ、前記高分子保護材を含有しない混合物を常圧下で加熱して、前記ナノ粒子を合成するとともに、該ナノ粒子を前記担持体に担持させる工程１を有し、該工程１における加熱温度は、１００〜３００℃であり、前記加熱温度で保持する時間は、１０〜３００分であり、前記ナノ粒子がＲｕ粒子であり、該Ｒｕ粒子はｆｃｃ構造を有していることを特徴とする。 The method for producing a polymer protective material-free supported catalyst according to the present invention is a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material. A mixture containing a compound as a synthetic raw material, the carrier, and a reducing organic solvent having 2 or more carbon atoms and not containing the polymer protective material is heated under normal pressure to obtain the above. It has a step 1 of synthesizing nanoparticles and supporting the nanoparticles on the carrier, the heating temperature in the step 1 is 100 to 300 ° C., and the holding time at the heating temperature is 10 to 300. Minutes, the nanoparticles are Ru particles, and the Ru particles have an fcc structure.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記有機溶媒の沸点は１００℃以上であることが好ましい。取り扱い性に優れる。また、担持触媒をより安全に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability. Moreover, the supported catalyst can be obtained more safely.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記有機溶媒は、多価アルコール、ブタノール、イソブタノール、エトキシエタノール、ジメチルホルムアミド、Ｎ−メチルピロリジノン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、トリプロピレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、トリエチレングリコールモノメチルエーテル及びポリエチレングリコールモノメチルエーテルの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 The method for producing a polymer protective material free supported catalyst according to the present invention, the organic solvent is a polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamidine de, N - methyl pyrrolidinopyridine down, profile propylene glycol monomethyl ether , ethylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, di ethylene glycol monomethyl ether, collected by polypropylene glycol dimethyl ether, di ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, collected by Riechiren is preferably at least one selected from glycol monomethyl ether及beauty polyethylene glycol monomethyl ether. The supported catalyst can be obtained more safely and more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記多価アルコールは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール及びブチレングリコールの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the polyhydric alcohol is preferably one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. The supported catalyst can be obtained more safely and more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。 In the method for producing a polymer protective material-free carrier catalyst according to the present invention, the carrier includes a form in which either one or both of carbon and ceramics are used.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記担持体は、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト、シリコンカーバイド、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ及びカーボンナノホーンの中から選ばれる１種以上である形態を包含する。 In the method for producing a polymer protective material-free carrier catalyst according to the present invention, the carrier is alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lanthana, lanthana alumina, tin oxide, and oxidation. Selected from tungsten, aluminosilicate, aluminophosphate, borosilicate, phosphotoxynic acid, hydroxyapatite, hydrotalcite, perovskite, cordierite, mulite, silicon carbide, activated carbon, carbon black, acetylene black, carbon nanotubes and carbon nanohorns. Includes one or more forms.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記ナノ粒子がＲｕ粒子であり、前記ナノ粒子の合成原料となる化合物はＲｕ有機化合物であることが好ましい。担持触媒をより効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, it is preferable that the nanoparticles are Ru particles and the compound used as a synthetic raw material for the nanoparticles is a Ru organic compound. The supported catalyst can be obtained more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記Ｒｕ有機化合物は、ジケトナート又はアセテートを含有する化合物であることが好ましい。担持触媒をより効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, the Ru organic compound is preferably a compound containing diketonate or acetate. The supported catalyst can be obtained more efficiently.
本発明に係る高分子保護材フリー担持触媒の製造方法では、前記Ｒｕ有機化合物がＲｕ（ａｃａｃ）３又は酢酸Ｒｕであることが好ましい。担持触媒をより効率的に得ることができる。 In the method for producing a polymer protective material-free supported catalyst according to the present invention, it is preferable that the Ru organic compound is Ru (acac) 3 or Ru acetate. The supported catalyst can be obtained more efficiently.
本発明は、触媒の性能を低下させる高分子保護材を用いず、触媒の効果を十分に発揮できる高分子保護材フリー担持触媒を、従来の方法よりも効率的に得ることができる製造方法を提供することができる。 The present invention provides a production method capable of more efficiently obtaining a polymer protective material-free supported catalyst capable of fully exerting the effect of the catalyst without using a polymer protective material that deteriorates the performance of the catalyst, as compared with the conventional method. Can be provided.
次に本発明について実施形態を示して詳細に説明するが本発明はこれらの記載に限定して解釈されない。本発明の効果を奏する限り、実施形態は種々の変形をしてもよい。 Next, the present invention will be described in detail by showing embodiments, but the present invention is not construed as being limited to these descriptions. The embodiments may be modified in various ways as long as the effects of the present invention are exhibited.
本実施形態に係る高分子保護材フリー担持触媒の製造方法は、ナノ粒子が担持体に担持され、高分子保護材を含有しない高分子保護材フリー担持触媒の製造方法であって、ナノ粒子の合成原料となる化合物と、担持体と、炭素数が２以上の還元性をもつ有機溶媒と、を含有し、かつ、高分子保護材を含有しない混合物を加熱して、ナノ粒子を合成するとともに、該ナノ粒子を前記担持体に担持させる工程１を有する。 The method for producing a polymer protective material-free supported catalyst according to the present embodiment is a method for producing a polymer protective material-free supported catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material. Nanoparticles are synthesized by heating a mixture containing a compound as a synthetic raw material, a carrier, and a reducing organic solvent having 2 or more carbon atoms and not containing a polymer protective material. , a step 1 for supporting the nanoparticles on the carrier.
本実施形態に係る担持触媒の製造方法は、高分子保護材を用いずにナノ粒子を合成する点、及びナノ粒子の合成とナノ粒子の担持体への担持とを同時に行う点が、例えば非特許文献１に記載されたような従来の製造方法と異なる点である。高分子保護材を用いないことで、触媒の作用を十分の発揮させることができる担持触媒を製造することができる。また、ナノ粒子の合成とナノ粒子の担持体への担持とを同時に行うことで、従来の製造方法と比較して製造工程を少なくすることができる。本明細書において、ナノ粒子とは、平均粒子径が１００ｎｍ以下の微細粒子をいう。ナノ粒子の平均粒子径は、透過型電子顕微鏡（ＴＥＭ）によって得られた粒子像から少なくとも１００個以上の粒子の粒子径を計測し、その平均を求めることによって算出した値である。ＴＥＭの観察倍率は、例えば、１２００００倍又は１５００００倍であることが好ましい。ナノ粒子は、例えば、Ｒｕ粒子、Ｐｄ粒子、Ｐｔ粒子、Ｉｒ粒子、Ａｕ粒子である。ナノ粒子の平均粒子径の下限は、特に限定されないが、１ｎｍ以上であることが好ましい。 The method for producing a supported catalyst according to the present embodiment is not characterized in that nanoparticles are synthesized without using a polymer protective material, and that nanoparticles are synthesized and nanoparticles are supported on a carrier at the same time, for example. This is a difference from the conventional manufacturing method as described in Patent Document 1. By not using the polymer protective material, it is possible to produce a supported catalyst capable of fully exerting the action of the catalyst. Further, by simultaneously synthesizing the nanoparticles and supporting the nanoparticles on the carrier, the number of manufacturing steps can be reduced as compared with the conventional manufacturing method. In the present specification, nanoparticles refer to fine particles having an average particle diameter of 100 nm or less. The average particle size of nanoparticles is a value calculated by measuring the particle size of at least 100 or more particles from a particle image obtained by a transmission electron microscope (TEM) and calculating the average. The observation magnification of the TEM is preferably, for example, 120,000 times or 150,000 times. The nanoparticles are, for example, Ru particles, Pd particles, Pt particles, Ir particles, and Au particles. The lower limit of the average particle size of the nanoparticles is not particularly limited, but is preferably 1 nm or more.
次に、工程１で用いる各物質について説明する。 Next, each substance used in step 1 will be described.
（ナノ粒子の合成原料となる化合物）
本実施形態に係る高分子保護材フリー担持触媒の製造方法では、ナノ粒子がＲｕ粒子であるとき、合成原料はＲｕ化合物である。Ｒｕ化合物はＲｕ有機化合物であることが好ましい。担持触媒をより効率的に得ることができる。Ｒｕ有機化合物は、ジケトナート又はアセテートを含有する化合物であることが好ましい。ジケトナートを含有するＲｕ有機化合物は、例えば、トリス（アセチルアセトナト）ルテニウム（ＩＩＩ）（以降、Ｒｕ（ａｃａｃ）３という。）である。アセテートを含有するＲｕ有機化合物は、例えば、酢酸ルテニウム（以降、酢酸Ｒｕという。）である。
(Compounds used as raw materials for synthesizing nanoparticles)
In the method for producing a polymer protective material-free supported catalyst according to the present embodiment, when the nanoparticles are Ru particles, the synthetic raw material is a Ru compound. The Ru compound is preferably a Ru organic compound. The supported catalyst can be obtained more efficiently. The Ru organic compound is preferably a compound containing diketonate or acetate. Ru organic compounds containing diketonate is, for example, tris (Asechiruase preparative isocyanatomethyl) ruthenium (III) (hereinafter, Ru (acac) 3 that.). The Ru organic compound containing acetate is, for example, ruthenium acetate (hereinafter referred to as Ru acetate).
（担持体）
担持体は、カーボン若しくはセラミックスのいずれか一方又は両方である形態を包含する。セラミックスは、例えば、アルミナ、シリカ、シリカアルミナ、カルシア、マグネシア、チタニア、セリア、ジルコニア、セリアジルコニア、ランタナ、ランタナアルミナ、酸化スズ、酸化タングステン、アルミノシリケート、アルミノホスフェート、ボロシリケート、リンタングステン酸、ヒドロキシアパタイト、ハイドロタルサイト、ペロブスカイト、コージェライト、ムライト又はシリコンカーバイドである。カーボンは、例えば、活性炭、カーボンブラック、アセチレンブラック、カーボンナノチューブ又はカーボンナノホーンである。本実施形態では、これらの担持体の中から１種だけを使用するか、又は２種以上を併用してもよい。２種以上を併用する場合は、セラミックスから２種以上を組合せて用いるか、カーボンから２種以上を組合せて用いるか、又はセラミックスから１種以上及びカーボンから１種以上を組合せて用いてもよい。より好ましくは、アルミナ、シリカ、チタニア、セリア、ジルコニア、活性炭及びカーボンブラックの中から選ばれる１種以上を用いる。
(Supporter)
The carrier includes a form in which either one or both of carbon and ceramics are used. Ceramics include, for example, alumina, silica, silica alumina, calcia, magnesia, titania, ceria, zirconia, ceria zirconia, lanthana, lanthana alumina, tin oxide, tungsten oxide, aluminosilicate, aluminophosphate, borosilicate, phosphotungstic acid, hydroxy. Apatite, hydrotalcite, perovskite, corgerite, mullite or silicon carbide. The carbon is, for example, activated carbon, carbon black, acetylene black, carbon nanotubes or carbon nanohorns. In the present embodiment, only one of these carriers may be used, or two or more thereof may be used in combination. When two or more types are used in combination, two or more types of ceramics may be used in combination, two or more types of carbon may be used in combination, or one or more types of ceramics and one or more types of carbon may be used in combination. .. More preferably, one or more selected from alumina, silica, titania, ceria, zirconia, activated carbon and carbon black are used.
（有機溶媒）
有機溶媒は、炭素数が２以上であり、還元性をもつ。有機溶媒の炭素数は、４以上であることがより好ましい。有機溶媒の炭素数の上限は、特に限定されないが、常温において液体であることが望ましい。
(Organic solvent)
The organic solvent has 2 or more carbon atoms and has reducing property. The organic solvent preferably has 4 or more carbon atoms. The upper limit of the number of carbon atoms of the organic solvent is not particularly limited, but it is desirable that the organic solvent be liquid at room temperature.
有機溶媒の沸点は１００℃以上であることが好ましい。取り扱い性に優れる。また、担持触媒をより安全に得ることができる。有機溶媒の沸点は、１６０℃以上であることがより好ましい。有機溶媒の沸点の上限は、特に限定されないが、担持触媒から溶媒をより容易に除去できる点で、３００℃以下であることが好ましく、２９０℃以下であることがより好ましい。 The boiling point of the organic solvent is preferably 100 ° C. or higher. Excellent handleability. Moreover, the supported catalyst can be obtained more safely. The boiling point of the organic solvent is more preferably 160 ° C. or higher. The upper limit of the boiling point of the organic solvent is not particularly limited, but is preferably 300 ° C. or lower, more preferably 290 ° C. or lower, in that the solvent can be more easily removed from the supported catalyst.
有機溶媒は多価アルコール、ブタノール、イソブタノール、エトキシエタノール、ジメチルホルムアミド、Ｎ−メチルピロリジノン、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、ジプロピレングリコールジメチルエーテル、ジプロピレングリコールモノメチルエーテル、ジエチレングリコールモノメチルエーテル、トリプロピレングリコールジメチルエーテル、ジエチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、トリエチレングリコールモノメチルエーテル及びポリエチレングリコールモノメチルエーテルの中から選ばれる１種以上であることが好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。このうち、多価アルコールがより好ましい。 The organic solvent is a polyhydric alcohol, butanol, isobutanol, ethoxyethanol, dimethylformamidine de, N - methyl pyrrolidinopyridine down, profile propylene glycol monomethyl ether, ethylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether, di ethylene glycol monomethyl ether, collected by polypropylene glycol dimethyl ether, di ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, 1 or more selected from among preparative triethylene glycol monomethyl ether及beauty polyethylene glycol monomethyl ether Is preferable. The supported catalyst can be obtained more safely and more efficiently. Of these, polyhydric alcohols are more preferable.
多価アルコールは、エチレングリコール、ジエチレングリコール、トリエチレングリコール、プロピレングリコール及びブチレングリコールの中から選ばれる１種以上であることが好ましい。このうち、トリエチレングリコールがより好ましい。担持触媒をより安全、かつ、より効率的に得ることができる。 The polyhydric alcohol is preferably one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol and butylene glycol. Of these, triethylene glycol is more preferable. The supported catalyst can be obtained more safely and more efficiently.
（高分子保護材）
本実施形態では、高分子保護材を用いない。高分子保護材は、例えば、ポリビニルピロリドン（ＰＶＰ）である。
(Polymer protective material)
In this embodiment, the polymer protective material is not used. The polymer protective material is, for example, polyvinylpyrrolidone (PVP).
次に、工程１について、ナノ粒子がＲｕ粒子である形態を例にとって説明する。 Next, step 1 will be described by taking a form in which the nanoparticles are Ru particles as an example.
本実施形態に係る担持触媒の製造方法では、ナノ粒子がＲｕ粒子であり、工程１が、Ｒｕ化合物と、担持体と、有機溶媒と、を含有し、高分子保護材を含有しない混合物を作製した後に加熱する工程であることが好ましい。 In the method for producing a carrier catalyst according to the present embodiment, the nanoparticles are Ru particles, and step 1 prepares a mixture containing a Ru compound, a carrier, and an organic solvent, and does not contain a polymer protective material. It is preferable that the step is to heat the particles.
工程１では、まず、Ｒｕ化合物と、担持体と、有機溶媒と、を含有する混合物を作製する。混合物中のＲｕ化合物の濃度は、１２５ｍＭ（ｍｍｏｌ／ｌ）以下であることが好ましく、１００ｍＭ（ｍｍｏｌ／ｌ）以下であることがより好ましい。また、Ｒｕ化合物と担持体との割合は、担持触媒中のＲｕ粒子の担持量が所定の範囲となるように調整する。担持触媒中のＲｕ粒子の担持量は、０．００１〜６０質量％であることが好ましい。ここで、担持量は、乾燥状態の担持触媒の質量に対するナノ粒子の質量の割合であり、例えば高周波誘導結合プラズマ発光分光分析、原子吸光分光光度分析で測定することができる。 In step 1, first, a mixture containing a Ru compound, a carrier, and an organic solvent is prepared. The concentration of the Ru compound in the mixture is preferably 125 mM (mmol / l) or less, more preferably 100 mM (mmol / l) or less. Further, the ratio of the Ru compound and the carrier is adjusted so that the amount of Ru particles supported in the supported catalyst is within a predetermined range. The amount of Ru particles supported in the supported catalyst is preferably 0.001 to 60% by mass. Here, the supported amount is the ratio of the mass of the nanoparticles to the mass of the supported catalyst in the dry state, such as high-frequency inductively coupled plasma emission spectroscopy, it can be measured by atomic absorption spectrophotometric analysis.
混合物の作製にあたり、Ｒｕ化合物及び担持体を有機溶媒中に懸濁させた後、例えば超音波などの分散機を用いて分散させることが好ましい。本発明は、各物質の添加順は特に限定されない。 In preparing the mixture, it is preferable that the Ru compound and the carrier are suspended in an organic solvent and then dispersed using a disperser such as ultrasonic waves. In the present invention, the order of addition of each substance is not particularly limited.
次いで、混合物を加熱する。加熱方法は、特に限定されず、例えば、オイルバス、マントルヒーター、ブロックヒーター若しくは熱媒循環式ジャケットなどの外部加熱方式、又はマイクロ波照射方式である。加熱温度は、１００〜３００℃であることが好ましく、１８０〜２３０℃であることがより好ましい。目的とする加熱温度に到達させるまでの昇温速度は、４℃／分以上であることが好ましく、６℃／分以上であることがより好ましい。昇温速度を所定の範囲とすることで、ｆｃｃ構造を有するＲｕ粒子を形成することができる。また、目的とする加熱温度で保持する時間は、使用する化合物の種類、混合物の液量又は加熱温度などに依存するが、例えば、１０〜３００分であることが好ましく、１２０〜２４０分であることがより好ましい。 The mixture is then heated. The heating method is not particularly limited, and is, for example, an external heating method such as an oil bath, a mantle heater, a block heater, or a heat medium circulation jacket, or a microwave irradiation method. The heating temperature is preferably 100 to 300 ° C, more preferably 180 to 230 ° C. The rate of temperature rise until the target heating temperature is reached is preferably 4 ° C./min or more, and more preferably 6 ° C./min or more. By setting the heating rate within a predetermined range, Ru particles having an fcc structure can be formed. The time for holding at the target heating temperature depends on the type of the compound used, the amount of the mixture, the heating temperature, and the like, but is preferably 10 to 300 minutes, preferably 120 to 240 minutes, for example. Is more preferable.
工程１では、Ｒｕ化合物が有機溶媒によって還元され、担持体の表面でＲｕ粒子の核生成及び粒成長が起こる。そして、Ｒｕ粒子が担持体に担持された担持触媒が得られる。このＲｕ粒子はｆｃｃ構造を有している。Ｒｕ粒子がｆｃｃ構造を有することで、ｈｃｐ構造を有するＲｕ粒子を担持させた触媒と比較し、異なる触媒活性を得ることができる。Ｒｕ粒子の結晶構造は、例えば、Ｘ線回折パターン（ＸＲＤパターン）によって確認できる。Ｒｕ粒子の平均粒子径は、３０ｎｍ以下であることが好ましく、１０ｎｍ以下であることがより好ましい。Ｒｕ粒子の平均粒子径の下限は、特に限定されないが、１ｎｍ以上であることが好ましい。 In step 1, the Ru compound is reduced by an organic solvent, causing nucleation and grain growth of Ru particles on the surface of the carrier. Then, a supported catalyst in which Ru particles are supported on the carrier is obtained. The Ru particles have an fcc structure. Since the Ru particles have an fcc structure, different catalytic activities can be obtained as compared with a catalyst supporting Ru particles having a hcp structure. The crystal structure of Ru particles can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). The average particle size of the Ru particles is preferably 30 nm or less, and more preferably 10 nm or less. The lower limit of the average particle size of Ru particles is not particularly limited, but is preferably 1 nm or more.
工程１の後、担持触媒を溶媒から分離精製することが好ましい。担持触媒を分離精製する方法は、特に限定されないが、例えば、温度が下がった混合物をろ過し、洗浄・乾燥する方法である。 After step 1, it is preferable to separate and purify the supported catalyst from the solvent. The method for separating and purifying the supported catalyst is not particularly limited, and is, for example, a method of filtering, washing, and drying a mixture whose temperature has dropped.
本実施形態に係る製造方法で得られた担持触媒は、担持触媒の外表面に高分子保護材が存在しない。また、ナノ粒子と担持体との間に高分子保護材が介在しないことが好ましい。担持触媒が高分子保護材を含有するか否かは、例えば、Ｘ線回折パターン（ＸＲＤパターン）によって確認できる。例えば高分子保護材がＰＶＰであるとき、室温でλ＝ＣｕＫαの測定条件で測定したＸＲＤパターンにおいて、１０°付近にＰＶＰ由来のパターンの有無によって確認することができる。 The supported catalyst obtained by the production method according to the present embodiment does not have a polymer protective material on the outer surface of the supported catalyst. Further, it is preferable that the polymer protective material does not intervene between the nanoparticles and the carrier. Whether or not the supported catalyst contains a polymer protective material can be confirmed by, for example, an X-ray diffraction pattern (XRD pattern). For example, when the polymer protective material is PVP, it can be confirmed by the presence or absence of a PVP-derived pattern in the vicinity of 10 ° in the XRD pattern measured under the measurement condition of λ = CuKα at room temperature.
以降、実施例を示しながら本発明についてさらに詳細に説明するが、本発明は実施例に限定して解釈されない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention will not be construed as being limited to Examples.
（実施例１Ａ）
フラスコにトリエチレングリコール（以下、ＴＥＧ）を１２５ｍＬ投入した。トリス（アセチルアセトナト）ルテニウム（ＩＩＩ）（以下、Ｒｕ（ａｃａｃ）３）を１．９９１８ｇ（５ｍｍｏｌ）と活性炭（ＦＡＭ−５０、日本エンバイロケミカルズ社製）を４．５０３１ｇとを秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎ分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分（濾物）をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 1A)
125 mL of triethylene glycol (hereinafter, TEG) was put into the flask. Weigh 1.9918 g (5 mmol) of tris (acetylacetonato) ruthenium (III) (hereinafter, Ru (acac) 3 ) and 4.5031 g of activated carbon (FAM-50, manufactured by Japan Enviro Chemicals) in the TEG. And dispersed by ultrasonic waves for 30 minutes to prepare a mixed solution. No polymer protective material was added to the mixture. The mixed solution was heated to 200 ° C. at a heating rate of 6 ° C./min, heated and stirred at 200 ° C. for 3 hr, and then cooled. The cooled mixed solution was filtered under reduced pressure, the solid component (filter) was thoroughly washed with ethanol, and then dried under reduced pressure to obtain a supported catalyst.
（実施例２Ａ）
フラスコにＴＥＧを４０ｍＬ投入した。Ｒｕ（ａｃａｃ）３を１．９９２０ｇ（５ｍｍｏｌ）と活性炭（ＦＡＭ−５０）を４．５０２２ｇとを秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎ分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分（濾物）をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 2A)
40 mL of TEG was put into the flask. 1.9920 g (5 mmol) of Ru (acac) 3 and 4.5022 g of activated carbon (FAM-50) were weighed and added to the TEG, and the mixture was dispersed by ultrasonic waves for 30 minutes to prepare a mixed solution. No polymer protective material was added to the mixture. The mixed solution was heated to 200 ° C. at a heating rate of 6 ° C./min, heated and stirred at 200 ° C. for 3 hr, and then cooled. The cooled mixed solution was filtered under reduced pressure, the solid component (filter) was thoroughly washed with ethanol, and then dried under reduced pressure to obtain a supported catalyst.
（実施例３Ａ）
フラスコにＴＥＧを１８５ｍＬ投入した。Ｒｕ（ａｃａｃ）３を５．９０５６ｇ（１４．８ｍｍｏｌ）とケッチェンブラック（ＥＣ３００Ｊ、ライオン社製）とを４．５０２２ｇ秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎの間分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。冷却した混合液を減圧ろ過し、固体成分（濾物）をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 3A)
185 mL of TEG was put into the flask. 5.9056 g (14.8 mmol) of Ru (acac) 3 and 4.5022 g of Ketchen Black (EC300J, manufactured by Lion) were weighed and added to the TEG, and the mixture was dispersed by ultrasonic waves for 30 minutes. Was produced. No polymer protective material was added to the mixture. The mixed solution was heated to 200 ° C. at a heating rate of 6 ° C./min, heated and stirred at 200 ° C. for 3 hr, and then cooled. The cooled mixed solution was filtered under reduced pressure, the solid component (filter) was thoroughly washed with ethanol, and then dried under reduced pressure to obtain a supported catalyst.
（実施例４Ａ）
フラスコにＴＥＧを１２５ｍＬ投入した。Ｒｕ（ａｃａｃ）３を０．９８６９ｇ（２．５ｍｍｏｌ）と活性炭（ＦＡＭ−５０）を４．７４９６ｇとを秤とり前記ＴＥＧ中に添加し、超音波で３０ｍｉｎの間分散して混合液を作製した。混合液に高分子保護材は添加しなかった。この混合液を６℃／分の昇温速度で２００℃まで加熱し、２００℃で３ｈｒ加熱撹拌し、その後冷却した。遠心分離を用いて冷却後の混合液から固体成分を沈降させ上澄みを除去し、固体成分をエタノールで十分に洗浄した後減圧乾燥を実施し、担持触媒を得た。
(Example 4A)
125 mL of TEG was put into the flask. 0.9869 g (2.5 mmol) of Ru (acac) 3 and 4.7496 g of activated carbon (FAM-50) were weighed and added to the TEG, and the mixture was dispersed by ultrasonic waves for 30 minutes to prepare a mixed solution. .. No polymer protective material was added to the mixture. The mixed solution was heated to 200 ° C. at a heating rate of 6 ° C./min, heated and stirred at 200 ° C. for 3 hr, and then cooled. The solid component was precipitated from the cooled mixed solution by centrifugation to remove the supernatant, and the solid component was thoroughly washed with ethanol and then dried under reduced pressure to obtain a supported catalyst.
（Ｒｕ粒子の平均粒子径）
実施例１Ａ及び実施例２Ａの担持触媒をＴＥＭでそれぞれ倍率１５００００倍、２０００００倍で観察し、得られた粒子像から１００個の粒子の粒子径を計測し、その平均を求め、Ｒｕ粒子の平均粒子径とした。図１に実施例１ＡのＴＥＭ像を、図２に実施例２ＡのＴＥＭ像を示す。実施例１Ａの平均粒子径は３．３４ｎｍ、実施例２Ａの平均粒子径は３．１４ｎｍであった。また、図１及び図２から、凝集した粒子の存在は確認されなかった。
(Average particle size of Ru particles)
The supported catalysts of Examples 1A and 2A were observed with TEM at magnifications of 150,000 times and 200,000 times, respectively, the particle diameters of 100 particles were measured from the obtained particle images, the average was calculated, and the average of Ru particles was obtained. The particle size was used. FIG. 1 shows a TEM image of Example 1A, and FIG. 2 shows a TEM image of Example 2A. The average particle size of Example 1A was 3.34 nm, and the average particle size of Example 2A was 3.14 nm. Further, from FIGS. 1 and 2, the presence of agglomerated particles was not confirmed.
（結晶状態）
実施例１Ａ及び実施例２Ａの担持触媒について、ＸＲＤ測定を行った。ＸＲＤ測定条件は、室温でλ＝ＣｕＫαである。図３に実施例１ＡのＸＲＤパターンを、図４に実施例２ＡのＸＲＤパターンを示す。図３において、Ｒｕのパターンは（ｆｃｃ）Ｒｕのパターンを示しており、Ｒｕ粒子がｆｃｃ構造を有することが確認できた。図４において、Ｒｕのパターンは（ｆｃｃ）Ｒｕのパターン及び（ｈｃｐ）Ｒｕのパターンを含むことが示されていた。
(Crystal state)
XRD measurements were performed on the supported catalysts of Examples 1A and 2A. The XRD measurement condition is λ = CuKα at room temperature. FIG. 3 shows the XRD pattern of Example 1A, and FIG. 4 shows the XRD pattern of Example 2A. In FIG. 3, the Ru pattern shows the (fcc) Ru pattern, and it was confirmed that the Ru particles have an fcc structure. In FIG. 4, it was shown that the Ru pattern included a (fcc) Ru pattern and a (hcp) Ru pattern.
Claims (9)
前記ナノ粒子の合成原料となる化合物と、前記担持体と、炭素数が２以上の還元性をもつ有機溶媒と、を含有し、かつ、前記高分子保護材を含有しない混合物を常圧下で加熱して、前記ナノ粒子を合成するとともに、該ナノ粒子を前記担持体に担持させる工程１を有し、
該工程１における加熱温度は、１００〜３００℃であり、前記加熱温度で保持する時間は、１０〜３００分であり、
前記ナノ粒子がＲｕ粒子であり、該Ｒｕ粒子はｆｃｃ構造を有していることを特徴とする高分子保護材フリー担持触媒の製造方法。 A method for producing a polymer protective material-free carrier catalyst in which nanoparticles are supported on a carrier and does not contain a polymer protective material.
A mixture containing the compound as a raw material for synthesizing the nanoparticles, the carrier, and a reducing organic solvent having 2 or more carbon atoms and not containing the polymer protective material is heated under normal pressure. The step 1 is to synthesize the nanoparticles and to support the nanoparticles on the carrier.
The heating temperature in the step 1 is 100 to 300 ° C., and the holding time at the heating temperature is 10 to 300 minutes.
A method for producing a polymer protective material-free supported catalyst, wherein the nanoparticles are Ru particles, and the Ru particles have an fcc structure.
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