JP2010092799A - Electrode catalyst for polymer electrolyte fuel cell - Google Patents
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- 239000000446 fuel Substances 0.000 title claims abstract description 22
- 239000005518 polymer electrolyte Substances 0.000 title claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 30
- 239000013078 crystal Substances 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 28
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 18
- 229910052697 platinum Inorganic materials 0.000 claims description 13
- 229910052741 iridium Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 229910052703 rhodium Inorganic materials 0.000 claims description 6
- 229910052707 ruthenium Inorganic materials 0.000 claims description 6
- 229910052715 tantalum Inorganic materials 0.000 claims description 6
- 229910052718 tin Inorganic materials 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- 229910000077 silane Inorganic materials 0.000 claims description 4
- -1 silane compound Chemical class 0.000 claims description 4
- 239000010411 electrocatalyst Substances 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 4
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
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- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000007872 degassing Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
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- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 description 1
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- IXSUHTFXKKBBJP-UHFFFAOYSA-L azanide;platinum(2+);dinitrite Chemical compound [NH2-].[NH2-].[Pt+2].[O-]N=O.[O-]N=O IXSUHTFXKKBBJP-UHFFFAOYSA-L 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- OSXYHAQZDCICNX-UHFFFAOYSA-N dichloro(diphenyl)silane Chemical compound C=1C=CC=CC=1[Si](Cl)(Cl)C1=CC=CC=C1 OSXYHAQZDCICNX-UHFFFAOYSA-N 0.000 description 1
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 description 1
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 229910003472 fullerene Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000005055 methyl trichlorosilane Substances 0.000 description 1
- 239000005048 methyldichlorosilane Substances 0.000 description 1
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000005054 phenyltrichlorosilane Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- GTCKPGDAPXUISX-UHFFFAOYSA-N ruthenium(3+);trinitrate Chemical compound [Ru+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GTCKPGDAPXUISX-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- ZOYFEXPFPVDYIS-UHFFFAOYSA-N trichloro(ethyl)silane Chemical compound CC[Si](Cl)(Cl)Cl ZOYFEXPFPVDYIS-UHFFFAOYSA-N 0.000 description 1
- ORVMIVQULIKXCP-UHFFFAOYSA-N trichloro(phenyl)silane Chemical compound Cl[Si](Cl)(Cl)C1=CC=CC=C1 ORVMIVQULIKXCP-UHFFFAOYSA-N 0.000 description 1
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 description 1
- ZNOCGWVLWPVKAO-UHFFFAOYSA-N trimethoxy(phenyl)silane Chemical compound CO[Si](OC)(OC)C1=CC=CC=C1 ZNOCGWVLWPVKAO-UHFFFAOYSA-N 0.000 description 1
- DQZNLOXENNXVAD-UHFFFAOYSA-N trimethoxy-[2-(7-oxabicyclo[4.1.0]heptan-4-yl)ethyl]silane Chemical compound C1C(CC[Si](OC)(OC)OC)CCC2OC21 DQZNLOXENNXVAD-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は固体高分子型燃料電池用電極触媒に関する。 The present invention relates to an electrode catalyst for a polymer electrolyte fuel cell.
燃料電池用電極触媒として、例えば、特許文献１には、触媒粒子の（１１１）結晶面に垂直な方向の結晶子径の平均値Ｄ111と（１００）結晶面に垂直な方向の結晶子径Ｄ100との比がＤ100／Ｄ111＜１であり、触媒粒子の平均結晶子径が５ｎｍ以下である燃料電池用電極触媒体が記載されている。 As an electrode catalyst for a fuel cell, for example, Patent Document 1 discloses an average value D111 of crystallite diameters in a direction perpendicular to the (111) crystal plane of catalyst particles and a crystallite diameter D100 in a direction perpendicular to the (100) crystal plane. The fuel cell electrode catalyst body is described in which the ratio of D100 / D111 <1 and the average crystallite diameter of the catalyst particles is 5 nm or less.
本発明の目的は、優れた触媒活性を示す固体高分子型燃料電池用電極触媒を提供することにある。 An object of the present invention is to provide an electrode catalyst for a polymer electrolyte fuel cell exhibiting excellent catalytic activity.
白金（Ｐｔ）を含む触媒成分の結晶構造が面心立方構造である場合、（１１１）面は表面エネルギーが（１００）面あるいは（１１０）面より小さく、結晶面が表面に現れやすいが、触媒活性は（１００）面あるいは（ｌ１０）面より低い。一方、（１００）面や（１１０）面の表面エネルギーは（１１１）面より高いが（１１１）面より触媒活性が高い。よって、（１００）面あるいは（１１０）面がより表面に現れている電極触媒ほど高い性能が得られるといえる。 When the crystal structure of the catalyst component containing platinum (Pt) is a face-centered cubic structure, the (111) plane has a surface energy smaller than the (100) plane or the (110) plane, and the crystal plane tends to appear on the surface. The activity is lower than the (100) plane or the (l10) plane. On the other hand, the surface energy of the (100) plane and the (110) plane is higher than that of the (111) plane, but the catalytic activity is higher than that of the (111) plane. Therefore, it can be said that the higher the performance of the electrode catalyst, the more the (100) plane or (110) plane appears on the surface.
本発明者らは、鋭意検討を行った結果、固体高分子型燃料電池用アノード触媒では、導電性カーボン担体にＰｔを含む触媒成分の結晶構造が面心立方構造を有し、（１１１）面の結晶子径が３．８ｎｍより大きく５ｎｍ以下であり、（２２０）面の結晶子径が３．０ｎｍより大きく４ｎｍ以下である触媒が好適であることを見出した。また、（１１１）面の結晶子径（Ｄ１）と（２２０）面の結晶子径（Ｄ２）との比（Ｄ１／Ｄ２）が１．２１／１〜１．２６／１である触媒が好適であることを見出した。 As a result of intensive studies, the present inventors have found that in the anode catalyst for a polymer electrolyte fuel cell, the crystal structure of the catalyst component containing Pt in the conductive carbon support has a face-centered cubic structure, and the (111) plane It was found that a catalyst having a crystallite diameter of 3.8 nm to 5 nm or less and a (220) plane crystallite diameter of more than 3.0 nm to 4 nm or less is suitable. A catalyst having a ratio (D1 / D2) of the crystallite diameter (D1) of the (111) plane to the crystallite diameter (D2) of the (220) plane is preferably 1.21 / 1-1.26 / 1. I found out.
（２２０）面は（１１０）面の倍周期であるので、（１１０）面の結晶子径と（２２０）面の結晶子径は等価であるので、（２２０）面の結晶子径を代用することが可能である。したがって、（１１１）面の結晶子径と（２２０）面の結晶子径との比は、（１１１）面の結晶子径と（１１０）面の結晶子径との比とみなすことができる。 Since the (220) plane has a period twice that of the (110) plane, the crystallite diameter of the (110) plane and the crystallite diameter of the (220) plane are equivalent, so the crystallite diameter of the (220) plane is substituted. It is possible. Therefore, the ratio between the crystallite diameter of the (111) plane and the crystallite diameter of the (220) plane can be regarded as the ratio of the crystallite diameter of the (111) plane and the crystallite diameter of the (110) plane.
本発明は次のとおりのものである。
（１）白金（Ｐｔ）を含む触媒成分が導電性カーボンに担持された固体高分子型燃料電池用電極触媒であって、該白金を含む触媒成分の結晶構造が面心立方構造を有し、（１１１）面の結晶子径（Ｄ１）が３．８ｎｍより大きく５ｎｍ以下であり、（２２０）面の結晶子径（Ｄ２）が３．０ｎｍより大きく４ｎｍ以下であり、かつ、比（Ｄ１／Ｄ２）が１．２１／１〜１．２６／１であることを特徴とする固体高分子型燃料電池用電極触媒。
（２）触媒成分がＰｔとＲｕ、Ｉｒ、Ａｕ、Ｏｓ、Ｒｈ、Ｗ、Ｍｏ、ＳｎおよびＴａから選ばれる少なくとも１種の元素とを含む上記（１）の固体高分子型燃料電池用電極触媒。
（３）ＰｔとＲｕ、Ｉｒ、Ａｕ、Ｏｓ、Ｒｈ、Ｗ、Ｍｏ、ＳｎおよびＴａから選ばれる少なくとも１種の元素との割合（原子比）が３０：７０〜６０：４０である上記（２）の固体高分子型燃料電池用電極触媒。
（４）導電性カーボンがＳｉＯ２ 修飾導電性カーボンであって、その比表面積が１００〜８００ｍ２／ｇである上記（１）、（２）または（３）の固体高分子型燃料電池用電極触媒。
（５）ＳｉＯ２ 担持量が、導電性カーボン担体とＳｉＯ２ との総質量に対し、１〜４０質量％である上記（４）の固体高分子型燃料電池用電極触媒。
（６）ＳｉＯ２ 修飾導電性カーボンが、シランカップリング剤を導電性カーボンに吸着担持させた後、シラン化合物で処理して得られたものである上記（４）または（５）の固体高分子型燃料電池用電極触媒。
The present invention is as follows.
(1) A solid polymer fuel cell electrode catalyst in which a catalyst component containing platinum (Pt) is supported on conductive carbon, and the crystal structure of the catalyst component containing platinum has a face-centered cubic structure, The crystallite diameter (D1) of the (111) plane is greater than 3.8 nm and 5 nm or less, the crystallite diameter (D2) of the (220) plane is greater than 3.0 nm and 4 nm or less, and the ratio (D1 / D2) is 1.21 / 1-1.26 / 1, and is a polymer electrolyte fuel cell electrode catalyst.
(2) The electrode catalyst for a polymer electrolyte fuel cell according to (1), wherein the catalyst component includes Pt and at least one element selected from Ru, Ir, Au, Os, Rh, W, Mo, Sn, and Ta. .
(3) The ratio (atomic ratio) between Pt and at least one element selected from Ru, Ir, Au, Os, Rh, W, Mo, Sn and Ta is 30:70 to 60:40 (2 ) Electrocatalyst for polymer electrolyte fuel cell.
(4) The polymer electrolyte fuel cell electrode according to (1), (2) or (3) above, wherein the conductive carbon is SiO 2 -modified conductive carbon and the specific surface area is 100 to 800 m 2 / g. catalyst.
(5) The electrode catalyst for a polymer electrolyte fuel cell according to (4), wherein the amount of SiO 2 supported is 1 to 40% by mass with respect to the total mass of the conductive carbon support and SiO 2 .
(6) The solid polymer of (4) or (5) above, wherein the SiO 2 -modified conductive carbon is obtained by adsorbing and supporting a silane coupling agent on the conductive carbon and then treating with a silane compound. Type fuel cell electrode catalyst.
本発明の電極触媒は優れた触媒性能を発揮する。 The electrode catalyst of the present invention exhibits excellent catalytic performance.
本発明において、（１１１）面および（２２０）面の結晶子径はＣｕＫα線を用いた粉末Ｘ線回折法により算出する。すなわち、粉末Ｘ線回折法により、３０°〜５０°、６５°〜７５°を保持時間１００〜４００秒で測定し、得られる回折パターンから（１１１）面および（２２０）面の回折ピークの半値幅（β）を求め、シェラーの式：Ｄ＝Ｋλ／βｃｏｓθにより各結晶子径を算出する。ここで、シェーラー定数（Ｋ）＝１、測定Ｘ線波長（λ）＝１．５４０５である。 In the present invention, the crystallite diameters of the (111) plane and the (220) plane are calculated by a powder X-ray diffraction method using CuKα rays. That is, by powder X-ray diffractometry, 30 ° to 50 ° and 65 ° to 75 ° were measured at a holding time of 100 to 400 seconds, and from the obtained diffraction pattern, half of the diffraction peaks of the (111) plane and the (220) plane were measured. The value width (β) is obtained, and each crystallite diameter is calculated according to Scherrer's formula: D = Kλ / βcos θ. Here, the Scherrer constant (K) = 1 and the measured X-ray wavelength (λ) = 1.5405.
本発明の触媒成分としては、例えば、ＰｔとＲｕ、Ｉｒ、Ａｕ、Ｏｓ、Ｒｈ、Ｗ、Ｍｏ、ＳｎおよびＴａから選ばれる少なくとも１種の元素との組み合わせを挙げることができる。ＰｔとＲｕ、Ｉｒ、Ａｕ、Ｏｓ、Ｒｈ、Ｗ、Ｍｏ、ＳｎおよびＴａから選ばれる少なくとも１種の元素との割合（原子比）は、通常、３０：７０〜６０：４０である。 Examples of the catalyst component of the present invention include a combination of Pt and at least one element selected from Ru, Ir, Au, Os, Rh, W, Mo, Sn, and Ta. The ratio (atomic ratio) of Pt to at least one element selected from Ru, Ir, Au, Os, Rh, W, Mo, Sn and Ta is usually 30:70 to 60:40.
触媒成分の担持量は、導電性カーボン担体とＳｉＯ２ との総質量に対して、０．１〜２０質量％、好ましくは１〜１０質量％である。 The supported amount of the catalyst component is 0.1 to 20% by mass, preferably 1 to 10% by mass, based on the total mass of the conductive carbon support and SiO 2 .
本発明で用いる導電性カーボン担体としては、この種の電極触媒の製造に一般に用いられているものを用いることができる。例えば、カーボンブラック、カーボンナノホン、活性炭カーボン、カーボンナノチューブ、フラレンなどが用いられるが、なかでも、カーボンブラックが好適に用いられる。 As the conductive carbon carrier used in the present invention, those generally used in the production of this type of electrode catalyst can be used. For example, carbon black, carbon nanophone, activated carbon, carbon nanotube, fullerene and the like are used, and among these, carbon black is preferably used.
本発明においては、導電性カーボン担体として、ＳｉＯ２ 修飾導電性カーボンであって、その比表面積が１００〜８００ｍ２／ｇ、好ましくは１５０〜６００ｍ２／ｇであるものが好適に用いられる。 In the present invention, as the conductive carbon carrier, a SiO 2 modified conductive carbon having a specific surface area of 100 to 800 m 2 / g, preferably 150 to 600 m 2 / g is suitably used.
上記ＳｉＯ２ 修飾導電性カーボンにおける、ＳｉＯ２ 担持量は、導電性カーボン担体とＳｉＯ２ との総質量に対し、１〜４０質量％、好ましくは５〜３０質量％である。 The amount of SiO 2 supported in the SiO 2 -modified conductive carbon is 1 to 40% by mass, preferably 5 to 30% by mass, based on the total mass of the conductive carbon support and SiO 2 .
上記ＳｉＯ２ 修飾導電性カーボンは、常法により、シランカップリング剤を導電性カーボンに吸着担持させた後、シラン化合物で処理して得るのが好ましい。 The SiO 2 modified conductive carbon, by a conventional method, After adsorption carry a silane coupling agent on a conductive carbon, preferably obtained by treating with a silane compound.
上記シラン化合物としては、メチルトリクロロシラン、メチルジクロロシラン、エチルトリクロロシラン、フェニルトリクロロシラン、ジフェニルジクロロシラン等のクロロシラン；テトラメトキシシラン、メチルトリメトキシシラン、フェニルトリメトキシシラン等のアルコキシシラン；テトラエチルオルトシリケートなどが挙げられる。 Examples of the silane compound include chlorosilanes such as methyltrichlorosilane, methyldichlorosilane, ethyltrichlorosilane, phenyltrichlorosilane, and diphenyldichlorosilane; alkoxysilanes such as tetramethoxysilane, methyltrimethoxysilane, and phenyltrimethoxysilane; tetraethylorthosilicate Etc.
上記シランカップリング剤としては、ビニルトリエトキシシラン、β−（３，４−エポキシシクロヘキシル）エチルトリメトキシシラン、γ−グリシドキシプロピルトリエトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−メタクリロキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−クロロプロピルトリメトキシシラン、γ−メルカプトプロピルトリメトキシシランなどが挙げられる。なかでも、エチルトリメトキシシラン、ビニルトリエトキシシランが好適に用いられる。 Examples of the silane coupling agent include vinyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ -Methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane and the like. Of these, ethyltrimethoxysilane and vinyltriethoxysilane are preferably used.
（実施例１）
エタノール２５０ｇに３−アミノプロピルトリエトキシシラン５ｇおよびカーボンブラック（ＶｕｌｃａｎＸＣ７２、Ｃａｂｏｔ社）１０ｇを添加し、３０分間、室温で攪拌を行った。次に、ろ過、水洗後、窒素雰囲気下、１１０℃で乾燥し、ＳｉＯ２ 修飾導電性カーボン担体を得た。次に、このＳｉＯ２ 修飾導電性カーボン担体を１規定の硝酸水溶液１００ｇに加え、室温で２時間攪拌した後、ろ過、水洗を行い、窒素雰囲気下１１０℃で乾燥した。次に、上記硝酸処理したＳｉＯ２ 修飾導電性カーボン担体を、テトラエチルオルトシリケート２１ｇおよびエタノール２３０ｇの溶液に加え、室温で１５分間攪拌した後、２５％アンモニアすい６．８ｇ、水１１．２ｇを添加し、室温で約１０時間攪拌を行った。その後、ろ過、水洗を行い、窒素雰囲気下１１０℃で乾燥し、担体Ａを得た。
＜触媒調製＞
エチレングリコール１００ｍＬにＮａＯＨ（顆粒状）２ｇを添加し、窒素雰囲気下、７０℃で溶解させた。次に、エチレングリコール１００ｍＬにジニトロジアンミン白金硝酸水溶液（Ｐｔ：０．３８６ｇ）４．７９ｇ、硝酸ルテニウム水溶液（Ｒｕ：０．４２５ｇ）９．３４ｇを添加した。このエチレングリコール溶液に、ＮａＯＨを溶解させたエチレングリコール溶液を添加し、窒素雰囲気下、室温で１時間攪拌した（脱気）。次に、この溶液を、窒素雰囲気下、９０℃（液温）で３時間還流した。冷却後、この溶液に担体Ａを０．３８６ｇ添加し、窒素雰囲気下、室温で、１時間攪拌した（脱気）後で、１６０℃（液温）で、窒素雰囲気下、３時間還流した。冷却後、攪拌しながら、１Ｎ硝酸水溶液を徐々に滴下し、ｐＨ１に調整した。固体をろ過し、イオン交換水で十分に洗浄し、窒素雰囲気下１１０℃で乾燥した後に、水素を用いて３００℃で２時間還元処理して触媒Ａを作成した。得られた触媒Ａを分析したところ、その組成は、Ｐｔ：Ｒｕ：ＳｉＯ２ ：カーボンブラック＝３８：２３：９：３０（質量％）であった。この触媒をＸ線回折法で分析を行ったところ、触媒Ａの結晶構造は面心立方構造であった。なお、（１１１）面の結晶子経（Ｄ１）、（２２０）面の結晶子経（Ｄ２）、およびＤ１／Ｄ２を表１に示す。
＜性能評価＞
触媒Ａ１０ｍｇを５％ナフィオン溶液（Ａｌｄｒｉｃｈ社製）を加え、超音波により十分に分散させ触媒ペーストを作成した。この触媒ペースト５μＬをグラッシーカーボン電極上に固定化し試験電極とした。
Example 1
To 250 g of ethanol, 5 g of 3-aminopropyltriethoxysilane and 10 g of carbon black (Vulcan XC72, Cabot) were added and stirred at room temperature for 30 minutes. Next, after filtration and washing with water, it was dried at 110 ° C. in a nitrogen atmosphere to obtain a SiO 2 -modified conductive carbon carrier. Next, this SiO 2 -modified conductive carbon carrier was added to 100 g of 1N aqueous nitric acid solution, stirred at room temperature for 2 hours, filtered, washed with water, and dried at 110 ° C. in a nitrogen atmosphere. Next, the nitric acid-treated SiO 2 -modified conductive carbon carrier was added to a solution of 21 g of tetraethylorthosilicate and 230 g of ethanol, stirred for 15 minutes at room temperature, and then added with 6.8 g of 25% ammonia and 11.2 g of water. The mixture was stirred at room temperature for about 10 hours. Thereafter, filtration, washing with water were performed, and drying was performed at 110 ° C. in a nitrogen atmosphere, whereby Carrier A was obtained.
<Catalyst preparation>
2 g of NaOH (granular) was added to 100 mL of ethylene glycol and dissolved at 70 ° C. in a nitrogen atmosphere. Next, 4.79 g of dinitrodiammine platinum nitrate aqueous solution (Pt: 0.386 g) and 9.34 g of ruthenium nitrate aqueous solution (Ru: 0.425 g) were added to 100 mL of ethylene glycol. To this ethylene glycol solution, an ethylene glycol solution in which NaOH was dissolved was added and stirred at room temperature for 1 hour under a nitrogen atmosphere (degassing). Next, this solution was refluxed at 90 ° C. (liquid temperature) for 3 hours under a nitrogen atmosphere. After cooling, 0.386 g of carrier A was added to this solution, stirred for 1 hour at room temperature in a nitrogen atmosphere (degassing), and then refluxed at 160 ° C. (liquid temperature) in a nitrogen atmosphere for 3 hours. After cooling, 1N nitric acid aqueous solution was gradually added dropwise with stirring to adjust the pH to 1. The solid was filtered, thoroughly washed with ion-exchanged water, dried at 110 ° C. under a nitrogen atmosphere, and then reduced with hydrogen at 300 ° C. for 2 hours to prepare Catalyst A. When the obtained catalyst A was analyzed, the composition was Pt: Ru: SiO 2 : carbon black = 38: 23: 9: 30 (mass%). When this catalyst was analyzed by an X-ray diffraction method, the crystal structure of the catalyst A was a face-centered cubic structure. Table 1 shows the crystallite length (D1) of the (111) plane, the crystallite length (D2) of the (220) plane, and D1 / D2.
<Performance evaluation>
A catalyst paste was prepared by adding 10 mg of catalyst A to a 5% Nafion solution (manufactured by Aldrich) and sufficiently dispersing with ultrasonic waves. 5 μL of this catalyst paste was fixed on a glassy carbon electrode to obtain a test electrode.
触媒性能の評価は、硫酸水溶液にメタノールを１ｍｏｌ／Ｌとなるように添加した。２５℃に保持されたこの溶液中に上記試験電極を浸漬し、作用極とし、対極には白金線、参照極には可逆水素電極（ＲＨＥ）を用いて電位規制法によりメタノール酸化電流と電極電位の関係を測定し、０．６Ｖ．ｖｓ．ＲＨＥにおける酸化電流値をグラッシーカーボン電極上に塗布した触媒中に含有される白金質量で除した値（白金質量当たりの酸化電流値）とした。電流値が高いほど高性能である。結果を表１に示す。
（比較例１）
Ｊｏｈｎｓｏｎ Ｍａｔｔｅｙ社製のＰｔＲｕ担持カーボン触媒（ＨｉＳＰＥＣ１０１００）を用いて実施例１と同様にして性能評価を行った。この触媒の結晶構造は面心立方構造であった。（１１１）面の結晶子経（Ｄ１）、（２２０）面の結晶子経（Ｄ２）、およびＤ１／Ｄ２、それに性能評価結果を表１に示す。
（比較例２）
Ｅ−ＴＥＫ社製のＰｔＲｕ担持カーボン触媒（ＨＰ６０％、Ｐｔ：Ｒｕ＝１：１ｏｎ ＤＭＦＣｏｐｉｍｉｚｅｄ ｃａｒｂｏｎ、Ｃ２０−６０）を用いて実施例１と同様にして性能評価を行った。この触媒の結晶構造は面心立方構造であった。（１１１）面の結晶子経（Ｄ１）、（２２０）面の結晶子経（Ｄ２）、およびＤ１／Ｄ２、それに性能評価結果を表１に示す。
（比較例３）
石福金属社製のＰｔＲｕ担持カーボン触媒（ＩＦＤＭ４０Ａ、ＰｔＲｕ（６０％）／ＫｅｔｊｅｎＢｌａｃｋＥＣ）を用いて実施例１と同様にして性能評価を行った。この触媒の結晶構造は面心立方構造であった。（１１１）面の結晶子経（Ｄ１）、（２２０）面の結晶子経（Ｄ２）、およびＤ１／Ｄ２、それに性能評価結果を表１に示す。
For the evaluation of the catalyst performance, methanol was added to the sulfuric acid aqueous solution so as to be 1 mol / L. The test electrode is immersed in this solution maintained at 25 ° C. to serve as a working electrode, a platinum wire as a counter electrode, and a reversible hydrogen electrode (RHE) as a reference electrode, and a methanol oxidation current and an electrode potential by a potential regulation method. The relationship of 0.6V. vs. The value obtained by dividing the oxidation current value in RHE by the mass of platinum contained in the catalyst coated on the glassy carbon electrode (oxidation current value per platinum mass) was used. The higher the current value, the higher the performance. The results are shown in Table 1.
(Comparative Example 1)
Performance evaluation was performed in the same manner as in Example 1 using a PtRu-supported carbon catalyst (HiSPEC10100) manufactured by Johnson Mattey. The crystal structure of this catalyst was a face-centered cubic structure. Table 1 shows the crystallite size (D1) of the (111) plane, the crystallite size (D2) of the (220) plane, D1 / D2, and performance evaluation results.
(Comparative Example 2)
Performance evaluation was performed in the same manner as in Example 1 using a PtRu-supported carbon catalyst (HP 60%, Pt: Ru = 1: 1 on DMF Coupled carbon, C20-60) manufactured by E-TEK. The crystal structure of this catalyst was a face-centered cubic structure. Table 1 shows the crystallite size (D1) of the (111) plane, the crystallite size (D2) of the (220) plane, D1 / D2, and performance evaluation results.
(Comparative Example 3)
Performance evaluation was performed in the same manner as in Example 1 using a PtRu-supported carbon catalyst (IFDM40A, PtRu (60%) / KetjenBlackEC) manufactured by Ishifuku Metal Co., Ltd. The crystal structure of this catalyst was a face-centered cubic structure. Table 1 shows the crystallite size (D1) of the (111) plane, the crystallite size (D2) of the (220) plane, D1 / D2, and performance evaluation results.
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