JP2007035289A - Electrode catalyst for fuel cell, electrode composition, and fuel cell - Google Patents
Electrode catalyst for fuel cell, electrode composition, and fuel cell Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 title claims abstract description 31
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 120
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 112
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 52
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 51
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 51
- 239000003921 oil Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 24
- 239000000956 alloy Substances 0.000 claims abstract description 24
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 18
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 16
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052715 tantalum Inorganic materials 0.000 claims abstract description 16
- 238000010521 absorption reaction Methods 0.000 claims description 27
- 239000004020 conductor Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- 238000002360 preparation method Methods 0.000 description 34
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 25
- 229910052707 ruthenium Inorganic materials 0.000 description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 229910004298 SiO 2 Inorganic materials 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000005518 polymer electrolyte Substances 0.000 description 9
- 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 8
- 239000000126 substance Substances 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 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 7
- 239000007787 solid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 239000006229 carbon black Substances 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910000420 cerium oxide Inorganic materials 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000004570 mortar (masonry) Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910021488 crystalline silicon dioxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- GJKFIJKSBFYMQK-UHFFFAOYSA-N lanthanum(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GJKFIJKSBFYMQK-UHFFFAOYSA-N 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000035699 permeability Effects 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
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 150000003058 platinum compounds Chemical class 0.000 description 1
- -1 polytetrafluoroethylene Polymers 0.000 description 1
- 230000002940 repellent Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
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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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
Description
本発明は、燃料電池用電極触媒、燃料電池用電極組成物および燃料電池に関し、詳しくは、触媒活性成分を二酸化ケイ素に担持してなる燃料電池用電極触媒、特に固体高分子型燃料電池に用いるに好適な電極触媒、この電極触媒と導電性物質とプロトン伝導性物質とを含む電極組成物、およびこの電極組成物を用いて電極を構成してなる燃料電池に関する。 The present invention relates to an electrode catalyst for a fuel cell, an electrode composition for a fuel cell, and a fuel cell. More specifically, the present invention is used for an electrode catalyst for a fuel cell in which a catalytic active component is supported on silicon dioxide, particularly a solid polymer fuel cell. The present invention relates to a suitable electrode catalyst, an electrode composition comprising the electrode catalyst, a conductive material and a proton conductive material, and a fuel cell comprising an electrode using the electrode composition.
燃料電池は、化学反応を利用して、その化学エネルギーを直接電気エネルギーに変換する発電システムである。現状の石油や天然ガスを燃焼し、その熱エネルギーを電気エネルギーに変換するシステムに比べて、発電効率が高く、ＮＯｘやＳＯｘが排出されないため、次世代のクリーンエネルギーとして注目されている。燃料電池は、電解質の種類からリン酸型燃料電池、溶融炭酸型燃料電池、固体高分子型燃料電池、固体酸化物型燃料電池に分類することができる。そのなかでも固体高分子型燃料電池は、他の燃料電池より低い温度領域において発電させることができ、小型化が容易なことから自動車用電源、家庭用電源、携帯用電源など種々の用途に適用できる可能性がある。 A fuel cell is a power generation system that uses chemical reaction to directly convert chemical energy into electrical energy. Compared to the current system that burns oil and natural gas and converts the thermal energy into electric energy, it has high power generation efficiency and does not emit NOx or SOx. Fuel cells can be classified into phosphoric acid fuel cells, molten carbonate fuel cells, polymer electrolyte fuel cells, and solid oxide fuel cells according to the type of electrolyte. Among them, the polymer electrolyte fuel cell can generate power in a lower temperature range than other fuel cells, and is easy to downsize, so it can be applied to various applications such as automobile power supplies, household power supplies, and portable power supplies. There is a possibility.
固体高分子型燃料電池では、プロトン伝導性を示す固体高分子型電解質膜（例えば、米国デュポン社製のナフィオン膜）の両側に触媒とプロトン伝導性高分子電解質とを含んだ触媒層とその外面に通気性および導電性を併せ持つガス拡散層（例えば、ポリテトラフルオロエチレン（ＰＴＦＥ）などで撥水処理を行ったカーボンペーパーやカーボンクロス等）が設けられている。触媒層とガス拡散層とを合わせて電極と呼び、固体高分子電解質膜の両側に燃料極および空気極を設けた電極−固体高分子型電解質膜を基本単位とする。燃料極に水素やメタノールなどの燃料を、空気極に酸素や空気を供給し、燃料またはガスと固体高分子電解質膜と電極の３相界面において反応を進行させることにより電気を取り出すことができる。 In a polymer electrolyte fuel cell, a catalyst layer containing a catalyst and a proton conductive polymer electrolyte on both sides of a solid polymer electrolyte membrane exhibiting proton conductivity (for example, Nafion membrane manufactured by DuPont, USA) and its outer surface A gas diffusion layer having both air permeability and conductivity (for example, carbon paper or carbon cloth subjected to water repellent treatment with polytetrafluoroethylene (PTFE) or the like) is provided. The catalyst layer and the gas diffusion layer are collectively referred to as an electrode, and the basic unit is an electrode-solid polymer electrolyte membrane in which a fuel electrode and an air electrode are provided on both sides of the solid polymer electrolyte membrane. Electricity can be taken out by supplying a fuel such as hydrogen or methanol to the fuel electrode and supplying oxygen or air to the air electrode and allowing the reaction to proceed at the three-phase interface of the fuel or gas, the solid polymer electrolyte membrane, and the electrode.
燃料極および空気極に使用される電極触媒としては、導電性担体としてのカーボンブラックに白金などの貴金属を担持したものが主流となっている。しかし、一般の方法によりカーボンブラックに貴金属を担持した電極触媒を用いて得られる燃料電池は、電池特性にばらつきがあって、その実用化にはなお問題が残されている。そこで、このような問題を解決することを目的として、二酸化ケイ素（ＳｉＯ２）を主成分とする担体に白金またはその合金を担持して電極触媒とし、これを導電性物質とプロトン伝導性物質とを組み合わせて電極とすることが提案されている（特許文献１）。 As the electrode catalyst used for the fuel electrode and the air electrode, the one in which a noble metal such as platinum is supported on carbon black as a conductive carrier has become the mainstream. However, fuel cells obtained using an electrode catalyst in which a noble metal is supported on carbon black by a general method have variations in cell characteristics, and problems still remain in practical use. Therefore, for the purpose of solving such problems, platinum or an alloy thereof is supported on a carrier mainly composed of silicon dioxide (SiO 2 ) to form an electrode catalyst, which is composed of a conductive substance, a proton conductive substance, It has been proposed to form an electrode by combining (Patent Document 1).
本発明の目的は、二酸化ケイ素に白金などの触媒活性成分を担持してなる電極触媒であって、より実用性の高い燃料電池を製造可能な、燃料電池用、特に固体高分子型燃料電池用の電極触媒、さらにはこの電極触媒を用いてなる燃料電池用電極組成物および燃料電池を提供することにある。 An object of the present invention is an electrode catalyst in which a catalytic active component such as platinum is supported on silicon dioxide, and can be used to produce a more practical fuel cell, particularly for a fuel cell, particularly for a polymer electrolyte fuel cell It is another object of the present invention to provide an electrode composition for a fuel cell and a fuel cell using the electrode catalyst.
本発明者らの研究によれば、二酸化ケイ素のなかでもＢＥＴ比表面積および吸油量が特定範囲にあるものを担体として用い、これに触媒活性成分としての白金またはその合金を特定量担持すると上記目的が達成できることがわかった。また、触媒活性成分として、白金またはその合金と、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物とを二酸化ケイ素に担持することによっても上記目的が達成できることがわかった。本発明は、これらの知見に基づいて完成されたものであり、次のとおりのものである。
（１）白金またはその合金をＢＥＴ比表面積１００〜５００ｍ２／ｇ、吸油量１．６〜３．７ｍＬ／ｇの二酸化ケイ素に５０〜８０質量％の割合で担持してなることを特徴とする燃料電池用電極触媒。
（２）さらにセリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物を担持してなる上記（１）の燃料電池用電極触媒。
（３）白金またはその合金と、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物とを二酸化ケイ素に担持してなることを特徴とする燃料電池用電極触媒。
（４）上記（１）、（２）または（３）の燃料電池用電極触媒と導電性物質とプロトン伝導性物質とを含有する燃料電池用電極組成物。
（５）上記（１）、（２）または（３）の燃料電池用電極触媒を用いて得られる燃料電池。
According to the researches of the present inventors, when silicon dioxide having a BET specific surface area and an oil absorption amount in a specific range is used as a support, and a specific amount of platinum or an alloy thereof as a catalyst active component is supported on the carrier, the above object is achieved. It was found that can be achieved. It has also been found that the above object can also be achieved by supporting platinum or an alloy thereof and an oxide of at least one element selected from cerium, lanthanum and tantalum on silicon dioxide as catalytic active components. The present invention has been completed based on these findings, and is as follows.
(1) Platinum or an alloy thereof is supported on silicon dioxide having a BET specific surface area of 100 to 500 m 2 / g and an oil absorption of 1.6 to 3.7 mL / g at a ratio of 50 to 80% by mass. Fuel cell electrode catalyst.
(2) The fuel cell electrode catalyst according to (1), further comprising an oxide of at least one element selected from cerium, lanthanum and tantalum.
(3) A fuel cell electrode catalyst comprising platinum or an alloy thereof and an oxide of at least one element selected from cerium, lanthanum and tantalum supported on silicon dioxide.
(4) A fuel cell electrode composition comprising the fuel cell electrode catalyst according to the above (1), (2) or (3), a conductive material and a proton conductive material.
(5) A fuel cell obtained using the fuel cell electrode catalyst according to (1), (2) or (3).
二酸化ケイ素のなかでも、ＢＥＴ比表面積が１００〜５００ｍ２／ｇ、また吸油量が１．６〜３．７ｍＬ／ｇという限定的な表面特性を有する二酸化ケイ素を選択し、これに白金またはその合金、もしくは白金またはその合金とセリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物とを特定の割合で担持することにより、一段と触媒性能に優れた電極触媒を得ることができる。 Among silicon dioxides, silicon dioxide having limited surface properties such as a BET specific surface area of 100 to 500 m 2 / g and an oil absorption of 1.6 to 3.7 mL / g is selected, and platinum or an alloy thereof is selected. Alternatively, by supporting platinum or an alloy thereof and an oxide of at least one element selected from cerium, lanthanum, and tantalum at a specific ratio, an electrode catalyst having further excellent catalytic performance can be obtained.
また、二酸化ケイ素に、白金またはその合金に加えて、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物を担持することにより、白金またはその合金を単独で担持したものに比べて、触媒性能に優れた電極触媒を得ることができる。 Further, in addition to platinum or an alloy thereof, in addition to platinum or an alloy thereof, by supporting an oxide of at least one element selected from cerium, lanthanum, and tantalum, compared to the one in which platinum or an alloy thereof is supported alone, An electrode catalyst having excellent catalytic performance can be obtained.
本発明の電極触媒の一つ（以下、電極触媒Ａという。）は、白金またはその合金をＢＥＴ比表面積１００〜５００ｍ２／ｇ、吸油量１．６〜３．７ｍＬ／ｇ、好ましくは１．８〜３．６ｍＬ／ｇの二酸化ケイ素に５０〜８０質量％の割合で担持してなるものである。ここで、「吸油量」は、ＪＩＳ Ｋ５１０１の方法により測定したものである。また、触媒活性成分の担持割合は、電極触媒の全質量を基準とするものである。 One of the electrode catalysts of the present invention (hereinafter referred to as electrode catalyst A) is platinum or an alloy thereof having a BET specific surface area of 100 to 500 m 2 / g and an oil absorption of 1.6 to 3.7 mL / g, preferably 1. 8 to 3.6 mL / g of silicon dioxide is supported at a ratio of 50 to 80% by mass. Here, the “oil absorption amount” is measured by the method of JIS K5101. Further, the loading ratio of the catalytically active component is based on the total mass of the electrode catalyst.
ＢＥＴ比表面積、吸油量および担持量はそれぞれ１００〜５００ｍ２／ｇ、１．６〜３．７ｍＬ／ｇおよび５０〜８０質量％という範囲内になければならず、ＢＥＴ比表面積および担持量がそれぞれ１００〜５００ｍ２／ｇおよび５０〜８０質量％という条件を満たしていても、吸油量が１．６ｍＬ／ｇより小さい二酸化ケイ素、あるいは吸油量が３．７ｍＬ／ｇより大きな二酸化ケイ素を用いては目的とする電極触媒を得ることはできない。特に、吸油量の１．６〜３．７ｍＬ／ｇという範囲は臨界的であり、この数値外では触媒性能が著しく低下する。 The BET specific surface area, oil absorption amount and loading amount must be in the range of 100 to 500 m 2 / g, 1.6 to 3.7 mL / g and 50 to 80% by mass, respectively. Even if the conditions of 100 to 500 m 2 / g and 50 to 80% by mass are satisfied, silicon dioxide having an oil absorption of less than 1.6 mL / g or silicon dioxide having an oil absorption of more than 3.7 mL / g should be used. The target electrode catalyst cannot be obtained. Particularly, the range of 1.6 to 3.7 mL / g of oil absorption is critical, and the catalyst performance is remarkably reduced outside this value.
上記電極触媒（Ａ）において、触媒活性成分として、白金またはその合金に加えて、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物を担持することにより、白金またはその合金を単独で担持したものに比べて、触媒性能がより優れた電極触媒を得ることができる。 In the electrode catalyst (A), in addition to platinum or an alloy thereof as a catalyst active component, platinum or an alloy thereof is singly supported by supporting an oxide of at least one element selected from cerium, lanthanum and tantalum. It is possible to obtain an electrode catalyst having more excellent catalytic performance as compared with the supported catalyst.
上記のＢＥＴ比表面積１００〜５００ｍ２／ｇ、吸油量１．６〜３．７ｍＬ／ｇの二酸化ケイ素は一般に入手可能であり、市販の二酸化ケイ素から適宜選択して使用することができる。例えば、Ｔｏｋｕｓｉｌ ＧＵ、Ｔｏｋｕｓｉｌ Ｕ、Ｔｏｋｕｓｉｌ ＮＲ（以上、株式会社トクヤマ製）、Ｎｉｐｇｅｌ ＡＺ２００、Ｎｉｐｇｅｌ ＢＹ４００（以上、東ソー・シリカ（株）製）などを用いることができる。 The silicon dioxide having a BET specific surface area of 100 to 500 m 2 / g and an oil absorption of 1.6 to 3.7 mL / g is generally available, and can be appropriately selected from commercially available silicon dioxide. For example, Tokusil GU, Tokusil U, Tokusil NR (manufactured by Tokuyama Corporation), Nipgel AZ200, Nipgel BY400 (manufactured by Tosoh Silica Co., Ltd.) can be used.
二酸化ケイ素は、通常、粒子の形態で用いられるが、その平均粒子径は、１０ｎｍ〜１μｍの範囲にあるのが好ましい。 Silicon dioxide is usually used in the form of particles, but the average particle diameter is preferably in the range of 10 nm to 1 μm.
上記の白金合金は、燃料電池用電極触媒に一般に用いられている白金合金であればいずれでもよく、例えば、白金とルテニウム、ロジウム、イリジウム、オスミウム、パラジウムなどの１種または２種以上との合金を挙げることができる。 白金またはその合金の担持量は、５０〜８０質量％、好ましくは６０〜８０質量％であり、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物の担持量は０．２〜１０質量％、好ましくは０．５〜５質量％である。 The platinum alloy may be any platinum alloy that is generally used for an electrode catalyst for fuel cells. For example, an alloy of platinum and one or more of ruthenium, rhodium, iridium, osmium, palladium and the like. Can be mentioned. The supported amount of platinum or an alloy thereof is 50 to 80% by mass, preferably 60 to 80% by mass, and the supported amount of an oxide of at least one element selected from cerium, lanthanum and tantalum is 0.2 to 10%. % By mass, preferably 0.5 to 5% by mass.
本発明のもう一つの電極触媒（以下、電極触媒Ｂという。）は、白金またはその合金と、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物とを二酸化ケイ素に担持してなるものである。 Another electrode catalyst of the present invention (hereinafter referred to as electrode catalyst B) is formed by supporting platinum or an alloy thereof and an oxide of at least one element selected from cerium, lanthanum and tantalum on silicon dioxide. Is.
上記の電極触媒Ｂに用いる二酸化ケイ素の表面特性には特に制限はないが、ＢＥＴ比表面積が１０〜１０００ｍ２／ｇ、好ましくは１００〜５００ｍ２／ｇであり、吸油量が１〜５ｍＬ／ｇ、好ましくは１．６〜３．７ｍＬ／ｇ、より好ましくは１．８〜３．６ｍＬ／ｇである二酸化ケイ素が好適に用いられる。なかでも、ＢＥＴ比表面積１００〜５００ｍ２／ｇ、吸油量が１．６〜３．７ｍＬ／ｇである二酸化ケイ素に、白金またはその合金を５０〜８０質量％、好ましくは６０〜８０質量％、またセリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物を０．２〜１０質量％、好ましくは０．５〜５質量％の割合で担持して得られる電極触媒が特に優れた電池特性を発揮するので好ましいものである。 There is no particular limitation on the surface properties of the silicon dioxide used for the above electrode catalyst B, BET specific surface area of 10 to 1000 m 2 / g, preferably 100 to 500 m 2 / g, an oil absorption of 1-5 mL / g , Preferably 1.6 to 3.7 mL / g, more preferably 1.8 to 3.6 mL / g of silicon dioxide. Of these, silicon or a BET specific surface area of 100 to 500 m 2 / g and an oil absorption of 1.6 to 3.7 mL / g, platinum or an alloy thereof is 50 to 80% by mass, preferably 60 to 80% by mass, A battery in which an electrode catalyst obtained by supporting an oxide of at least one element selected from cerium, lanthanum and tantalum in a proportion of 0.2 to 10% by mass, preferably 0.5 to 5% by mass is particularly excellent. This is preferable because it exhibits its characteristics.
電極触媒（Ａ）または（Ｂ）における、触媒活性成分の二酸化ケイ素への担持方法については、例えば、触媒活性成分として白金またはその合金を用いる場合、この種の電極触媒の調製に一般に用いられている方法にしたがって調製することができる。例えば、ジニトロジアンミン白金などの白金化合物を無水エタノールなどの溶媒に溶解し、これに二酸化ケイ素を懸濁させ、十分に攪拌した後、溶媒を蒸発させ、次いで、水素含有窒素などの還元性雰囲気下、１００〜８００℃程度の温度で還元処理を行えばよい。また、触媒活性成分として白金またはその合金とセリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物のうち、例えば、セリウム酸化物を担持する場合は、硝酸セリウム、酢酸セリウムなどの金属塩を純水などの溶媒に所定量溶解し、得られる金属塩含有溶液に二酸化ケイ素を添加して均一に分散させた後、溶媒を蒸発させるなどして金属塩を二酸化ケイ素に担持し、次いで、得られた粉体を空気などの酸素含有ガス中で２００〜７００℃で加熱処理することで金属塩を分解、酸化してセリウム酸化物を二酸化ケイ素に担持させる方法を例示することができる。このように、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の元素の酸化物を担持した後に、上記と同様にして、白金またはその合金を担持すればよい。 Regarding the method for supporting the catalytically active component on silicon dioxide in the electrode catalyst (A) or (B), for example, when platinum or an alloy thereof is used as the catalytically active component, it is generally used for the preparation of this type of electrode catalyst. Can be prepared according to the existing methods. For example, a platinum compound such as dinitrodiammine platinum is dissolved in a solvent such as anhydrous ethanol, silicon dioxide is suspended in this, and after sufficient stirring, the solvent is evaporated, and then in a reducing atmosphere such as hydrogen-containing nitrogen. The reduction treatment may be performed at a temperature of about 100 to 800 ° C. In addition, among the oxides of at least one element selected from platinum or an alloy thereof and cerium, lanthanum, and tantalum as a catalyst active component, for example, when supporting cerium oxide, a metal salt such as cerium nitrate or cerium acetate Is dissolved in a predetermined amount of a solvent such as pure water, and silicon dioxide is added and uniformly dispersed in the resulting metal salt-containing solution, and then the metal salt is supported on the silicon dioxide by evaporating the solvent, etc. An example is a method in which the obtained powder is heat-treated at 200 to 700 ° C. in an oxygen-containing gas such as air to decompose and oxidize the metal salt to support the cerium oxide on silicon dioxide. Thus, after supporting an oxide of at least one element selected from cerium, lanthanum and tantalum, platinum or an alloy thereof may be supported in the same manner as described above.
本発明の燃料電池用電極組成物は、上述した燃料電池用電極触媒（Ａ）または（Ｂ）と導電性物質とプロトン伝導性物質とを含有するものである。本発明の電極触媒は、非導電性の二酸化ケイ素に触媒活性成分を担持したものなので、電極に導電性を付与するために導電性物質を配合することが必要である。 The fuel cell electrode composition of the present invention comprises the above-described fuel cell electrode catalyst (A) or (B), a conductive material, and a proton conductive material. Since the electrode catalyst of the present invention is a non-conductive silicon dioxide carrying a catalytically active component, it is necessary to blend a conductive material in order to impart conductivity to the electrode.
上記の導電性物質は、電極組成物、ひいてはこの電極組成物を用いて得られる電極に必要な導電性を付与し得るものであればよく、例えば、カーボン粒子、カーボンファイバー、カーボンナノチューブなどの炭素材料のほかに、金属粒子を挙げることができる。 The conductive material may be any material that can impart the necessary conductivity to the electrode composition, and thus the electrode obtained using the electrode composition. For example, carbon such as carbon particles, carbon fibers, and carbon nanotubes. In addition to the materials, mention may be made of metal particles.
上記のプロトン伝導性物質は、上記導電性物質と同様に、必要なプロトン伝導性を付与し得るものであればよく、例えば、ナフィオン（デュポン社製）、フレミオン（旭化成（株）製）、アシブレック（旭硝子（株）製）などのスルホン酸基を有するフッ素樹脂や、タングステン酸、リンタングステン酸などの無機物などを挙げることができる。 The proton conductive material may be any material as long as it can provide the necessary proton conductivity, for example, Nafion (manufactured by DuPont), Flemion (manufactured by Asahi Kasei Co., Ltd.), Ashiblek. Examples thereof include fluororesins having a sulfonic acid group such as (manufactured by Asahi Glass Co., Ltd.) and inorganic substances such as tungstic acid and phosphotungstic acid.
本発明の電極組成物における、導電性物質およびプロトン伝導性物質の割合については、電極としたときに必要な導電性とプロトン伝導性とが得られるように適宜決定すればよく、例えば、電極触媒１００質量部に対し、導電性物質を５０〜５００質量部、またプロトン伝導性物質を１０〜２００質量部の割合で適宜配合すればよい。 The ratio of the conductive substance and the proton conductive substance in the electrode composition of the present invention may be appropriately determined so as to obtain the necessary conductivity and proton conductivity when used as an electrode. For example, an electrode catalyst What is necessary is just to mix | blend a conductive substance suitably with the ratio of 50-500 mass parts and a proton-conductive substance 10-200 mass parts with respect to 100 mass parts.
本発明の電極組成物および燃料電池は、電極触媒として上述の電極触媒（Ａ）または（Ｂ）を用いる点を除けば、一般に知られた方法により調製することが可能であり、これについては、例えば、前記特許文献１を参考とすることができる。
The electrode composition and fuel cell of the present invention can be prepared by a generally known method except that the above-described electrode catalyst (A) or (B) is used as an electrode catalyst. For example,
本発明の有利な実施態様を示している以下の実施例を挙げて、本発明を更に具体的に説明する。 The invention is further illustrated by the following examples, which illustrate advantageous embodiments of the invention.
（触媒調製例１）
比表面積が１１９ｍ２／ｇ、吸油量が１．６ｍＬ／ｇである株式会社トクヤマ製非晶質二酸化ケイ素Ｔｏｋｕｓｉｌ ＧＵを１１０℃にて乾燥した後、メノウ乳鉢で粉砕し、４５μｍ以下にメッシュを揃えた後、その０．７ｇを無水エタノール１００ｍＬに投入し、攪拌・縣濁させた。次いで、金属として０．６９２ｇの白金を含むジニトロジアンミン白金、また、金属として０．３５８ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させた後、上記二酸化ケイ素０．７ｇを縣濁させた無水エタノール溶液に加え、十分に攪拌した後、ロータリーエバポレータを用いて窒素気流下、６０〜７０℃に保持して無水エタノールを蒸発させた。その後、５％水素含有窒素を用いて３００℃にて２時間還元処理を行って触媒Ａを調製した。この触媒Ａの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０（質量％）であった（触媒金属担持量：６０質量％）。
（触媒調製例２）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が１８３ｍ２／ｇ、吸油量が１．８ｍＬ／ｇである株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ Ｕを用いた以外は触媒調製例１と同様にして触媒Ｂを調製した。この触媒Ｂの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０（質量％）であった（触媒金属担持量：６０質量％）。
（触媒調製例３）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が１９５ｍ２／ｇ、吸油量が２．５ｍＬ／ｇである株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＮＲを用いた以外は触媒調製例１と同様にして触媒Ｃを調製した。この触媒Ｃの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０（質量％）であった（触媒金属担持量：６０質量％）。
（触媒調製例４）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が２９０ｍ２／ｇ、吸油量が３．６ｍＬ／ｇである東ソー・シリカ株式会社製非晶質二酸化ケイ素Ｎｉｐｇｅｌ ＡＺ２００を用いた以外は触媒調製例１と同様にして触媒Ｄを調製した。この触媒Ｄの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０（質量％）であった（触媒金属担持量：６０質量％）。
（触媒調製例５）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵ代えて、比表面積が４５０ｍ２／ｇ、吸油量が２．１ｍＬ／ｇである東ソー・シリカ株式会社製非晶質二酸化ケイ素Ｎｉｐｇｅｌ ＢＹ４００を用いた以外は触媒調製例１と同様にして触媒Ｅを調製した。この触媒Ｅの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０（質量％）であった（触媒金属担持量：６０質量％）。
（触媒調製例６）
金属として０．０８１ｇの白金を含むジニトロジアンミン白金、また、金属として０．０４２ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させたものに変更した以外は触媒調製例２と同様にして触媒Ｆを調製した。この触媒Ｆの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝１０：５：８５ (質量％)であった（触媒金属担持量：１５質量％）。
（触媒調製例７）
金属として０．１９８ｇの白金を含むジニトロジアンミン白金、また、金属として０．１０２ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させたものに変更した以外は触媒調製例２と同様にして触媒Ｇを調製した。この触媒Ｇの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝２０：１０：７０ (質量％)であった（触媒金属担持量：３０質量％）。
（触媒調製例８）
金属として０．４６１ｇの白金を含むジニトロジアンミン白金、また、金属として０．２３９ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させたものに変更した以外は触媒調製例２と同様にして触媒Ｈを調製した。この触媒Ｈの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝３３：１７：５０ (質量％)であった（触媒金属担持量：５０質量％）。
（触媒調製例９）
金属として１．８４ｇの白金を含むジニトロジアンミン白金、また、金属として０．９５６ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させたものに変更した以外は触媒調製例２と同様にして触媒Ｉを調製した。この触媒Ｉの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝５３：２７：２０ (質量％)であった（触媒金属担持量：８０質量％）。
（触媒調製例１０）
金属として４．１５ｇの白金を含むジニトロジアンミン白金、また、金属として２．１５ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させたものに変更した以外は触媒調製例２と同様にして触媒Ｊを調製した。この触媒Ｊの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝６０：３０：１０ (質量％)であった（触媒金属担持量：９０質量％）。
（触媒調製例１１）
比表面積が１８３ｍ２／ｇ、吸油量が１．８ｍＬ／ｇである株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ Ｕを１１０℃にて乾燥した後、メノウ乳鉢で粉砕し、４５μｍ以下にメッシュを揃えた後、その１．０ｇを硝酸セリウム・６水和物を０．１０５ｇ溶解させた水溶液中に添加し、十分に攪拌した後、ロータリーエバポレータを用いて窒素気流下、１００℃に保持して水分を蒸発させた。得られた粉体を、空気中４５０℃にて２時間焼成し、酸化セリウムを二酸化ケイ素に担持させた。その後、酸化セリウム担持二酸化ケイ素をメノウ乳鉢で粉砕し、４５μｍ以下にメッシュを揃え、その０．７ｇを無水エタノール１００ｍＬに投入し、攪拌・縣濁させた。次いで、金属として０．６９２ｇの白金を含むジニトロジアンミン白金、また、金属として０．３５８ｇのルテニウムを含む硝酸ルテニウムを無水エタノール１００ｍＬに溶解させた後、酸化セリウム担持二酸化ケイ素０．７ｇを縣濁させた無水エタノール溶液に加え、十分に攪拌した後、ロータリーエバポレータを用いて窒素気流下、６０〜７０℃に保持して無水エタノールを蒸発させた。その後、５％水素含有窒素を用いて３００℃にて２時間還元処理を行って触媒Ｋを調製した。この触媒Ｋの組成は、白金：ルテニウム：酸化セリウム : 二酸化ケイ素（Ｐｔ：Ｒｕ：ＣｅＯ２：ＳｉＯ２）＝４０：２０：２：３８ (質量％)であった（触媒金属担持量：６０質量％）。
（触媒調製例１２）
硝酸セリウム・６水和物を０．１０５ｇを硝酸ランタン・６水和物０．１４ｇに変更した以外は、触媒調製例１１と同様にして触媒Ｌを調製した。この触媒Ｌの組成は、白金：ルテニウム：酸化ランタン : 二酸化ケイ素（Ｐｔ：Ｒｕ：Ｌａ２Ｏ３：ＳｉＯ２）＝４０：２０：２：３８ (質量％)であった（触媒金属担持量：６０質量％）。
（触媒調製例１３）
硝酸セリウム・６水和物を０．１０５ｇ溶解させた水溶液に代えて塩化タンタル０．０８５ｇを無水エタノールに溶解させたものを用いた以外は、触媒調製例１１と同様にして触媒Ｍを調製した。この触媒Ｍの組成は、白金：ルテニウム：酸化タンタル : 二酸化ケイ素（Ｐｔ：Ｒｕ：Ｔａ２Ｏ５：ＳｉＯ２）＝４０：２０：２：３８ (質量％)であった（触媒金属担持量：６０質量％）。
（触媒調製例１４）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が６８９ｍ２／ｇ、吸油量が１．２ｍＬ／ｇである東ソー・シリカ株式会社製非晶質二酸化ケイ素Ｎｉｇｅｌ ＣＸ２００を用いた以外は触媒調製例１と同様にして触媒Ｎを調製した。この触媒Ｎの組成は、白金：ルテニウム：二酸化ケイ素＝４０：２０：４０（Ｐｔ：Ｒｕ：ＳｉＯ２）(質量％)であった（触媒金属担持量：６０質量％）。
（触媒調製例１５）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が４５ｍ２／ｇ、吸油量が１．８ｍＬ／ｇである東ソー・シリカ株式会社製非晶質二酸化ケイ素Ｎｉｐｓｉｌ Ｅ−７４Ｐを用いた以外は触媒調製例１と同様にして触媒Ｏを調製した。この触媒Ｏの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０ (質量％)であった（触媒金属担持量：６０質量％）。
（触媒調製例１６）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が６９０ｍ２／ｇ、吸油量が３．８ｍＬ／ｇである旭硝子株式会社製非晶質二酸化ケイ素Ｓｕｎｓｐｈｅｒｅ Ｈ−３３を用いた以外は触媒調製例１と同様にして触媒Ｐを調製した。この触媒Ｐの組成は、白金：ルテニウム：二酸化ケイ素（Ｐｔ：Ｒｕ：ＳｉＯ２）＝４０：２０：４０ (質量％)であった（触媒金属担持量：６０質量％）。
（触媒調製例１７）
株式会社トクヤマ製非晶質二酸化ケイ素ＴｏｋｕｓｉＬ ＧＵに代えて、比表面積が７９３ｍ２／ｇ、吸油量が３．６ｍＬ／ｇである三菱化学株式会社製カーボンブラックＫｅｔｊｅｎ Ｂｌａｃｋ ＥＣを用いた以外は触媒調製例１と同様にして触媒Ｑを調製した。この触媒Ｑの組成は、白金：ルテニウム：カーボンブラック（Ｐｔ：Ｒｕ：Ｃ）＝４０：２０：４０ (質量％)であった（触媒金属担持量：６０質量％）。
（性能評価）
触媒調製例１〜１７で得られた触媒Ａ〜Ｑ (触媒Ｆ、Ｇ、Ｊ、Ｎ、Ｏ、Ｐ、Ｑは比較用)の電極触媒としての性能を評価した。触媒性能の評価は、固体高分子型燃料電池用電極触媒の評価に有効であり、かつ、燃料電池性能と良い相関性が得られる回転電極法にて実施した。
＜評価方法＞
触媒１０ｍｇおよびカーボンブラック(キャボット社製Ｖｕｌｃａｎ ＸＣ７２)１０ｍｇを５％ナフィオン溶液 (アルドリッチ社製)１ｍＬに加え、超音波により十分に分散させて触媒ペーストを作成した。次いで、この触媒ペーストをグラッシーカーボン電極上に塗布し、十分に乾燥させて触媒層を回転グラッシーカーボン電極上に固定化して試験電極とした。触媒性能は、２５℃に保持した１規定の過塩素酸水溶液に１モル / Ｌとなるようにメタノールを加え、この溶液中に該試験電極を浸漬して作用極とし、対極に白金線、参照電極に可逆水素電極（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、０．７Ｖｖｓ．ＲＨＥにおける酸化電流値を比較することで行った。酸化電流値が高いほど触媒性能が優れていることを示す。結果を表１に示した。なお、メタノール酸化電流値は、測定された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貴金属重量で除した値 (貴金属質量あたりの酸化電流値) とした。
(Catalyst Preparation Example 1)
After the specific surface area has dried 119m 2 / g, oil absorption of Tokuyama amorphous silicon dioxide Tokusil GU Corporation, a 1.6 mL / g at 110 ° C., and ground in an agate mortar, align the mesh to 45μm or less After that, 0.7 g of the solution was put into 100 mL of absolute ethanol, and stirred and suspended. Next, dinitrodiammine platinum containing 0.692 g of platinum as a metal and ruthenium nitrate containing 0.358 g of ruthenium as a metal were dissolved in 100 mL of absolute ethanol, and then anhydrous silicon dioxide 0.7 g was suspended. In addition to the ethanol solution, after sufficiently stirring, absolute ethanol was evaporated by maintaining at 60 to 70 ° C under a nitrogen stream using a rotary evaporator. Thereafter, reduction treatment was performed at 300 ° C. for 2 hours using 5% hydrogen-containing nitrogen to prepare Catalyst A. The composition of the catalyst A was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst preparation example 2)
Instead of Tokuyama Amorphous Silicon Dioxide TokuLu GU, a catalyst was used except that Tokuyama Amorphous Silicon Dioxide TokuiL U with a specific surface area of 183 m 2 / g and an oil absorption of 1.8 mL / g was used. Catalyst B was prepared in the same manner as in Preparation Example 1. The composition of this catalyst B was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst Preparation Example 3)
Instead of the Tokuyama amorphous silicon dioxide TokusiL GU, a catalyst other than the Tokuyama amorphous silicon dioxide TokusiL NR having a specific surface area of 195 m 2 / g and an oil absorption of 2.5 mL / g was used. Catalyst C was prepared in the same manner as in Preparation Example 1. The composition of the catalyst C was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst Preparation Example 4)
Instead of using Tokuyama amorphous silicon dioxide Tokusi L GU, Tosoh Silica Co., Ltd. amorphous silicon dioxide Nippon AZ200 having a specific surface area of 290 m 2 / g and an oil absorption of 3.6 mL / g was used. Prepared Catalyst D in the same manner as Catalyst Preparation Example 1. The composition of the catalyst D was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst Preparation Example 5)
Instead of using Tokuyama amorphous silicon dioxide TokusiL GU, Tosoh Silica Co., Ltd. amorphous silicon dioxide BY400 having a specific surface area of 450 m 2 / g and an oil absorption of 2.1 mL / g was used. Catalyst E was prepared in the same manner as in Catalyst Preparation Example 1. The composition of the catalyst E was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst Preparation Example 6)
Catalyst F was prepared in the same manner as in Catalyst Preparation Example 2, except that dinitrodiammine platinum containing 0.081 g of platinum as metal and ruthenium nitrate containing 0.042 g of ruthenium as metal were dissolved in 100 mL of absolute ethanol. Was prepared. The composition of this catalyst F are platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2) = 10: 5: 85 was (wt%) (catalytic amount of metal supported: 15 wt%).
(Catalyst Preparation Example 7)
Catalyst G was prepared in the same manner as in Catalyst Preparation Example 2, except that dinitrodiammine platinum containing 0.198 g of platinum as a metal and ruthenium nitrate containing 0.102 g of ruthenium as a metal was dissolved in 100 mL of absolute ethanol. Was prepared. The composition of the catalyst G was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 20: 10: 70 (mass%) (catalyst metal loading: 30 mass%).
(Catalyst Preparation Example 8)
Catalyst H in the same manner as in Catalyst Preparation Example 2, except that dinitrodiammine platinum containing 0.461 g of platinum as a metal and ruthenium nitrate containing 0.239 g of ruthenium as a metal was dissolved in 100 mL of absolute ethanol. Was prepared. The composition of this catalyst H was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 33: 17: 50 (mass%) (catalyst metal loading: 50 mass%).
(Catalyst Preparation Example 9)
Catalyst I was prepared in the same manner as in Catalyst Preparation Example 2, except that dinitrodiammine platinum containing 1.84 g of platinum as a metal and ruthenium nitrate containing 0.956 g of ruthenium as a metal was dissolved in 100 mL of absolute ethanol. Was prepared. The composition of this catalyst I was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 53: 27: 20 (mass%) (catalyst metal loading: 80 mass%).
(Catalyst Preparation Example 10)
Catalyst J was prepared in the same manner as Catalyst Preparation Example 2, except that dinitrodiammine platinum containing 4.15 g of platinum as metal and ruthenium nitrate containing 2.15 g of ruthenium as metal were dissolved in 100 mL of absolute ethanol. Was prepared. The composition of the catalyst J was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 60: 30: 10 (mass%) (catalyst metal loading: 90 mass%).
(Catalyst Preparation Example 11)
After drying amorphous silicon dioxide TokuiL U made by Tokuyama Co., Ltd., which has a specific surface area of 183 m 2 / g and oil absorption of 1.8 mL / g, at 110 ° C., it is pulverized in an agate mortar, and a mesh of 45 μm or less is prepared. Then, 1.0 g of the solution was added to an aqueous solution in which 0.105 g of cerium nitrate hexahydrate was dissolved, and after sufficiently stirring, the water was maintained at 100 ° C. under a nitrogen stream using a rotary evaporator. Was evaporated. The obtained powder was fired in air at 450 ° C. for 2 hours, and cerium oxide was supported on silicon dioxide. Thereafter, cerium oxide-supporting silicon dioxide was pulverized in an agate mortar, and a mesh was prepared to be 45 μm or less, and 0.7 g thereof was added to 100 mL of absolute ethanol, and stirred and suspended. Next, dinitrodiammine platinum containing 0.692 g of platinum as a metal and ruthenium nitrate containing 0.358 g of ruthenium as a metal are dissolved in 100 mL of absolute ethanol, and then 0.7 g of cerium oxide-supporting silicon dioxide is suspended. In addition to the absolute ethanol solution, after sufficiently stirring, the absolute ethanol was evaporated by maintaining at 60-70 ° C. under a nitrogen stream using a rotary evaporator. Thereafter, reduction treatment was performed at 300 ° C. for 2 hours using 5% hydrogen-containing nitrogen to prepare catalyst K. The composition of this catalyst K was platinum: ruthenium: cerium oxide: silicon dioxide (Pt: Ru: CeO 2 : SiO 2 ) = 40: 20: 2: 38 (mass%) (catalyst metal loading: 60 mass) %).
(Catalyst Preparation Example 12)
Catalyst L was prepared in the same manner as in Catalyst Preparation Example 11, except that 0.105 g of cerium nitrate hexahydrate was changed to 0.14 g of lanthanum nitrate hexahydrate. The composition of the catalyst L was platinum: ruthenium: lanthanum oxide: silicon dioxide (Pt: Ru: La 2 O 3 : SiO 2 ) = 40: 20: 2: 38 (mass%) (catalyst metal loading: 60% by mass).
(Catalyst Preparation Example 13)
Catalyst M was prepared in the same manner as in Catalyst Preparation Example 11, except that 0.085 g of tantalum chloride was dissolved in absolute ethanol instead of an aqueous solution in which 0.105 g of cerium nitrate hexahydrate was dissolved. . The composition of the catalyst M was platinum: ruthenium: tantalum oxide: silicon dioxide (Pt: Ru: Ta 2 O 5 : SiO 2 ) = 40: 20: 2: 38 (mass%) (catalyst metal loading: 60% by mass).
(Catalyst Preparation Example 14)
Instead of using Tokuyama amorphous silicon dioxide TokusiL GU, Tosoh Silica Co., Ltd. amorphous silicon dioxide Nigel CX200 having a specific surface area of 689 m 2 / g and an oil absorption of 1.2 mL / g was used. Prepared Catalyst N in the same manner as in Catalyst Preparation Example 1. The composition of this catalyst N is platinum: ruthenium: silicon dioxide = 40: 20: 40 (Pt : Ru: SiO 2) was (wt%) (catalytic amount of metal supported: 60 wt%).
(Catalyst Preparation Example 15)
Instead of Tokuyama amorphous silicon dioxide TokusiL GU, Tosoh Silica Co., Ltd. amorphous silicon dioxide Nippon E-74P with a specific surface area of 45 m 2 / g and oil absorption of 1.8 mL / g is used. Catalyst O was prepared in the same manner as in Catalyst Preparation Example 1 except that The composition of the catalyst O was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst Preparation Example 16)
Instead of using Tokuyama amorphous silicon dioxide TokusiL GU, non-crystalline silicon dioxide Sunsphere H-33 manufactured by Asahi Glass Co., Ltd. having a specific surface area of 690 m 2 / g and an oil absorption of 3.8 mL / g Prepared Catalyst P in the same manner as in Catalyst Preparation Example 1. The composition of the catalyst P was platinum: ruthenium: silicon dioxide (Pt: Ru: SiO 2 ) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Catalyst Preparation Example 17)
Catalyst preparation except that carbon black Ketjen Black EC manufactured by Mitsubishi Chemical Co., Ltd. having a specific surface area of 793 m 2 / g and an oil absorption of 3.6 mL / g was used in place of Tokuyama amorphous silicon dioxide Tokusi GU Catalyst Q was prepared as in Example 1. The composition of the catalyst Q was platinum: ruthenium: carbon black (Pt: Ru: C) = 40: 20: 40 (mass%) (catalyst metal loading: 60 mass%).
(Performance evaluation)
The performance of the catalysts A to Q (catalysts F, G, J, N, O, P, and Q for comparison) obtained in Catalyst Preparation Examples 1 to 17 as electrode catalysts was evaluated. The evaluation of the catalyst performance was carried out by a rotating electrode method that is effective for the evaluation of a solid polymer fuel cell electrode catalyst and has a good correlation with the fuel cell performance.
<Evaluation method>
10 mg of the catalyst and 10 mg of carbon black (Vulcan XC72 manufactured by Cabot) were added to 1 mL of a 5% Nafion solution (manufactured by Aldrich) and sufficiently dispersed by ultrasonic waves to prepare a catalyst paste. Next, this catalyst paste was applied onto a glassy carbon electrode and sufficiently dried to immobilize the catalyst layer on the rotating glassy carbon electrode to obtain a test electrode. The catalyst performance is as follows: methanol is added to a 1N perchloric acid aqueous solution maintained at 25 ° C. so that the concentration is 1 mol / L, and the test electrode is immersed in this solution to form a working electrode, and a counter electrode is a platinum wire. Using a reversible hydrogen electrode (RHE) as an electrode, the relationship between the methanol oxidation current and the electrode potential was measured by a potential regulation method, and 0.7 V vs. This was done by comparing the oxidation current values in RHE. The higher the oxidation current value, the better the catalyst performance. The results are shown in Table 1. The methanol oxidation current value was a value obtained by dividing the measured oxidation current value by the weight of the noble metal contained in the catalyst applied on the glassy carbon electrode (oxidation current value per noble metal mass).
表１の結果から次のことがわかる。
（ａ）二酸化ケイ素のＢＥＴ比表面積１００〜５００ｍ２／ｇ、吸油量１．６〜３．７ｍＬ／ｇ、それに触媒活性成分担持量５０〜８０質量％という条件をすべて満たすことにより良好な触媒性能が得られる。
（ｂ）白金またはその合金に加えて、セリウム、ランタンおよびタンタルから選ばれる少なくとも１種の酸化物を使用することにより、より良好な触媒性能が得られる。
The following can be seen from the results in Table 1.
(A) Good catalytic performance by satisfying all the conditions of BET specific surface area of silicon dioxide of 100 to 500 m 2 / g, oil absorption of 1.6 to 3.7 mL / g, and catalytic active component loading of 50 to 80% by mass Is obtained.
(B) By using at least one oxide selected from cerium, lanthanum and tantalum in addition to platinum or an alloy thereof, better catalytic performance can be obtained.
さらに、上記の触媒のなかから触媒Ａ〜Ｅおよび触媒Ｎ、Ｐをピックアップし、二酸化ケイ素の吸油量とメタノール酸化電流値との関係をグラフにして、図１に示した。図１のグラフから、吸油量１．６ｍＬ／ｇおよび３．７ｍＬ／ｇを境に、メタノール酸化電流値が著しく低下することがわかる。 Furthermore, the catalysts A to E and the catalysts N and P were picked up from the above catalysts, and the relationship between the oil absorption amount of silicon dioxide and the methanol oxidation current value was graphed and shown in FIG. From the graph of FIG. 1, it can be seen that the methanol oxidation current value significantly decreases at the oil absorption amounts of 1.6 mL / g and 3.7 mL / g.
Claims (5)
A fuel cell obtained using the fuel cell electrode catalyst according to claim 1, 2 or 3.
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| PCT/JP2006/305144 WO2006100982A1 (en) | 2005-03-18 | 2006-03-15 | Electrode catalyst for fuel cell |
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| JP2010237584A (en) * | 2009-03-31 | 2010-10-21 | Nippon Paper Chemicals Co Ltd | Anti-glare hard coat film |
| JP2011014475A (en) * | 2009-07-06 | 2011-01-20 | Toyota Motor Corp | Electrode catalyst for fuel cell, manufacturing method thereof, and solid polymer fuel cell |
| JP2016505193A (en) * | 2012-08-29 | 2016-02-18 | ソルビコア・ゲーエムベーハー・ウント・コ・カーゲー | Colloidal dispersions containing noble metal particles and acidic ionomer components and methods for their production and use |
| KR20180013500A (en) * | 2016-07-29 | 2018-02-07 | 울산과학기술원 | Self-supported mesoporous structure nanometal catalysts, manufacturing method thereof and fuel cell comprising the same |
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| JP2010237584A (en) * | 2009-03-31 | 2010-10-21 | Nippon Paper Chemicals Co Ltd | Anti-glare hard coat film |
| JP2011014475A (en) * | 2009-07-06 | 2011-01-20 | Toyota Motor Corp | Electrode catalyst for fuel cell, manufacturing method thereof, and solid polymer fuel cell |
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| KR20180013500A (en) * | 2016-07-29 | 2018-02-07 | 울산과학기술원 | Self-supported mesoporous structure nanometal catalysts, manufacturing method thereof and fuel cell comprising the same |
| KR101881209B1 (en) * | 2016-07-29 | 2018-07-23 | 울산과학기술원 | Self-supported mesoporous structure nanometal catalysts, manufacturing method thereof and fuel cell comprising the same |
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