JP2017202463A - Method for producing oxygen reduction catalyst - Google Patents
Method for producing oxygen reduction catalyst Download PDFInfo
- Publication number
- JP2017202463A JP2017202463A JP2016096213A JP2016096213A JP2017202463A JP 2017202463 A JP2017202463 A JP 2017202463A JP 2016096213 A JP2016096213 A JP 2016096213A JP 2016096213 A JP2016096213 A JP 2016096213A JP 2017202463 A JP2017202463 A JP 2017202463A
- Authority
- JP
- Japan
- Prior art keywords
- oxygen reduction
- reduction catalyst
- titanium oxide
- producing
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 81
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000001301 oxygen Substances 0.000 title claims abstract description 49
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 98
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000012298 atmosphere Substances 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims abstract description 17
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 9
- 238000007580 dry-mixing Methods 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 238000002156 mixing Methods 0.000 claims description 25
- 239000004408 titanium dioxide Substances 0.000 claims description 19
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 14
- 239000006229 carbon black Substances 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 229910044991 metal oxide Inorganic materials 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 9
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 229910001882 dioxygen Inorganic materials 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 4
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000002134 carbon nanofiber Substances 0.000 claims description 3
- 229910021389 graphene Inorganic materials 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 description 32
- 235000010215 titanium dioxide Nutrition 0.000 description 18
- 239000010936 titanium Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 13
- 238000010304 firing Methods 0.000 description 11
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 9
- 239000004570 mortar (masonry) Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000009257 reactivity Effects 0.000 description 5
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000003273 ketjen black Substances 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 239000010955 niobium Substances 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- QBNKFXYJSJOGEL-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ti+4] QBNKFXYJSJOGEL-UHFFFAOYSA-N 0.000 description 1
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960004889 salicylic acid Drugs 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
- Catalysts (AREA)
Abstract
Description
本発明は、チタン酸化物を含む酸素還元触媒の製造方法に関する。 The present invention relates to a method for producing an oxygen reduction catalyst containing titanium oxide.
チタン酸化物は、光触媒や酸化還元反応にかかわる触媒として用いられている。中でも、チタン酸化物触媒の酸素還元触媒能を利用して、燃料電池の電極触媒とすることもできることが知られている。 Titanium oxide is used as a catalyst for photocatalysts and oxidation-reduction reactions. Among them, it is known that the oxygen reduction catalytic ability of a titanium oxide catalyst can be used as a fuel cell electrode catalyst.
特許文献１では、窒素含有有機物とチタン化合物を溶媒に混合し、高い酸素還元触媒能を有するチタン酸化物触媒の製造方法が報告されている。また、非特許文献１には、前駆体としてオキシチタニウムフタロシアニンとカーボンブラック及びサリチル酸を溶媒に混合して、高い酸素還元触媒能を持つチタン酸化物触媒を製造する方法が報告されている。
しかし、これらの製造方法は、溶媒を使用することで、得られた混合物を乾燥し、焼成など製造工程が複雑である。また、高価なフタロシアニン錯体原料を使うことで触媒の製造コストも高くなり、工業的な触媒製造方法としては好ましくない。 However, these production methods use a solvent, and thus the obtained mixture is dried and the production process such as firing is complicated. Further, the use of an expensive phthalocyanine complex raw material increases the production cost of the catalyst, which is not preferable as an industrial catalyst production method.
本発明は、工業的に有利で安価なチタン酸化物を含む酸素還元触媒の製造方法を提供する。 The present invention provides an industrially advantageous and inexpensive method for producing an oxygen reduction catalyst containing titanium oxide.
本発明は以下の［１］〜［９］を含む。
［１］ チタン酸化物を含む酸素還元触媒の製造方法であって、
原料チタン酸化物とフタロシアニンとを乾式混合する混合工程（ａ）と、
前記混合工程（ａ）で得られた混合物をガス雰囲気下で７００〜１１００℃で焼成する工程（ｂ）とを含むことを特徴とする酸素還元触媒の製造方法。
［２］ 前記原料チタン酸化物は、二酸化チタン、還元型酸化チタン、ドープ型二酸化チタン及びチタン水酸化物からなる群から選ばれる少なくとも１種である前項［１］に記載の酸素還元触媒の製造方法。
［３］ 前記原料チタン酸化物が、前記混合工程（ａ）の前に、カーボン及び／またはチタン酸化物以外の金属酸化物と混合されている前項［１］または［２］に記載の酸素還元触媒の製造方法。以下、「チタン酸化物以外の金属酸化物」を単に「金属酸化物」という。
［４］ 前記カーボンが、カーボンブラック、活性炭、グラファイト化カーボンブラック、グラファイト、カーボンナノチューブ、カーボンナノファイバー及びグラフェンからなる群から選ばれる少なくとも１種である前項［３］に記載の酸素還元触媒の製造方法。
［５］ 前記金属酸化物が、ドープ型二酸化スズである前項［３］または［４］に記載の酸素還元触媒の製造方法。
［６］ 前記ガス雰囲気が、窒素ガス及び／またはアルゴンガス雰囲気である前項［１］〜［５］のいずれかに記載の酸素還元触媒の製造方法。
［７］ 前記ガス雰囲気は、酸素ガス濃度が０．５体積％以下である前項［６］に記載の酸素還元触媒の製造方法。
［８］ 前記ガス雰囲気は、水素ガス濃度が１０体積％以下のである前項［６］または［７］に記載の酸素還元触媒の製造方法。
［９］ 電極触媒として酸素還元触媒を備える燃料電池の製造方法であって、
前記酸素還元触媒を前項［１］〜［８］のいずれかの方法で得ることを特徴とする燃料電池の製造方法。
The present invention includes the following [1] to [9].
[1] A method for producing an oxygen reduction catalyst containing titanium oxide,
A mixing step (a) of dry mixing raw material titanium oxide and phthalocyanine;
And (b) calcining the mixture obtained in the mixing step (a) at 700 to 1100 ° C. in a gas atmosphere.
[2] The production of the oxygen reduction catalyst according to [1], wherein the raw material titanium oxide is at least one selected from the group consisting of titanium dioxide, reduced titanium oxide, doped titanium dioxide, and titanium hydroxide. Method.
[3] The oxygen reduction according to item [1] or [2], wherein the raw material titanium oxide is mixed with carbon and / or a metal oxide other than titanium oxide before the mixing step (a). A method for producing a catalyst. Hereinafter, “metal oxide other than titanium oxide” is simply referred to as “metal oxide”.
[4] The production of the oxygen reduction catalyst according to [3], wherein the carbon is at least one selected from the group consisting of carbon black, activated carbon, graphitized carbon black, graphite, carbon nanotube, carbon nanofiber, and graphene. Method.
[5] The method for producing an oxygen reduction catalyst according to [3] or [4] above, wherein the metal oxide is doped tin dioxide.
[6] The method for producing an oxygen reduction catalyst according to any one of [1] to [5], wherein the gas atmosphere is a nitrogen gas and / or argon gas atmosphere.
[7] The method for producing an oxygen reduction catalyst according to [6], wherein the gas atmosphere has an oxygen gas concentration of 0.5% by volume or less.
[8] The method for producing an oxygen reduction catalyst according to [6] or [7] above, wherein the gas atmosphere has a hydrogen gas concentration of 10% by volume or less.
[9] A method for producing a fuel cell comprising an oxygen reduction catalyst as an electrode catalyst,
A method for producing a fuel cell, wherein the oxygen reduction catalyst is obtained by any one of the methods [1] to [8].
本発明により、溶媒を使わずに安価なフタロシアニンとチタン酸化物を混合することで、チタン酸化物を含む酸素還元触媒を製造することができる。 According to the present invention, an oxygen reduction catalyst containing titanium oxide can be produced by mixing inexpensive phthalocyanine and titanium oxide without using a solvent.
本発明の酸素還元触媒の製造方法は、原料チタン酸化物とフタロシアニンとを乾式混合する混合工程（ａ）と、前記混合工程（ａ）で得られた混合物をガス雰囲気下で７００〜１１００℃で焼成する工程（ｂ）とを含むことを特徴とする。 The method for producing an oxygen reduction catalyst of the present invention comprises a mixing step (a) in which raw material titanium oxide and phthalocyanine are dry-mixed, and a mixture obtained in the mixing step (a) at 700 to 1100 ° C. in a gas atmosphere. And a step (b) of firing.
（原料：チタン酸化物）
本発明の工程（ａ）で用いる原料チタン酸化物は、二酸化チタン、還元型酸化チタン、ドープ型二酸化チタン及びチタン水酸化物からなる群から選ばれる少なくとも１種であることが好ましく、特に反応性と安定性の観点から、二酸化チタンまたは水酸化チタンがより好ましい。なお、これらのチタン酸化物は１種単独でもよく、２種以上併用してもよい。
(Raw material: Titanium oxide)
The raw material titanium oxide used in the step (a) of the present invention is preferably at least one selected from the group consisting of titanium dioxide, reduced titanium oxide, doped titanium dioxide and titanium hydroxide, and is particularly reactive. From the viewpoint of stability, titanium dioxide or titanium hydroxide is more preferable. These titanium oxides may be used alone or in combination of two or more.
前記二酸化チタンとしては、ルチル型二酸化チタン、アナターゼ型二酸化チタン、ブルッカイト型二酸化チタンが好ましい。反応性と安定性の観点からは、アナターゼ型二酸化チタンまたはブルッカイト型二酸化チタンがより好ましい。なお、これらの二酸化チタンは１種単独でもよく、２種以上併用してもよい。 As the titanium dioxide, rutile type titanium dioxide, anatase type titanium dioxide and brookite type titanium dioxide are preferable. From the viewpoint of reactivity and stability, anatase type titanium dioxide or brookite type titanium dioxide is more preferable. These titanium dioxides may be used alone or in combination of two or more.
前記還元型酸化チタンとしては、Ｔｉ２Ｏ３、Ｔｉ３Ｏ５，Ｔｉ４Ｏ７、Ｔｉ５Ｏ９などが挙げられる。触媒の活性と耐久性の観点からはＴｉ２Ｏ３、Ｔｉ３Ｏ５、Ｔｉ４Ｏ７が好ましく、Ｔｉ４Ｏ７がより好ましい。なお、これらの還元型酸化チタンは１種単独でもよく、２種以上併用してもよい。 Examples of the reduced titanium oxide include Ti 2 O 3 , Ti 3 O 5 , Ti 4 O 7 , and Ti 5 O 9 . From the viewpoint of the activity and durability of the catalyst, Ti 2 O 3 , Ti 3 O 5 and Ti 4 O 7 are preferable, and Ti 4 O 7 is more preferable. These reduced titanium oxides may be used alone or in combination of two or more.
前記ドープ型二酸化チタンとしては、特に限定はないが、触媒の導電性向上の観点からニオブドープ二酸化チタン（Ｎｂ−ＴｉＯ２）またはタンタルドープ二酸化チタン（Ｔａ−ＴｉＯ２）が好ましく、ニオブドープ二酸化チタンがより好ましい。なお、これらのドープ型チタン酸化物は１種単独でもよく、２種以上併用してもよい。 The doped titanium dioxide is not particularly limited, but niobium doped titanium dioxide (Nb—TiO 2 ) or tantalum doped titanium dioxide (Ta—TiO 2 ) is preferable from the viewpoint of improving the conductivity of the catalyst, and niobium doped titanium dioxide is more preferable. preferable. These doped titanium oxides may be used alone or in combination of two or more.
前記原料チタン酸化物は、焼成反応性や触媒活性の観点から前記混合工程（ａ）の前に、カーボン及び／または金属酸化物と混合されていることが好ましく、カーボン及び／または金属酸化物に担持されていることがより好ましいく、チタン酸化物担持カーボンであることがさらにより好ましい。 The raw material titanium oxide is preferably mixed with carbon and / or metal oxide before the mixing step (a) from the viewpoint of firing reactivity and catalytic activity. It is more preferable that it is supported, and even more preferable is titanium oxide-supported carbon.
前記チタン酸化物とカーボン及び／またはチタン酸化物以外の金属酸化物との混合は、混合方法や混合状態に特に制限はなく、例えば、両者の粒子同士を混合することなどの物理的混合でもよく、カーボン及び／または金属酸化物に担持させるなどの化学的混合でも良い。 The mixing of the titanium oxide and the metal oxide other than carbon and / or titanium oxide is not particularly limited in the mixing method and the mixed state, and may be physical mixing such as mixing both particles. Further, chemical mixing such as loading on carbon and / or metal oxide may be used.
前記チタン酸化物は、反応性と触媒活性を高める観点から、体積換算基準の累計５０％粒子径（以下単に「平均粒子径」と言うことがある。）が、１〜１００ｎｍを有することが好ましく、１〜５０ｎｍであることがより好ましく、１〜１０ｎｍであることが特に好ましい。 From the viewpoint of enhancing reactivity and catalytic activity, the titanium oxide preferably has a cumulative 50% particle size on a volume conversion basis (hereinafter sometimes simply referred to as “average particle size”) of 1 to 100 nm. 1 to 50 nm is more preferable, and 1 to 10 nm is particularly preferable.
前記カーボンは、例えば、カーボンブラック、活性炭、グラファイト化カーボンブラック、グラファイト、カーボンナノチューブ、カーボンナノファイバー及びグラフェンからなる群から選ばれる少なくとも１種が挙げられ、活性を高める観点から、カーボンブラック、グラファイト化カーボンブラック及びカーボンナノチューブが好ましく、カーボンブラックがさらに好ましい。なお、これらのカーボンは１種単独でもよく、２種以上併用してもよい。 Examples of the carbon include at least one selected from the group consisting of carbon black, activated carbon, graphitized carbon black, graphite, carbon nanotube, carbon nanofiber, and graphene. From the viewpoint of increasing activity, carbon black, graphitized Carbon black and carbon nanotubes are preferred, and carbon black is more preferred. These carbons may be used alone or in combination of two or more.
前記カーボンブラックは、触媒活性の観点からはＢＥＴ比表面積が１００〜２５００ｍ２／ｇが好ましく、２００〜１５００ｍ２／ｇがより好ましく、５００〜１５００ｍ２／ｇが特に好ましい。 The carbon black, BET specific surface area from the viewpoint of catalytic activity preferably 100~2500m 2 / g, more preferably 200~1500m 2 / g, 500~1500m 2 / g is particularly preferred.
前記金属酸化物は、特に限定はないが、触媒の導電性向上の観点からドープ型二酸化スズが好ましい。前記ドープ型二酸化スズとしては、特に限定はないが、触媒の導電性向上の観点からニオブドープ二酸化スズ（Ｎｂ−ＳｎＯ２）、タンタルドープ二酸化スズ（Ｔａ−ＳｎＯ２）、アンチモンドープ二酸化スズ（Ｓｂ−ＳｎＯ２）が好ましく、ニオブドープ二酸化スズ、アンチモンドープ二酸化スズがより好ましい。 The metal oxide is not particularly limited, but doped tin dioxide is preferable from the viewpoint of improving the conductivity of the catalyst. The doped tin dioxide is not particularly limited, but niobium doped tin dioxide (Nb—SnO 2 ), tantalum doped tin dioxide (Ta—SnO 2 ), antimony doped tin dioxide (Sb—) from the viewpoint of improving the conductivity of the catalyst. SnO 2 ) is preferable, and niobium-doped tin dioxide and antimony-doped tin dioxide are more preferable.
（原料：フタロシアニン）
本発明の工程（ａ）で用いるフタロシアニンは、混合工程のコスト削減や工程の簡素化のためには、粉末状であることが好ましい。
(Raw material: phthalocyanine)
The phthalocyanine used in the step (a) of the present invention is preferably in the form of a powder for cost reduction of the mixing step and simplification of the step.
（混合工程（ａ））
混合工程（ａ）でのチタン酸化物とフタロシアニンとの混合方法は、乾式、即ち溶媒を用いない方式であれば特に制限はなく、例えば、ボールミル、ロール転動ミル、ビーズミル、媒体攪拌ミル、気流粉砕機、乳鉢、自動混練乳鉢あるいはジェットミルを用いて混合することができ、混合の均一性とコスト的な観点からはボールミル、ビーズミル、自動混練乳鉢が好ましく、ボールミルまたは自動混練乳鉢がより好ましい。また、混合時間としては、通常１分〜１０時間程度で十分である。
(Mixing step (a))
The mixing method of the titanium oxide and phthalocyanine in the mixing step (a) is not particularly limited as long as it is dry, that is, a method that does not use a solvent. For example, a ball mill, a roll rolling mill, a bead mill, a medium stirring mill, an air flow They can be mixed using a pulverizer, a mortar, an automatic kneading mortar or a jet mill. From the viewpoint of uniformity of mixing and cost, a ball mill, a bead mill and an automatic kneading mortar are preferable, and a ball mill or an automatic kneading mortar is more preferable. In addition, the mixing time is usually about 1 minute to 10 hours.
（焼成工程（ｂ））
焼成工程（ｂ）では、前記混合工程（ａ）で得られた混合物をガス雰囲気下で焼成を行い、チタン酸化物を含む酸素還元触媒を得る。
(Firing step (b))
In the firing step (b), the mixture obtained in the mixing step (a) is fired in a gas atmosphere to obtain an oxygen reduction catalyst containing titanium oxide.
前記ガス雰囲気としては、窒素ガス及び／またはアルゴンガス雰囲気であることが好ましく、さらに、水素ガス及び／または酸素ガスを含むことがより好ましい。前記水素ガスの濃度は１０体積％以下であることがより好ましく、コストと焼成反応性の観点からは４体積％以下がより好ましく、１〜３体積％がさらに好ましい。また、前記酸素ガスの濃度は０．５体積％以下であることが好ましく、焼成反応性と触媒活性向上の観点から０．１体積％以下がより好ましい。前記ガス雰囲気に水素ガス及び／または酸素ガスを含ませることで、チタン酸化物の触媒活性点形成がより容易になり、反応面積を大きくすることができる。 The gas atmosphere is preferably nitrogen gas and / or argon gas atmosphere, and more preferably includes hydrogen gas and / or oxygen gas. The concentration of the hydrogen gas is more preferably 10% by volume or less, more preferably 4% by volume or less, and further preferably 1 to 3% by volume from the viewpoint of cost and firing reactivity. Further, the concentration of the oxygen gas is preferably 0.5% by volume or less, and more preferably 0.1% by volume or less from the viewpoint of improving the firing reactivity and catalytic activity. By containing hydrogen gas and / or oxygen gas in the gas atmosphere, formation of catalytic active sites of titanium oxide becomes easier and the reaction area can be increased.
前記焼成の温度は、７００〜１１００℃であり、好ましくは８００〜１０００℃であり、より好ましくは８００〜１０００℃である。焼成処理温度が前記温度範囲よりも高いと、得られる酸素還元触媒の粒子相互間においての焼結、粒子成長が起こり、結晶構造の変化や触媒の比表面積が小さくなるために、触媒性能が劣る場合がある。一方、焼成温度が上記温度範囲よりも低いと、高い触媒活性を有する酸素還元触媒を得ることが困難になる。 The calcination temperature is 700 to 1100 ° C, preferably 800 to 1000 ° C, and more preferably 800 to 1000 ° C. When the calcination temperature is higher than the above temperature range, sintering and particle growth occur between the particles of the obtained oxygen reduction catalyst, and the crystal structure changes and the specific surface area of the catalyst becomes small, resulting in poor catalyst performance. There is a case. On the other hand, when the calcination temperature is lower than the above temperature range, it is difficult to obtain an oxygen reduction catalyst having high catalytic activity.
前記焼成の時間は、好ましくは１０分〜５時間であり、より好ましくは１時間〜３時間である。焼成時間が前記範囲内であれば、得られる酸素還元触媒の粒子相互間においての焼結、粒子成長が起こりにくく、また、結晶構造の変化や触媒の比表面積が小さくなりにくく、触媒性能を高く保てる。 The firing time is preferably 10 minutes to 5 hours, more preferably 1 hour to 3 hours. If the firing time is within the above range, sintering and particle growth between the particles of the resulting oxygen reduction catalyst are difficult to occur, and the change in crystal structure and the specific surface area of the catalyst are unlikely to be reduced, resulting in high catalyst performance. I can keep it.
（用途）
本発明の方法で得られた酸素還元触媒は、燃料電池等の電極触媒として用いることができる。前記電極触媒を有する電極（アノード及び／又はカソード）の作製は、例えば、前記酸素還元触媒をインクに加工し、前記インクを電極基体に塗布するなどし、前記電極基体表面に酸素還元触媒を含む触媒層を形成することにより、前記電極触媒を備える電極を得ることができる。
(Use)
The oxygen reduction catalyst obtained by the method of the present invention can be used as an electrode catalyst for a fuel cell or the like. The production of the electrode (anode and / or cathode) having the electrode catalyst includes, for example, processing the oxygen reduction catalyst into ink, applying the ink to the electrode substrate, and the like, and including the oxygen reduction catalyst on the surface of the electrode substrate. By forming the catalyst layer, an electrode including the electrode catalyst can be obtained.
前記電極を、カソード及び／又はアノードとして用い、前記カソードとアノードとの間に高分子電解質膜を配置し膜電極接合体を形成することができる。さらに、前記膜電極接合体を備える燃料電池を得ることができる。 The electrode can be used as a cathode and / or an anode, and a polymer electrolyte membrane can be disposed between the cathode and the anode to form a membrane electrode assembly. Furthermore, a fuel cell provided with the said membrane electrode assembly can be obtained.
［実施例１］
（１）原料チタン酸化物
ケッチェンブラック（ＥＣ６００、ライオン社製）１ｇを２−プロパノール１５０ｍＬ及びイオン交換水１５０ｍＬの混合溶液に入れ、ホモジナイザー（ＵＰ４００Ｓ、ヒールッシャ−社製）で２０分間分散させた。得られた分散液に、ブルッカイト型二酸化チタン１０質量％含有スラリー（ＮＴＢ（登録商標）−２００、昭和電工社製）を１０ｇ入れ、溶液のｐＨが３になるように０．５Ｍ硫酸水溶液で調整し、ホモジナイザーで２０分間分散させた。得られ分散液を吸引ろ過し、乾燥機で乾燥することで、原料チタン酸化物として二酸化チタン担持カーボン（以下、「チタン酸化物（１）」という。）を２．０ｇを得た。
[Example 1]
(1) Raw material titanium oxide 1 g of ketjen black (EC600, manufactured by Lion Corporation) was put into a mixed solution of 150 mL of 2-propanol and 150 mL of ion-exchanged water, and was dispersed for 20 minutes with a homogenizer (UP400S, manufactured by Healerscher). 10 g of a slurry containing 10% by mass of brookite type titanium dioxide (NTB (registered trademark) -200, manufactured by Showa Denko KK) is added to the obtained dispersion, and adjusted with a 0.5 M sulfuric acid aqueous solution so that the pH of the solution is 3. And dispersed with a homogenizer for 20 minutes. The obtained dispersion was subjected to suction filtration and dried with a drier to obtain 2.0 g of titanium dioxide-supporting carbon (hereinafter referred to as “titanium oxide (1)”) as a raw material titanium oxide.
（２）混合工程
チタン酸化物（１）２．０ｇ（Ｔｉ：１２．５ｍｍｏｌ）とフタロシアニン（和光純薬工業社製）１．３２８ｇ（１２．５ｍｍｏｌ）を乳鉢で均一に混合し、混合物（１）を得た。
(2) Mixing step Titanium oxide (1) 2.0 g (Ti: 12.5 mmol) and phthalocyanine (Wako Pure Chemical Industries, Ltd.) 1.328 g (12.5 mmol) are uniformly mixed in a mortar to obtain a mixture (1 )
（３）焼成工程
石英管状炉を用いて、混合物（１）を酸素ガス０．０５体積％及び水素ガス２体積％含有窒素ガス（ガス流量３００ｍＬ／分）の雰囲気下で昇温温度１０℃／分で９００℃まで昇温し、３時間焼成を行うことで、酸素還元触媒（以下、「触媒（１）」という。）を得た。
(3) Firing step Using a quartz tube furnace, the mixture (1) is heated at a temperature of 10 ° C./temperature in an atmosphere of nitrogen gas (
（４）電気化学測定
（触媒電極作製）
得られた触媒の酸素還元活性測定は次のように行った。触媒（１）１５ｍｇ、２−プロパノール１．０ｍＬ、イオン交換水１．０ｍＬ、及び、５％ナフィオン水溶液（ＮＡＦＩＯＮ（登録商標）、和光純薬社製）６２μＬを混合した溶液に超音波を照射して攪拌し、懸濁した。この混合物２０μＬをグラッシ―カーボン電極（東海カーボン社製、直径：５．２ｍｍ）に塗布し、７０℃で１時間乾燥し、触媒活性測定の触媒電極を得た。
(4) Electrochemical measurement (catalyst electrode production)
The oxygen reduction activity of the obtained catalyst was measured as follows. Ultrasonic was applied to a solution in which 15 mg of catalyst (1), 1.0 mL of 2-propanol, 1.0 mL of ion-exchanged water, and 62 μL of 5% Nafion aqueous solution (NAFION (registered trademark), manufactured by Wako Pure Chemical Industries, Ltd.) were mixed. Stirred and suspended. 20 μL of this mixture was applied to a glassy carbon electrode (manufactured by Tokai Carbon Co., Ltd., diameter: 5.2 mm) and dried at 70 ° C. for 1 hour to obtain a catalyst electrode for measuring catalytic activity.
（触媒活性測定）
触媒（１）の酸素還元活性触媒能の電気化学評価は、次のように行った。作製した触媒電極を、酸素雰囲気及び窒素雰囲気で、０．５Ｍ硫酸水溶液中、３０℃、５ｍＶ／秒で電位走査速度を分極し、電流―電位曲線を測定した。また、酸素雰囲気で分極してない状態の自然電位（開回路電位）を得た。その際、同濃度の硫酸水溶液中での可逆水素電極を参照電極とした。
(Catalyst activity measurement)
The electrochemical evaluation of the oxygen reduction activity catalytic ability of the catalyst (1) was performed as follows. The produced catalyst electrode was polarized in a 0.5 M sulfuric acid aqueous solution at 30 ° C. and 5 mV / sec in an oxygen atmosphere and a nitrogen atmosphere, and a current-potential curve was measured. In addition, a natural potential (open circuit potential) that was not polarized in an oxygen atmosphere was obtained. At that time, a reversible hydrogen electrode in an aqueous sulfuric acid solution having the same concentration was used as a reference electrode.
前記酸素ガス雰囲気での電流―電位曲線から窒素ガス雰囲気での電流―電位曲線を引いた電流―電位曲線（１）を図１に示した。また、電流―電位曲線（１）から求めた１０μＡでの電極電位と酸素ガス雰囲気での自然電位を用いて、触媒（１）の酸素還元触媒能を評価し、表１に示した。なお、触媒（１）だけでなく、後述する実施例及び比較例で得られた触媒（２）〜（８）についても、同様に触媒活性測定を行い、結果を図２〜図８及び表１に示した。 FIG. 1 shows a current-potential curve (1) obtained by subtracting a current-potential curve in a nitrogen gas atmosphere from the current-potential curve in the oxygen gas atmosphere. Further, using the electrode potential at 10 μA obtained from the current-potential curve (1) and the natural potential in an oxygen gas atmosphere, the oxygen reduction catalytic ability of the catalyst (1) was evaluated and shown in Table 1. In addition, not only the catalyst (1) but also the catalysts (2) to (8) obtained in Examples and Comparative Examples described later, the catalytic activity was measured in the same manner, and the results are shown in FIGS. It was shown to.
［実施例２〜３］
実施例１と同様に行い酸素還元触媒（以下、実施例２で得たものを「触媒（２）」、実施例３で得たものを「触媒（３）」という。）を得た。ただし、焼成条件を表１の通りとした。
[Examples 2-3]
An oxygen reduction catalyst (hereinafter referred to as “catalyst (2)” obtained in Example 2 and “catalyst (3)” obtained in Example 3) was obtained in the same manner as in Example 1. However, the firing conditions were as shown in Table 1.
［実施例４］
ブルッカイト型二酸化チタン１０質量％含有スラリー（ＮＴＢ−２００、昭和電工製）１０ｇから溶媒を除去し、二酸化チタンのチタン酸化物（２）１．０ｇを得た。得られたチタン酸化物（２）１．０ｇ（Ｔｉ：１２．５ｍｍｏｌ）とフタロシアニン（和光純薬工業製）１．３２８ｇ（１２．５ｍｍｏｌ）とを乳鉢で均一に混合し、混合物（２）を得た。混合物（２）を実施例１と同様に焼成して焼成物を得、得られた焼成物１．０ｇとケッチェングラック１．０ｇを乳鉢で混合して、酸素還元触媒（以下、「触媒（４）」という。）を得た。
[Example 4]
The solvent was removed from 10 g of brookite-type titanium dioxide-containing slurry (NTB-200, manufactured by Showa Denko) to obtain 1.0 g of titanium dioxide titanium oxide (2). 1.0 g (Ti: 12.5 mmol) of the obtained titanium oxide (2) and 1.328 g (12.5 mmol) of phthalocyanine (manufactured by Wako Pure Chemical Industries, Ltd.) were uniformly mixed in a mortar, and the mixture (2) was Obtained. The mixture (2) was calcined in the same manner as in Example 1 to obtain a calcined product, and 1.0 g of the obtained calcined product and 1.0 g of ketchung rack were mixed in a mortar to prepare an oxygen reduction catalyst (hereinafter referred to as “catalyst ( 4) ".
［実施例５］
ケッチェンブラック（ＥＣ６００、ライオン社製）１ｇを２−プロパノール１５０ｍＬ及びイオン交換水１５０ｍＬの混合溶液に入れ、ホモジナイザー（ＵＰ４００Ｓ、ヒールッシャ−社製）で２０分間分散させた。得られた分散液にチタンテトライソプロポキシド（［（ＣＨ３）２ＣＨＯ］）４Ｔｉ、和光純薬社製）３．７ｍＬ（Ｔｉ：１２．５ｍｍｏｌ）を滴下し、３０分間攪拌後、イオン交換水３０ｍＬ滴下し、さらに６０分間攪拌した。得られた溶液を吸引ろ過し、乾燥機で乾燥することでチタン酸化物担持カーボン（以下、「チタン酸化物（３）」という。）２．０ｇを得た。
[Example 5]
1 g of ketjen black (EC600, manufactured by Lion Corporation) was placed in a mixed solution of 150 mL of 2-propanol and 150 mL of ion-exchanged water, and was dispersed for 20 minutes with a homogenizer (UP400S, manufactured by Healerscher). 3.7 mL (Ti: 12.5 mmol) of titanium tetraisopropoxide ([(CH 3 ) 2 CHO]) 4 Ti, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise to the resulting dispersion, and the mixture was stirred for 30 minutes. 30 mL of exchange water was added dropwise, and the mixture was further stirred for 60 minutes. The obtained solution was subjected to suction filtration and dried with a drier to obtain 2.0 g of titanium oxide-supporting carbon (hereinafter referred to as “titanium oxide (3)”).
実施例１と同様に、チタン酸化物（３）１．０ｇ（Ｔｉ：１２．５ｍｍｏｌ）とフタロシアニン（和光純薬社製）１．３２８ｇ（１２．５ｍｍｏｌ）とを乳鉢で均一に混合し、混合物（３）を得た。得られた混合物（３）を実施例１と同様に焼成し、触媒（５）を得た。 As in Example 1, 1.0 g (Ti: 12.5 mmol) of titanium oxide (3) and 1.328 g (12.5 mmol) of phthalocyanine (manufactured by Wako Pure Chemical Industries, Ltd.) were uniformly mixed in a mortar, and the mixture (3) was obtained. The obtained mixture (3) was calcined in the same manner as in Example 1 to obtain a catalyst (5).
［比較例１］
フタロシアニンを添加しなかったことを除き、実施例１と同様に行い、酸素還元触媒（以下、「触媒（６）」という。）を得た。
[Comparative Example 1]
An oxygen reduction catalyst (hereinafter referred to as “catalyst (6)”) was obtained in the same manner as in Example 1 except that phthalocyanine was not added.
［比較例２］
実施例４に記載のチタン酸化物（２）１．０ｇとケッチェンブラック１．０ｇとを乳鉢で混合して、チタン酸化物を含む組成物（以下、「触媒（７）」という。）を得た。
[Comparative Example 2]
1.0 g of titanium oxide (2) described in Example 4 and 1.0 g of ketjen black were mixed in a mortar to prepare a composition containing titanium oxide (hereinafter referred to as “catalyst (7)”). Obtained.
［比較例３］
フタロシアニンを添加しなかったことを除き、実施例５と同様に行い、酸素還元触媒（以下、「触媒（８）」という。）を得た。
[Comparative Example 3]
An oxygen reduction catalyst (hereinafter referred to as “catalyst (8)”) was obtained in the same manner as in Example 5 except that phthalocyanine was not added.
表１に示すように、実施例１〜５で得られた触媒（１）〜（５）は酸素還元能を有し、比較例で得られた触媒に比べ高い電極電位と自然電位を示した。 As shown in Table 1, the catalysts (1) to (5) obtained in Examples 1 to 5 had oxygen reducing ability, and showed higher electrode potential and natural potential than the catalysts obtained in Comparative Examples. .
＜産業上の利用可能性＞
本発明の製造方法により工業的に有利で安価なチタン酸化物を含む酸素還元触媒を提供できるので、例えば、燃料電池自動車用電源、家庭用コージェネレーション電源など多用途に利用できる。
<Industrial applicability>
Since the production method of the present invention can provide an industrially advantageous and inexpensive oxygen reduction catalyst containing titanium oxide, it can be used for various purposes such as a power source for fuel cell automobiles and a household cogeneration power source.
Claims (9)
原料チタン酸化物とフタロシアニンとを乾式混合する混合工程（ａ）と、
前記混合工程（ａ）で得られた混合物をガス雰囲気下で７００〜１１００℃で焼成する工程（ｂ）とを含むことを特徴とする酸素還元触媒の製造方法。 A method for producing an oxygen reduction catalyst containing titanium oxide,
A mixing step (a) of dry mixing raw material titanium oxide and phthalocyanine;
And (b) calcining the mixture obtained in the mixing step (a) at 700 to 1100 ° C. in a gas atmosphere.
前記酸素還元触媒を請求項１〜８のいずれかの方法で得ることを特徴とする燃料電池の製造方法。
A method for producing a fuel cell comprising an oxygen reduction catalyst as an electrode catalyst,
A method for producing a fuel cell, wherein the oxygen reduction catalyst is obtained by the method according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016096213A JP6634340B2 (en) | 2016-05-12 | 2016-05-12 | Method for producing oxygen reduction catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016096213A JP6634340B2 (en) | 2016-05-12 | 2016-05-12 | Method for producing oxygen reduction catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2017202463A true JP2017202463A (en) | 2017-11-16 |
| JP6634340B2 JP6634340B2 (en) | 2020-01-22 |
Family
ID=60321773
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2016096213A Expired - Fee Related JP6634340B2 (en) | 2016-05-12 | 2016-05-12 | Method for producing oxygen reduction catalyst |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6634340B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817992A (en) * | 2019-01-12 | 2019-05-28 | 袁玲燕 | A kind of preparation method of the dedicated redox elctro-catalyst of magnesium air fuel cell |
| JP2021072263A (en) * | 2019-11-01 | 2021-05-06 | 凸版印刷株式会社 | Catalyst for fuel cells, electrode catalyst layers, membrane electrode assembly, polymer electrolyte fuel cell, production method of catalyst for fuel cells, and production method of electrode catalyst layers |
| JP2021072276A (en) * | 2019-11-01 | 2021-05-06 | 凸版印刷株式会社 | Catalyst for fuel cells, electrode catalyst layers, membrane electrode assembly, polymer electrolyte fuel cell, production method of catalyst for fuel cells, and production method of electrode catalyst layers |
| JP2021141041A (en) * | 2020-03-05 | 2021-09-16 | 大日精化工業株式会社 | Oxide-based electrode catalyst and polymer electrolyte fuel cell |
-
2016
- 2016-05-12 JP JP2016096213A patent/JP6634340B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109817992A (en) * | 2019-01-12 | 2019-05-28 | 袁玲燕 | A kind of preparation method of the dedicated redox elctro-catalyst of magnesium air fuel cell |
| JP2021072263A (en) * | 2019-11-01 | 2021-05-06 | 凸版印刷株式会社 | Catalyst for fuel cells, electrode catalyst layers, membrane electrode assembly, polymer electrolyte fuel cell, production method of catalyst for fuel cells, and production method of electrode catalyst layers |
| JP2021072276A (en) * | 2019-11-01 | 2021-05-06 | 凸版印刷株式会社 | Catalyst for fuel cells, electrode catalyst layers, membrane electrode assembly, polymer electrolyte fuel cell, production method of catalyst for fuel cells, and production method of electrode catalyst layers |
| JP7360129B2 (en) | 2019-11-01 | 2023-10-18 | Ｔｏｐｐａｎホールディングス株式会社 | Fuel cell catalyst, electrode catalyst layer, membrane electrode assembly, polymer electrolyte fuel cell, method for manufacturing fuel cell catalyst, and method for manufacturing electrode catalyst layer |
| JP2021141041A (en) * | 2020-03-05 | 2021-09-16 | 大日精化工業株式会社 | Oxide-based electrode catalyst and polymer electrolyte fuel cell |
| JP7418753B2 (en) | 2020-03-05 | 2024-01-22 | 大日精化工業株式会社 | Oxide-based electrode catalyst and polymer electrolyte fuel cell |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6634340B2 (en) | 2020-01-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Du et al. | Pt@ Nb-TiO2 catalyst membranes fabricated by electrospinning and atomic layer deposition | |
| JP5254975B2 (en) | Metal oxide electrode catalyst and use thereof, and method for producing metal oxide electrode catalyst | |
| Li et al. | Co9S8-porous carbon spheres as bifunctional electrocatalysts with high activity and stability for oxygen reduction and evolution reactions | |
| Fan et al. | Pt/TiO2− C with hetero interfaces as enhanced catalyst for methanol electrooxidation | |
| Savych et al. | On the effect of non-carbon nanostructured supports on the stability of Pt nanoparticles during voltage cycling: a study of TiO2 nanofibres | |
| Bauer et al. | Improved stability of mesoporous carbon fuel cell catalyst support through incorporation of TiO2 | |
| JP5474250B2 (en) | Electrode catalyst layer, membrane electrode assembly, and fuel cell | |
| JP6634340B2 (en) | Method for producing oxygen reduction catalyst | |
| CA2715150A1 (en) | High surface area graphitized carbon and processes for making same | |
| JP5144244B2 (en) | Electrocatalyst and use thereof, and method for producing electrode catalyst | |
| CN112458495B (en) | Electrocatalyst of ruthenium-based transition metal oxide solid solution and preparation method and application thereof | |
| WO2015083383A1 (en) | Electrode catalyst for water electrolysis, and water electrolysis device using the same | |
| JP6634339B2 (en) | Oxygen reduction catalyst and method for producing the same | |
| Zheng et al. | Microstructure effect of carbon nanofiber on electrocatalytic oxygen reduction reaction | |
| Huynh et al. | High conductivity of novel Ti0. 9Ir0. 1O2 support for Pt as a promising catalyst for low-temperature fuel cell applications | |
| Sun et al. | Synthesis of Nitrogen-doped Niobium Dioxide and its co-catalytic effect towards the electrocatalysis of oxygen reduction on platinum | |
| JP6387213B1 (en) | Oxygen reduction catalyst | |
| Jung et al. | Induced changes of Pt/C in activity and durability through heat-treatment for oxygen reduction reaction in acidic medium | |
| JP2019169289A (en) | Air electrode catalyst for fuel cell, manufacturing method of the same, and fuel cell using fuel cell air electrode catalyst | |
| Kumar et al. | Electro-oxidation of formic acid on composites from polycarbazole and WO3 | |
| JP6331580B2 (en) | Electrode catalyst, catalyst layer precursor, catalyst layer, and fuel cell | |
| JP6659916B2 (en) | Oxygen reduction catalyst | |
| JP5650254B2 (en) | Oxygen reduction catalyst | |
| Mohamed et al. | A template-assisted method for synthesizing TiO2 nanoparticles and Ni/TiO2 nanocomposites for urea electrooxidation | |
| JP5417618B2 (en) | Method for producing metal oxide-supported carbon material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20160808 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20190205 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20191023 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20191203 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20191216 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6634340 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| LAPS | Cancellation because of no payment of annual fees |