JP2018023929A - Platinum catalyst, fuel cell electrode and fuel cell - Google Patents
Platinum catalyst, fuel cell electrode and fuel cell Download PDFInfo
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- JP2018023929A JP2018023929A JP2016157206A JP2016157206A JP2018023929A JP 2018023929 A JP2018023929 A JP 2018023929A JP 2016157206 A JP2016157206 A JP 2016157206A JP 2016157206 A JP2016157206 A JP 2016157206A JP 2018023929 A JP2018023929 A JP 2018023929A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 45
- 239000000446 fuel Substances 0.000 title claims abstract description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000009835 boiling Methods 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical group [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 7
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 5
- 238000001354 calcination Methods 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 13
- 150000002739 metals Chemical class 0.000 abstract description 2
- 239000012621 metal-organic framework Substances 0.000 description 16
- 239000013259 porous coordination polymer Substances 0.000 description 16
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- 238000010304 firing Methods 0.000 description 6
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- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
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- 230000003213 activating effect Effects 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 229920002313 fluoropolymer Polymers 0.000 description 2
- 239000004811 fluoropolymer Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
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- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
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- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- LMQAPFFRSLSOFH-UHFFFAOYSA-N 1h-pyrazole;2h-triazole Chemical compound C=1C=NNC=1.C1=CNN=N1 LMQAPFFRSLSOFH-UHFFFAOYSA-N 0.000 description 1
- QMEQBOSUJUOXMX-UHFFFAOYSA-N 2h-oxadiazine Chemical compound N1OC=CC=N1 QMEQBOSUJUOXMX-UHFFFAOYSA-N 0.000 description 1
- BCHZICNRHXRCHY-UHFFFAOYSA-N 2h-oxazine Chemical compound N1OC=CC=C1 BCHZICNRHXRCHY-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 125000004432 carbon atom Chemical group C* 0.000 description 1
- QKYHAGLNCAABEZ-UHFFFAOYSA-N carboxy(phenyl)carbamic acid Chemical compound OC(=O)N(C(O)=O)C1=CC=CC=C1 QKYHAGLNCAABEZ-UHFFFAOYSA-N 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 238000007731 hot pressing Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- QUMITRDILMWWBC-UHFFFAOYSA-N nitroterephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C([N+]([O-])=O)=C1 QUMITRDILMWWBC-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- CQDAMYNQINDRQC-UHFFFAOYSA-N oxatriazole Chemical compound C1=NN=NO1 CQDAMYNQINDRQC-UHFFFAOYSA-N 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- VLLMWSRANPNYQX-UHFFFAOYSA-N thiadiazole Chemical compound C1=CSN=N1.C1=CSN=N1 VLLMWSRANPNYQX-UHFFFAOYSA-N 0.000 description 1
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 description 1
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
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- Catalysts (AREA)
- Inert Electrodes (AREA)
- Fuel Cell (AREA)
Abstract
Description
本発明は、窒素ドープカーボンに白金を担持した白金触媒及びそれを用いた燃料電池に関する。 The present invention relates to a platinum catalyst in which platinum is supported on nitrogen-doped carbon and a fuel cell using the same.
固体高分子形燃料電池（以下ＰＥＦＣと称す）の電極触媒として白金担持カーボンが現在の主流であるが、今後のＰＥＦＣの本格的な普及に向け、貴金属である白金以外の金属を用いた非白金触媒の開発あるいは耐久性の向上や白金触媒の高活性化による省白金による低コスト化が急務である。 Platinum-supported carbon is currently the mainstream as an electrocatalyst for polymer electrolyte fuel cells (hereinafter referred to as PEFC), but non-platinum using metals other than platinum, which is a precious metal, for the full-scale spread of PEFC in the future. There is an urgent need to reduce the cost of platinum development by improving the durability of the catalyst or increasing the platinum catalyst activation.
また、白金触媒を高活性化するために担持する炭素材料の開発も進められている。
白金触媒を高活性化するために担持する炭素材料に関する先行技術の例示として特許文献１及び特許文献２を示す。
In addition, development of a carbon material to be supported for highly activating the platinum catalyst is also in progress.
Patent Document 1 and Patent Document 2 are shown as examples of prior art relating to a carbon material supported to activate a platinum catalyst.
本発明の目的は、触媒担持体の製造原料として多孔性金属錯体（以下、適宜「ＰＣＰ／ＭＯＦ」と称する場合がある。）を焼成して得られる窒素ドープカーボン（以下、適宜「ＮＤＣ」と称する場合がある。）を利用することにより、高耐久性かつ高活性な触媒の製造を可能にすることにある。 An object of the present invention is to form nitrogen-doped carbon (hereinafter referred to as “NDC” as appropriate) obtained by firing a porous metal complex (hereinafter sometimes referred to as “PCP / MOF” as appropriate) as a raw material for producing a catalyst carrier. In other words, it is possible to produce a highly durable and highly active catalyst.
本発明者らは、上記問題を解決すべく鋭意検討した結果、低沸点金属を構成要素とするＰＣＰ／ＭＯＦを焼成することにより得られるＮＤＣに少量の白金を担持した白金触媒が高活性であることを見出したことから、本発明に到達した。 As a result of intensive studies to solve the above problems, the inventors of the present invention have a high activity of a platinum catalyst in which a small amount of platinum is supported on NDC obtained by firing PCP / MOF containing a low boiling point metal as a constituent element. As a result, the present invention has been reached.
すなわち、本発明は、以下の技術的手段から構成される。
〔１〕 低沸点金属を含む多孔性金属錯体（ＰＣＰ／ＭＯＦ）を焼成した窒素ドープカーボンに白金を担持した白金触媒。
〔２〕 前記低沸点金属が亜鉛である前記〔１〕に記載の白金触媒。
〔３〕 前記窒素ドープカーボンの窒素含有量が２ｗｔ％〜２０ｗｔ％である前記〔１〕又は前記〔２〕に記載の白金触媒。
〔４〕 前記窒素ドープカーボンの比表面積が５００ｍ２／ｇ〜２０００ｍ２／ｇである前記〔１〕〜〔３〕のいずれかに記載の白金触媒。
〔５〕 前記〔１〕〜〔４〕のいずれかに記載の白金触媒を含む燃料電池電極。
〔６〕 前記〔５〕に記載の燃料電池電極を含む燃料電池。
That is, the present invention comprises the following technical means.
[1] A platinum catalyst in which platinum is supported on nitrogen-doped carbon obtained by calcining a porous metal complex (PCP / MOF) containing a low boiling point metal.
[2] The platinum catalyst according to [1], wherein the low boiling point metal is zinc.
[3] The platinum catalyst according to [1] or [2], wherein the nitrogen content of the nitrogen-doped carbon is 2 wt% to 20 wt%.
[4] a platinum catalyst according to any of the specific surface area of the nitrogen-doped carbon is 500m 2 / g~2000m 2 / g [1] to [3].
[5] A fuel cell electrode comprising the platinum catalyst according to any one of [1] to [4].
[6] A fuel cell comprising the fuel cell electrode according to [5].
本発明の触媒担持体の製造法によれば、低沸点金属により構成されるＰＣＰ／ＭＯＦを製造原料として用いるため原料由来の金属をほとんど含まず、大きな比表面積を有するＮＤＣである触媒担持体を得ることができ、少量の白金担持により高活性な白金触媒を得ることができる。加えて、製造原料であるＰＣＰ／ＭＯＦ由来の金属が含まれないため、焼成条件を自由に設定できる優位性を有する。すなわち、原料として用いるＰＣＰ／ＭＯＦの有機化合物リンカーの変更や焼成温度の調節により、得られるＮＤＣ中の含窒素量や結晶化度をコントロールすることが可能となる。 According to the method for producing a catalyst carrier of the present invention, since a PCP / MOF composed of a low boiling point metal is used as a production raw material, a catalyst carrier that is an NDC having a large specific surface area and containing almost no metal derived from the raw material is obtained. A highly active platinum catalyst can be obtained by loading a small amount of platinum. In addition, since a metal derived from PCP / MOF, which is a manufacturing raw material, is not included, there is an advantage that firing conditions can be set freely. That is, it is possible to control the nitrogen content and crystallinity in the obtained NDC by changing the organic compound linker of PCP / MOF used as a raw material and adjusting the firing temperature.
以下、本発明を実施するための最良の形態を説明する。
本発明におけるＮＤＣは、窒素原子を含有する有機化合物をリンカーとし、低沸点金属を格子点とするＰＣＰ／ＭＯＦを焼成することによって得られる。ＰＣＰ／ＭＯＦは、リンカーとなる有機分子と、格子点となる金属原子から構成される三次元の広がりを有する多孔性の有機金属錯体であり、本発明の実施には、市販品あるいは合成品のいずれのＰＣＰ／ＭＯＦも用いることができる。
Hereinafter, the best mode for carrying out the present invention will be described.
NDC in the present invention can be obtained by firing PCP / MOF having an organic compound containing a nitrogen atom as a linker and a low boiling point metal as a lattice point. PCP / MOF is a porous organometallic complex having a three-dimensional extension composed of an organic molecule serving as a linker and a metal atom serving as a lattice point. Any PCP / MOF can be used.
本発明においてＮＤＣの原料として用いるＰＣＰ／ＭＯＦのリンカーである窒素原子を含有する有機化合物としては、窒素原子を含む複素環化合物であれば特に制限を受けないが、例えば、イミダゾール、ピラゾールトリアゾール、チアゾール、オキサゾール、オキサジアゾール、オキサトリアゾール、チアジアゾール、ピリジン、ピラジン、トリアジン、オキサジン、オキサジアジン、ジカルボキシルアニリン、２−ニトロテレフタル酸、トリフェニルアミン、およびそれら構造を含む誘導体を用いることができる。 The organic compound containing a nitrogen atom which is a PCP / MOF linker used as a raw material for NDC in the present invention is not particularly limited as long as it is a heterocyclic compound containing a nitrogen atom. For example, imidazole, pyrazole triazole, thiazole , Oxazole, oxadiazole, oxatriazole, thiadiazole, pyridine, pyrazine, triazine, oxazine, oxadiazine, dicarboxylaniline, 2-nitroterephthalic acid, triphenylamine, and derivatives containing these structures can be used.
本発明においてＮＤＣの原料として用いることのできるＰＣＰ／ＭＯＦとしては、１０００℃程度である程度の蒸気圧が得られる低沸点金属を格子点とするＰＣＰ／ＭＯＦを用いることができる。例えば、ナトリウム、マグネシウム、マンガン、亜鉛、インジウムからなる群から選択される金属を格子点とするようなＰＣＰ／ＭＯＦを例示することができる。
これらの中でも、亜鉛を格子点とするＰＣＰ／ＭＯＦが数多く知られており、亜鉛を低沸点金属とするのが好ましい。
As the PCP / MOF that can be used as a raw material for NDC in the present invention, PCP / MOF having a lattice point of a low boiling point metal that can obtain a certain vapor pressure at about 1000 ° C. can be used. For example, PCP / MOF in which a metal selected from the group consisting of sodium, magnesium, manganese, zinc, and indium is used as a lattice point can be exemplified.
Among these, many PCP / MOFs having zinc as a lattice point are known, and zinc is preferably a low boiling point metal.
（ＮＤＣの製造方法）
本発明におけるＮＤＣの製造方法は、まず原料となるＰＣＰ／ＭＯＦを不活性ガス通気下、熱処理により焼成し黒鉛化する。その後、無機酸による洗浄により、焼成で生じた金属成分を除去する。その後、アンモニアガス通気下、熱処理により賦活化することで黒色粉体としてＮＤＣを得る。上記黒鉛化に用いる不活性ガスとしては、焼成温度において安定であり炭素原子を酸化しないアルゴンガス、窒素ガス、ヘリウムガスなどを例示することができる。また、金属成分の除去に用いる無機酸としては、硫酸、硝酸、塩酸あるいはそれらの混合物などの使用を例示できる。
(Manufacturing method of NDC)
In the method for producing NDC in the present invention, first, PCP / MOF as a raw material is fired and graphitized by heat treatment under aeration gas. Then, the metal component produced by baking is removed by washing with an inorganic acid. Then, NDC is obtained as black powder by activating by heat treatment under ammonia gas flow. Examples of the inert gas used for the graphitization include argon gas, nitrogen gas, and helium gas that are stable at the firing temperature and do not oxidize carbon atoms. Examples of the inorganic acid used for removing the metal component include use of sulfuric acid, nitric acid, hydrochloric acid, or a mixture thereof.
上記焼成方法により、比表面積が５００ｍ２／ｇ〜２０００ｍ２／ｇであり、窒素含有量が２ｗｔ％〜２０ｗｔ％であるＮＤＣが通常得られる。後述する炭素材料表面への白金触媒担持の観点から、白金ナノ粒子の高分散な担持のため比表面積は５００ｍ２／ｇ以上であることが好ましく、比表面積が２０００ｍ２／ｇ以上になると炭素材料の電子伝導性が低下してくるため触媒担体として不適当である。また、窒素含有量に関しては、担持する白金触媒との相互作用の観点から２ｗｔ％以上含んでいることが好ましく、黒鉛化することで電気化学的な酸化条件における安定性を確保するという観点から２０ｗｔ％以下程度の窒素含有量であることが好ましい。 By the calcination process, the specific surface area of 500m 2 / g~2000m 2 / g, a nitrogen content of NDC is obtained usually in the 2 wt% 20 wt%. From the viewpoint of supporting a platinum catalyst on the surface of the carbon material, which will be described later, the specific surface area is preferably 500 m 2 / g or more for high dispersion of platinum nanoparticles, and when the specific surface area is 2000 m 2 / g or more, the carbon material This is unsuitable as a catalyst carrier because the electron conductivity of the catalyst is lowered. Further, the nitrogen content is preferably 2 wt% or more from the viewpoint of interaction with the supported platinum catalyst, and 20 wt% from the viewpoint of ensuring stability under electrochemical oxidation conditions by graphitization. The nitrogen content is preferably about% or less.
（ＮＤＣへの白金担持法）
本発明においてＮＤＣへの白金担持はいずれの担持方法を用いても良いが、一例をあげるとポリオール法により実施することができる。具体的には、上記焼成により得られるＮＤＣ粉末をエチレングリコールに加え、超音波処理により分散液を得る。その後、所定量の白金前駆体を加え、続いて還元剤を加えることで、系中で白金ナノ粒子を発生させＮＤＣ表面に担持させる。白金前駆体として用いる化合物としては、塩化白金酸や種々の二価の白金錯体などを例示することができる。得られた白金担持触媒の白金担持量は熱重量分析やＩＣＰ−ＭＳ分析により求めることができる。
(Platinum loading method on NDC)
In the present invention, any supporting method may be used for supporting platinum on NDC, but as an example, it can be performed by a polyol method. Specifically, NDC powder obtained by the above baking is added to ethylene glycol, and a dispersion is obtained by ultrasonic treatment. Thereafter, a predetermined amount of platinum precursor is added, and subsequently a reducing agent is added, thereby generating platinum nanoparticles in the system and supporting them on the NDC surface. Examples of the compound used as the platinum precursor include chloroplatinic acid and various divalent platinum complexes. The platinum carrying amount of the obtained platinum carrying catalyst can be determined by thermogravimetric analysis or ICP-MS analysis.
（触媒インクの調製）
本発明における白金担持触媒の活性評価法を例示する。上記製造方法により得られる粉末を用い触媒インクを調製する。触媒インクは、白金担持触媒と高分子電解質とを任意の溶媒に分散することで調製される。高分子電解質としてはプロトン伝導性のフッ素系高分子電解質あるいは炭化水素系高分子電解質を用いることができる。また、分散溶媒としては、メタノール、エタノールなどの低級アルコールや、アセトン、メチルエチルケトン、シクロヘキサノンなどのケトン類、あるいはテトラヒドロフラン、ジオキサン、ジブチルエーテルなどのエーテル類、その他ジメチルホルムアミド、ジメチルアセトアミド、エチレングリコールなどの極性溶媒などの各種有機溶媒を用いることができる。これらは単独、あるいは二種以上の混合溶媒としても用いることができる。また、触媒インクの発火性の危険を低減するために、水を混合溶媒として用いることもできる。
(Preparation of catalyst ink)
The activity evaluation method of the platinum supported catalyst in this invention is illustrated. A catalyst ink is prepared using the powder obtained by the above production method. The catalyst ink is prepared by dispersing a platinum-supported catalyst and a polymer electrolyte in an arbitrary solvent. As the polymer electrolyte, a proton-conductive fluorine-based polymer electrolyte or a hydrocarbon-based polymer electrolyte can be used. Dispersing solvents include lower alcohols such as methanol and ethanol, ketones such as acetone, methyl ethyl ketone, and cyclohexanone, or ethers such as tetrahydrofuran, dioxane, and dibutyl ether, and polar substances such as dimethylformamide, dimethylacetamide, and ethylene glycol. Various organic solvents such as a solvent can be used. These can be used alone or as a mixed solvent of two or more. Also, water can be used as a mixed solvent in order to reduce the risk of ignition of the catalyst ink.
（白金担持ＮＤＣ触媒の評価方法）
調製した触媒インクを所定量塗布した作用電極を用い、回転ディスク電極（ＲＤＥ）法により評価する。例えば、触媒インクをグラッシーカーボン上に塗布した電極を作用電極とし、酸素飽和の過塩素酸電解質溶液中で回転電極装置を用いて活性を評価することができる。
(Evaluation method of platinum-supported NDC catalyst)
Using a working electrode coated with a predetermined amount of the prepared catalyst ink, evaluation is performed by a rotating disk electrode (RDE) method. For example, the activity can be evaluated using a rotating electrode apparatus in an oxygen-saturated perchloric acid electrolyte solution using an electrode obtained by applying catalyst ink on glassy carbon as a working electrode.
（燃料電池電極の作製）
本発明における燃料電池電極の作製について記載する。本発明において得られる触媒粉末を用い、上述の調製法により触媒インクを調製する。得られた触媒インクを固体高分子電解質膜に塗布することでカソード（空気極）触媒層を作製する。用いる固体高分子膜としては、例えば市販のフッ素系高分子電解質であるＮａｆｉｏｎ（登録商標）が挙げられる。塗布法としては、スプレー塗布装置を用いる方法、あるいはバーコーターを用いる方法のいずれによっても可能である。カソード触媒塗布面の対面に、アノード（燃料極）触媒として任意の触媒を用いた触媒インクを塗布することで触媒層が両面塗布された固体高分子電解質膜を得る。得られた触媒塗布電解質膜の両側をガス拡散層で挟むように積層し、ホットプレスにより密着させることで膜電極複合体：ＭＥＡ（ｍｅｍｂｒａｎｅ ｅｌｅｃｔｒｏｄｅ ａｓｓｅｍｂｌｙ）が作製される。得られるＭＥＡを燃料電池電極とし、所定のセルに組み付けることでＰＥＦＣが完成する。
(Fabrication of fuel cell electrode)
The production of the fuel cell electrode in the present invention will be described. Using the catalyst powder obtained in the present invention, a catalyst ink is prepared by the above-described preparation method. The obtained catalyst ink is applied to a solid polymer electrolyte membrane to produce a cathode (air electrode) catalyst layer. Examples of the solid polymer membrane used include Nafion (registered trademark), which is a commercially available fluoropolymer electrolyte. As a coating method, either a method using a spray coating device or a method using a bar coater is possible. By applying a catalyst ink using an arbitrary catalyst as an anode (fuel electrode) catalyst on the opposite side of the cathode catalyst application surface, a solid polymer electrolyte membrane having both catalyst layers applied is obtained. By laminating both sides of the obtained catalyst-coated electrolyte membrane so as to be sandwiched between gas diffusion layers and bringing them into close contact with each other by hot pressing, a membrane electrode assembly: MEA (membrane electrode assembly) is produced. The obtained MEA is used as a fuel cell electrode and assembled into a predetermined cell to complete the PEFC.
以下、実施例及び比較例により本発明をさらに説明するが、本発明はこれらに限定されるものではない。 Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these.
〔実施例１〕
（ＮＤＣの製造）
市販のＰＣＰ／ＭＯＦであるＢａｓｏｌｉｔｅ（登録商標）Ｚ１２００をセラミックボートに入れ石英管内に静置し、高純度アルゴンガス通気下、電気管状炉で１０５０℃まで昇温し、１時間加熱した。その後、アルゴンガス通気下、自然放冷により室温まで冷却し黒色粉体を得た。得られた粉体を１Ｍ Ｈ２ＳＯ４水溶液に加え一晩撹拌後、不溶物をろ取し、濾液が中性になるまでイオン交換水により洗浄した。洗浄後の粉体を、再びセラミックボートに入れ石英管内に静置し、アンモニアガス通気下、電気管状炉で９５０℃まで昇温し、１５分間加熱した。放冷後、黒色のＮＤＣを得た。得られたＮＤＣは、窒素ガス等温吸着線より比表面積が９８９ｍ２／ｇであり、元素分析より窒素含有量が２．５１ｗｔ％、亜鉛含有量が０．２７ｗｔ％であった。
[Example 1]
(Manufacturing NDC)
A commercially available PCP / MOF, Basolite (registered trademark) Z1200, was placed in a ceramic boat and allowed to stand in a quartz tube, and heated to 1050 ° C. in an electric tubular furnace under high-purity argon gas ventilation, and heated for 1 hour. Then, it cooled to room temperature by natural cooling under argon gas ventilation, and obtained black powder. The obtained powder was added to a 1M H 2 SO 4 aqueous solution and stirred overnight, and then insoluble matters were collected by filtration and washed with ion-exchanged water until the filtrate became neutral. The powder after washing was again placed in a ceramic boat and allowed to stand in a quartz tube. The temperature was raised to 950 ° C. in an electric tubular furnace under ammonia gas flow and heated for 15 minutes. After cooling, black NDC was obtained. The obtained NDC had a specific surface area of 989 m 2 / g from the nitrogen gas isotherm adsorption line, and the elemental analysis showed a nitrogen content of 2.51 wt% and a zinc content of 0.27 wt%.
〔実施例２〕
（白金触媒の製造）
実施例１で得られたＮＤＣ粉末４ｍｇを、エチレングリコールに加え、超音波処理により分散液とした。２５ｍＭに調整したＨ２ＰｔＣｌ６エチレングリコール溶液を０．７０ｍＬ加え撹拌後、１ＭのＮａＯＨのエチレングリコール溶液にてｐＨ１０に調整した。フラスコに調製液を移し、還流管を取り付け後、１４０℃で３時間加熱還流した。反応後、遠心分離により不溶物を単離し、白金担持ＮＤＣ触媒を得た。得られた白金担時触媒の白金担持量を熱重量分析により求めたところ、２．８ｗｔ％の白金が担持されていることが明らかとなった。
[Example 2]
(Production of platinum catalyst)
4 mg of the NDC powder obtained in Example 1 was added to ethylene glycol, and a dispersion was obtained by ultrasonic treatment. 0.70 mL of H 2 PtCl 6 ethylene glycol solution adjusted to 25 mM was added and stirred, and then adjusted to pH 10 with 1 M NaOH ethylene glycol solution. The prepared solution was transferred to the flask, and a reflux tube was attached, followed by heating to reflux at 140 ° C. for 3 hours. After the reaction, insoluble matter was isolated by centrifugation to obtain a platinum-supported NDC catalyst. The amount of platinum supported on the obtained platinum-supported catalyst was determined by thermogravimetric analysis, and it was revealed that 2.8 wt% of platinum was supported.
〔実施例３〕
（活性評価）
実施例２で得られた白金担持ＮＤＣ触媒２ｍｇと市販のフッ素系高分子電解質である１０％Ｎａｆｉｏｎ（登録商標）５．７μＬを水：エタノール＝１：１の混合溶液２ｍＬに加え超音波処理により分散させて触媒インクを調製した。得られた触媒インクをグラッシーカーボン電極に塗布し乾燥させ活性評価を行った結果を図１に示す。
Example 3
(Activity evaluation)
2 mg of the platinum-supported NDC catalyst obtained in Example 2 and 5.7 μL of 10% Nafion (registered trademark), which is a commercially available fluoropolymer electrolyte, are added to 2 mL of a mixed solution of water: ethanol = 1: 1 by sonication. A catalyst ink was prepared by dispersing. The obtained catalyst ink was applied to a glassy carbon electrode, dried, and the results of activity evaluation were shown in FIG.
〔比較例１〕
実施例１で得られたＮＤＣ粉末２ｍｇを用い、実施例３と同様の方法で調製した触媒インクを用いて活性評価を行った結果を図１に示す。
[Comparative Example 1]
FIG. 1 shows the results of activity evaluation using 2 mg of the NDC powder obtained in Example 1 and the catalyst ink prepared by the same method as in Example 3.
〔比較例２〕
市販Ｐｔ／Ｃ触媒（田中貴金属工業株式会社製ＴＥＣ１０Ｖ３０Ｅ、担持体：ＶＵＬＣＡＮ（登録商標）ＸＣ７２、白金担持量：３０ｗｔ％）を２ｍｇ使用し、実施例３と同様の方法で調製した触媒インクを用いて活性評価を行った結果を図１に示す。
[Comparative Example 2]
Using 2 mg of a commercially available Pt / C catalyst (TEC10V30E manufactured by Tanaka Kikinzoku Kogyo Co., Ltd., support: VULCAN (registered trademark) XC72, platinum loading: 30 wt%), and using a catalyst ink prepared in the same manner as in Example 3. The results of the activity evaluation are shown in FIG.
図１に実施例３、比較例１および比較例２の酸素還元活性評価の結果を示す。
電解質溶液に０．１Ｍ過塩素酸水溶液、対極に白金コイル、参照極に硝酸銀を用い、回転数１６００ｐｐｍで回転ディスク電極（ＲＤＥ）法により評価した。
図１において、０．９Ｖでの酸素還元電流を比較すると、（比較例１）０．０３２ｍＡ／ｃｍ２、（実施例３）１．１８ｍＡ／ｃｍ２および（比較例２）１．９５ｍＡ／ｃｍ２であった。この電流値から使用した白金重量あたりの活性を比較すると、実施例３の活性が１．１７Ａ／ｍｇ、比較例２の市販触媒（ＴＥＣ１０Ｖ３０Ｅ）の活性が０．２９Ａ／ｍｇであり、約４倍の活性向上が確認された。
FIG. 1 shows the results of the oxygen reduction activity evaluation of Example 3, Comparative Example 1 and Comparative Example 2.
A 0.1M perchloric acid aqueous solution was used for the electrolyte solution, a platinum coil was used for the counter electrode, and silver nitrate was used for the reference electrode, and evaluation was performed by the rotating disk electrode (RDE) method at a rotational speed of 1600 ppm.
In FIG. 1, the oxygen reduction current at 0.9 V is compared. (Comparative Example 1) 0.032 mA / cm 2 (Example 3) 1.18 mA / cm 2 and (Comparative Example 2) 1.95 mA / cm 2 . When the activity per weight of platinum used was compared from the current value, the activity of Example 3 was 1.17 A / mg, and the activity of the commercial catalyst (TEC10V30E) of Comparative Example 2 was 0.29 A / mg, which was about 4 times. The activity improvement of was confirmed.
本発明のＮＤＣおよびそれらを担持体として使用し調製される白金担持ＮＤＣ触媒は自動車産業やコジェネレーションに代表される燃料電池の分野の電極触媒に使用できる。
The NDC catalyst of the present invention and the platinum-supported NDC catalyst prepared by using them as a support can be used as an electrode catalyst in the field of fuel cells represented by the automobile industry and cogeneration.
Claims (6)
A fuel cell comprising the fuel cell electrode according to claim 5.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing |
| CN113270599A (en) * | 2021-05-25 | 2021-08-17 | 西安交通大学 | Electrode catalyst, composite electrode and preparation process thereof |
| CN114899437A (en) * | 2022-05-27 | 2022-08-12 | 北京理工大学 | Preparation method of nitrogen-doped mesoporous carbon supported Pt fuel cell cathode catalyst |
| CN115133051A (en) * | 2022-08-10 | 2022-09-30 | 北京亿华通科技股份有限公司 | Ultralow platinum fuel cell catalyst and preparation method thereof |
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2016
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109950566A (en) * | 2019-04-15 | 2019-06-28 | 南京大学 | A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing |
| CN113270599A (en) * | 2021-05-25 | 2021-08-17 | 西安交通大学 | Electrode catalyst, composite electrode and preparation process thereof |
| CN114899437A (en) * | 2022-05-27 | 2022-08-12 | 北京理工大学 | Preparation method of nitrogen-doped mesoporous carbon supported Pt fuel cell cathode catalyst |
| CN115133051A (en) * | 2022-08-10 | 2022-09-30 | 北京亿华通科技股份有限公司 | Ultralow platinum fuel cell catalyst and preparation method thereof |
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