JP2017135061A - Method for reducing oxygen and hydrogen peroxide using metal complex, fuel cell, and power generation method - Google Patents
Method for reducing oxygen and hydrogen peroxide using metal complex, fuel cell, and power generation method Download PDFInfo
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- 239000000446 fuel Substances 0.000 title claims abstract description 92
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 238000010248 power generation Methods 0.000 title claims description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 67
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 16
- 238000006722 reduction reaction Methods 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 239000000243 solution Substances 0.000 description 15
- 239000001257 hydrogen Substances 0.000 description 14
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 238000009792 diffusion process Methods 0.000 description 9
- 239000003792 electrolyte Substances 0.000 description 9
- 238000011156 evaluation Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 229910052697 platinum Inorganic materials 0.000 description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
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- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000005518 polymer electrolyte Substances 0.000 description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052707 ruthenium Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
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- 229920000554 ionomer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- DEPMYWCZAIMWCR-UHFFFAOYSA-N nickel ruthenium Chemical compound [Ni].[Ru] DEPMYWCZAIMWCR-UHFFFAOYSA-N 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
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- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 2
- 0 CC*N(C)CI=C Chemical compound CC*N(C)CI=C 0.000 description 1
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- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
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- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 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
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Abstract
Description
本発明は、酸素と過酸化水素の両方を還元できる金属錯体に関し、特に、燃料電池用触媒として機能する金属錯体に関する。更に、該金属錯体を燃料電池用触媒に用いた燃料電池および発電方法に関する。 The present invention relates to a metal complex that can reduce both oxygen and hydrogen peroxide, and more particularly to a metal complex that functions as a catalyst for a fuel cell. Furthermore, the present invention relates to a fuel cell and a power generation method using the metal complex as a fuel cell catalyst.
水素−酸素燃料電池のカソードでは酸素を還元している。現在、カソードには白金触媒が用いられている。カソードにおける酸素の還元反応は４電子還元で水を与えるが、還元が十分でないと２電子還元を起こし過酸化水素（Ｈ２Ｏ２）を生じる。過酸化水素は燃料電池において触媒やプロトン透過膜（電解質膜）を劣化させる要因となる。 Oxygen is reduced at the cathode of the hydrogen-oxygen fuel cell. Currently, a platinum catalyst is used for the cathode. The reduction reaction of oxygen at the cathode gives water by 4-electron reduction, but if the reduction is not sufficient, 2-electron reduction occurs and hydrogen peroxide (H 2 O 2 ) is generated. Hydrogen peroxide is a factor that degrades a catalyst and a proton permeable membrane (electrolyte membrane) in a fuel cell.
酸素を還元する金属錯体は非特許文献１に報告されており、それらを用いた燃料電池は非特許文献２及び特許文献１に記載されている。そして、過酸化水素を生じない燃料電池として、錯体触媒を固定したカソードを用いた燃料電池が開発されている。
Metal complexes that reduce oxygen are reported in Non-Patent Document 1, and fuel cells using them are described in
白金は高価であり代替触媒が求められているが、白金触媒だけでは過酸化水素の発生を抑えることは困難であり、過酸化水素を効率よく還元できる電極触媒が求められている。また、金属錯体を用いた触媒は選択性が高いが、活性および安定性に問題がある。 Platinum is expensive and an alternative catalyst is required. However, it is difficult to suppress the generation of hydrogen peroxide with only a platinum catalyst, and an electrode catalyst capable of efficiently reducing hydrogen peroxide is required. Moreover, although the catalyst using a metal complex has high selectivity, there exists a problem in activity and stability.
従って、本発明は、酸素と過酸化水素の両方を還元する能力を有し、燃料電池用触媒として機能する金属錯体、およびそれをカソード電極に用いた燃料電池を提供することを目的とする。 Accordingly, an object of the present invention is to provide a metal complex that has the ability to reduce both oxygen and hydrogen peroxide and functions as a catalyst for a fuel cell, and a fuel cell using the metal complex as a cathode electrode.
本発明者らは、上記課題を検討した結果、特定の異種二核金属錯体が酸素と過酸化水素の両者を還元できることを見出し、前記触媒をカソードに固定した燃料電池を作製し、酸素ガスおよび過酸化水素のどちらを用いても燃料電池として機能することを確認した。更に、過酸化水素を含む酸素ガスを用いても電池性能は落ちないことを確認し、本発明を完成させた。 As a result of examining the above problems, the present inventors have found that a specific heterobinuclear metal complex can reduce both oxygen and hydrogen peroxide, and produced a fuel cell in which the catalyst is fixed to a cathode. It was confirmed that either hydrogen peroxide can function as a fuel cell. Furthermore, it was confirmed that the battery performance did not deteriorate even when oxygen gas containing hydrogen peroxide was used, and the present invention was completed.
すなわち、本発明は下記の通りである。
１．下記式（１）で表される金属錯体および下記式（２）で表される金属錯体を用いて、酸素および過酸化水素を還元する方法。
That is, the present invention is as follows.
1. A method of reducing oxygen and hydrogen peroxide using a metal complex represented by the following formula (1) and a metal complex represented by the following formula (2).
式（１）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。 In the formula (1), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
式（２）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。
２．過酸化水素の還元反応が、下記の工程で示される前記１に記載の方法。
（工程Ａ）上記式（２）で表される異種二核ペルオキソ錯体［Ｍ−Ｏ２］を還元し異種二核中間体［Ｍ＊］を生成する工程。
［Ｍ−Ｏ２］＋（Ｈ＋＋２ｅ−）→［Ｍ＊］＋２Ｈ２Ｏ
（工程Ｂ）過酸化水素（Ｈ２Ｏ２）に異種二核中間体［Ｍ＊］を作用させ、異種二核ペルオキソ錯体［Ｍ−Ｏ２］を再生する工程。
Ｈ２Ｏ２＋［Ｍ＊］→［Ｍ−Ｏ２］＋２Ｈ＋
３．下記式（２）で表される異種二核ペルオキソ錯体［Ｍ−Ｏ２］を含むカソード電極を用いることを特徴とする水素−過酸化水素燃料電池。
In the formula (2), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
2. 2. The method according to 1 above, wherein the reduction reaction of hydrogen peroxide is shown in the following steps.
(Step A) A step of reducing the heterobinuclear peroxo complex [M-O 2 ] represented by the above formula (2) to produce a heterobinuclear intermediate [M * ].
[M−O 2 ] + (H + + 2e − ) → [M * ] + 2H 2 O
(Step B) A step of allowing a heterobinuclear intermediate [M * ] to act on hydrogen peroxide (H 2 O 2 ) to regenerate the heterobinuclear peroxo complex [M-O 2 ].
H 2 O 2 + [M * ] → [M−O 2 ] + 2H +
3. A hydrogen-hydrogen peroxide fuel cell characterized by using a cathode electrode containing a heterobinuclear peroxo complex [M-O 2 ] represented by the following formula (2).
式（２）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。
４．下記式（１）で表される金属錯体および下記式（２）で表される金属錯体を含むカソード電極を用い、カソードガスとして過酸化水素を含むことを特徴とする水素−酸素燃料電池。
In the formula (2), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
4). A hydrogen-oxygen fuel cell comprising a cathode complex containing a metal complex represented by the following formula (1) and a metal complex represented by the following formula (2), and containing hydrogen peroxide as a cathode gas.
式（１）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。 In the formula (1), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
式（２）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。
５．下記式（１）で表される金属錯体および下記式（２）で表される金属錯体から選択される少なくとも一つを含有する燃料電池用電極触媒を用いた発電方法。
In the formula (2), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
5. A power generation method using a fuel cell electrode catalyst comprising at least one selected from a metal complex represented by the following formula (1) and a metal complex represented by the following formula (2).
式（１）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。 In the formula (1), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
式（２）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。 In the formula (2), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
本発明の酸素および過酸化水素を還元する方法は、酸素と過酸化水素を両方還元できるニッケル・ルテニウム錯体を電極材料に用いることにより、燃料電池用電極において、過酸化水素が発生しても性能低下しない電極触媒を提供できる。そのため、現行の水素−酸素燃料電池の問題を解決することが可能であり、電気エネルギーの効率向上に寄与する効果は大きい。 The method for reducing oxygen and hydrogen peroxide according to the present invention uses a nickel-ruthenium complex capable of reducing both oxygen and hydrogen peroxide as an electrode material, so that performance can be achieved even when hydrogen peroxide is generated in a fuel cell electrode. An electrode catalyst that does not decrease can be provided. Therefore, it is possible to solve the problem of the current hydrogen-oxygen fuel cell, and the effect of contributing to the improvement of electric energy efficiency is great.
以下、本発明を更に詳しく説明するが、本発明の範囲はそれに限定されない。 Hereinafter, the present invention will be described in more detail, but the scope of the present invention is not limited thereto.
本発明の異種二核錯体を用いて水素および一酸化炭素を酸化する方法および燃料電池は、出発物質として、下記式（１）及び下記式（２）で表される異種二核錯体を用いる。 The method for oxidizing hydrogen and carbon monoxide using the heterobinuclear complex of the present invention and the fuel cell use heterobinuclear complexes represented by the following formulas (1) and (2) as starting materials.
前記式（１）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。 In the formula (1), l, m and n are each independently an integer of 2 to 4. Each R is independently an alkyl group having 1 to 5 carbon atoms.
前記式（２）において、ｌ、ｍおよびｎは、それぞれ独立して２〜４の整数である。Ｒはそれぞれ独立して、炭素数１〜５のアルキル基である。 In said Formula (2), l, m, and n are the integers of 2-4 each independently. Each R is independently an alkyl group having 1 to 5 carbon atoms.
前記異種二核錯体を用いたときの過酸化水素の還元反応は、下記の工程で示される。
（工程Ａ）前記式（２）で表される異種二核ペルオキソ錯体［Ｍ−Ｏ２］を還元し異種二核中間体［Ｍ＊］を生成する工程。
［Ｍ−Ｏ２］＋（Ｈ＋＋２ｅ−）→［Ｍ＊］＋２Ｈ２Ｏ
（工程Ｂ）過酸化水素（Ｈ２Ｏ２）に異種二核中間体［Ｍ＊］を作用させ、異種二核ペルオキソ錯体［Ｍ−Ｏ２］を再生する工程。
Ｈ２Ｏ２＋［Ｍ＊］→［Ｍ−Ｏ２］＋２Ｈ＋
The reduction reaction of hydrogen peroxide when using the heterobinuclear complex is shown in the following steps.
(Step A) A step of reducing the heterobinuclear peroxo complex [M-O 2 ] represented by the formula (2) to produce a heterobinuclear intermediate [M * ].
[M−O 2 ] + (H + + 2e − ) → [M * ] + 2H 2 O
(Step B) A step of allowing a heterobinuclear intermediate [M * ] to act on hydrogen peroxide (H 2 O 2 ) to regenerate the heterobinuclear peroxo complex [M-O 2 ].
H 2 O 2 + [M * ] → [M−O 2 ] + 2H +
前記式（１）及び式（２）で表される本願発明に使用する金属錯体の製造方法は特に限定されるものではなく、金属錯体に配位する配位子に応じて適宜好ましい製造方法を従来公知の方法から選択し、または、組み合わせて用いればよい。また、上記金属錯体として市販されているものを利用しても差し支えない。 The production method of the metal complex used in the present invention represented by the formula (1) and the formula (2) is not particularly limited, and a suitable production method is appropriately selected according to the ligand coordinated to the metal complex. It may be selected from conventionally known methods or used in combination. In addition, a commercially available metal complex may be used.
（燃料電池用電極触媒）
本発明に係る燃料電池用電極触媒は、上記金属錯体を含有している。本発明に係る燃料電池用電極触媒は、どのような燃料電池にも好ましく用いることができるが、特に固体高分子型燃料電池により好ましく用いることができる。
(Electrocatalyst for fuel cell)
The fuel cell electrode catalyst according to the present invention contains the metal complex. The fuel cell electrode catalyst according to the present invention can be preferably used for any fuel cell, but can be particularly preferably used for a polymer electrolyte fuel cell.
固体高分子型燃料電池は、一般的には電解質膜をアノードとカソードとで挟んで構成され、燃料である水素等と酸化剤である酸素（または空気）から電気化学反応を用いて電気と熱エネルギーを取り出す。このとき、カソード（正極または空気極ともいう）では酸化剤の還元が起こる。 A polymer electrolyte fuel cell is generally configured by sandwiching an electrolyte membrane between an anode and a cathode. Electricity and heat are generated by using an electrochemical reaction from hydrogen or the like as a fuel and oxygen (or air) as an oxidant. Extract energy. At this time, reduction of the oxidant occurs at the cathode (also referred to as positive electrode or air electrode).
燃料としては、水素の他、ガソリン、メタノール、ジエチルエーテルまたは炭化水素等を用いることもでき、これらを水素に改質して燃料電池に供給する。また、メタノールまたはジエチルエーテル等を直接燃料として供給可能な直接型の燃料電池にも、本発明に係る燃料電池用電極触媒を用いることができる。 As fuel, gasoline, methanol, diethyl ether, hydrocarbons, or the like can be used in addition to hydrogen, and these are reformed into hydrogen and supplied to the fuel cell. Further, the fuel cell electrode catalyst according to the present invention can also be used in a direct fuel cell capable of supplying methanol or diethyl ether directly as fuel.
本発明に掛かる燃料電池用電極触媒は、Ｎｉ／Ｒｕ金属錯体から選ばれる１以上の金属錯体を含有していればよい。従って、本発明に係る燃料電池用電極触媒は、前記金属錯体から選ばれる単一の金属錯体を含有していてもよいし、前記金属錯体から選ばれる２種類以上の金属錯体を含有していてもよい。 The electrode catalyst for fuel cells according to the present invention only needs to contain one or more metal complexes selected from Ni / Ru metal complexes. Therefore, the fuel cell electrode catalyst according to the present invention may contain a single metal complex selected from the metal complexes, or two or more metal complexes selected from the metal complexes. Also good.
また、本発明に係る燃料電池用電極触媒は、上記金属錯体のみを含有していてもよいし、必要に応じて他の成分を含有していてもよい。 Moreover, the electrode catalyst for fuel cells which concerns on this invention may contain only the said metal complex, and may contain the other component as needed.
かかる他の成分としては、例えば、バルカン（Ｃａｂｏｔ社製）、カーボンブラック、アセチレンブラック、ファーネスブラック、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、黒煙、炭素繊維および活性炭等の触媒担持体；ポリアセチレン、ポリピロール、ポリチオール、ポリイミダゾール、ポリピリジン、ポリアニリンおよびポリチオフェン等の導電性高分子を挙げることができる。 Examples of such other components include catalyst carriers such as Vulcan (manufactured by Cabot), carbon black, acetylene black, furnace black, graphite, carbon nanotube, carbon nanofiber, black smoke, carbon fiber and activated carbon; polyacetylene, polypyrrole , Conductive polymers such as polythiol, polyimidazole, polypyridine, polyaniline and polythiophene.
他の成分が含有される場合の上記燃料電池用電極触媒に含有される分子性金属錯体と、上記他の成分との割合も特に限定されるものではないが、分子性金属錯体に対する上記触媒担持体の割合は好ましくは０重量％以上５０重量％以下であり、分子性金属錯体に対する上記導電性高分子の割合は好ましくは０重量％以上５０重量％以下である。 The ratio of the molecular metal complex contained in the fuel cell electrode catalyst and the other components when other components are contained is not particularly limited, but the catalyst is supported on the molecular metal complex. The ratio of the body is preferably 0% by weight to 50% by weight, and the ratio of the conductive polymer to the molecular metal complex is preferably 0% by weight to 50% by weight.
さらに、本発明に係る燃料電池用電極触媒には、必要に応じてナフィオン（登録商標）、フレミオン（登録商標）、アシプレックス（登録商標）等のプロトン伝導性高分子電解質が含有されていてもよい。 Furthermore, the fuel cell electrode catalyst according to the present invention may contain a proton conductive polymer electrolyte such as Nafion (registered trademark), Flemion (registered trademark), and Aciplex (registered trademark) as necessary. Good.
（本発明に係る燃料電池用電極触媒の利用）
本発明に係る燃料電池用電極触媒は、安価、かつ、触媒能力の制御が容易にできることから、これを用いた燃料電池用電極、燃料電池、及び、発電方法に好ましく用いることができる。それゆえ、本発明には、上記燃料電池用電極触媒を用いた燃料電池用電極、燃料電池、及び、発電方法も含まれる。
(Utilization of fuel cell electrode catalyst according to the present invention)
Since the fuel cell electrode catalyst according to the present invention is inexpensive and can easily control the catalyst capacity, it can be preferably used in a fuel cell electrode, a fuel cell, and a power generation method using the same. Therefore, the present invention also includes a fuel cell electrode, a fuel cell, and a power generation method using the fuel cell electrode catalyst.
（燃料電池用電極）
本発明に係る燃料電池用電極は、上記燃料電池用電極触媒を含有するものであれば特に限定されるものではなく、燃料電池の種類に応じて、従来公知の様々な構成を備えうる。
(Fuel cell electrode)
The fuel cell electrode according to the present invention is not particularly limited as long as it contains the fuel cell electrode catalyst, and may have various conventionally known configurations depending on the type of fuel cell.
例えば、固体高分子型燃料電池を例として挙げれば、本発明に係る燃料電池用電極は、カソード用の、触媒層付ガス拡散層電極として構成することができる。かかる触媒層付ガス拡散層電極では、上記燃料電池用電極触媒を含有する触媒層は、ガス拡散層上に積層されている。上記ガス拡散層は、カーボンクロスまたはカーボンペーパー等のような多孔質カーボン等からなっており、ガス流路から供給された燃料または酸素（空気）を拡散させ効率よく触媒に供給するようになっている。 For example, taking a polymer electrolyte fuel cell as an example, the fuel cell electrode according to the present invention can be configured as a gas diffusion layer electrode with a catalyst layer for a cathode. In such a gas diffusion layer electrode with a catalyst layer, the catalyst layer containing the fuel cell electrode catalyst is laminated on the gas diffusion layer. The gas diffusion layer is made of porous carbon or the like such as carbon cloth or carbon paper, and diffuses the fuel or oxygen (air) supplied from the gas flow path and efficiently supplies it to the catalyst. Yes.
かかるガス拡散層上に形成された触媒層は、例えば、上記燃料電池用電極触媒を、溶液、懸濁液、スラリーまたはペースト等として、上記ガス拡散層に塗布し、乾燥させることにより形成される。ここで、上記燃料電池用電極触媒を、溶液、懸濁液、スラリーまたはペースト等とするための媒体も特に限定されるものではなく、従来公知の媒体から適宜選択して用いればよい。塗布量は０．１〜１０ｍｇ／ｍ２とすることが好ましく、より好ましくは０．５〜５ｍｇ／ｍ２である。 The catalyst layer formed on the gas diffusion layer is formed, for example, by applying the fuel cell electrode catalyst as a solution, suspension, slurry, paste, or the like to the gas diffusion layer and drying it. . Here, the medium for making the fuel cell electrode catalyst into a solution, suspension, slurry, paste or the like is not particularly limited, and may be appropriately selected from conventionally known media. The coating amount is preferably set to 0.1 to 10 mg / m 2, more preferably from 0.5 to 5 mg / m 2.
なお、上記触媒層は、上記燃料電池用電極触媒に加え、必要に応じて、上記触媒担持体、導電性高分子またはアイオノマー等を含有していてもよい。上記触媒担持体、導電性高分子またはアイオノマー等は、上記燃料電池用電極触媒の溶液、懸濁液、スラリーまたはペースト等に添加してもよいし、上記燃料電池用電極触媒の溶液、懸濁液、スラリーまたはペースト等とは別に、溶液、懸濁液、溶液、スラリーまたはペースト等として、触媒層を塗布する前、同時、又は後に塗布してもよい。 In addition to the fuel cell electrode catalyst, the catalyst layer may contain the catalyst support, a conductive polymer, an ionomer, or the like, if necessary. The catalyst carrier, conductive polymer or ionomer may be added to the solution, suspension, slurry or paste of the fuel cell electrode catalyst, or the solution or suspension of the fuel cell electrode catalyst. Apart from the liquid, slurry or paste, the catalyst layer may be applied before, simultaneously with, or after application as a solution, suspension, solution, slurry or paste.
（燃料電池）
本発明に係る燃料電池の構成は、通常燃料電池に採用される構成であれば特に限定されるものではないが、例えば、少なくとも電解質膜、アノードおよびカソードを備え、電解質膜をアノードとカソードとで挟んだ構造を有している。
(Fuel cell)
The configuration of the fuel cell according to the present invention is not particularly limited as long as it is a configuration normally employed in a fuel cell. For example, the fuel cell includes at least an electrolyte membrane, an anode, and a cathode, and the electrolyte membrane is composed of an anode and a cathode. It has a sandwiched structure.
かかる燃料電池は、例えば、上述したように、カソード用の触媒層付ガス拡散層電極およびアノード用の触媒層付ガス拡散層電極を作製し、これらの触媒層付ガス拡散層電極の間に、触媒層が電解質膜を挟んで対向するように電解質膜を挟み、膜電極接合体（ＭＥＡ）を作製すればよい。かかる膜電極接合体を燃料電池セルに組み込んで使用することができる。 Such a fuel cell, for example, as described above, produces a gas diffusion layer electrode with a catalyst layer for a cathode and a gas diffusion layer electrode with a catalyst layer for an anode, and between these gas diffusion layer electrodes with a catalyst layer, A membrane electrode assembly (MEA) may be produced by sandwiching the electrolyte membrane so that the catalyst layers face each other with the electrolyte membrane interposed therebetween. Such a membrane electrode assembly can be used by being incorporated in a fuel cell.
ここで、本発明に係る燃料電池は、上記燃料電池用電極触媒を、カソードに含有していればよい。対向する電極触媒には、従来公知の触媒を用いればよく、例えば、白金単体、白金合金等を含有する触媒を用いればよい。 Here, the fuel cell according to the present invention only needs to contain the fuel cell electrode catalyst in the cathode. A conventionally known catalyst may be used as the opposing electrode catalyst, for example, a catalyst containing platinum alone or a platinum alloy may be used.
上記電解質膜は、水素イオン伝導性の高い高分子膜であれば特に限定されるものではなく、ナフィオン（登録商標）、フレミオン（登録商標）またはアシプレックス（登録商標）のパーフルオロスルホン酸系のプロトン交換膜等、通常用いられる電解質膜を用いればよい。 The electrolyte membrane is not particularly limited as long as it is a polymer membrane having high hydrogen ion conductivity, and is a Nafion (registered trademark), Flemion (registered trademark) or Aciplex (registered trademark) perfluorosulfonic acid-based one. A commonly used electrolyte membrane such as a proton exchange membrane may be used.
（発電方法）
本発明に係る発電方法は、上記燃料電池用電極触媒を用いて、燃料の酸化反応を行う工程、および／または、上記燃料電池用電極触媒を用いて、酸化剤の還元反応を行う工程を含んでいればよい。すなわち、本発明に係る発電方法は、上記燃料電池用電極触媒を用いて、燃料の酸化反応を行う工程、および、上記燃料電池用電極触媒を用いて、酸化剤の還元反応を行う工程の両方を含んでいてもよいし、いずれか一方を含んでいてもよい。
(Power generation method)
The power generation method according to the present invention includes a step of performing a fuel oxidation reaction using the fuel cell electrode catalyst and / or a step of performing a reduction reaction of an oxidant using the fuel cell electrode catalyst. Just go out. That is, the power generation method according to the present invention includes both a step of performing a fuel oxidation reaction using the fuel cell electrode catalyst and a step of performing a reduction reaction of an oxidant using the fuel cell electrode catalyst. May be included, or any one of them may be included.
より具体的には、例えば、本発明に係る発電方法は、上記燃料電池用電極触媒を用いて水素分子から電子を放出させて水素イオンとする工程、および／または、上記燃料電池用電極触媒を用いて、酸素分子、水素イオンおよび電子を反応させて水を生成する工程を含む。 More specifically, for example, the power generation method according to the present invention includes a step of releasing electrons from hydrogen molecules to form hydrogen ions using the fuel cell electrode catalyst, and / or the fuel cell electrode catalyst. And a step of generating water by reacting oxygen molecules, hydrogen ions and electrons.
本発明に係る発電方法は、従来公知の方法により行えばよく、特に限定されるものではないが、一例を説明すると、燃料電池のアノード側に水素ガスを、カソード側に酸素を供給する。このとき水素ガスおよび酸素はバブラーを通して加湿してもよい。この際、本発明における電極触媒を用いると、カソード側に過酸化水素を供給してもよく、過酸化水素の濃度が好ましくは１０％〜３０％、より好ましくは２５〜３０％であれば、燃料電池として機能する。 The power generation method according to the present invention may be performed by a conventionally known method, and is not particularly limited. For example, hydrogen gas is supplied to the anode side of the fuel cell and oxygen is supplied to the cathode side. At this time, hydrogen gas and oxygen may be humidified through a bubbler. At this time, if the electrode catalyst in the present invention is used, hydrogen peroxide may be supplied to the cathode side, and the concentration of hydrogen peroxide is preferably 10% to 30%, more preferably 25 to 30%. Functions as a fuel cell.
アノード側から水素ガスが供給されると、水素ガスが上記燃料電池用電極触媒の作用によって水素分子から電子を放出して水素イオンとなる。この水素イオンは電解質膜を通過して対向するカソードに移動する。カソードでは、上記燃料電池用電極触媒の作用により、移動してきた水素イオンと、カソードに供給される酸素分子とが反応して水を生成する。このとき、電線に生じる電子の流れが直流電流として取り出される。 When hydrogen gas is supplied from the anode side, the hydrogen gas releases electrons from the hydrogen molecules by the action of the fuel cell electrode catalyst to become hydrogen ions. The hydrogen ions pass through the electrolyte membrane and move to the opposite cathode. At the cathode, the hydrogen ions that have moved and oxygen molecules supplied to the cathode react to generate water by the action of the fuel cell electrode catalyst. At this time, the flow of electrons generated in the electric wire is taken out as a direct current.
以下に実施例を挙げて本発明を更に詳細に説明するが、本発明の範囲はそれに限定されない。 The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited thereto.
（材料および方法）
全ての実験は、標準のシュレンク技術及びグローブボックスを用いることによってＮ２又はＡｒ雰囲気下で実施した。
(Materials and methods)
All experiments were performed under N 2 or Ar atmosphere by using standard Schlenk techniques and glove boxes.
［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＩ（Ｈ２Ｏ）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）及び［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）は、文献（Ｃｈｅｍ．Ａｓｉａｎ Ｊ． ２０１２，７，１３９４−１４００）に記載の方法により［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＩ（Ｈ２Ｏ）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）及び［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）において記述されている方法によって調製した（Ｎ２Ｓ２＝Ｎ、Ｎ’−ｄｉｍｅｔｈｙｌ−３，７−ｄｉａｚａｎｏｎａｎｅ−１，９−ｄｉｔｈｉｏｌａｔｏ）。 [Ni II (N 2 S 2 ) Ru II (H 2 O) (η 5 -C 5 Me 5)] (NO 3) and [Ni II (N 2 S 2 ) Ru IV (η 2 -O 2) ( η 5 -C 5 Me 5 )] (NO 3 ) can be obtained from [Ni II (N 2 S 2 ) Ru II (H 2 O] by the method described in the literature (Chem. Asian J. 2012, 7, 1394-1400). ) (Η 5 -C 5 Me 5 )] (NO 3 ) and [Ni II (N 2 S 2 ) Ru IV (η 2 -O 2 ) (η 5 -C 5 Me 5 )] (NO 3 ) It was prepared by the method (N 2 S 2 = N, N'-dimethyl-3,7-diazanonane-1,9-dithiolato).
Ｈ２ガス、Ｏ２ガスは、太陽東洋酸素株式会社から購入した。Ｈ２Ｏ２はシグマアルドリッチジャパンから購入した（純度３０％）。Ｈ２Ｏは、和光純薬工業株式会社から購入した。これらは、更に精製することなしに使用した。
H 2 gas and O 2 gas were purchased from Taiyo Toyo Oxygen Corporation. H 2 O 2 was purchased from Sigma Aldrich Japan (
・赤外スペクトル
ＫＢｒディスク中に含まれる固体化合物の赤外スペクトルは、２５℃で２ｃｍ−１の標準解像度を用いて４００から４０００ｃｍ−１までの領域をサーモ・ニコレーＮＥＸＵＳ８７００ＦＲ−ＩＲ計器で測定した。
And infrared spectrum of the solid compound contained in the infrared spectrum in KBr disc was measured area from 400 using a standard resolution of 2 cm -1 at 25 ° C. until 4000 cm -1 in Thermo Nicolet NEXUS8700FR-IR instrument.
・紫外線可視スペクトル
紫外線可視スペクトルは、２５℃にて日本分光Ｖ−６７０ ＵＶ−Ｖｉｓｉｂｌｅ−ＮＩＲ分光計（セルの長さ１．０ｃｍ）で測定した。
-UV visible spectrum The UV visible spectrum was measured at 25 ° C with JASCO V-670 UV-Visible-NIR spectrometer (cell length 1.0 cm).
・元素分析データ
元素分析データは、パーキンエルマー２４００ＩＩシリーズＣＨＮＳ／Ｏ分析器によって得た。
Elemental analysis data Elemental analysis data was obtained with a Perkin Elmer 2400II series CHNS / O analyzer.
・Ｘ線結晶学的解析
測定は、共焦点単色化Ｍｏ−Ｋａ放射光（ｌ＝０．７１０７Å）を備えたリガク／ＭＳＣサターンＣＣＤ回析装置で行った。データを集め、ＣｒｙｓｔａｌＣｌａｅｒプログラム（リガク社）を用いて処理した。全ての計算は、モレキュラー・ストラクチャー・コーポレーションのｔｅＸａｎ結晶学ソフトウェア・パッケージを用いて実施した。
X-ray crystallographic analysis The measurement was performed with a Rigaku / MSC Saturn CCD diffractometer equipped with confocal monochromated Mo-Ka radiation (l = 0.7107 Å). Data was collected and processed using the CrystalClear program (Rigaku). All calculations were performed using Molecular Structure Corporation's teXan crystallography software package.
［実施例１］ニッケル・ルテニウムアクア錯体［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＩ（Ｈ２Ｏ）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）を用いたＯ２の触媒的還元反応
［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＩ（Ｈ２Ｏ）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）（３．０ｍｇ）を含むメタノール溶液(２００μＬ)に１８Ｏ２（５ｍＬ）を加えた（Ｎ２Ｓ２＝Ｎ、Ｎ’−ｄｉｍｅｔｈｙｌ−３，７−ｄｉａｚａｎｏｎａｎｅ−１，９−ｄｉｔｈｉｏｌａｔｏ）。その溶液にヒドロキノン（５．５ｍｇ）を含むメタノール溶液(６０μＬ)およびＮａＢＨ４（１．９ｍｇ）のメタノール溶液(１００μＬ)、ＨＢＦ４(６．８μＬ)を加え、６時間撹拌した。得られた溶液にカリボール（１７ｍｇ）を加え、生じた沈殿をろ別した。得られた溶液をＧＳ−ＭＳで分析することにより、Ｈ２ １８Ｏを定量し、ＴＯＮを算出した（ＴＯＮ＝０．１）。
Example 1 Catalytic Reduction Reaction of O 2 Using Nickel / Ruthenium Aqua Complex [Ni II (N 2 S 2 ) Ru II (H 2 O) (η 5 -C 5 Me 5 )] (NO 3 ) 18 O 2 (5 mL) was added to a methanol solution (200 μL) containing [Ni II (N 2 S 2 ) Ru II (H 2 O) (η 5 -C 5 Me 5 )] (NO 3 ) (3.0 mg). the added (N 2 S 2 = N, N'-dimethyl-3,7-diazanonane-1,9-dithiolato). A methanol solution (60 μL) containing hydroquinone (5.5 mg), a methanol solution (100 μL) of NaBH 4 (1.9 mg), and HBF 4 (6.8 μL) were added to the solution, and the mixture was stirred for 6 hours. Caribol (17 mg) was added to the resulting solution, and the resulting precipitate was filtered off. The resulting solution by analyzing at GS-MS, to quantitate the H 2 18 O, was calculated TON (TON = 0.1).
［実施例２］ニッケル・ルテニウムペルオキソ錯体［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）を用いたＨ２Ｏ２の触媒的還元反応
［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３） （３．０ｍｇ）のメタノール溶液(２００μＬ)にヒドロキノン（５．５ｍｇ）のメタノール溶液(１００μＬ)および２％ Ｈ２ １８Ｏ２／Ｈ２Ｏ(６０μＬ)、ＨＢＦ４(６．８μＬ)を加え、６時間撹拌した。得られた溶液にカリボール（１７ｍｇ）を加え、生じた沈殿をろ別した。得られた溶液をＧＳ−ＭＳで分析することにより、Ｈ２ １８Ｏを定量し、ＴＯＮを算出した（ＴＯＮ＝１．３）。
[Example 2] H 2 O 2 using a nickel / ruthenium peroxo complex [Ni II (N 2 S 2 ) Ru IV (η 2 -O 2 ) (η 5 -C 5 Me 5 )] (NO 3 ) Catalytic Reduction Reaction Hydroquinone (Ni II (N 2 S 2 ) Ru IV (η 2 -O 2 ) (η 5 -C 5 Me 5 )) (NO 3 ) (3.0 mg) in methanol (200 μL) 5.5 mg) of a methanol solution (100 μL) and 2% H 2 18 O 2 / H 2 O (60 μL) and HBF 4 (6.8 μL) were added, and the mixture was stirred for 6 hours. Caribol (17 mg) was added to the resulting solution, and the resulting precipitate was filtered off. The resulting solution by analyzing at GS-MS, to quantitate the H 2 18 O, was calculated TON (TON = 1.3).
［実施例３］ニッケル・ルテニウムペルオキソ錯体をアノード触媒に用いた水素−過酸化水素燃料電池評価実験
［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）（５ｍｇ）をカーボンブラック（５ｍｇ）と混合し、カーボンクロス上に塗布することで、カソード電極を作成した。アノード電極としてはＰｔ／Ｃ（１０ｍｇ）をカーボンクロス上に塗布したものを用いた。以上の電極を用いて電池を作成し、アノード側から水素、カソードガス側から空気下で過酸化水素水（３０％）をフィード（１ｍＬ／ｍｉｎ）し、６０℃での燃料電池評価を行った結果、図１に示すように電池として機能した。
[Example 3] Hydrogen-hydrogen peroxide fuel cell evaluation experiment using a nickel-ruthenium peroxo complex as an anode catalyst [Ni II (N 2 S 2 ) Ru IV (η 2 -O 2 ) (η 5 -C 5 Me 5 )] (NO 3 ) (5 mg) was mixed with carbon black (5 mg) and coated on carbon cloth to form a cathode electrode. As the anode electrode, an electrode in which Pt / C (10 mg) was applied on a carbon cloth was used. A battery was prepared using the electrodes described above, hydrogen peroxide solution (30%) was fed (1 mL / min) under hydrogen from the anode side and air from the cathode gas side, and a fuel cell evaluation at 60 ° C. was performed. As a result, it functioned as a battery as shown in FIG.
［実施例４］ニッケル・ルテニウムペルオキソ錯体と白金の混合物をアノード触媒に用いた燃料電池評価実験
（１）水素−酸素燃料電池評価
［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）（２．５ｍｇ）をカーボンブラック（２．５ｍｇ）およびＰｔ／Ｃ（５ｍｇ）と混合し、カーボンクロス上に塗布することで、カソード電極を作成した。アノード電極としてはＰｔ／Ｃ（１０ｍｇ）をカーボンクロス上に塗布したものを用いた。以上の電極を用いて電池を作成し、アノードガスとして水素、カソードガスとして酸素を用い、６０℃での燃料電池評価を行った結果、図２に示すように電池として機能した。
[Example 4] Fuel cell evaluation experiment using a mixture of nickel / ruthenium peroxo complex and platinum as an anode catalyst (1) Hydrogen-oxygen fuel cell evaluation [Ni II (N 2 S 2 ) Ru IV (η 2 -O 2 ) (Η 5 -C 5 Me 5 )] (NO 3 ) (2.5 mg) is mixed with carbon black (2.5 mg) and Pt / C (5 mg), and applied onto the carbon cloth to form a cathode electrode It was created. As the anode electrode, an electrode in which Pt / C (10 mg) was applied on a carbon cloth was used. A battery was prepared using the above electrodes, and a fuel cell was evaluated at 60 ° C. using hydrogen as the anode gas and oxygen as the cathode gas. As a result, the battery functioned as shown in FIG.
（２）水素−酸素／過酸化水素燃料電池評価
（１）で［ＮｉＩＩ（Ｎ２Ｓ２）ＲｕＩＶ（η２−Ｏ２）（η５−Ｃ５Ｍｅ５）］（ＮＯ３）とＰｔ／Ｃを用いて作成したカソード電極を用いた電池を用い、アノード側から水素、カソードガス側から空気下で過酸化水素水（３０％）をフィード（１ｍＬ／ｍｉｎ）し、６０℃での燃料電池評価を行った結果、図３に示すように電池として機能した。
(2) Hydrogen-oxygen / hydrogen peroxide fuel cell evaluation In (1), [Ni II (N 2 S 2 ) Ru IV (η 2 -O 2 ) (η 5 -C 5 Me 5 )] (NO 3 ) Using a battery using a cathode electrode made of Pt / C, hydrogen peroxide water (30%) was fed (1 mL / min) under hydrogen from the anode side and air from the cathode gas side (1 mL / min). As a result of the fuel cell evaluation, it functioned as a battery as shown in FIG.
Claims (5)
（工程Ａ）上記式（２）で表される異種二核ペルオキソ錯体［Ｍ−Ｏ２］を還元し異種二核中間体［Ｍ＊］を生成する工程。
［Ｍ−Ｏ２］＋（Ｈ＋＋２ｅ−）→ ［Ｍ＊］＋２Ｈ２Ｏ
（工程Ｂ）過酸化水素（Ｈ２Ｏ２）に異種二核中間体［Ｍ＊］を作用させ、異種二核ペルオキソ錯体［Ｍ−Ｏ２］を再生する工程。
Ｈ２Ｏ２＋［Ｍ＊］→［Ｍ−Ｏ２］＋２Ｈ＋ The method according to claim 1, wherein the reduction reaction of hydrogen peroxide is represented by the following steps.
(Step A) A step of reducing the heterobinuclear peroxo complex [M-O 2 ] represented by the above formula (2) to produce a heterobinuclear intermediate [M * ].
[M−O 2 ] + (H + + 2e − ) → [M * ] + 2H 2 O
(Step B) A step of allowing a heterobinuclear intermediate [M * ] to act on hydrogen peroxide (H 2 O 2 ) to regenerate the heterobinuclear peroxo complex [M-O 2 ].
H 2 O 2 + [M * ] → [M−O 2 ] + 2H +
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