JP6213958B2 - Fuel cell - Google Patents
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- JP6213958B2 JP6213958B2 JP2013211926A JP2013211926A JP6213958B2 JP 6213958 B2 JP6213958 B2 JP 6213958B2 JP 2013211926 A JP2013211926 A JP 2013211926A JP 2013211926 A JP2013211926 A JP 2013211926A JP 6213958 B2 JP6213958 B2 JP 6213958B2
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- 239000000446 fuel Substances 0.000 title claims description 37
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 105
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 239000007864 aqueous solution Substances 0.000 claims description 45
- 239000011941 photocatalyst Substances 0.000 claims description 38
- 239000002253 acid Substances 0.000 claims description 23
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 21
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 20
- 229910001882 dioxygen Inorganic materials 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000003014 ion exchange membrane Substances 0.000 claims description 7
- 238000002834 transmittance Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 24
- 239000011521 glass Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 15
- 230000008859 change Effects 0.000 description 15
- 239000007789 gas Substances 0.000 description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000003760 magnetic stirring Methods 0.000 description 10
- 230000005611 electricity Effects 0.000 description 9
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 9
- 239000001569 carbon dioxide Substances 0.000 description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 230000005587 bubbling Effects 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 238000013032 photocatalytic reaction Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 4
- 229910002012 Aerosil® Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000006864 oxidative decomposition reaction Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011260 aqueous acid Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- -1 but for example Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000007540 photo-reduction reaction Methods 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-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
Landscapes
- Fuel Cell (AREA)
- Catalysts (AREA)
- Hybrid Cells (AREA)
Description
本発明は、燃料電池に関する。 The present invention relates to a fuel cell.
燃料電池とは、燃料の酸化還元反応を用いることにより電気を取り出すことのできる電池であり、一般に、酸素と水素の反応を用いて電気を取り出すものであって、重金属等を使う他の化学電池に比べ地球環境に優しく、現在も活発に研究開発が行われている。 A fuel cell is a cell that can take out electricity by using a redox reaction of fuel, and generally takes out electricity using a reaction between oxygen and hydrogen, and is another chemical cell that uses heavy metals or the like. Compared to, it is friendly to the global environment, and research and development are still underway.
また、上記燃料電池において、光エネルギーを用いてより効率的に電気を取り出そうとする試みがなされており、例えば下記特許文献１に、光触媒を用いた燃料電池が開示されている。 In the fuel cell, attempts have been made to extract electricity more efficiently using light energy. For example, Patent Document 1 below discloses a fuel cell using a photocatalyst.
しかしながら、上記特許文献１に記載の技術は、メタノール等の液相燃料を使用しており、その場で燃料を合成するような仕組みではない。さらに、液相燃料の酸化反応を含むため、温室効果ガスである二酸化炭素が発電時に発生してしまうといった課題がある。 However, the technique described in Patent Document 1 uses a liquid phase fuel such as methanol and is not a mechanism for synthesizing the fuel on the spot. Furthermore, since the oxidation reaction of liquid phase fuel is included, there is a problem that carbon dioxide, which is a greenhouse gas, is generated during power generation.
そこで、本発明は上記課題を鑑み、二酸化炭素を発生させることなく、より簡便な構成により電気を発生することのできる光触媒を用いた燃料電池を提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a fuel cell using a photocatalyst that can generate electricity with a simpler configuration without generating carbon dioxide.
上記課題を解決する本発明の一の観点に係る燃料電池は、酸水溶液と、酸水溶液中に浸される一対の電極と、酸水溶液中の水を分解する光触媒と、酸水溶液、一対の電極及び光触媒を収容し、少なくとも一部が透過性を有する部材で構成される収容部材と、を有することを特徴とする。 A fuel cell according to one aspect of the present invention that solves the above problems includes an acid aqueous solution, a pair of electrodes immersed in the acid aqueous solution, a photocatalyst that decomposes water in the acid aqueous solution, an acid aqueous solution, and a pair of electrodes. And a photocatalyst, and at least a part of the housing member made of a permeable member.
以上、本発明により、二酸化炭素を発生させることなく、より簡便な構成により電気を発生することのできる光触媒を用いた燃料電池を提供することができる。 As described above, the present invention can provide a fuel cell using a photocatalyst capable of generating electricity with a simpler configuration without generating carbon dioxide.
以下、本発明の実施形態について、図面を用いて詳細に説明する。ただし、本発明は多くの異なる形態による実施が可能であり、以下に示す実施形態、実施例の例示に限定されるものではない。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. However, the present invention can be implemented in many different forms, and is not limited to the following embodiments and examples.
図１は、本実施形態に係る燃料電池（以下「本電池」という。）１の概略を示す図である。本電池１は、酸水溶液２と、窒素ガスまたは酸素ガス３と、酸水溶液２中に浸される一対の電極４と、酸水溶液２中の水を分解する光触媒５と、酸水溶液２、窒素ガスまたは酸素ガス３、一対の電極４及び光触媒５を収容し、少なくとも一部が透過性を有する部材で構成される収容部材６と、を有する。本電池は、一対の電極を電子部品を介して導線により接続することで一対の電極間に電気を流すことができる。 FIG. 1 is a diagram showing an outline of a fuel cell (hereinafter referred to as “the present battery”) 1 according to the present embodiment. The battery 1 includes an acid aqueous solution 2, nitrogen gas or oxygen gas 3, a pair of electrodes 4 immersed in the acid aqueous solution 2, a photocatalyst 5 for decomposing water in the acid aqueous solution 2, an acid aqueous solution 2, nitrogen And a housing member 6 that houses a gas or oxygen gas 3, a pair of electrodes 4 and a photocatalyst 5 and at least a part of which has permeability. In the present battery, electricity can flow between the pair of electrodes by connecting the pair of electrodes with a conductive wire via an electronic component.
本実施形態において酸水溶液２は、酸を含み酸性を示す水溶液をいう。酸性とすることで、水溶液内でプロトンが関わる化学反応を速めるといった効果がある。ｐＨとしては、上記効果を達成することができる限りにおいて限定されるわけではないが６以下であることが好ましく、より好ましくは２以上５以下の範囲である。 In this embodiment, the acid aqueous solution 2 refers to an aqueous solution containing an acid and showing acidity. By making it acidic, there is an effect of accelerating a chemical reaction involving protons in an aqueous solution. The pH is not limited as long as the above effect can be achieved, but is preferably 6 or less, more preferably 2 or more and 5 or less.
また本実施形態において、酸水溶液２に含まれる酸としては、本実施形態の効果を達成することができる限りにおいて限定されるわけではないが、例えば塩酸、硫酸、硝酸、リン酸、炭酸、等を挙げることができる。とりわけ、酸水溶液の濃度を変化させることが容易な、強酸性の塩酸、硫酸、硝酸がとりわけ好適である。酸水溶液２は、水溶液中の水が光触媒によって分解される際に生ずる電子を外部回路に供給するのに対応してプロトンをもう一方の電極触媒に伝達するのに必要な物質である。 In the present embodiment, the acid contained in the acid aqueous solution 2 is not limited as long as the effects of the present embodiment can be achieved. For example, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, carbonic acid, etc. Can be mentioned. In particular, strongly acidic hydrochloric acid, sulfuric acid, and nitric acid, which can easily change the concentration of the aqueous acid solution, are particularly suitable. The acid aqueous solution 2 is a substance necessary for transmitting protons to the other electrode catalyst in response to supplying electrons generated when water in the aqueous solution is decomposed by the photocatalyst to an external circuit.
また本実施形態において、酸素ガス３は、プロトン及び電子と反応して水となり、一対の電極間に電気を流すのに必要な物質である。酸素ガス３は、収容部材外部から常時供給する構成としてもよく、また収容部材６中に密封された状態としても、または外部から供給せずに収容部材６内で循環する構成としてもよい。密封する場合、酸素ガスの圧力（分圧）としては、例えば０．２ａｔｍ以上１．１ａｔｍ以下の範囲内にあることが好ましい。 In the present embodiment, the oxygen gas 3 reacts with protons and electrons to become water, and is a substance necessary for flowing electricity between a pair of electrodes. The oxygen gas 3 may be constantly supplied from the outside of the housing member, may be sealed in the housing member 6, or may be circulated in the housing member 6 without being supplied from the outside. In the case of sealing, the pressure (partial pressure) of the oxygen gas is preferably in the range of 0.2 atm or more and 1.1 atm or less, for example.
また本実施形態において一対の電極４は、酸水溶液２中に浸されるとともに、水溶液中の水が光触媒によって分解される際に生ずる電子を外部回路に供給する一方、外部回路を経由して戻ってきた電子が電極４内において、酸水溶液２からイオン交換膜を通過したプロトン及び酸素ガスと反応して水を発生させる。本実施形態に係る電極４の材料としては、上記機能を有する限りにおいて限定されるわけではないが、Ｃ、ＩＴＯ（Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）、ＦＴＯ（ｆｌｕｏｒｉｎｅ−ｄｏｐｅｄ Ｔｉｎ Ｏｘｉｄｅ）、ＴＯ（Ｔｉｎ Ｏｘｉｄｅ）などを含んだものを採用することができる。なお、ＩＴＯ等の薄膜を電極として用いる場合、ガラス等の基板上に付することが好ましい。 In the present embodiment, the pair of electrodes 4 are immersed in the acid aqueous solution 2 and supply electrons generated when the water in the aqueous solution is decomposed by the photocatalyst to the external circuit, while returning via the external circuit. The generated electrons react with protons and oxygen gas that have passed through the ion exchange membrane from the acid aqueous solution 2 in the electrode 4 to generate water. The material of the electrode 4 according to the present embodiment is not limited as long as it has the above function, but C, ITO (Indium Tin Oxide), FTO (fluorine-doped Tin Oxide), TO (Tin Oxide), etc. It is possible to adopt one that includes In addition, when using thin films, such as ITO, as an electrode, attaching to substrates, such as glass, is preferable.
また本実施形態において光触媒５（アノード側）は、光が照射されることによって水溶液中の水を分解することができるものであり、より具体的には水を酸素、プロトン、電子に分解させるものである。本実施形態に係る光触媒５の例としては、上記機能を有する限りにおいて限定されるわけではないが、ＷＯ３、ＴｉＯ２、ＳｎＯ、及びＺｎＯの少なくともいずれかを含むものであることが好ましい。これらは２００ｎｍ以上７００ｎｍ以下の範囲の波長領域において上記分解活性を十分に発揮することができ、とりわけ紫外可視領域近傍の光で発電することが可能となる。 In the present embodiment, the photocatalyst 5 (anode side) is capable of decomposing water in the aqueous solution when irradiated with light, and more specifically, decomposes water into oxygen, protons, and electrons. It is. Examples of the photocatalyst 5 according to the present embodiment are not limited as long as the photocatalyst 5 has the above functions, but preferably include at least one of WO 3 , TiO 2 , SnO, and ZnO. These can sufficiently exhibit the above-described decomposition activity in a wavelength range of 200 nm or more and 700 nm or less, and in particular, can generate electric power with light in the vicinity of the ultraviolet-visible range.
なお、下記に、光触媒による反応について示す。本電池では、アノードで水を光分解して水素を得て、カソードでその水素を化学反応させる。この際の両極間での電子の移動を電力として得る。具体的には、水溶液に浸けたアノード電極光触媒に紫外可視光を照射すると、光触媒内に励起電子と正孔が発生する。この正孔が消費されることで、水が酸素とプロトンとに分解されて（下記反応式１）、電子が過剰の状態になる。この電子が外部回路を、反応１で生じたプロトンが酸水溶液および膜をそれぞれ伝わり、カソードに到達する。カソード電極光触媒の選択により、たとえばプロトンを酸素と反応させ、水に戻すことができる（下記反応式２）。またプロトンと電子との反応により水素ガスとして取り出すこともできる（下記反応式３）。
また本実施形態において、光触媒は、上記電極の両方の上に形成されていることが好ましい。電極上に光触媒を配置すると、電極に極めて近い位置で光触媒反応を起こし、水を酸素とプロトンに分解させる一方、電子を外部回路に供給させやすくなる。 また光触媒を、カソード側においても配置することが好ましい。カソード側の電極上に配置することで外部回路経由で伝達してきた電子が光触媒内に取り込まれやすくなり、その結果酸素ガスの光を利用した還元反応がより促進されるといった効果がある。 本実施形態に係る光触媒５（カソード側）の例としては、上記機能を有する限りにおいて限定されるわけではないが、ＷＯ３、およびナノ粒子担持ｎ型半導体、例えばＰｔ−ＴｉＯ２、Ａｇ−ＴｉＯ２、および各種ｐ型半導体、例えばＢｉＯＣｌ，ＣａＦｅ２Ｏ４，ＺｎＭｎ２Ｏ４，ＩｎＰ，ＡｇＧａＳ２の少なくともいずれかを含むものであることが好ましいが、これに限定されるものではない。ここでより仕事関数が大きい金属のナノ粒子に接した担持ｎ型半導体は、金属ナノ粒子との界面においてバンドが高エネルギー側に曲がるため、ｎ型半導体から金属ナノ粒子に流れた電子は逆に戻りにくくなり、整流作用を示すことでカソードにおいて円滑に光還元作用を示すと考えることができる。一方、各種ｐ型半導体では水溶液との界面においてバンドが低エネルギー側に曲がるため、カソードに用いた場合には水溶液中に電子を移行させやすく、やはり円滑に光還元作用を示すといえる。 In the present embodiment, the photocatalyst is preferably formed on both of the electrodes. When a photocatalyst is disposed on the electrode, a photocatalytic reaction occurs at a position very close to the electrode, and water is decomposed into oxygen and protons, while electrons are easily supplied to an external circuit. Moreover, it is preferable to arrange the photocatalyst also on the cathode side. By disposing on the cathode side electrode, the electrons transmitted through the external circuit are easily taken into the photocatalyst, and as a result, the reduction reaction using the light of oxygen gas is further promoted. Examples of the photocatalyst 5 (cathode side) according to the present embodiment are not limited as long as the photocatalyst 5 (cathode side) has the above function, but WO 3 and nanoparticle-supported n-type semiconductors such as Pt—TiO 2 and Ag—TiO 2 and various p-type semiconductors such as BiOCl, CaFe 2 O 4 , ZnMn 2 O 4 , InP, and AgGaS 2 are preferable, but are not limited thereto. Here, a supported n-type semiconductor in contact with a metal nanoparticle having a higher work function has a band that bends to the high energy side at the interface with the metal nanoparticle, so the electrons flowing from the n-type semiconductor to the metal nanoparticle are reversed. It becomes difficult to return, and it can be considered that the photoreduction action is smoothly shown in the cathode by showing the rectifying action. On the other hand, in various p-type semiconductors, the band bends to the low energy side at the interface with the aqueous solution, so that when used for the cathode, it is easy to transfer electrons into the aqueous solution, and it can be said that the photoreduction action is smoothly exhibited.
また本実施形態において、収容部材６は、上記のとおり、酸水溶液２、窒素ガスまたは酸素ガス３、一対の電極４及び光触媒５を収容し、少なくとも一部が透過性を有する部材で構成されている。ここでいう透過性とは、光触媒による反応に必要な範囲の光のうち６０％以上透過させるものをいい、より具体的には、上記２００ｎｍ以上７００ｎｍの波長範囲にある光のうち６０％を透過するものをいい、より好ましくは７０％、更に好ましくは８０％以上である。本実施形態に係る収容部材の材料としては、上記機能を有し、酸水溶液や酸素ガスと不要な反応をしない限りにおいて限定されるわけではないが、例えば金属やガラス等を用いることができ、一部に透過性を有する部材として、石英ガラス、耐熱ガラス等を用いることが好ましい。なおこの透過性を有する部材近傍に、電極を配置することが反応効率の観点から好ましい。 Moreover, in this embodiment, the accommodating member 6 accommodates the acid aqueous solution 2, the nitrogen gas or oxygen gas 3, the pair of electrodes 4 and the photocatalyst 5 as described above, and at least a part thereof is made of a permeable member. Yes. The term “transmittance” as used herein refers to light that transmits 60% or more of the light in the range necessary for the reaction by the photocatalyst, and more specifically, transmits 60% of the light in the wavelength range of 200 nm to 700 nm. More preferably, it is 70%, more preferably 80% or more. The material of the housing member according to the present embodiment is not limited as long as it has the above function and does not react unnecessarily with the aqueous acid solution or oxygen gas, but for example, metal or glass can be used, It is preferable to use quartz glass, heat-resistant glass, or the like as a partly permeable member. In addition, it is preferable from a viewpoint of reaction efficiency to arrange | position an electrode near the member which has this permeability | transmittance.
また本電池は、一対の電極の間に配置され、収容部材を分けるイオン交換膜７を有する。このイオン交換膜は異符号のイオンの通過を阻止し、同符号のイオンのみを通過させる性質を持ち、材料としては、上記機能を有する限りにおいて限定されるわけではないが、フッ素樹脂等の高分子樹脂中に、硫酸基やカルボキシル基などを含んだものを採用することができる。なおこのイオン交換膜７によって収納部材６の内部は２つに分割されることとなり、一方で水から酸素とプロトンが、他方からプロトンと酸素の反応によって水をえるものであるため、一方に酸素ガスを、他方に非酸化性のガス（例えば窒素ガス）等を充填させることが好ましい。またこのイオン交換膜７はイオンの効率的な移動のためには備えておくことが好ましいが、後述の実施例からも明らかなように、設けない場合も可能である。さらに、酸素ガスを外部から供給することなく、収容部材６内で循環させる構成も可能である。 Moreover, this battery has the ion exchange membrane 7 which is arrange | positioned between a pair of electrodes and divides an accommodating member. This ion-exchange membrane has the property of blocking the passage of ions with different signs and allowing only the ions with the same sign to pass through, and the material is not limited as long as it has the above functions, A molecular resin containing a sulfate group or a carboxyl group can be used. The ion exchange membrane 7 divides the inside of the housing member 6 into two parts. On the other hand, oxygen and protons are obtained from water and water is obtained from the other by the reaction of protons and oxygen. It is preferable to fill the other side with a non-oxidizing gas (for example, nitrogen gas) or the like. The ion exchange membrane 7 is preferably provided for the efficient movement of ions. However, as is apparent from the examples described later, the ion exchange membrane 7 may be omitted. Furthermore, a configuration in which oxygen gas is circulated in the housing member 6 without being supplied from the outside is also possible.
以上、本電池により、二酸化炭素を発生させることなく、より簡便な構成により電気を発生することのできる光触媒を用いた燃料電池を提供することができる。特に、本電池では、燃料としての水素を光触媒によって水から、なおかつ、その場で得ることができる。この動作原理により、従来の燃料としての水素あるいは有機燃料をセル自身に投入する必要がなく、原理的にきわめてクリーンで、安全である。水を分解してまた水に戻るというサイクルを中心にするため、二酸化炭素などの余計な環境負荷となる生成物も生じない。 As described above, this battery can provide a fuel cell using a photocatalyst that can generate electricity with a simpler configuration without generating carbon dioxide. In particular, in this battery, hydrogen as a fuel can be obtained from water and in situ by a photocatalyst. With this operating principle, it is not necessary to put hydrogen or organic fuel as a conventional fuel into the cell itself, and in principle it is extremely clean and safe. Since the center is a cycle in which water is decomposed and returned to water, no extra environmental load such as carbon dioxide is produced.
以下、上記実施形態にかかる電池の効果について実際に作成を行ない、その効果を確認した。以下具体的に示す。 Hereinafter, the effect of the battery according to the above embodiment was actually created, and the effect was confirmed. This is specifically shown below.
（実施例１：ＷＯ３） まず、タングステン酸アンモニウム５水和物（（ＮＨ
４）１０Ｗ１２Ｏ４１・５Ｈ２Ｏ）３．０１グラムを空気中、７００℃で、４時間焼成し酸化タングステンＷＯ３を得た。このＷＯ３について紫外可視スペクトルを測定すると、紫外光領域から４００〜５００ｎｍの可視光領域にかかる吸収端を示した。この結果を図２に示す。これより、このＷＯ３は半導体性を有することが分かった。
(Example 1: WO 3 ) First, ammonium tungstate pentahydrate ((NH
4) 10 W 12 O 41 · 5H 2 O) in air 3.01 grams at 700 ° C., to obtain a tungsten oxide WO 3 and fired 4 hours. When the UV-visible spectrum was measured for this WO 3 , an absorption edge from the ultraviolet light region to the visible light region of 400 to 500 nm was shown. The result is shown in FIG. From this, it was found that this WO 3 has semiconducting properties.
次に、上記で得られたＷＯ３１５９ミリグラムを石英窓付き耐熱ガラス製ガラス容器に入れ、ｐＨ２の塩酸水溶液、および犠牲酸化剤として５７ミリグラムの塩化鉄（ＩＩＩ）６水和物を加えた。４００ｒｐｍ（回転／分）で磁気攪拌を行いながら２時間アルゴンガスを流通させることで、水溶液中の溶存酸素を除去した。その後、容器を密閉し４８０Ｗキセノンアーク灯から光照射し、同じく４００ｒｐｍで磁気攪拌を続けた。アーク灯照射直前、２．５時間後、５時間後、７．５時間後、１０時間後の容器中各気相部分を取り出し、熱伝導度検出器（ＴＣＤ）式ガスクロマトグラフィで分析した。分析結果を図３および下記表１に示す。１０時間の反応試験でＯ２ガスの継続的生成が認められ、生成Ｏ２量は時間とともに直線的に増加した。以上から、ＷＯ３により水の光酸化分解が起き、Ｏ２ガスが生成することが示された。 Next, 159 mg of WO 3 obtained above was put into a glass container made of heat-resistant glass with a quartz window, and an aqueous hydrochloric acid solution having pH 2 and 57 mg of iron (III) chloride hexahydrate as a sacrificial oxidizing agent were added. Dissolved oxygen in the aqueous solution was removed by circulating argon gas for 2 hours while performing magnetic stirring at 400 rpm (rotation / min). Thereafter, the container was sealed and irradiated with light from a 480 W xenon arc lamp, and magnetic stirring was continued at 400 rpm. Immediately before irradiation with the arc lamp, 2.5 hours, 5 hours, 7.5 hours, and 10 hours, each gas phase portion in the container was taken out and analyzed by a thermal conductivity detector (TCD) type gas chromatography. The analysis results are shown in FIG. In the 10-hour reaction test, continuous production of O 2 gas was observed, and the amount of produced O 2 increased linearly with time. From the above, it was shown that the photo-oxidative decomposition of water occurs by WO 3 and O 2 gas is generated.
一方、上記で得られたＷＯ３１６０ミリグラムを石英窓付き耐熱ガラス製ガラス容器に入れ、ｐＨ２の塩酸水溶液、および犠牲酸化剤として５８ミリグラムの塩化鉄（ＩＩＩ）６水和物を加えた。容器をアルミホイルで覆って完全に遮光し、４００ｒｐｍで磁気攪拌を行いながら２時間アルゴンガスを流通させ水溶液中の溶存酸素を除去した。さらに容器を遮光したまま密閉し４００ｒｐｍで磁気攪拌を続けた。５時間後の容器中の気相部分をＴＣＤ式ガスクロマトグラフィで分析した。分析結果を下記表１に示す。遮光時にはＯ２ガスの生成が認められず、ＷＯ３による水の酸化分解は光照射が原因となって起きたことの裏付けとなった。
また、カーボン紙（ケミックス製；面積２０×２１ ｍｍ２）に２８ミリグラムのＷＯ３をマウントし、ＷＯ３電極とした。同様にカーボン紙に酸化チタン（Ｐ２５、日本アエロジル製）６４ミリグラムをマウントしＴｉＯ２電極とした。 Further, 28 mg of WO 3 was mounted on carbon paper (made by Chemix; area 20 × 21 mm 2 ) to obtain a WO 3 electrode. Similarly, 64 mg of titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was mounted on carbon paper to form a TiO 2 electrode.
そして、両側に石英窓が付いた耐熱ガラスガラス容器の中央をプロトン伝導性高分子膜で仕切って反応セルとした（図４）。両側にｐＨ３の塩酸水溶液を加え、ＷＯ３電極およびＴｉＯ２電極を、それぞれの水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。 Then, the center of a heat-resistant glass glass container with quartz windows on both sides was partitioned with a proton conductive polymer membrane to form a reaction cell (FIG. 4). A hydrochloric acid aqueous solution of pH 3 was added to both sides, and a WO 3 electrode and a TiO 2 electrode were immersed in each aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised.
その後、ＷＯ３電極およびＴｉＯ２電極に、それぞれ窒素、酸素ガスを１００ｍＬ／ｍｉｎの速度でバブリングしながら流通させ、ＷＯ３電極に４８０Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。ガスは流通させたままとした。このｏｎ／ｏｆｆサイクルを５回繰り返し、回路に流れる電流の変化をモニターした。 Thereafter, nitrogen and oxygen gas were passed through the WO 3 electrode and the TiO 2 electrode while bubbling at a rate of 100 mL / min, respectively, and the WO 3 electrode was irradiated with light from a 480 W arc lamp. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. The gas remained in circulation. This on / off cycle was repeated 5 times, and the change in the current flowing through the circuit was monitored.
この測定結果を図６に示す。アーク灯照射中にＴｉＯ２電極からＷＯ３電極への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。２Ｈ２Ｏ→Ｏ２＋４Ｈ＋＋４ｅ−の反応式に従いＴｉＯ２電極が水を光酸化して、光反応セルその場でプロトンが得られたことが分かる。電流値は１．４〜５．８μＡの間であった（下記表３参照）。 The measurement results are shown in FIG. Electron movement from the TiO 2 electrode to the WO 3 electrode (or current in the reverse direction) was observed during the arc lamp irradiation, and as soon as the arc lamp irradiation was stopped, the electron movement also stopped. It can be seen that the TiO 2 electrode photooxidized water according to the reaction formula of 2H 2 O → O 2 + 4H + + 4e − , and protons were obtained in situ in the photoreaction cell. The current value was between 1.4 and 5.8 μA (see Table 3 below).
（実施例２：酸化チタン） まず、ヘキサクロロ白金酸６水和物（Ｈ＋ ２［ＰｔＩＶＣｌ６］２−・６Ｈ２Ｏ、３０ミリグラム）を含む水溶液（３ ｍＬ）に、酸化チタン（Ｐ２５、日本アエロジル製）を１．０２グラム加えた。磁気攪拌および超音波処理し、湯浴で水を留去後１００℃で２４時間乾燥させた。乾燥後の粉末を空気中４００℃で２時間焼成し、Ｐｔ／ＴｉＯ２を得た。カーボン紙（面積２．０ ｃｍ２）にＴｉＯ２（６５ミリグラム）を物理的にマウントし、ＴｉＯ２電極とした。また、カーボン紙（面積２．０ ｃｍ２）にＰｔ／ＴｉＯ２（６０ミリグラム）を物理的にマウントし、Ｐｔ／ＴｉＯ２電極とした。 (Example 2: Titanium oxide) First, the hexachloroplatinic acid hexahydrate (H + 2 [Pt IV Cl 6] 2- · 6H 2 O, 30 mg) aqueous solution containing (3 mL), titanium oxide (P25 , Nippon Aerosil Co., Ltd.) was added. Magnetic stirring and sonication were performed, and water was distilled off in a hot water bath, followed by drying at 100 ° C. for 24 hours. The dried powder was fired in air at 400 ° C. for 2 hours to obtain Pt / TiO 2 . TiO 2 (65 mg) was physically mounted on carbon paper (area 2.0 cm 2 ) to form a TiO 2 electrode. Further, Pt / TiO 2 (60 milligrams) was physically mounted on carbon paper (area 2.0 cm 2 ) to form a Pt / TiO 2 electrode.
そして、両側に石英窓が付いた耐熱ガラスガラス容器の中央をプロトン伝導性高分子膜で仕切って反応セルとした（図４）。両側にｐＨ３の塩酸水溶液を加えた。上記で作成したＴｉＯ２電極およびＰｔ／ＴｉＯ２電極を、それぞれの水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。ＴｉＯ２電極およびＰｔ／ＴｉＯ２電極に、それぞれ窒素、酸素ガスを１００ ｍＬ／ｍｉｎの速度でバブリングしながら流通させ、ＴｉＯ２電極およびＰｔ／ＴｉＯ２電極双方に４８０ Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。ガスは流通させたままとした。このｏｎ／ｏｆｆサイクルを５回繰り返し、回路に流れる電流の変化をモニターした。 Then, the center of a heat-resistant glass glass container with quartz windows on both sides was partitioned with a proton conductive polymer membrane to form a reaction cell (FIG. 4). A pH 3 aqueous hydrochloric acid solution was added to both sides. The TiO 2 electrode and Pt / TiO 2 electrode prepared above were immersed in each aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised. The TiO 2 electrodes and Pt / TiO 2 electrode, respectively nitrogen, is circulated while bubbling oxygen gas at a rate of 100 mL / min, and the light irradiated from the TiO 2 electrode and Pt / TiO 2 electrode both the 480 W arc lamp. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. The gas remained in circulation. This on / off cycle was repeated 5 times, and the change in the current flowing through the circuit was monitored.
測定結果を図７に示す。アーク灯照射中にＴｉＯ２電極からＰｔ／ＴｉＯ２電極への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。２Ｈ２Ｏ→Ｏ２＋４Ｈ＋＋４ｅ−の反応式に従い、ＴｉＯ２電極が水を光酸化してその場でプロトンが得られ、同時に得られた電子が外部回路を経てカソード側の光触媒Ｐｔ／ＴｉＯ２によってプロトンとの光触媒反応により消費されたことが分かった。電流値は２７〜５９μＡの間であった（下記表３参照）。 The measurement results are shown in FIG. Electron movement from the TiO 2 electrode to the Pt / TiO 2 electrode (or current in the reverse direction) was observed during the arc lamp irradiation, and the electron movement stopped as soon as the arc lamp irradiation was stopped. According to the reaction formula of 2H 2 O → O 2 + 4H + + 4e − , the TiO 2 electrode photooxidizes water to obtain protons on the spot, and at the same time, the obtained electrons pass through an external circuit to the photocatalyst Pt / TiO on the cathode side 2 was found to be consumed by photocatalytic reaction with protons. The current value was between 27 and 59 μA (see Table 3 below).
（実施例３） まず、０．１５ ｍＬの水に、実施例２で得られたＰｔ／ＴｉＯ２を１０．７ミリグラム加え撹拌し、Ｐｔ／ＴｉＯ２ペーストを作成した。 (Example 3) First, 10.7 milligrams of Pt / TiO 2 obtained in Example 2 was added to 0.15 mL of water and stirred to prepare a Pt / TiO 2 paste.
ＩＴＯ被膜付ガラス（面積２５×１７ｍｍ２）にＴｉＯ２ペースト（Ｐｅｃｃｅｌｌ製）を塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ １０．５ミリグラム）とした。同様に、ＩＴＯ被膜付ガラス（面積１６×８ｍｍ２）にＰｔ／ＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＰｔ／ＴｉＯ２電極（Ｐｔ／ＴｉＯ２ ６．０ミリグラム）とした。 A glass with ITO coating (area 25 × 17 mm 2 ) was coated with a TiO 2 paste (Peccell), dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to obtain a TiO 2 electrode (TiO 2 10.5 mg). . Similarly, a Pt / TiO 2 paste is applied to ITO-coated glass (area 16 × 8 mm 2 ), dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to form a Pt / TiO 2 electrode (Pt / TiO 2 6. 0 milligrams).
上記実施例２と同様の反応セル（図４）中、両側にｐＨ３の塩酸水溶液を加えた。上記で作成したＴｉＯ２電極およびＰｔ／ＴｉＯ２電極を、それぞれの水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。ＴｉＯ２電極およびＰｔ／ＴｉＯ２電極に、それぞれ窒素、酸素ガスを１００ｍＬ／ｍｉｎの速度でバブリングしながら流通させ、ＴｉＯ２電極およびＰｔ／ＴｉＯ２電極双方に４８０Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。ガスは流通させたままとした。このｏｎ／ｏｆｆサイクルを５回繰り返し、回路に流れる電流の変化をモニターした。合計５時間のモニター後、アーク灯照射下で１５分間、アーク灯消灯下で１５分間、この光燃料電池の起電力を測定した。 In the same reaction cell as in Example 2 (FIG. 4), an aqueous hydrochloric acid solution having pH 3 was added to both sides. The TiO 2 electrode and Pt / TiO 2 electrode prepared above were immersed in each aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised. The TiO 2 electrodes and Pt / TiO 2 electrode, respectively nitrogen, oxygen gas was passed through bubbling at a rate of 100 mL / min, was irradiated with light from 480W arc lamp on both TiO 2 electrodes and Pt / TiO 2 electrode. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. The gas remained in circulation. This on / off cycle was repeated 5 times, and the change in the current flowing through the circuit was monitored. After monitoring for a total of 5 hours, the electromotive force of this photovoltaic cell was measured for 15 minutes under irradiation with an arc lamp and for 15 minutes with the arc lamp turned off.
測定結果を図８、９に示す。アーク灯照射中にＰｔ／ＴｉＯ２電極側への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。これに加えて、アーク灯の照射時は電位差も１４倍程度に大幅に増加している。２Ｈ２Ｏ→Ｏ２＋４Ｈ＋＋４ｅ−の反応式に従い、ＴｉＯ２電極が水を光酸化してその場でプロトンが得られ、その電子がカソード側の光触媒Ｐｔ／ＴｉＯ２によってプロトンとの光触媒反応により消費され、電流および０．８９Ｖの起電力が生じたことが分かった。電流値は１８〜４０μＡの間であった（下記表３参照）。 The measurement results are shown in FIGS. Electron movement toward the Pt / TiO 2 electrode side (or current in the reverse direction) was observed during arc lamp irradiation, and as soon as the arc lamp irradiation was stopped, electron movement also stopped. In addition to this, the potential difference greatly increases by about 14 times when the arc lamp is irradiated. According to the reaction formula of 2H 2 O → O 2 + 4H + + 4e − , the TiO 2 electrode photooxidizes water to obtain protons in situ, and the electrons undergo photocatalytic reaction with protons by the photocatalyst Pt / TiO 2 on the cathode side. It was found that a current and an electromotive force of 0.89V were generated. The current value was between 18 and 40 μA (see Table 3 below).
（実施例４） まず、酸化チタン（Ｐ２５）１．００グラムを３ｍＬの水に加え、磁気攪拌および超音波処理し、湯浴で水を留去後１００℃で２４時間乾燥させた。乾燥後の粉末を空気中４００℃で２時間焼成した。０．１５ｍＬの水に焼成済ＴｉＯ２を１１．１ミリグラム加え、撹拌してＴｉＯ２ペーストを作成した。 (Example 4) First, 1.00 g of titanium oxide (P25) was added to 3 mL of water, subjected to magnetic stirring and ultrasonic treatment, water was distilled off in a hot water bath, and then dried at 100 ° C for 24 hours. The dried powder was fired in air at 400 ° C. for 2 hours. 11.1 milligrams of baked TiO 2 was added to 0.15 mL of water and stirred to create a TiO 2 paste.
ＩＴＯ被膜付ガラス（面積１３×９ｍｍ２）にＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ ５．０ミリグラム）とした。同様に、上記実施例と同様にしてＰｔ／ＴｉＯ２電極（面積１４×１０ｍｍ２、Ｐｔ／ＴｉＯ２ ５．７ミリグラム）を得た。 A glass with ITO coating (area 13 × 9 mm 2 ) was coated with a TiO 2 paste, dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to form a TiO 2 electrode (TiO 2 5.0 mg). Similarly, a Pt / TiO 2 electrode (area 14 × 10 mm 2 , Pt / TiO 2 5.7 mg) was obtained in the same manner as in the above example.
次に、両側に石英窓が付いた耐熱ガラス製反応セル（図１０）中に、ｐＨ３の塩酸水溶液を加えた。上記で作成したＴｉＯ２電極およびＰｔ／ＴｉＯ２電極を水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。セル内に酸素ガスを１００ｍＬ／ｍｉｎの速度で５時間バブリングして流通させた。その後容器を密閉し、ＴｉＯ２電極およびＰｔ／ＴｉＯ２電極双方に４８０ Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。このｏｎ／ｏｆｆサイクルを５回繰り返し、回路に流れる電流の変化をモニターした。 Next, an aqueous hydrochloric acid solution having a pH of 3 was added into a heat-resistant glass reaction cell (FIG. 10) with quartz windows on both sides. The TiO 2 electrode and Pt / TiO 2 electrode prepared above were immersed in an aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised. Oxygen gas was bubbled through the cell for 5 hours at a rate of 100 mL / min. Thereafter, the container was sealed, and both the TiO 2 electrode and the Pt / TiO 2 electrode were irradiated with light from a 480 W arc lamp. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. This on / off cycle was repeated 5 times, and the change in the current flowing through the circuit was monitored.
測定結果を図１１に示す。アーク灯照射中にＴｉＯ２電極からＰｔ／ＴｉＯ２電極への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。光燃料電池を完全に閉鎖した系とし、酸素や窒素を流通させるのではなく酸素を充填した条件で、さらにアノード側・カソード側の両電解槽をプロトン電導膜で仕切らずに同一電解槽とした条件でも発電が可能であることが示された。電流値は６．４〜１４μＡの間であった（下記表３参照）。
（実施例５） まず、酸化チタン（Ｐ２５）１．００グラムを３ｍＬの水に加え、磁気攪拌および超音波処理し、湯浴で水を留去後１００℃で２４時間乾燥させた。乾燥後の粉末を空気中４００℃で２時間焼成した。０．１５ｍＬの水に焼成済ＴｉＯ２を１０．２ミリグラム加え、撹拌してＴｉＯ２ペーストを作成した。 (Example 5) First, 1.00 g of titanium oxide (P25) was added to 3 mL of water, subjected to magnetic stirring and ultrasonic treatment, water was distilled off in a hot water bath, and dried at 100 ° C for 24 hours. The dried powder was fired in air at 400 ° C. for 2 hours. 10.2 milligrams of baked TiO 2 was added to 0.15 mL of water and stirred to create a TiO 2 paste.
ＩＴＯ被膜付ガラス（面積１７×１０ｍｍ２）にＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ ５．５ミリグラム）とした。 A TiO 2 paste was applied to glass with an ITO film (area: 17 × 10 mm 2 ), dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to form a TiO 2 electrode (TiO 2 5.5 mg).
ＩＴＯ被膜付ガラス（面積１６×９ｍｍ２）にＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ ４．３ミリグラム）とした。 A TiO 2 paste was applied to glass with an ITO coating (area 16 × 9 mm 2 ), dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to form a TiO 2 electrode (TiO 2 4.3 mg).
ＩＴＯ被膜付ガラス（面積１６×１０ｍｍ２）にＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ ４．９ミリグラム）とした。 A TiO 2 paste was applied to glass with an ITO film (area 16 × 10 mm 2 ), dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to obtain a TiO 2 electrode (4.9 mg of TiO 2 ).
硝酸銀（ＡｇＮО３、１８ミリグラム）を含む水溶液（１０．３ｍＬ）に、酸化チタン（Ｐ２５、日本アエロ
ジル製）を３．４３グラム加えた。磁気攪拌および超音波処理し、湯浴で水を留去後１００℃で２４時間乾燥させた。乾燥後の粉末を空気中４００℃で２時間焼成し、Ａｇ／ＴｉＯ２（０．３３重量％−Ａｇ）を得た。ＩＴＯ被膜付ガラス（面積１６×８ｍｍ２）にＡｇ／ＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＡｇ／ＴｉＯ２（０．３３重量％−Ａｇ）電極５．６ミリグラムを得た。
To an aqueous solution (10.3 mL) containing silver nitrate (AgNO 3 , 18 mg), 3.43 g of titanium oxide (P25, manufactured by Nippon Aerosil Co., Ltd.) was added. Magnetic stirring and sonication were performed, and water was distilled off in a hot water bath, followed by drying at 100 ° C. for 24 hours. The dried powder was fired in air at 400 ° C. for 2 hours to obtain Ag / TiO 2 (0.33% by weight-Ag). An ITO / coated glass (area 16 × 8 mm 2 ) was coated with an Ag / TiO 2 paste, dried at 100 ° C., heated in air at 300 ° C. for 30 minutes, and Ag / TiO 2 (0.33% by weight-Ag) electrode 5 .6 milligrams were obtained.
硝酸銀（２４ミリグラム）を含む水溶液（４．６５ｍＬ）に、酸化チタン（Ｐ２５）を１．５４グラム加えた。磁気攪拌および超音波処理し、湯浴で水を留去後１００℃で２４時間乾燥させた。乾燥後の粉末を空気中４００℃で２時間焼成し、Ａｇ／ＴｉＯ２（１．０重量％−Ａｇ）を得た。上記と同様にしてＡｇ／ＴｉＯ２（１．０重量％−Ａｇ）電極５．３ミリグラムを得た。 To an aqueous solution (4.65 mL) containing silver nitrate (24 milligrams), 1.54 grams of titanium oxide (P25) was added. Magnetic stirring and sonication were performed, and water was distilled off in a hot water bath, followed by drying at 100 ° C. for 24 hours. The dried powder was fired in air at 400 ° C. for 2 hours to obtain Ag / TiO 2 (1.0 wt% -Ag). In the same manner as described above, 5.3 mg of an Ag / TiO 2 (1.0 wt% -Ag) electrode was obtained.
硝酸銀（６５ミリグラム）を含む水溶液（４．１ｍＬ）に、酸化チタン（Ｐ２５）を１．３８グラム加えた。磁気攪拌および超音波処理し、湯浴で水を留去後１００℃で２４時間乾燥させた。乾燥後の粉末を空気中４００℃で２時間焼成し、Ａｇ／ＴｉＯ２（３．０重量％−Ａｇ）を得た。上記と同様にしてＡｇ／ＴｉＯ２（３．０重量％−Ａｇ）電極５．８ミリグラムを得た。 1.38 g of titanium oxide (P25) was added to an aqueous solution (4.1 mL) containing silver nitrate (65 mg). Magnetic stirring and sonication were performed, and water was distilled off in a hot water bath, followed by drying at 100 ° C. for 24 hours. The dried powder was fired in air at 400 ° C. for 2 hours to obtain Ag / TiO 2 (3.0 wt% -Ag). In the same manner as described above, 5.8 mg of an Ag / TiO 2 (3.0 wt% -Ag) electrode was obtained.
上記実施例２および３と同様の反応セル（図４）中、両側にｐＨ３の塩酸水溶液を加えた。上記実施例で作成したＴｉＯ２電極および上記のＡｇ／ＴｉＯ２（０．３３、１．０、あるいは３．０重量％−Ａｇ）電極を、それぞれの水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。ＴｉＯ２電極およびＡｇ／ＴｉＯ２電極に、それぞれ窒素、酸素ガスを１００ｍＬ／ｍｉｎの速度でバブリングしながら流通させ、ＴｉＯ２電極およびＡｇ／ＴｉＯ２電極双方に４８０Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。ガスは流通させたままとした。このｏｎ／ｏｆｆサイクルを５回繰り返し、回路に流れる電流の変化をモニターした。 In the same reaction cell as in Examples 2 and 3 (FIG. 4), a hydrochloric acid aqueous solution having a pH of 3 was added to both sides. The TiO 2 electrode prepared in the above example and the above Ag / TiO 2 (0.33, 1.0, or 3.0 wt% -Ag) electrode were immersed in each aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised. The TiO 2 electrode and Ag / TiO 2 electrode, respectively nitrogen, oxygen gas was passed through bubbling at a rate of 100 mL / min, was irradiated with light from 480W arc lamp on both TiO 2 electrode and Ag / TiO 2 electrode. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. The gas remained in circulation. This on / off cycle was repeated 5 times, and the change in the current flowing through the circuit was monitored.
測定結果を図１２に示す。アーク灯照射中にＴｉＯ２電極からＡｇ／ＴｉＯ２電極への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。カソード触媒がＡｇ／ＴｉＯ２でも発電が可能であることが示され、電流値もＡｇの担持量に応じて上昇することが示された。電流値はＡｇ／ＴｉＯ２（０．３３重量％−Ａｇ）電極、Ａｇ／ＴｉＯ２（１．０重量％−Ａｇ）電極、Ａｇ／ＴｉＯ２（３．０重量％−Ａｇ）電極、でそれぞれ９．４〜１３μＡ、１５〜２１μＡ、２２〜２７μＡの間であった（下記表５参照）。 The measurement results are shown in FIG. Electron movement from the TiO 2 electrode to the Ag / TiO 2 electrode (or current in the reverse direction) was observed during the arc lamp irradiation, and as soon as the arc lamp irradiation was stopped, the electron movement also stopped. It was shown that power can be generated even when the cathode catalyst is Ag / TiO 2 , and the current value was also shown to increase according to the amount of Ag supported. The current values are Ag / TiO 2 (0.33% by weight-Ag) electrode, Ag / TiO 2 (1.0% by weight-Ag) electrode, and Ag / TiO 2 (3.0% by weight-Ag) electrode, respectively. It was between 9.4-13 μA, 15-21 μA, 22-27 μA (see Table 5 below).
（実施例６）
エチレングリコール６５ｍＬに１．６１グラムの硝酸ビスマス・５水和物（Ｂｉ（ＮＯ３）３・５Ｈ２Ｏ）とＣＴＡＣ（セチルトリメチルアンモニウムクロリド）（［（ＣＨ３）３ＮＣ１６Ｈ３３］Ｃｌ）１．０６グラムを混合、１７℃で１時間攪拌した。これに１．０Ｍ ＫＯＨのエチレングリコール溶液を加えｐＨを１．０に調整した。この溶液をオートクレーブに封入し、１６０℃で１２時間置いた。得られた沈殿物を水とエタノールで洗浄し、５０℃で１８時間乾燥させ、オキシ塩化ビスマスＢｉＯＣｌを得た。
(Example 6)
1.61 grams of bismuth nitrate pentahydrate (Bi (NO 3 ) 3 .5H 2 O) and CTAC (cetyltrimethylammonium chloride) ([(CH 3 ) 3 NC 16 H 33 ] Cl) in 65 mL of ethylene glycol 1.06 grams were mixed and stirred at 17 ° C. for 1 hour. To this was added 1.0M KOH ethylene glycol solution to adjust the pH to 1.0. This solution was sealed in an autoclave and placed at 160 ° C. for 12 hours. The obtained precipitate was washed with water and ethanol and dried at 50 ° C. for 18 hours to obtain bismuth oxychloride BiOCl.
上記ＢｉＯＣｌについて紫外可視スペクトルを測定すると３００〜４００ ｎｍの紫外光領域に吸収端を示した。この結果を図１３に示す。これより、このＢｉＯＣｌは半導体性を有することが分かった。 When an ultraviolet-visible spectrum was measured for the BiOCl, an absorption edge was shown in the ultraviolet light region of 300 to 400 nm. The result is shown in FIG. From this, it was found that this BiOCl has semiconducting properties.
０．１５ｍＬの水に、ＴｉＯ２（Ｐ２５）を１０．１ミリグラム加え撹拌し、ＴｉＯ２ペーストを作成した。ＩＴＯ被膜付ガラス（面積１３×１０ｍｍ２）にＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ ６．３ミリグラム）とした。同様に、ＢｉＯＣｌ電極（面積１４×１０ｍｍ２、ＢｉＯＣｌ ３．３ミリグラム）を得た。 10.1 milligrams of TiO 2 (P25) was added to 0.15 mL of water and stirred to prepare a TiO 2 paste. A glass with ITO coating (area 13 × 10 mm 2 ) was coated with a TiO 2 paste, dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to form a TiO 2 electrode (TiO 2 6.3 mg). Similarly, a BiOCl electrode (area 14 × 10 mm 2 , BiOCl 3.3 mg) was obtained.
上記実施例２、３および５と同様の反応セル（図４）中、両側にｐＨ３の塩酸水溶液を加えた。上記で作成したＴｉＯ２電極およびＢｉＯＣｌ電極を、それぞれの水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。ＴｉＯ２電極およびＢｉＯＣｌ電極に、それぞれ窒素、酸素ガスを１００ ｍＬ／ｍｉｎの速度でバブリングしながら流通させ、ＴｉＯ２電極およびＢｉＯＣｌ電極双方に４８０Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。ガスは流通させたままとした。このｏｎ／ｏｆｆサイクルを５回繰り返し、回路に流れる電流の変化をモニターした。 In the same reaction cell as in Examples 2, 3 and 5 (FIG. 4), an aqueous hydrochloric acid solution having pH 3 was added to both sides. The TiO 2 electrode and BiOCl electrode prepared above were immersed in each aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised. The TiO 2 electrode and BiOCl electrodes, respectively nitrogen, oxygen gas was passed through bubbling at a rate of 100 mL / min, it was irradiated with light from 480W arc lamp on both TiO 2 electrode and BiOCl electrode. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. The gas remained in circulation. This on / off cycle was repeated 5 times, and the change in the current flowing through the circuit was monitored.
測定結果を図１４に示す。アーク灯照射中にＴｉＯ２電極からＢｉＯＣｌ電極への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。２Ｈ２Ｏ→Ｏ２＋４Ｈ＋＋４ｅ−の反応式に従い、ＴｉＯ２電極が水を光酸化してその場でプロトンが得られ、同時に得られた電子が外部回路を経てカソード側の光触媒ＢｉＯＣｌによってプロトンとの光触媒反応により消費されたことが分かった。電流値は２６〜３４μＡの間であった（下記表７参照）。 The measurement results are shown in FIG. Electron movement from the TiO 2 electrode to the BiOCl electrode (or current in the reverse direction) was observed during the arc lamp irradiation, and the electron movement stopped as soon as the arc lamp irradiation was stopped. According to the reaction formula of 2H 2 O → O 2 + 4H + + 4e − , the TiO 2 electrode photooxidizes water to obtain protons on the spot, and simultaneously the obtained electrons are protonated by the photocatalyst BiOCl on the cathode side through an external circuit. It was found that the photocatalytic reaction was consumed. The current value was between 26 and 34 μA (see Table 7 below).
（実施例７）
０．１５ｍＬの水に、ＴｉＯ２（Ｐ２５）を１０．３ミリグラム加え撹拌し、ＴｉＯ２ペーストを作成した。ＩＴＯ被膜付ガラス（面積１４×９ｍｍ２）にＴｉＯ２ペーストを塗布し１００℃で乾燥後、空気中３００℃で３０分間加熱しＴｉＯ２電極（ＴｉＯ２ ６．４ミリグラム）とした。同様に、ＢｉＯＣｌ電極（面積１５×１０ｍｍ２、ＢｉＯＣｌ ３．７ミリグラム）を得た。
(Example 7)
10.3 milligrams of TiO 2 (P25) was added to 0.15 mL of water and stirred to prepare a TiO 2 paste. A TiO 2 paste was applied to glass with an ITO film (area: 14 × 9 mm 2 ), dried at 100 ° C., and then heated in air at 300 ° C. for 30 minutes to form a TiO 2 electrode (TiO 2 6.4 mg). Similarly, a BiOCl electrode (area 15 × 10 mm 2 , BiOCl 3.7 mg) was obtained.
上記実施例２、３および５と同様の反応セル（図４）中、両側にｐＨ２の塩酸水溶液を加えた。上記で作成したＴｉＯ２電極およびＢｉＯＣｌ電極を、それぞれの水溶液に浸した。さらに両電極を結線した回路（図５）を構成した。ＴｉＯ２電極およびＢｉＯＣｌ電極に、それぞれ窒素、酸素ガスを１００ ｍＬ／ｍｉｎの速度でバブリングしながら流通させ、ＴｉＯ２電極およびＢｉＯＣｌ電極双方に４８０Ｗアーク灯から光照射した。３０分間光照射した後、光照射を３０分間停止した。ガスは流通させたままとした。このｏｎ／ｏｆｆサイクルを５回繰り返した後、１時間光照射を続け、回路に流れる電流の変化をモニターした。 In the same reaction cell as in Examples 2, 3 and 5 (FIG. 4), an aqueous hydrochloric acid solution having pH 2 was added on both sides. The TiO 2 electrode and BiOCl electrode prepared above were immersed in each aqueous solution. Furthermore, the circuit (FIG. 5) which connected both electrodes was comprised. The TiO 2 electrode and BiOCl electrodes, respectively nitrogen, oxygen gas was passed through bubbling at a rate of 100 mL / min, it was irradiated with light from 480W arc lamp on both TiO 2 electrode and BiOCl electrode. After 30 minutes of light irradiation, the light irradiation was stopped for 30 minutes. The gas remained in circulation. After repeating this on / off cycle 5 times, light irradiation was continued for 1 hour, and the change in the current flowing through the circuit was monitored.
測定結果を図１５に示す。アーク灯照射中にＴｉＯ２電極からＢｉＯＣｌ電極への電子移動（あるいは逆方向への電流）が認められ、アーク灯の照射を止めるとすぐに電子移動も停止した。２Ｈ２Ｏ→Ｏ２＋４Ｈ＋＋４ｅ−の反応式に従い、ＴｉＯ２電極が水を光酸化してその場でプロトンが得られ、同時に得られた電子が外部回路を経てカソード側の光触媒ＢｉＯＣｌによってプロトンとの光触媒反応により消費されたことが分かった。電流値は５９〜２１１μＡの間であった（下記表７参照）。 The measurement results are shown in FIG. Electron movement from the TiO 2 electrode to the BiOCl electrode (or current in the reverse direction) was observed during the arc lamp irradiation, and the electron movement stopped as soon as the arc lamp irradiation was stopped. According to the reaction formula of 2H 2 O → O 2 + 4H + + 4e − , the TiO 2 electrode photooxidizes water to obtain protons on the spot, and simultaneously the obtained electrons are protonated by the photocatalyst BiOCl on the cathode side through an external circuit. It was found that the photocatalytic reaction was consumed. The current value was between 59 and 211 μA (see Table 7 below).
以上、本電池により、二酸化炭素を発生させることなく、より簡便な構成により電気を発生することのできる光触媒を用いた燃料電池を提供することができることを確認した。特に、本電池では、燃料としての水素を光触媒によって水から、なおかつ、その場で得ることができる。この動作原理により、従来の燃料としての水素あるいは有機燃料をセル自身に投入する必要がなく、原理的にきわめてクリーンで、安全である。水を分解してまた水に戻るというサイクルを中心にするため、二酸化炭素などの余計な環境負荷となる生成物も生じないといった効果もある。 As described above, it was confirmed that this battery can provide a fuel cell using a photocatalyst that can generate electricity with a simpler configuration without generating carbon dioxide. In particular, in this battery, hydrogen as a fuel can be obtained from water and in situ by a photocatalyst. With this operating principle, it is not necessary to put hydrogen or organic fuel as a conventional fuel into the cell itself, and in principle it is extremely clean and safe. Since it is centered on a cycle of decomposing water and returning to water, there is also an effect that no extra environmental load such as carbon dioxide is produced.
Claims (6)
前記酸水溶液中に浸され、一方が前記酸水溶液中の水を酸素とプロトンに分解する光触媒が形成されてなり、他方が前記プロトンと酸素を反応させて水に戻す光触媒が形成されてなる一対の電極と、
前記酸水溶液、酸素ガス、及び、前記光触媒が形成された一対の電極を収容し、少なくとも一部が光透過性を有する部材で構成される収容部材と、
前記一対の電極の間に配置され、前記収容部材を分け、かつ、前記プロトンを透過可能なイオン交換膜と、
を有する燃料電池。 An acid aqueous solution;
A pair formed by forming a photocatalyst that is immersed in the acid aqueous solution, one of which decomposes the water in the acid aqueous solution into oxygen and proton, and the other that reacts the proton with oxygen to return to water. Electrodes,
A housing member that houses the acid aqueous solution, oxygen gas, and a pair of electrodes on which the photocatalyst is formed, and at least a part of which is made of a light- transmissive member;
An ion exchange membrane disposed between the pair of electrodes, separating the housing member , and permeable to the protons ;
A fuel cell.
The fuel cell according to claim 1, wherein a space for accommodating the acid aqueous solution, the oxygen gas, the pair of electrodes, and the photocatalyst is sealed.
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