JP5657913B2 - Hydrogen production method using nanocomposite semiconductor photocatalyst material and aqueous methanol solution - Google Patents
Hydrogen production method using nanocomposite semiconductor photocatalyst material and aqueous methanol solution Download PDFInfo
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- JP5657913B2 JP5657913B2 JP2010108000A JP2010108000A JP5657913B2 JP 5657913 B2 JP5657913 B2 JP 5657913B2 JP 2010108000 A JP2010108000 A JP 2010108000A JP 2010108000 A JP2010108000 A JP 2010108000A JP 5657913 B2 JP5657913 B2 JP 5657913B2
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- titanium oxide
- hydrogen
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims description 57
- 239000001257 hydrogen Substances 0.000 title claims description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 39
- 239000002114 nanocomposite Substances 0.000 title claims description 38
- 239000011941 photocatalyst Substances 0.000 title claims description 37
- 239000004065 semiconductor Substances 0.000 title claims description 36
- 239000000463 material Substances 0.000 title claims description 31
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 40
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 33
- 239000003115 supporting electrolyte Substances 0.000 claims description 17
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- VZTDIZULWFCMLS-UHFFFAOYSA-N ammonium formate Chemical compound [NH4+].[O-]C=O VZTDIZULWFCMLS-UHFFFAOYSA-N 0.000 claims description 13
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000005751 Copper oxide Substances 0.000 claims description 12
- 229910000431 copper oxide Inorganic materials 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000002245 particle Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000001699 photocatalysis Effects 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 238000002156 mixing Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 229910002012 Aerosil® Inorganic materials 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000007540 photo-reduction reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VEALVRVVWBQVSL-UHFFFAOYSA-N strontium titanate Chemical compound [Sr+2].[O-][Ti]([O-])=O VEALVRVVWBQVSL-UHFFFAOYSA-N 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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Description
本発明は、ギ酸アンモニウム支持塩を加えたメタノール水溶液にナノコンポジット半導体光触媒材料を混入し、紫外線及び可視光線を含む人工光源若しくは太陽光を照射して水素を製造する方法、更にはそのナノコンポジット半導体光触媒材料の高活性化に関するものである。 The present invention relates to a method for producing hydrogen by mixing a nanocomposite semiconductor photocatalyst material in an aqueous methanol solution to which an ammonium formate-supporting salt is added, and irradiating an artificial light source including ultraviolet rays and visible light or sunlight, and further the nanocomposite semiconductor. The present invention relates to high activation of the photocatalytic material.
特許文献１には、酸化チタン等の半導体光触媒を用いて水溶液を光分解し、燃料電池等のエネルギー源となる水素を生成する発明が開示されている。
特許文献２には、反応溶液として水に、メタノール、エタノール、１―プロパノール、２−プロパノール、１−ブタノール、２−ブタノール、１，２−ブタンジオール、１，３−ブタンジオール、１，４−ブタンジオールなどを加えたアルコール水溶液を用いることで光触媒を活性化させ、また、反応溶液の水は、必ずしも純水に限定されず、炭酸塩や炭酸水素塩の塩類を混合、溶解させた水溶液を用いて水素の生成効率を向上させる発明が開示されている。
Patent Document 1 discloses an invention in which an aqueous solution is photodecomposed using a semiconductor photocatalyst such as titanium oxide to generate hydrogen that serves as an energy source for a fuel cell or the like.
Patent Document 2 discloses that as a reaction solution, water, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,2-butanediol, 1,3-butanediol, 1,4- The photocatalyst is activated by using an alcohol aqueous solution to which butanediol or the like is added, and the water in the reaction solution is not necessarily limited to pure water, and an aqueous solution in which carbonates or bicarbonates are mixed and dissolved is used. An invention that uses it to improve the production efficiency of hydrogen is disclosed.
しかしながら、これらの支持電解質（支持塩）を用いても光触媒による水素生成効率や水素発生量は小さく、光触媒物質を用いた水素製造法の実用化及び産業化には、大きな懸念が持たれている。 However, even if these supporting electrolytes (supporting salts) are used, the hydrogen production efficiency and the amount of hydrogen generated by the photocatalyst are small, and there is great concern for the practical use and industrialization of the hydrogen production method using the photocatalytic substance. .
本発明は、従来技術の支持電解質と光触媒を用いた水素生成方法より、更に高効率に水素を生成できる支持電解質の提供と、該支持電解質と組合わせて用いるナノコンポジット半導体光触媒材料と、これら材料を用いたメタノール水溶液からの水素製造方法、更にはナノコンポジット半導体光触媒材料を高活性化させる方法の提供などを目的とする。 The present invention is a hydrogen-producing formation method using the prior art supporting electrolyte and photocatalyst, and provides the supporting electrolyte which can produce hydrogen more efficiently, and the nanocomposite semiconductor photocatalyst material used in combination with the supporting electrolyte, these An object of the present invention is to provide a method for producing hydrogen from an aqueous methanol solution using the material and a method for highly activating the nanocomposite semiconductor photocatalyst material.
請求項１に記載の発明では、まず、メタノール水溶液を収容する容器にギ酸アンモニウムとナノコンポジット半導体光触媒材料を添加混合する。ギ酸アンモニウムは溶解し支持電解質として作用し、ナノコンポジット半導体光触媒材料は水溶液に不溶で懸濁状態、或いは沈降状態となる。次いで容器内のメタノール水溶液に人口光源（紫外線及び可視光線を含む）や太陽光を照射して水素ガスを生成させる。
請求項２に記載の発明は、請求項１の構成において、前記ナノコンポジット半導体光触媒材料が、少なくとも一部に酸化銅／酸化アルミニウム／酸化チタンの３成分系からなるナノコンポジットを含有することを特徴とする。
請求項３に記載の発明は、請求項１又は請求項２の構成において、前記ナノコンポジット半導体光触媒材料が、少なくとも一部にアナターゼ型の酸化チタンを含有することを特徴とする。
請求項４に記載の発明は、請求項１乃至請求項３の何れか一つの構成において、前記ギ酸アンモニウム支持電解質の濃度が０．１〜０．２５Ｍであることを特徴とする。
上記目的を達成するために、請求項５に記載の発明は、請求項１又は請求項３又は請求項４の構成において、前記ナノコンポジット半導体光触媒材料が酸化アルミニウム／酸化チタンの２成分系からなり、メタノール水溶液にさらに銅イオンとギ酸アンモニウム支持電解質を添加し、光還元により酸化アルミニウム／酸化チタンナノコンポジット表面に銅粒子を析出させながら水素を製造することを特徴とする。
請求項６に記載の発明は、請求項５の構成において、メタノール水溶液中銅イオンと酸化チタンとの重量比が、０．０００５：１から０．００４：１の範囲にあることを特徴とする。
In the first aspect of the invention, first, ammonium formate and the nanocomposite semiconductor photocatalyst material are added and mixed in a container containing an aqueous methanol solution. Ammonium formate dissolves and acts as a supporting electrolyte, and the nanocomposite semiconductor photocatalyst material is insoluble in an aqueous solution and becomes suspended or settled. Next, the aqueous methanol solution in the container is irradiated with artificial light sources (including ultraviolet rays and visible rays) and sunlight to generate hydrogen gas.
The invention according to claim 2 is characterized in that, in the configuration of claim 1, the nanocomposite semiconductor photocatalyst material contains at least a nanocomposite composed of a three-component system of copper oxide / aluminum oxide / titanium oxide. And
According to a third aspect of the present invention, in the configuration of the first or second aspect, the nanocomposite semiconductor photocatalyst material contains anatase-type titanium oxide at least partially.
According to a fourth aspect of the present invention, in any one of the first to third aspects, the concentration of the ammonium formate supporting electrolyte is 0.1 to 0.25M.
In order to achieve the above object, according to a fifth aspect of the present invention, in the configuration of the first, third, or fourth aspect, the nanocomposite semiconductor photocatalytic material comprises a two-component system of aluminum oxide / titanium oxide. Further, copper ions and ammonium formate supporting electrolyte are further added to a methanol aqueous solution, and hydrogen is produced while copper particles are precipitated on the surface of the aluminum oxide / titanium oxide nanocomposite by photoreduction.
The invention according to claim 6 is characterized in that, in the constitution of claim 5, the weight ratio of copper ions and titanium oxide in the methanol aqueous solution is in the range of 0.0005: 1 to 0.004: 1. .
本発明によれば、これまで用いられてきた炭酸塩などの支持電解質を用いた場合より、水素生成効率が向上できる。具体的は、これまでの炭酸塩を用いた場合の水素生成量より２倍から３倍程度水素生成量が増加する。従って、光触媒物質を用いた水素製造法の実用化及び産業化に大きく前進する。 According to the present invention, the hydrogen generation efficiency can be improved as compared with the case where a supporting electrolyte such as a carbonate used so far is used. Specifically, the hydrogen production amount increases by about 2 to 3 times the hydrogen production amount when using the conventional carbonate. Therefore, a significant advance is made in the practical application and industrialization of hydrogen production methods using photocatalytic substances.
以下、本発明の実施の形態を説明する。
[ナノコンポジット半導体光触媒材料の製造方法]
まず、本発明に用いられるナノコンポジット半導体光触媒材料には、酸化チタン、酸化亜鉛、チタン酸ストロンチウム、炭化ケイ素、酸化鉄、酸化銅、セレン化カドミウム、硫化カドミウムなどの半導体の複合体が利用される。ナノコンポジット化には、これらの半導体を組み合わせて複合化する方法や、白金、パラジウム、ロジウム、金、銀などの金属を半導体に修飾する手法が用いられる。さらに、酸化アルミニウムや酸化イリジウムなどの酸化物を半導体に修飾する手法も用いられる。
Embodiments of the present invention will be described below.
[Method for producing nanocomposite semiconductor photocatalyst material]
First, as the nanocomposite semiconductor photocatalyst material used in the present invention, a semiconductor composite such as titanium oxide, zinc oxide, strontium titanate, silicon carbide, iron oxide, copper oxide, cadmium selenide, cadmium sulfide is used. . For nanocompositing, a method of combining these semiconductors into a composite and a method of modifying metals such as platinum, palladium, rhodium, gold, and silver into semiconductors are used. Furthermore, a method of modifying an oxide such as aluminum oxide or iridium oxide with a semiconductor is also used.
また、ナノコンポジット半導体光触媒材料は粉末状のものが望ましい。光を有効に利用するためには、比表面積が大きい粒子、すなわち径の小さい粒子が有利だからで、具体的には１ｎｍ〜２００ｎｍの範囲の粒子径の粉末が好適には用いられる。粒子を適宜成型加工して板状等の形態としたり、適当な基板上に固定化したりすることもできる。 The nanocomposite semiconductor photocatalyst material is preferably in powder form. In order to effectively use light, particles having a large specific surface area, that is, particles having a small diameter are advantageous. Specifically, powders having a particle diameter in the range of 1 nm to 200 nm are preferably used. The particles can be appropriately molded to form a plate or the like, or can be fixed on a suitable substrate.
さらに、ナノコンポジット半導体光触媒材料が、少なくとも一部に酸化銅／酸化アルミニウム／酸化チタンの３成分系からなるナノコンポジットを含有することが望ましい。ここで、酸化アルミニウムは、重量％で０．１〜３．０％となるように配合するのが望ましい。当該配合以外では、光触媒活性が低くなり、水素生成能力が低下するからである。また、酸化銅も、重量％で０．２〜３．０％となるように配合するのが望ましい。当該配合以外では、光触媒活性が低くなり、水素生成能力が低下するからである。 Furthermore, it is desirable that the nanocomposite semiconductor photocatalyst material contains at least a nanocomposite composed of a three-component system of copper oxide / aluminum oxide / titanium oxide. Here, it is desirable to mix aluminum oxide so that it may be 0.1 to 3.0% by weight. It is because photocatalytic activity will become low and hydrogen generation capability will fall except the said mixing | blending. Moreover, it is desirable to mix copper oxide so that it may be 0.2 to 3.0% by weight. It is because photocatalytic activity will become low and hydrogen generation capability will fall except the said mixing | blending.
また、酸化チタンを含有するナノコンポジット半導体光触媒材料では、少なくとも一部にアナターゼ型の酸化チタンを含有するのが望ましい。酸化チタンには、アナターゼ型酸化チタン、ルチル型酸化チタン、ブルッカイト型酸化チタン等の各種酸化チタンがあるが、一般的にアナターゼ型のものが光触媒活性が高いことから、アナターゼ型酸化チタン単独、又はアナターゼ型酸化チタンを主成分とする、例えばアナターゼ型／ルチル型酸化チタン混合物を含有しているのが、水素生成には有利となる。 Moreover, in the nanocomposite semiconductor photocatalyst material containing titanium oxide, it is desirable to contain anatase-type titanium oxide at least in part. There are various types of titanium oxide such as anatase-type titanium oxide, rutile-type titanium oxide, brookite-type titanium oxide, etc., but since anatase-type ones generally have high photocatalytic activity, anatase-type titanium oxide alone, or It is advantageous for hydrogen generation to contain an anatase type titanium oxide as a main component, for example, an anatase type / rutile type titanium oxide mixture.
[水素生成方法]
上記のナノコンポジット半導体光触媒材料による水素生成は、ギ酸アンモニウム支持電解質を加えられたメタノール水溶液を反応溶液とし、人工光源若しくは太陽光源からの紫外線及び可視光線を照射することにより行われる。メタノールなどのアルコール水溶液中では、アルコール分子と水分子とが水素結合で繋がった会合体を形成し、さらに上下のアルコール会合体を水分子が水素結合のネットワークで繋ぎ、水和クラスターを形成していると考えられる。このアルコール水溶液を用いることで、光触媒が活性化されて水素発生反応が進行する。また、ギ酸アンモニウム支持電解質を加えることにより、さらに光触媒が活性化されて水素生成量が向上する。
[Hydrogen generation method]
Hydrogen generation by the nanocomposite semiconductor photocatalyst material is performed by using an aqueous methanol solution to which an ammonium formate supporting electrolyte is added as a reaction solution and irradiating ultraviolet rays and visible rays from an artificial light source or a solar light source. In an aqueous alcohol solution such as methanol, an alcohol molecule and water molecule form an association with hydrogen bonds, and the upper and lower alcohol associations are joined by a network of hydrogen bonds to form a hydrated cluster. It is thought that there is. By using this aqueous alcohol solution, the photocatalyst is activated and the hydrogen generation reaction proceeds. Further, by adding an ammonium formate supporting electrolyte, the photocatalyst is further activated and the amount of hydrogen generation is improved.
上記反応溶液にナノコンポジット半導体光触媒材料を添加する場合の添加量は、基本的に入射した光が効率良く吸収できる量を選択する。照射する光は、ナノコンポジット半導体光触媒のバンドギャップを上回るエネルギーを持つ必要があり、紫外線が好適に使用されるが、活性なナノコンポジット半導体光触媒材料であれば、太陽光に含まれる紫外線でも有効に利用できるため、太陽光を照射しても良い。 The amount of the nanocomposite semiconductor photocatalyst material added to the reaction solution is basically selected so that incident light can be efficiently absorbed. The irradiation light needs to have energy exceeding the band gap of the nanocomposite semiconductor photocatalyst, and ultraviolet rays are preferably used. However, an active nanocomposite semiconductor photocatalyst material is effective even with ultraviolet rays contained in sunlight. Since it can be used, it may be irradiated with sunlight.
ナノコンポジット半導体光触媒材料として、酸化銅／酸化アルミニウム／酸化チタンの３成分系からなるナノコンポジット光触媒を使用した。使用した酸化チタンは日本エアロジル製Ｐ２５であり、この酸化チタンはアナターゼ構造約８０％、ルチル構造約２０％の酸化チタン混合物で、細孔の少ない多面構造となっている。平均粒径は約２０ｎｍであり、比表面積は約５０ｍ２／ｇであった。
酸化アルミニウムは、アルドリッチ社製のナノ粒子を用い、平均粒径は約４０〜４７ｎｍであり、比表面積は約３５〜４０ｍ２／ｇであった。
酸化銅は、アルドリッチ社製のナノ粒子を用い、平均粒径は約３３ｎｍであり、比表面積は約２９ｍ２／ｇであった。
As a nanocomposite semiconductor photocatalyst material, a nanocomposite photocatalyst composed of a three-component system of copper oxide / aluminum oxide / titanium oxide was used. The titanium oxide used was P25 made by Nippon Aerosil, and this titanium oxide is a titanium oxide mixture having anatase structure of about 80% and rutile structure of about 20%, and has a multifaceted structure with few pores. The average particle size was about 20 nm and the specific surface area was about 50 m 2 / g.
As the aluminum oxide, nanoparticles made by Aldrich were used, the average particle size was about 40 to 47 nm, and the specific surface area was about 35 to 40 m 2 / g.
As the copper oxide, Aldrich nanoparticles were used, the average particle size was about 33 nm, and the specific surface area was about 29 m 2 / g.
酸化銅の添加量は重量％で０．２％で、酸化アルミニウムの添加量は重量％で０．３％になるように、酸化チタン、酸化アルミニウム、酸化銅を配合し、メノウ乳鉢で約１５分間混合した。その後、空気中において、４℃／分の昇温速度で５００℃まで加熱して、その温度下で３時間焼成し、焼成後、メノウ乳鉢で約１５分間すりつぶして粉末状とし、酸化チタンに酸化アルミニウムと酸化銅とが担持されたナノコンポジット半導体光触媒材料とした。 Titanium oxide, aluminum oxide and copper oxide were blended so that the addition amount of copper oxide was 0.2% by weight and the addition amount of aluminum oxide was 0.3% by weight, and about 15 in an agate mortar. Mixed for minutes. After that, it is heated to 500 ° C. at a rate of temperature increase of 4 ° C./min in the air, baked at that temperature for 3 hours, ground and then ground in an agate mortar for about 15 minutes, and oxidized to titanium oxide. It was set as the nanocomposite semiconductor photocatalyst material with which aluminum and copper oxide were carry | supported.
パイレックス（登録商標）ガラス製の反応容器（容積５５．３ｍＬ）に、支持電解質が溶解した、体積％で１０％のメタノール水溶液３０ｍＬを入れ、ここにナノコンポジット半導体光触媒材料２０ｍｇを添加して、マグネティックスターラー撹拌子を入れて反応容器を密閉した。次に、マグネティックスターラーを用いてメタノール水溶液を撹拌し、ナノコンポジット半導体光触媒材料を液中に懸濁させた。液温は恒温槽を用いて５０℃で一定としている。
次に、反応容器の側面から、ブラックライト（東芝ライテック（株）製ネオボール５ブラックライト、ピーク波長３５２ｎｍ、光強度１．０ｍＷ／ｃｍ２）を用いて紫外線を照射した。３時間光照射を行った後、照射を中止して、反応容器内の気体をガスシリンジにより２５０μＬ採取し、水素生成量を熱伝導度検出器付きガスクロマトグラフィー（ＧＬサイエンス（株）製ＧＣ−３２０）で測定した。この水素生成量を表１に示す。なお、ここに記載の水素生成量は、１０回繰り返し実験を行った結果の平均値である。
Pyrex (registered trademark) glass reaction vessel (volume: 55.3 mL) was charged with 30 mL of 10% by volume methanol aqueous solution in which the supporting electrolyte was dissolved, and 20 mg of nanocomposite semiconductor photocatalyst material was added thereto, and magnetic A reaction vessel was sealed with a stir bar. Next, the methanol aqueous solution was stirred using a magnetic stirrer to suspend the nanocomposite semiconductor photocatalyst material in the liquid. The liquid temperature is constant at 50 ° C. using a thermostatic bath.
Next, ultraviolet rays were irradiated from the side of the reaction vessel using a black light (Neoball 5 black light manufactured by Toshiba Lighting & Technology Co., Ltd., peak wavelength 352 nm, light intensity 1.0 mW / cm 2 ). After 3 hours of light irradiation, the irradiation was stopped, the gas in the reaction vessel was sampled by 250 μL with a gas syringe, and the amount of hydrogen produced was measured by gas chromatography with a thermal conductivity detector (GC-produced by GL Science Co., Ltd.). 320). This hydrogen production amount is shown in Table 1. In addition, the hydrogen production amount described here is an average value of results obtained by repeating the experiment ten times.
ナノコンポジット半導体光触媒材料として、酸化アルミニウム／酸化チタンの２成分系からなるナノコンポジット光触媒を使用した。使用した酸化チタンは日本エアロジル製Ｐ２５であり、この酸化チタンはアナターゼ構造約８０％、ルチル構造約２０％の酸化チタン混合物で、細孔の少ない多面構造となっている。平均粒径は約２０ｎｍであり、比表面積は約５０ｍ２／ｇであった。
酸化アルミニウムは、アルドリッチ社製のナノ粒子を用い、平均粒径は約４０〜４７ｎｍであり、比表面積は約３５〜４０ｍ２／ｇであった。
As the nanocomposite semiconductor photocatalyst material, a nanocomposite photocatalyst composed of two components of aluminum oxide / titanium oxide was used. The titanium oxide used was P25 made by Nippon Aerosil, and this titanium oxide is a titanium oxide mixture having anatase structure of about 80% and rutile structure of about 20%, and has a multifaceted structure with few pores. The average particle size was about 20 nm and the specific surface area was about 50 m 2 / g.
As the aluminum oxide, nanoparticles made by Aldrich were used, the average particle size was about 40 to 47 nm, and the specific surface area was about 35 to 40 m 2 / g.
酸化アルミニウムの添加量は重量％で０．３％になるように、酸化チタン、酸化アルミニウム、酸化銅を配合し、メノウ乳鉢で約１５分間混合した。その後、空気中において、４℃／分の昇温速度で５００℃まで加熱して、その温度下で３時間焼成し、焼成後、メノウ乳鉢で約１５分間すりつぶして粉末状とし、酸化チタンに酸化アルミニウムと酸化銅が担持されたナノコンポジット半導体光触媒材料とした。 Titanium oxide, aluminum oxide, and copper oxide were blended so that the amount of aluminum oxide added was 0.3% by weight, and mixed in an agate mortar for about 15 minutes. After that, it is heated to 500 ° C. at a rate of temperature increase of 4 ° C./min in the air, baked at that temperature for 3 hours, ground and then ground in an agate mortar for about 15 minutes, and oxidized to titanium oxide. A nanocomposite semiconductor photocatalyst material carrying aluminum and copper oxide was obtained.
パイレックス（登録商標）ガラス製の反応容器（容積５５．３ｍＬ）に、ギ酸アンモニウム支持電解質と硝酸銅が溶解した、体積％で１０％のメタノール水溶液３０ｍＬを入れ、ここにナノコンポジット半導体光触媒材料２０ｍｇを添加して、マグネティックスターラー撹拌子を入れて反応容器を密閉した。この時のギ酸アンモニウム支持電解質の濃度は、２００ｍｍｏｌ／Ｌであった。次に、マグネティックスターラーを用いてメタノール水溶液を撹拌し、ナノコンポジット半導体光触媒材料を液中に懸濁させた。液温は恒温槽を用いて５０℃で一定としている。
次に、反応容器の側面から、ブラックライト（東芝ライテック（株）製ネオボール５ブラックライト、ピーク波長３５２ｎｍ、光強度１．０ｍＷ／ｃｍ２）を用いて紫外線を照射した。３時間光照射を行った後、照射を中止して、反応容器内の気体をガスシリンジにより２５０μＬ採取し、水素生成量を熱伝導度検出器付きガスクロマトグラフィー（ＧＬサイエンス（株）製ＧＣ−３２０）で測定した。この水素生成量を表２に示す。なお、ここに記載の水素生成量は、１０回繰り返し実験を行った結果の平均値である。
Pyrex (registered trademark) glass reaction vessel (volume: 55.3 mL) was charged with 30 mL of 10% by volume methanol aqueous solution in which ammonium formate supporting electrolyte and copper nitrate were dissolved, and 20 mg of nanocomposite semiconductor photocatalyst material was added here. The magnetic stirrer stir bar was added and the reaction vessel was sealed. The concentration of the ammonium formate supporting electrolyte at this time was 200 mmol / L. Next, the methanol aqueous solution was stirred using a magnetic stirrer to suspend the nanocomposite semiconductor photocatalyst material in the liquid. The liquid temperature is constant at 50 ° C. using a thermostatic bath.
Next, ultraviolet rays were irradiated from the side of the reaction vessel using a black light (Neoball 5 black light manufactured by Toshiba Lighting & Technology Co., Ltd., peak wavelength 352 nm, light intensity 1.0 mW / cm 2 ). After 3 hours of light irradiation, the irradiation was stopped, the gas in the reaction vessel was sampled by 250 μL with a gas syringe, and the amount of hydrogen produced was measured by gas chromatography with a thermal conductivity detector (GC-produced by GL Science Co., Ltd.). 320). This hydrogen production amount is shown in Table 2. In addition, the hydrogen production amount described here is an average value of results obtained by repeating the experiment ten times.
表１の結果を比較すると、これまで支持電解質として報告されている炭酸塩や炭酸水素塩より、ギ酸アンモニウム塩を用いた場合、優れた水素生成能力が得られていることが分かる。特に、ギ酸アンモニウム濃度２００ｍｍｏｌ／Ｌの場合には、炭酸水素塩を用いた場合より２．３倍水素生成量が増加した。また、表２の結果と比較すると、硝酸銅濃度１６．７μｍｏｌ／Ｌの場合には、３．３倍水素生成量が増加した。ギ酸アンモニウムは低廉であり、工業的に水素を大量に生産する場合に断然有利であると言える。
Comparing the results in Table 1, it can be seen that when ammonium formate salt is used, an excellent hydrogen generating ability is obtained from carbonates and hydrogen carbonates that have been reported as supporting electrolytes. In particular, when the ammonium formate concentration was 200 mmol / L, the amount of hydrogen generation increased 2.3 times compared to the case of using the bicarbonate. Further, when compared with the results in Table 2, the amount of hydrogen generation increased 3.3 times when the copper nitrate concentration was 16.7 μmol / L. Ammonium formate is inexpensive and can be said to be extremely advantageous when industrially producing hydrogen in large quantities.
Claims (6)
6. The method for producing hydrogen according to claim 5, wherein the weight ratio of copper ions to titanium oxide in the aqueous methanol solution according to claim 5 is in the range of 0.0005: 1 to 0.004: 1. .
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