JP5229947B2 - Semiconductor photocatalytic substance, method for producing the same, and method for producing hydrogen - Google Patents
Semiconductor photocatalytic substance, method for producing the same, and method for producing hydrogen Download PDFInfo
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- 239000004065 semiconductor Substances 0.000 title claims description 32
- 239000001257 hydrogen Substances 0.000 title claims description 28
- 229910052739 hydrogen Inorganic materials 0.000 title claims description 28
- 239000000126 substance Substances 0.000 title claims description 25
- 230000001699 photocatalysis Effects 0.000 title claims description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 48
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 40
- 239000011941 photocatalyst Substances 0.000 claims description 19
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 18
- 239000005751 Copper oxide Substances 0.000 claims description 18
- 229910000431 copper oxide Inorganic materials 0.000 claims description 18
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000010304 firing Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 229910052697 platinum Inorganic materials 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000000243 solution Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 150000002431 hydrogen Chemical class 0.000 description 4
- 239000000843 powder Substances 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
- 230000000052 comparative effect Effects 0.000 description 3
- 230000001678 irradiating effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000004570 mortar (masonry) 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
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 229910002012 Aerosil® Inorganic materials 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical class [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-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
- 238000004140 cleaning Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Description
本発明は、光活性に優れた半導体光触媒物質とその製造方法、さらには当該半導体光触媒物質を用いた水素生成方法とに関する。 The present invention relates to a semiconductor photocatalyst material excellent in photoactivity, a method for producing the same, and a hydrogen generation method using the semiconductor photocatalyst material.
例えば特許文献１に示すように、酸化チタン等の半導体光触媒を用いて水を光分解し、燃料電池等のエネルギー源となる水素を生成する試みが知られている。特に半導体光触媒としては、特許文献２に示すように、酸化チタンに助触媒として酸化イリジウムを担持させたり、特許文献３に示すように、酸化チタンに助触媒として白金やパラジウム等の白金族元素を担持させたりして、水素の発生効率を向上させる改良がなされている。 For example, as shown in Patent Document 1, an attempt is made to photolyze water using a semiconductor photocatalyst such as titanium oxide to generate hydrogen that serves as an energy source for a fuel cell or the like. In particular, as a semiconductor photocatalyst, as shown in Patent Document 2, iridium oxide is supported on titanium oxide as a promoter, or as shown in Patent Document 3, platinum group elements such as platinum and palladium are supported on titanium oxide as a promoter. Improvements have been made to improve the generation efficiency of hydrogen, for example, by supporting it.
しかし、これらの助触媒の金属は高価である上、助触媒に限らず多様な機器や装置において使用されているため、将来的に枯渇する可能性もある。従って、これらの金属を用いた半導体光触媒物質の実用化及び産業化には、大きな懸念が持たれている。 However, these promoter metals are expensive and are used not only in promoters but also in a variety of equipment and devices, and may be depleted in the future. Therefore, there are great concerns about the practical application and industrialization of semiconductor photocatalytic substances using these metals.
そこで、本発明は、上記従来の助触媒を用いた半導体光触媒と遜色ない光触媒活性を有し、安価で枯渇の懸念なく利用できる半導体光触媒物質及びその製造方法と、さらには低コストで効率的な水素の生成が可能となる水素生成方法とを提供することを目的としたものである。 Therefore, the present invention has a photocatalytic activity comparable to that of the conventional photocatalyst using the above-mentioned cocatalyst, is inexpensive and can be used without fear of depletion, a method for producing the same, and a low-cost and efficient method. An object of the present invention is to provide a hydrogen generation method that enables generation of hydrogen.
上記目的を達成するために、請求項１に記載の発明は、半導体光触媒物質であって、酸化チタンに、助触媒として酸化アルミニウムと酸化銅とを担持させたことを特徴とする。
請求項２に記載の発明は、請求項１の構成において、酸化チタンが、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。
上記目的を達成するために、請求項３に記載の発明は、半導体光触媒物質の製造方法であって、酸化チタンに、酸化アルミニウムと酸化銅とを所定量ずつ添加して混合し、２００〜１８００℃の範囲で選択された焼成温度で焼成することを特徴とする。
請求項４に記載の発明は、請求項３の構成において、前記酸化アルミニウムが０．１〜３．０重量％添加されることを特徴とする。
請求項５に記載の発明は、請求項３又は４の構成において、前記酸化銅が０．２〜３．０重量％添加されることを特徴とする。
上記目的を達成するために、請求項６に記載の発明は、請求項１又は２に記載の半導体光触媒物質を、水素発生源となる物質を含む反応溶液に添加し、これに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を特徴とする。
In order to achieve the above object, the invention described in claim 1 is a semiconductor photocatalyst material, characterized in that aluminum oxide and copper oxide are supported on titanium oxide as promoters.
The invention described in claim 2 is characterized in that, in the structure of claim 1, the titanium oxide contains anatase-type titanium oxide at least partially.
In order to achieve the above object, a third aspect of the present invention is a method for producing a semiconductor photocatalytic substance, wherein a predetermined amount of aluminum oxide and copper oxide are added to and mixed with titanium oxide, and 200 to 1800 is mixed. Baking is performed at a baking temperature selected in the range of ° C.
According to a fourth aspect of the present invention, in the configuration of the third aspect, 0.1 to 3.0% by weight of the aluminum oxide is added.
According to a fifth aspect of the present invention, in the configuration of the third or fourth aspect, 0.2 to 3.0% by weight of the copper oxide is added.
In order to achieve the above object, according to a sixth aspect of the present invention, the semiconductor photocatalytic substance according to the first or second aspect is added to a reaction solution containing a substance that becomes a hydrogen generation source , to which an artificial light source or solar light is added. It is characterized by irradiating ultraviolet rays and visible rays from a light source.
本発明によれば、比較的安価で枯渇の懸念が少ない酸化アルミニウムと酸化銅とを助触媒として使用しているため、白金等の貴金属を担持させた場合よりも原料コストが抑えられ、安価な半導体光触媒物質が得られる。而も光触媒作用による水素生成能力は、従来の助触媒を使用した場合と略同等となっている。従って、低コストで効率的な水素の生成が可能となる。
According to the present invention, since aluminum oxide and copper oxide, which are relatively inexpensive and less likely to be depleted, are used as promoters, raw material costs can be reduced compared to the case where noble metals such as platinum are supported, and inexpensive. A semiconductor photocatalytic material is obtained. The hydrogen generation capacity by photocatalysis is almost the same as that when a conventional promoter is used. Therefore, it is possible to efficiently generate hydrogen at a low cost.
以下、本発明の実施の形態を説明する。
［半導体光触媒物質の製造方法］
まず、本発明の半導体光触媒物質には、酸化チタンが用いられる。この酸化チタンは、アナターゼ型酸化チタン、ルチル型酸化チタン、無定形酸化チタン等の各種酸化チタンを意味する。但し、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で、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とするのが望ましい。
Embodiments of the present invention will be described below.
[Method for producing semiconductor photocatalytic substance]
First, titanium oxide is used for the semiconductor photocatalytic substance of the present invention. This titanium oxide means various titanium oxides such as anatase type titanium oxide, rutile type titanium oxide, and amorphous titanium oxide. However, since the anatase type has high photocatalytic activity, it is desirable to use anatase type titanium oxide alone or an anatase type titanium oxide as a main component, for example, an anatase type / rutile type titanium oxide mixture.
また、酸化チタン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用いられる。この場合、粒子のまま半導体光触媒物質を製造した後、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ができる。
但し、粒子のまま使用するものに限らず、例えば、粒子を板状又は薄膜状に成型したり、粉末を適当な基板上に固定化したりした後、半導体光触媒物質を製造することもできる。
The titanium oxide 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. In this case, after producing the semiconductor photocatalyst substance in the form of particles, it can be appropriately molded and formed into a plate-like form or immobilized on an appropriate substrate.
However, the semiconductor photocatalyst substance can also be produced after the particles are molded into a plate shape or a thin film shape, or the powder is fixed on a suitable substrate.
この酸化チタンに、酸化アルミニウムと酸化銅とを所定量ずつ添加して混合し、焼成することで、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半導体光触媒物質が得られる。
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。
A predetermined amount of aluminum oxide and copper oxide are added to titanium oxide, mixed, and baked to obtain a semiconductor photocatalytic substance in which aluminum oxide and copper oxide are supported on 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.
一方、焼成温度は、２００℃〜１８００℃の範囲で選択される。２００℃を下回ると、十分な焼成を行うことができず、酸化アルミニウムと酸化銅との酸化チタン表面上への担持が困難となり、１８００℃を超えると、酸化チタンの光触媒作用が低下するからである。このうち特に５００℃〜６００℃の範囲内で選択するのが望ましい。 On the other hand, the firing temperature is selected in the range of 200 ° C to 1800 ° C. If the temperature is lower than 200 ° C, sufficient firing cannot be performed, and it becomes difficult to support aluminum oxide and copper oxide on the surface of titanium oxide. If the temperature exceeds 1800 ° C, the photocatalytic action of titanium oxide decreases. is there. Among these, it is desirable to select in the range of 500 degreeC-600 degreeC especially.
［水素生成方法］
こうして得た半導体光触媒物質による水素生成は、水或いはアルコール、若しくはこれらを溶媒とする電解質溶液の何れかを反応溶液とし、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。反応溶液としては、アルコール類又はその水溶液を用いるのが好適で、アルコール類としては、例えばメタノール、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−ブタンジオール等が挙げられる。アルコール類の水溶液中では、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。なお、反応溶液に用いられる水としては純水に限定されず、炭酸塩や炭酸水素塩、ヨウ素塩、臭素塩等の塩類を混合、溶解した水を用いてもよい。
[Hydrogen generation method]
Hydrogen production by the semiconductor photocatalyst material thus obtained is carried out by irradiating ultraviolet rays and visible rays from an artificial light source or a solar light source using either water, alcohol, or an electrolyte solution containing these as a solvent. As the reaction solution, it is preferable to use an alcohol or an aqueous solution thereof. Examples of the alcohol include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1,2-butanediol, Examples include 1,3-butanediol and 1,4-butanediol. In an aqueous solution of alcohols, alcohol molecules and water molecules form an association formed by hydrogen bonds, and the upper and lower alcohol associations are joined by a network of hydrogen bonds to form a hydrated cluster. it is conceivable that. By using this aqueous alcohol solution, the photocatalyst is activated and the hydrogen generation reaction proceeds. The water used in the reaction solution is not limited to pure water, and water in which salts such as carbonate, hydrogen carbonate, iodine salt, bromine salt are mixed and dissolved may be used.
上記反応溶液に半導体光触媒物質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、半導体光触媒である酸化チタンのバンドギャップを超えるような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、本発明の半導体光触媒物質は非常に高効率であり、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よい。 The amount of addition of the semiconductor photocatalytic substance to the reaction solution is basically selected so that incident light can be efficiently absorbed. The light to be irradiated needs to have energy exceeding the band gap of titanium oxide, which is a semiconductor photocatalyst, and ultraviolet rays are preferably used. However, the semiconductor photocatalyst material of the present invention has very high efficiency, and sunlight Sunlight may be irradiated because it can be used effectively even in the ultraviolet rays contained in.
なお、上記形態では本発明の半導体光触媒物質を水素の生成に使用しているが、当該半導体光触媒物質は水素の生成に限らず、例えば水中や大気中の農薬や悪臭物質等の有機物の分解除去、或いは光触媒を塗布した固体表面のセルフクリーニング等に利用することもできる。反応形態は、有機物を含む水溶液に半導体光触媒物質を添加して、光照射することにより行うことができるが、悪臭物質の分解は気相反応により行うこともできる。有機物の分解の場合、分解される有機物は一般に電子供与体として働き、正孔によって酸化分解されると共に、電子によって水素が発生するか、酸素が還元される。 In the above embodiment, the semiconductor photocatalyst material of the present invention is used for the production of hydrogen. However, the semiconductor photocatalyst material is not limited to the production of hydrogen, for example, decomposition and removal of organic substances such as agricultural chemicals and malodorous substances in water or in the atmosphere. Alternatively, it can be used for self-cleaning of a solid surface coated with a photocatalyst. The reaction can be carried out by adding a semiconductor photocatalytic substance to an aqueous solution containing an organic substance and irradiating it with light, but the malodorous substance can also be decomposed by a gas phase reaction. In the case of decomposition of an organic substance, the organic substance to be decomposed generally acts as an electron donor and is oxidatively decomposed by holes, and hydrogen is generated by electrons or oxygen is reduced.
光触媒として粉末状の酸化チタン（ＴｉＯ２、日本アエロジル製Ｐ２５）を使用する。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。粒径は約２０ｎｍである。
一方、酸化チタンに添加する酸化アルミニウムは、アルドリッチ社のナノ粒子を用いる。粒径は４０〜４７ｎｍである。
また、酸化チタンに添加する酸化銅は、アルドリッチ社のナノ粒子を用いる。平均粒径は３３ｎｍである。
Powdered titanium oxide (TiO 2 , P25 manufactured by Nippon Aerosil) is used as the photocatalyst. This titanium oxide is a titanium oxide mixture having an anatase structure of about 80% and a rutile structure of about 20%, and has a multifaceted structure with few pores. The particle size is about 20 nm.
On the other hand, Aldrich nanoparticles are used as aluminum oxide to be added to titanium oxide. The particle size is 40-47 nm.
In addition, Aldrich nanoparticles are used as the copper oxide to be added to titanium oxide. The average particle size is 33 nm.
上記酸化チタン、酸化アルミニウム、酸化銅を、下記の表１に示す各割合で配合し、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物質を作成した。 The titanium oxide, aluminum oxide, and copper oxide were blended in the proportions shown in Table 1 below, and mixed in an agate mortar for about 15 minutes. Thereafter, in air, the mixture is heated to 500 ° C. at a rate of 4 ° C./min and baked at that temperature for 3 hours. After baking, the powder is ground in an agate mortar for about 15 minutes, and the titanium oxide is coated with aluminum oxide. A nanocomposite semiconductor photocatalytic material carrying copper and copper oxide was prepared.
パイレックス（登録商標）ガラス製の反応容器（容積５５．３ｍＬ）に、体積％で１０％のメタノール水溶液３０ｍＬを入れ、ここに上記半導体光触媒物質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、半導体光触媒物質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) is charged with 30 mL of 10% methanol aqueous solution by volume, 20 mg of the above-mentioned semiconductor photocatalyst material is added, and a magnetic stirrer stirrer is added for reaction. The container was sealed. Next, the aqueous methanol solution was stirred using a magnetic stirrer to suspend the semiconductor photocatalytic substance 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 irradiation for 3 hours, the irradiation was stopped, 250 μL of gas in the reaction vessel was collected with a gas syringe, and the amount of hydrogen produced was measured by gas chromatography (GC-320 manufactured by GL Science Co., Ltd.). 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.
［比較例］
従来の白金助触媒を担持した酸化チタンを作製した。目的の白金担持量になるように、テトラクロロ白金酸六水和物（Ｈ２ＰｔＣｌ６・Ｈ２Ｏ）を秤量した後、純水に溶解し、酸化チタンと次亜リン酸を添加して９０℃で一時間撹拌した。その後、０．４５ミクロンのメンブレンフィルターで濾過し、フィルター上の酸化チタンを１１０℃で１２時間乾燥し、６００℃で５時間焼成した。焼成後、メノウ乳鉢で約１５分間すりつぶし、白金担持酸化チタンを得た。
こうして得た白金担持酸化チタンを、先の実施例と同じ操作法及び条件で水素生成に利用した。この水素生成量を表２に示す。
[Comparative example]
Titanium oxide carrying a conventional platinum promoter was prepared. Tetrachloroplatinic acid hexahydrate (H 2 PtCl 6 · H 2 O) is weighed to achieve the target platinum loading, dissolved in pure water, and added with titanium oxide and hypophosphorous acid. Stir at 90 ° C. for 1 hour. Then, it filtered with the 0.45 micron membrane filter, the titanium oxide on a filter was dried at 110 degreeC for 12 hours, and baked at 600 degreeC for 5 hours. After firing, it was ground in an agate mortar for about 15 minutes to obtain platinum-supported titanium oxide.
The platinum-supported titanium oxide thus obtained was used for hydrogen generation under the same operating method and conditions as in the previous examples. This hydrogen production amount is shown in Table 2.
表１の結果と比較すると、本実施例では、酸化アルミニウムを０．１〜３．０重量％、酸化銅を０．２〜３．０重量％の範囲で添加した場合に、白金を添加した比較例と遜色ない水素生成能力が得られていることがわかる。特に、酸化アルミニウムを０．１〜１．０重量％、酸化銅を０．２〜１．０重量％の範囲で添加した試料No.12以降のものでは、水素生成量が何れも１０．０を超えており、白金を０．７重量％以上添加した比較例と略同等の水素生成能力となっている。白金は、酸化チタンに対する助触媒の中で、最も優れた助触媒であることが知られているが、今回の結果により、酸化チタンと酸化アルミニウムと酸化銅とのナノコンポジット半導体光触媒物質が同等程度の機能を有していることが初めて示されたものである。白金は貴金属で高価である一方、酸化アルミニウムと酸化銅とは低廉であり、工業的に大量生産する場合に断然有利であると言える。 Compared with the results in Table 1, in this example, platinum was added when aluminum oxide was added in the range of 0.1 to 3.0% by weight and copper oxide in the range of 0.2 to 3.0% by weight. It can be seen that the hydrogen generation ability comparable to the comparative example is obtained. In particular, in samples No. 12 and later to which aluminum oxide is added in the range of 0.1 to 1.0% by weight and copper oxide is added in the range of 0.2 to 1.0% by weight, the amount of hydrogen produced is 10.0. The hydrogen generation capacity is substantially equivalent to that of the comparative example in which 0.7 wt% or more of platinum is added. Platinum is known to be the best co-catalyst for titanium oxide, but this result shows that nanocomposite semiconductor photocatalytic materials of titanium oxide, aluminum oxide, and copper oxide are comparable. It has been shown for the first time that it has the following functions. While platinum is a noble metal and expensive, aluminum oxide and copper oxide are inexpensive, and can be said to be extremely advantageous when industrially mass-produced.
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