JP7024327B2 - Photocatalyst and method for manufacturing photocatalyst - Google Patents
Photocatalyst and method for manufacturing photocatalyst Download PDFInfo
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- JP7024327B2 JP7024327B2 JP2017210767A JP2017210767A JP7024327B2 JP 7024327 B2 JP7024327 B2 JP 7024327B2 JP 2017210767 A JP2017210767 A JP 2017210767A JP 2017210767 A JP2017210767 A JP 2017210767A JP 7024327 B2 JP7024327 B2 JP 7024327B2
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- 239000011941 photocatalyst Substances 0.000 title claims description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 11
- 238000000034 method Methods 0.000 title claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 76
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 75
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 63
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 26
- 239000000126 substance Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 230000001699 photocatalysis Effects 0.000 claims description 17
- 239000010949 copper Substances 0.000 claims description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- QUQFTIVBFKLPCL-UHFFFAOYSA-L copper;2-amino-3-[(2-amino-2-carboxylatoethyl)disulfanyl]propanoate Chemical compound [Cu+2].[O-]C(=O)C(N)CSSCC(N)C([O-])=O QUQFTIVBFKLPCL-UHFFFAOYSA-L 0.000 claims 1
- 239000000843 powder Substances 0.000 description 21
- 229910010413 TiO 2 Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 16
- 239000002184 metal Substances 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical group CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 8
- 238000000354 decomposition reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- 150000003254 radicals Chemical class 0.000 description 6
- 238000004435 EPR spectroscopy Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- VCUVETGKTILCLC-UHFFFAOYSA-N 5,5-dimethyl-1-pyrroline N-oxide Chemical compound CC1(C)CCC=[N+]1[O-] VCUVETGKTILCLC-UHFFFAOYSA-N 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000003463 adsorbent Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 238000006864 oxidative decomposition reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- -1 transition metal salt Chemical class 0.000 description 2
- 239000012028 Fenton's reagent Substances 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- MGZTXXNFBIUONY-UHFFFAOYSA-N hydrogen peroxide;iron(2+);sulfuric acid Chemical compound [Fe+2].OO.OS(O)(=O)=O MGZTXXNFBIUONY-UHFFFAOYSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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Description
本発明は窒素含有酸化チタンを用いる光触媒体に関する。 The present invention relates to a photocatalyst using nitrogen-containing titanium oxide.
有機物を分解する光触媒体が知られており、部材の表面にコーティングすることにより汚れを分解できるため、各種の用途に用いられている。特に、酸化チタン（ＴｉＯ２）が光触媒として機能することは古くから知られており、酸化チタンに窒素をドープした窒素含有酸化チタン（Ｎ－ＴｉＯ２）は可視光で光触媒活性を示すため広く普及している。 A photocatalyst that decomposes organic substances is known, and it is used for various purposes because it can decompose stains by coating the surface of a member. In particular, it has long been known that titanium oxide (TiO 2 ) functions as a photocatalyst, and nitrogen-containing titanium oxide (N-TiO 2 ) obtained by doping titanium oxide with nitrogen is widely used because it exhibits photocatalytic activity in visible light. is doing.
ここで、光触媒体は、有機物の分解効率はなるべく高い方がよい。そこで、効率改善について各種の提案がある。 Here, the photocatalyst should have as high a decomposition efficiency as possible for organic substances. Therefore, there are various proposals for improving efficiency.
特許文献１には、光触媒と光触媒でない吸着物質（ゼオライト等）の混合体が示されている。 Patent Document 1 discloses a mixture of a photocatalyst and an adsorbent (zeolite or the like) that is not a photocatalyst.
特許文献２には、吸収波長の異なる二つの光触媒材料の混合体が示されている。 Patent Document 2 shows a mixture of two photocatalytic materials having different absorption wavelengths.
特許文献３には、白金担持Ｎ－ＴｉＯ２とＣｕ担持Ｎ－ＴｉＯ２の混合体が示されている。
特許文献４には、Ｃｕ担持Ｎ－ＴｉＯ２とＡｇ担持Ｎ－ＴｉＯ２の混合体が示されている。 Patent Document 4 shows a mixture of Cu-supported N-TiO 2 and Ag-supported N-TiO 2 .
吸着剤との組み合わせでは、分解対象となる目的物質が吸着剤から離脱し難く、分解効率を十分に上昇することができない場合もある。また、２種類の光触媒の混合体では、異なる光触媒の特性が生かされる場合に性能が向上できるが、必ずしも性能向上が図られる訳ではない。白金や、銅などの酸化触媒を担持することで分解効率が上昇するが、さらに効率を上昇したいという要求がある。 In combination with an adsorbent, the target substance to be decomposed may not easily separate from the adsorbent, and the decomposition efficiency may not be sufficiently increased. Further, in a mixture of two types of photocatalysts, the performance can be improved when the characteristics of different photocatalysts are utilized, but the performance is not necessarily improved. The decomposition efficiency is increased by supporting an oxidation catalyst such as platinum or copper, but there is a demand for further increase in efficiency.
本発明に係る光触媒体は、銅を表面に担持した窒素含有酸化チタンからなる可視光応答型の第１光触媒物質と、銅を担持しない窒素含有酸化チタンからなる可視光応答型の第２光触媒物質と、が物理的に混合されており、第２光触媒物質の混合量が５重量％から９５重量％の範囲である。 The photocatalyst according to the present invention is a visible light responsive first photocatalyst substance made of nitrogen-containing titanium oxide having copper on its surface and a visible light responsive second photocatalyst substance made of nitrogen-containing titanium oxide not carrying copper . And are physically mixed , and the mixing amount of the second photocatalytic substance is in the range of 5% by weight to 95% by weight .
また、第１および第２光触媒物質を構成する窒素含有酸化チタンは、窒素の含有原子数比Ｘが０％＜Ｘ＜１０％であるとよい。 Further, the nitrogen-containing titanium oxide constituting the first and second photocatalytic substances may have a nitrogen-containing atomic number ratio X of 0% <X <10%.
また、第１光触媒における銅の含有量が０．０１重量％から６．０重量％であるとよい。 Further, the copper content in the first photocatalyst is preferably 0.01% by weight to 6.0% by weight.
また、第１光触媒物質がフェントン反応によりＯＨラジカルを優位に生成するとよい。 Further, it is preferable that the first photocatalytic substance predominantly generates OH radicals by the Fenton reaction.
また、上述した光触媒体の製造方法であって、第１または第２光触媒物質の窒素含有酸化チタンは、酸化チタンと尿素を混合するか、アンモニアガス雰囲気下のいずれかの条件で、３００～７００℃の範囲で熱処理して窒素をドープすることで製造するとよい。 Further, in the above-mentioned method for producing a photocatalyst, the nitrogen-containing titanium oxide of the first or second photocatalyst is 300 to 700 under the conditions of either mixing titanium oxide and urea or under an ammonia gas atmosphere. It may be produced by heat-treating in the temperature range of ° C and doping with nitrogen.
また、第１光触媒物質は、担持する金属触媒の金属の硝酸塩、硫酸塩、または塩化物を、窒素含有酸化チタンと接触させることで、窒素含有酸化チタンに金属触媒を担持させることで製造するとよい。 Further, the first photocatalyst substance may be produced by contacting the nitrate, sulfate, or chloride of the metal of the metal catalyst to be carried with the nitrogen-containing titanium oxide to support the metal catalyst on the nitrogen-containing titanium oxide. ..
本発明によれば、高い酸化反応活性の光触媒体が得られる。これにより、有機物の酸化分解効率を向上することができ、これまでの光触媒材料では実現できなかった高濃度の有害ガス分解や短時間での有害物質の処理が可能となる。 According to the present invention, a photocatalyst having high oxidation reaction activity can be obtained. As a result, the oxidative decomposition efficiency of organic substances can be improved, and high-concentration toxic gas decomposition and treatment of toxic substances in a short time, which could not be realized by conventional photocatalytic materials, become possible.
以下、本発明の実施形態について、図面に基づいて説明する。なお、本発明は、ここに記載される実施形態に限定されるものではない。 Hereinafter, embodiments of the present invention will be described with reference to the drawings. The present invention is not limited to the embodiments described here.
「実施形態」
本実施形態では、第１光触媒物質としての金属触媒担持窒素含有酸化チタンと第２光触媒物質としての金属触媒無担持の窒素含有酸化チタンと、を物理的に混合する。通常、２種類の触媒を物理的に混合した場合、それぞれの触媒の能力を合わせたものになると考えられる。例えば、性能指数２の金属触媒担持量０．５ｗｔ％の窒素含有酸化チタンと、性能指数１の金属触媒担持量０ｗｔ％の窒素含有酸化チタンを５０％ずつ物理混合した場合には、その能力は光触媒の性能が粉末量に依存することから、性能指数２の５０％と性能指数１の５０％を足し合わせた性能指数１．５になり、性能指数２よりも低下すると考えられる。
"Embodiment"
In the present embodiment, the metal catalyst-supported nitrogen-containing titanium oxide as the first photocatalyst substance and the nitrogen-containing titanium oxide without the metal catalyst as the second photocatalyst substance are physically mixed. Usually, when two kinds of catalysts are physically mixed, it is considered that the ability of each catalyst is combined. For example, when 50% each of nitrogen-containing titanium oxide having a figure of merit 2 with a metal catalyst carrying amount of 0.5 wt% and nitrogen-containing titanium oxide having a figure of merit 1 with a metal catalyst carrying amount of 0 wt% are physically mixed, their capacities are high. Since the performance of the photocatalyst depends on the amount of powder, the figure of merit is 1.5, which is the sum of 50% of the figure of merit 2 and 50% of the figure of merit 1, which is considered to be lower than the figure of merit 2.
ところが、物理混合した場合に、金属触媒を担持した窒素含有酸化チタンのみのものより、高性能の光触媒が得られた。 However, when physically mixed, a photocatalyst with higher performance was obtained than that of only nitrogen-containing titanium oxide carrying a metal catalyst.
なお、物理的な混合の方法としては、粉末の金属触媒無担持の窒素含有酸化チタンと、粉末の金属触媒担持の窒素含有酸化チタンを水中で物理的に混合することが好適である。 As a physical mixing method, it is preferable to physically mix the powdered nitrogen-containing titanium oxide without a metal catalyst and the powdered nitrogen-containing titanium oxide with a metal catalyst in water.
「製造方法」
物理混合光触媒の製造方法について、図１に基づいて説明する。まず、アナターゼ型の酸化チタンを用意する。そして、用意した酸化チタンに窒素をドープする（Ｓ１１）。これによって、可視光応答型の光触媒体である金属無担持窒素含有酸化チタンが生成される。
"Production method"
A method for producing a physically mixed photocatalyst will be described with reference to FIG. First, anatase-type titanium oxide is prepared. Then, nitrogen is doped into the prepared titanium oxide (S11). This produces metal-free nitrogen-containing titanium oxide, which is a visible light-responsive photocatalyst.
この金属無担持窒素含有酸化チタンについて、その表面に触媒機能を持つ金属を担持する（Ｓ１２）。これによって、金属担持窒素含有酸化チタンが生成される。 A metal having a catalytic function is supported on the surface of the metal-free nitrogen-containing titanium oxide (S12). This produces metal-supported nitrogen-containing titanium oxide.
このようにして、得られた金属無担持窒素含有酸化チタンと金属担持窒素含有酸化チタンを物理混合する（Ｓ１３）。これによって、金属無担持窒素含有酸化チタンと金属担持窒素含有酸化チタンが物理混合された光触媒体が得られる。 In this way, the obtained metal-supported nitrogen-containing titanium oxide and the metal-supported nitrogen-containing titanium oxide are physically mixed (S13). As a result, a photocatalyst in which metal-supported nitrogen-containing titanium oxide and metal-supported nitrogen-containing titanium oxide are physically mixed can be obtained.
＜窒素含有酸化チタン＞
Ｓ１１では、酸化チタンに窒素をドープする。例えば、市販の酸化チタン粉末を尿素と混合するか、アンモニアガス雰囲気下のいずれかの条件にて所定温度で熱処理することで、酸化チタンに窒素をドープすることができ、窒素含有酸化チタンの粉末が得られる。窒素含有酸化チタンにおける窒素の含有原子数比Ｘは、０％＜Ｘ＜１０％が好適あり、熱処理温度は３００から７００℃の範囲が好適である。
<Nitrogen-containing titanium oxide>
In S11, titanium oxide is doped with nitrogen. For example, by mixing commercially available titanium oxide powder with urea or heat-treating it at a predetermined temperature under any of the conditions of an ammonia gas atmosphere, the titanium oxide can be doped with nitrogen, and the nitrogen-containing titanium oxide powder can be doped. Is obtained. The nitrogen-containing atomic number ratio X of the nitrogen-containing titanium oxide is preferably 0% <X <10%, and the heat treatment temperature is preferably in the range of 300 to 700 ° C.
＜金属担持窒素含有酸化チタン＞
Ｓ１２では、窒素含有酸化チタンに５族から１２族の遷移金属の１種以上を担持する。この場合、担持金属材料の硝酸塩、硫酸塩、または塩化物を窒素含有酸化チタンと接触させて、窒素含有酸化チタンの表面に金属を担持するとよい。例えば、水中に窒素含有酸化チタン粉末を懸濁し、その粉末に対して遷移金属の塩の水溶液を加えて攪拌することで接触させる。そして、ろ過した後に乾燥させて金属担持窒素含有酸化チタン粉末を得る。担持金属としては、銅が好適であるが、５から１２族の遷移金属元素であって、銅、鉄及び、白金から選ばれるいずれか一種以上が好適であり、その含有量が０．０１重量％から６．０重量％とするとよい。
<Metal-supported nitrogen-containing titanium oxide>
In S12, one or more of group 5 to group 12 transition metals are supported on nitrogen-containing titanium oxide. In this case, the metal may be supported on the surface of the nitrogen-containing titanium oxide by contacting the nitrate, sulfate, or chloride of the supported metal material with the nitrogen-containing titanium oxide. For example, nitrogen-containing titanium oxide powder is suspended in water, and an aqueous solution of a transition metal salt is added to the powder and stirred to bring the powder into contact with the powder. Then, after filtering, it is dried to obtain a metal-supported nitrogen-containing titanium oxide powder. As the supporting metal, copper is preferable, but any one or more of group 5 to 12 transition metal elements selected from copper, iron and platinum is suitable, and the content thereof is 0.01 weight by weight. It is good to set from% to 6.0% by weight.
＜物理混合＞
そして、Ｓ１３では、金属担持窒素含有酸化チタン粉末と、窒素含有酸化チタン粉末を所定割合で物理混合する。例えば、両者の粉末を水中に投入し、ここで攪拌し、その後乾燥させる。なお、金属無担持の窒素含有酸化チタンの混合量が５重量％から９５重量％の範囲であることが好適である。
<Physical mixing>
Then, in S13, the metal-supported nitrogen-containing titanium oxide powder and the nitrogen-containing titanium oxide powder are physically mixed at a predetermined ratio. For example, both powders are put into water, stirred here, and then dried. It is preferable that the mixed amount of nitrogen-containing titanium oxide without metal support is in the range of 5% by weight to 95% by weight.
＜作用効果＞
このようにして得た、実施形態に係る光触媒体によれば、高い酸化反応活性が得られる。従って、これまでの光触媒材料では実現できなかった高濃度の有害ガス分解や短時間での有害物質の処理が可能となる。
<Action effect>
According to the photocatalyst according to the embodiment thus obtained, high oxidation reaction activity can be obtained. Therefore, it is possible to decompose harmful gases at a high concentration and treat harmful substances in a short time, which could not be realized by conventional photocatalytic materials.
ここで、窒素含有酸化チタンに銅や鉄を担持した光触媒体は、担持金属が作用するフェントン反応により酸化活性種であるＯＨラジカルなどが多く生成され高活性である。ただし、担持量が過剰になると活性が低下することが知られており、担持量の最適値が存在する。 Here, the photocatalyst in which copper or iron is supported on nitrogen-containing titanium oxide is highly active because a large amount of OH radicals, which are oxidatively active species, are generated by the Fenton reaction in which the supported metal acts. However, it is known that the activity decreases when the loading amount becomes excessive, and there is an optimum value for the loading amount.
窒素含有酸化チタンは励起光によって生成した電子が酸素に渡り、これが周辺の水と反応して、過酸化水素やＯＨラジカルなどの酸化活性種を発生させる。一方で、電子の抜けた正孔が分解対象の有機物の電子を引き抜き酸化させ、有機鎖を分断、または酸化分解しやすい状態にする。 In nitrogen-containing titanium oxide, electrons generated by excitation light pass to oxygen, which reacts with surrounding water to generate oxidatively active species such as hydrogen peroxide and OH radical. On the other hand, the holes from which the electrons have escaped pull out the electrons of the organic substance to be decomposed and oxidize them, so that the organic chain is easily divided or oxidatively decomposed.
銅や鉄などのフェントン反応剤の役割を果たす金属を担持すると酸化反応種の生成量が増えるが、担持量が過剰な場合は有機鎖を分解する反応場が少なくなり、正孔の消費が抑制され、結果的に活性が低下する。 Supporting a metal that acts as a Fenton's reagent, such as copper or iron, increases the amount of oxidation reaction species produced, but if the amount of support is excessive, the reaction field that decomposes organic chains decreases, and hole consumption is suppressed. As a result, the activity decreases.
本実施形態では、酸化活性種を増加させる金属担持窒素含有酸化チタンに対して、有機鎖分解を優位に行う無担持の窒素含有酸化チタンを物理的に混合することで、各反応場を分離して、全体的な分解反応を効率的に進行させることで、高活性化を実現している。 In the present embodiment, each reaction field is separated by physically mixing the metal-supported nitrogen-containing titanium oxide that increases the number of oxidatively active species with the non-supported nitrogen-containing titanium oxide that predominantly decomposes the organic chain. Therefore, high activation is realized by efficiently advancing the overall decomposition reaction.
「実験例」
＜光触媒体の製造＞
市販のアナターゼ型の酸化チタン粉末を尿素と混合して熱処理し窒素含有酸化チタン粉末を得た。次に水中に窒素含有酸化チタン粉末を懸濁し、その粉末量に対して重量比で銅が０．５ｗｔ％となる量の硝酸銅水溶液を加えて攪拌し、ろ過した後に乾燥させて銅担持窒素含有酸化チタン粉末を得た。物理混合した光触媒体の粉末は、銅担持窒素含有酸化チタン粉末と窒素含有酸化チタン粉末を所定割合で混合し全体で１ｇとなるように調整し、３３ｍｌの水中で１時間攪拌し、１２０℃で乾燥させて製造した。
・実施例１：無担持窒素含有酸化チタン（Ｎ－ＴｉＯ２）の混合割合が５ｗｔ％のものを実施例１として用いた
・実施例２：Ｎ－ＴｉＯ２の混合割合が１５ｗｔ％のものを実施例２として用いた
・実施例３：Ｎ－ＴｉＯ２の混合割合が３３ｗｔ％のものを実施例３として用いた
・実施例４：Ｎ－ＴｉＯ２の混合割合が５０ｗｔ％のものを実施例４として用いた
・実施例５：Ｎ－ＴｉＯ２の混合割合が６７ｗｔ％のものを実施例５として用いた
・実施例６：Ｎ－ＴｉＯ２の混合割合が８０ｗｔ％のものを実施例６として用いた
・実施例７：Ｎ－ＴｉＯ２の混合割合が９５ｗｔ％のものを実施例７として用いた
・比較例１：物理混合用の銅無担持Ｎ－ＴｉＯ２が０ｗｔ％のものとして比較例１（銅担持Ｎ－ＴｉＯ２のみ）として用いた
・比較例２：物理混合用の銅無担持Ｎ－ＴｉＯ２が１００ｗｔ％のものとして比較例２として用いた
"Experimental example"
<Manufacturing of photocatalyst>
A commercially available anatase-type titanium oxide powder was mixed with urea and heat-treated to obtain a nitrogen-containing titanium oxide powder. Next, nitrogen-containing titanium oxide powder is suspended in water, an aqueous solution of copper nitrate having an amount of copper in an amount of 0.5 wt% by weight to the amount of the powder is added, stirred, filtered, and then dried to carry copper-supported nitrogen. The contained titanium oxide powder was obtained. The physically mixed photocatalyst powder is prepared by mixing copper-supported nitrogen-containing titanium oxide powder and nitrogen-containing titanium oxide powder in a predetermined ratio to make a total of 1 g, stirring in 33 ml of water for 1 hour, and stirring at 120 ° C. Manufactured by drying.
-Example 1: Titanium oxide containing unsupported nitrogen (N-TiO 2 ) having a mixing ratio of 5 wt% was used as Example 1.-Example 2: N-TiO 2 having a mixing ratio of 15 wt% was used. Used as Example 2-Example 3: The mixture ratio of N-TiO 2 was 33 wt% was used as Example 3-Example 4: The mixture ratio of N-TiO 2 was 50 wt%. Used as No. 4 ・ Example 5: The one having a mixing ratio of N—TiO 2 of 67 wt% was used as Example 5. ・ Example 6: The one having a mixed ratio of N—TiO 2 of 80 wt% was used as Example 6. Used-Example 7: A mixture ratio of N-TiO 2 of 95 wt% was used as Example 7.-Comparative Example 1: Copper-free N-TiO 2 for physical mixing was used as a comparative example of 0 wt%. Used as 1 (only copper-supported N-TiO 2 ) -Comparative Example 2: Copper-free N-TiO 2 for physical mixing was used as Comparative Example 2 with 100 wt%.
＜光触媒活性評価＞
光触媒活性は、アセトアルデヒド（ＡＡ）の完全分解により生成するＣＯ２量で評価した。１Ｌのガラス瓶に０．１ｇの光触媒体の粉末を入れて大気組成の酸素・窒素混合ガスで置換し、３％のＡＡガスを４０ｍＬの１２００ｐｐｍ相当量を注入して、１６時間暗所で静置した。その後、４１０ｎｍ以下カットフィルターを巻いた１０Ｗ蛍光灯で２００００Ｌｘの照度で光照射し、ガラス瓶内のＣＯ２濃度を測定した。２４時間後のＣＯ２濃度から光触媒活性を比較した。
<Evaluation of photocatalytic activity>
The photocatalytic activity was evaluated by the amount of CO 2 produced by the complete decomposition of acetaldehyde (AA). Put 0.1 g of photocatalyst powder in a 1 L glass bottle, replace it with an oxygen / nitrogen mixed gas of atmospheric composition, inject 40 mL of 1200 ppm equivalent of AA gas, and leave it in the dark for 16 hours. did. Then, a 10 W fluorescent lamp wrapped with a cut filter of 410 nm or less was irradiated with light at an illuminance of 20000 Lx, and the CO 2 concentration in the glass bottle was measured. The photocatalytic activity was compared from the CO 2 concentration after 24 hours.
＜酸化反応種の同定＞
銅無担持窒素含有酸化チタン（比較例１）と銅担持窒素含有酸化チタン（比較例２）はＥＳＲ（Electron Spin Resonance）測定により生成する反応種を同定した。各粉末２ｍと水２ｍｌを容量１３．５ｍｌ、内径２ｍｍの容器に入れて、マグネチックスターラーで攪拌しながら、上部からレンズで集光した光を照射した。光源は６００ＷのＨｇランプを使用し、窒素含有酸化チタンは４時間、銅担持窒素含有酸化チタンは３０分光照射した。光照射停止直後にラジカルトラップ剤であるＤＭＰＯ（5,5-Dimethyl-1-pyrroline N-Oxide、東京化成、９７％）を濃度が０．２５Ｍとなるように５７．５μＬ投入した。ＥＳＲ測定は表１の条件で実施した。
<Identification of oxidation reaction species>
Copper-free nitrogen-containing titanium oxide (Comparative Example 1) and copper-supported nitrogen-containing titanium oxide (Comparative Example 2) were identified as reaction species produced by ESR (Electron Spin Resonance) measurement. 2 m of each powder and 2 ml of water were placed in a container having a capacity of 13.5 ml and an inner diameter of 2 mm, and while stirring with a magnetic stirrer, light collected by a lens was irradiated from above. A 600 W Hg lamp was used as a light source, and nitrogen-containing titanium oxide was optically irradiated for 4 hours, and copper-supported nitrogen-containing titanium oxide was optically irradiated for 30 hours. Immediately after the light irradiation was stopped, 57.5 μL of DMPO (5,5-Dimethyl-1-pyrroline N-Oxide, Tokyo Kasei, 97%), which was a radical trapping agent, was added so that the concentration was 0.25 M. The ESR measurement was performed under the conditions shown in Table 1.
図２に実施例１－７と比較例１、比較例２のサンプルのＡＡ分解試験２４時間後のＣＯ２濃度を示す。図において、横軸が、金属無担持窒素含有酸化チタン(Ｎ－ＴｉＯ２)
の含有量であり、０％が金属担持窒素含有酸化チタン（比較例２）のみ、１００％が金属無担持窒素含有酸化チタン（比較例１）のみの結果である。また、図中、黒四角が１回目、グレーの菱形が２回目の実験結果である。このように、金属無担持窒素含有酸化チタンの混合量が増大すると４０～６０ｗｔ％の間で最もＣＯ２濃度が高く、光触媒活性が良好であることが確認された。０％の銅担持窒素含有酸化チタンに対して、最も良好な条件で１．４倍の性能向上が確認された。
FIG. 2 shows the CO 2 concentrations of the samples of Example 1-7, Comparative Example 1 and Comparative Example 2 after 24 hours of the AA decomposition test. In the figure, the horizontal axis is metal-free nitrogen-containing titanium oxide (N-TiO 2 ).
0% is the result of only the metal-supported nitrogen-containing titanium oxide (Comparative Example 2), and 100% is the result of only the metal-free nitrogen-containing titanium oxide (Comparative Example 1). In the figure, the black square is the result of the first experiment, and the gray rhombus is the result of the second experiment. As described above, it was confirmed that when the mixing amount of the metal-free nitrogen-containing titanium oxide was increased, the CO 2 concentration was the highest between 40 and 60 wt%, and the photocatalytic activity was good. It was confirmed that the performance of titanium oxide containing 0% copper-supported nitrogen was improved by 1.4 times under the best conditions.
図３に比較例１（窒素含有酸化チタン：Ｎ－ＴｉＯ２）と比較例２（銅担持窒素含有酸化チタンＣｕ／Ｎ－ＴｉＯ２）のＥＳＲ測定結果を示す。なお、比較例１では光照射４時間（４ｈ）、比較例２では光照射３０分（３０ｍｉｎ）とした。比較例１ではＤＭＰＯのメチル基が切れて検出されたメチルラジカルのピークが観察され、比較例２では典型的なＯＨラジカルのピークとＤＭＰＯの分解物でＮ由来のピークが検出された。これより比較例１の無担持窒素含有酸化チタンは、有機鎖分断が主な役割で正孔が優位に働いていると想定される。一方で、比較例２の銅担持窒素含有酸化チタンはＯＨラジカル生成の役割が大きいと言える。以上から、比較例１と２ではそれぞれ役割が異なり、混合することで光触媒活性が向上した理由は、銅担持で少なくなった正孔消費の反応場を無担持窒素含有酸化チタンで補填しているためと考えられる。
FIG. 3 shows the ESR measurement results of Comparative Example 1 (nitrogen-containing titanium oxide: N-TiO 2 ) and Comparative Example 2 (copper-supported nitrogen-containing titanium oxide Cu / N-TiO 2 ). In Comparative Example 1, light irradiation was set to 4 hours (4 hours), and in Comparative Example 2, light irradiation was set to 30 minutes (30 min). In Comparative Example 1, the peak of the methyl radical detected by breaking the methyl group of DMPO was observed, and in Comparative Example 2, the peak of typical OH radical and the peak derived from N were detected in the decomposition product of DMPO. From this, it is presumed that in the non-supported nitrogen-containing titanium oxide of Comparative Example 1, holes play a dominant role mainly in organic chain disruption. On the other hand, it can be said that the copper-supported nitrogen-containing titanium oxide of Comparative Example 2 plays a large role in OH radical generation. From the above, the roles of Comparative Examples 1 and 2 are different from each other, and the reason why the photocatalytic activity is improved by mixing is that the reaction field of hole consumption, which is reduced by supporting copper, is supplemented by titanium oxide containing unsupported nitrogen. It is thought that this is the reason.
Claims (6)
銅を担持しない窒素含有酸化チタンからなる可視光応答型の第２光触媒物質と、
が物理的に混合されており、
第２光触媒物質の混合量が５重量％から９５重量％の範囲である、
光触媒体。 A visible light-responsive first photocatalytic material consisting of nitrogen-containing titanium oxide with copper on its surface,
A visible light responsive second photocatalytic material made of nitrogen-containing titanium oxide that does not support copper ,
Is physically mixed ,
The mixing amount of the second photocatalytic substance is in the range of 5% by weight to 95% by weight.
Photocatalyst.
第１および第２光触媒物質を構成する窒素含有酸化チタンは、窒素の含有原子数比Ｘが０％＜Ｘ＜１０％である、
光触媒体。 The photocatalyst according to claim 1.
The nitrogen-containing titanium oxide constituting the first and second photocatalytic substances has a nitrogen-containing atomic number ratio X of 0% <X <10%.
Photocatalyst.
第１光触媒における銅の含有量が０．０１重量％から６．０重量％である、
光触媒体。 The photocatalyst according to claim 1 or 2.
The copper content in the first photocatalyst is 0.01% by weight to 6.0% by weight.
Photocatalyst.
第１光触媒物質がフェントン反応によりＯＨラジカルを優位に生成する光触媒体。 The photocatalyst according to claim 3.
A photocatalyst in which the first photocatalyst substance predominantly produces OH radicals by the Fenton reaction.
第１または第２光触媒物質の窒素含有酸化チタンは、酸化チタンと尿素を混合するか、アンモニアガス雰囲気下のいずれかの条件で、３００～７００℃の範囲で熱処理して窒素をドープすることで製造する、
光触媒体の製造方法。 The method for producing a photocatalyst according to any one of claims 1 to 4 .
The nitrogen-containing titanium oxide of the first or second photocatalyst substance is obtained by mixing titanium oxide and urea, or by heat-treating in the range of 300 to 700 ° C. under the conditions of either an ammonia gas atmosphere and doping with nitrogen. To manufacture,
A method for manufacturing a photocatalyst.
第１光触媒物質は、担持する銅の硝酸塩、硫酸塩、または塩化物を、窒素含有酸化チタンと接触させることで、窒素含有酸化チタンに銅を担持させることで製造する、
光触媒体の製造方法。 The method for producing a photocatalyst according to any one of claims 1 to 4 .
The first photocatalytic substance is produced by supporting copper on nitrogen-containing titanium oxide by contacting the nitrate, sulfate, or chloride of the supporting copper with nitrogen-containing titanium oxide.
A method for manufacturing a photocatalyst.
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| JP2001205104A (en) | 2000-01-27 | 2001-07-31 | Toyota Central Res & Dev Lab Inc | Photocatalytic material and photocatalytic body |
| JP2002154823A (en) | 2000-11-10 | 2002-05-28 | Toyota Central Res & Dev Lab Inc | Manufacturing method of inorganic oxynitride and inorganic oxynitride |
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