JP4240310B2 - Visible light responsive photocatalyst and synthesis method thereof - Google Patents
Visible light responsive photocatalyst and synthesis method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims description 22
- 238000001308 synthesis method Methods 0.000 title description 3
- 239000002131 composite material Substances 0.000 claims description 43
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 40
- 229910052718 tin Inorganic materials 0.000 claims description 30
- 239000001257 hydrogen Substances 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 26
- 238000010335 hydrothermal treatment Methods 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 24
- 239000002184 metal Substances 0.000 claims description 24
- 239000002905 metal composite material Substances 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims description 15
- 150000004703 alkoxides Chemical class 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000004140 cleaning Methods 0.000 claims description 12
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 10
- 238000010304 firing Methods 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 34
- 239000010936 titanium Substances 0.000 description 27
- 238000002441 X-ray diffraction Methods 0.000 description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 24
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 239000010955 niobium Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 4
- 229910001887 tin oxide Inorganic materials 0.000 description 4
- 229910052726 zirconium Inorganic materials 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 229910001936 tantalum oxide Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000511976 Hoya Species 0.000 description 2
- 235000002597 Solanum melongena Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- -1 tin (II) halides Chemical class 0.000 description 2
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 2
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 2
- NGCRLFIYVFOUMZ-UHFFFAOYSA-N 2,3-dichloroquinoxaline-6-carbonyl chloride Chemical compound N1=C(Cl)C(Cl)=NC2=CC(C(=O)Cl)=CC=C21 NGCRLFIYVFOUMZ-UHFFFAOYSA-N 0.000 description 1
- SDTMFDGELKWGFT-UHFFFAOYSA-N 2-methylpropan-2-olate Chemical compound CC(C)(C)[O-] SDTMFDGELKWGFT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- WRMFBHHNOHZECA-UHFFFAOYSA-N butan-2-olate Chemical compound CCC(C)[O-] WRMFBHHNOHZECA-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YJBKVPRVZAQTPY-UHFFFAOYSA-J tetrachlorostannane;dihydrate Chemical compound O.O.Cl[Sn](Cl)(Cl)Cl YJBKVPRVZAQTPY-UHFFFAOYSA-J 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- LTSUHJWLSNQKIP-UHFFFAOYSA-J tin(iv) bromide Chemical compound Br[Sn](Br)(Br)Br LTSUHJWLSNQKIP-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- YUOWTJMRMWQJDA-UHFFFAOYSA-J tin(iv) fluoride Chemical compound [F-].[F-].[F-].[F-].[Sn+4] YUOWTJMRMWQJDA-UHFFFAOYSA-J 0.000 description 1
- QPBYLOWPSRZOFX-UHFFFAOYSA-J tin(iv) iodide Chemical compound I[Sn](I)(I)I QPBYLOWPSRZOFX-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- LGQXXHMEBUOXRP-UHFFFAOYSA-N tributyl borate Chemical compound CCCCOB(OCCCC)OCCCC LGQXXHMEBUOXRP-UHFFFAOYSA-N 0.000 description 1
- 238000003828 vacuum filtration Methods 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Inorganic Compounds Of Heavy Metals (AREA)
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Description
本発明は、可視光応答型光触媒およびその合成方法に関する。より詳細には、本発明は、従来の可視光応答型光触媒よりも長波長の可視光を吸収し得るスズ／ｄ−ブロック金属複合材料からなる可視光応答型光触媒、およびその合成方法に関する。 The present invention relates to a visible light responsive photocatalyst and a synthesis method thereof. More specifically, the present invention relates to a visible light responsive photocatalyst composed of a tin / d-block metal composite material capable of absorbing visible light having a longer wavelength than a conventional visible light responsive photocatalyst, and a method for synthesizing the same.
酸化チタンは、高い光安定性、高い光触媒能、低コスト、高い安全性などの点で、現在のところ、光触媒として最も優れた材料である。しかし、酸化チタンが吸収・利用できる光は、紫外光領域に限られている。太陽エネルギーの有効利用の観点から、より長波長の光、すなわち可視光を利用できることが望ましい。 Titanium oxide is currently the most excellent material as a photocatalyst in terms of high light stability, high photocatalytic activity, low cost, and high safety. However, the light that can be absorbed and used by titanium oxide is limited to the ultraviolet light region. From the viewpoint of effective use of solar energy, it is desirable that light having a longer wavelength, that is, visible light can be used.
これまでに、いくつかの可視光応答型酸化チタン光触媒が開発されている。例えば、窒化チタンの酸化処理などにより得られる窒素ドープ酸化チタン（非特許文献１）、チオウレアとチタンテトライソプロポキシドとを空気中焼成処理することにより得られる硫黄ドープ二酸化チタン（非特許文献２）などがある。しかし、これらの吸収波長は最長で５００ｎｍ付近であり、太陽光の大部分の可視光を利用できないため、可視光応答効果は大きくはない。 So far, several visible light responsive titanium oxide photocatalysts have been developed. For example, nitrogen-doped titanium oxide obtained by oxidation treatment of titanium nitride (Non-Patent Document 1), sulfur-doped titanium dioxide obtained by firing in air with thiourea and titanium tetraisopropoxide (Non-Patent Document 2) and so on. However, since these absorption wavelengths are around 500 nm at the longest and most visible light of sunlight cannot be used, the visible light response effect is not great.
また、酸化チタン以外にも、酸化タンタル、酸化亜鉛、酸化スズなどの紫外線照射によって光触媒活性を示す材料が知られており、これらの材料についても、可視光応答型の光触媒の検討が行われている。例えば、酸化タンタルに窒素をドープしたタンタルオキシナイトライド（非特許文献３）、高温焼成により得られる２価のスズを含む酸化ニオブや酸化タンタル（非特許文献４）などがある。しかし、これらは、可視光下での酸化触媒能力が低く、あるいは最大吸収波長が５００ｎｍ付近であるため、可視光を十分に利用できるとは言い難い。 In addition to titanium oxide, materials that exhibit photocatalytic activity when irradiated with ultraviolet light, such as tantalum oxide, zinc oxide, and tin oxide, are known. Visible light-responsive photocatalysts have also been studied for these materials. Yes. For example, there are tantalum oxynitride in which tantalum oxide is doped with nitrogen (Non-patent Document 3), niobium oxide containing divalent tin obtained by high-temperature firing, tantalum oxide (Non-patent Document 4), and the like. However, these have low oxidation catalytic ability under visible light, or have a maximum absorption wavelength of around 500 nm, so it is difficult to say that visible light can be fully utilized.
このように、現状では、太陽エネルギーを有効利用するための光触媒は、実用レベルには至っていない。
本発明は、より長波長の可視光を吸収する光触媒を提供することを目的とする。 An object of the present invention is to provide a photocatalyst that absorbs visible light having a longer wavelength.
本発明は、２価の無機スズ塩と、チタン(IV)およびジルコニウム(IV)からなる群より選択されるｄ−ブロック金属のアルコキシドとを、アルカリ条件下で水熱処理することによって得られる、スズ／ｄ−ブロック金属複合材料を提供する。 The present invention includes a divalent inorganic tin salt, and an alkoxide of d- block metal selected from the group consisting of titanium (IV) Contact and zirconium (IV), obtained by hydrothermal treatment under alkaline conditions, A tin / d-block metal composite is provided.
好適な実施態様では、上記複合材料に含まれるｄ−ブロック金属は、チタン(IV)である。より好適な実施態様では、上記チタン(IV)とスズとの元素成分比は、３：２〜１：３である。 In a preferred embodiment, the d-block metal contained in the composite material is titanium (IV). In a more preferred embodiment, the elemental component ratio of titanium (IV) and tin is from 3: 2 to 1: 3.
他の好適な実施態様では、上記複合材料は、上記水熱処理後に、さらに焼成処理または酸洗浄が行われている。 In another preferred embodiment, the composite material is further subjected to a baking treatment or an acid cleaning after the hydrothermal treatment.
本発明はまた、上記のスズ／ｄ−ブロック金属複合材料からなる、可視光応答型光触媒を提供する。 The present invention also provides a visible light responsive photocatalyst comprising the above tin / d-block metal composite material.
本発明はさらに、スズ／ｄ−ブロック金属複合材料の製造方法を提供し、該方法は、２価の無機スズ塩と、チタン(IV)およびジルコニウム(IV)からなる群より選択されるｄ−ブロック金属のアルコキシドとを、アルカリ条件下で水熱処理する工程を含む。 The present invention further provides a method for producing a tin / d-block metal composite material, the method comprising the divalent inorganic tin salts are selected from the group consisting of titanium (IV) Contact and zirconium (IV) d A step of hydrothermally treating the alkoxide of the block metal under alkaline conditions.
好適な実施態様では、上記ｄ−ブロック金属は、チタン(IV)である。より好適な実施態様では、上記スズ／ｄ−ブロック金属複合材料中の上記チタン(IV)とスズとの元素成分比は、３：２〜１：３である。 In a preferred embodiment, the d-block metal is titanium (IV). In a more preferred embodiment, the elemental component ratio of titanium (IV) to tin in the tin / d-block metal composite is 3: 2 to 1: 3.
他の好適な実施態様では、上記方法は、得られた水熱処理物を焼成処理または酸洗浄する工程をさらに含む。 In another preferred embodiment, the method further comprises a step of subjecting the obtained hydrothermally treated product to a calcination treatment or an acid cleaning.
本発明はさらに、水素の生成方法を提供し、該方法は、上記のスズ／ｄ−ブロック金属複合材料または可視光応答型光触媒、白金助触媒、およびメタノールを含む水溶液に、可視光を照射する工程を含む。 The present invention further provides a method for producing hydrogen, which irradiates an aqueous solution containing the above tin / d-block metal composite material or visible light responsive photocatalyst, platinum promoter, and methanol with visible light. Process.
本発明の方法によれば、従来の光触媒とは異なる特性を有する、すなわち、より長波長の可視光を吸収する新規な光触媒を合成することができる。この方法により得られた、スズおよびｄ−ブロック金属を含む複合材料からなる本発明の可視光吸収型の光触媒は、可視光領域の光を吸収できるため、太陽エネルギーを有効に利用することが可能である。 According to the method of the present invention, it is possible to synthesize a novel photocatalyst having characteristics different from those of the conventional photocatalyst, that is, absorbing visible light having a longer wavelength. The visible light absorption photocatalyst of the present invention made of a composite material containing tin and a d-block metal obtained by this method can absorb light in the visible light region, so that solar energy can be used effectively. It is.
本発明のスズ／ｄ−ブロック金属複合材料は、２価の無機スズ塩と、チタン(IV)およびジルコニウム(IV)からなる群より選択されるｄ−ブロック金属のアルコキシドとを、アルカリ条件下で水熱処理する工程を含む方法によって製造される。 Tin / d- block metal composite material of the present invention, the divalent inorganic tin salt, and an alkoxide of d- block metal selected from the group consisting of titanium (IV) Contact and zirconium (IV), under alkaline conditions Manufactured by a method including a hydrothermal treatment step.
本発明の方法に用いられる２価の無機スズ塩としては、フッ化スズ、塩化スズ、臭化スズ、ヨウ化スズなどのスズ(II)ハロゲン化物；ＫＳｎＦ3、ＫＳｎＩ3、Ｋ2ＳｎＢｒ4、Ｋ4ＳｎＣｌ6、Ｋ4ＳｎＢｒ6などのハロゲノ塩などが挙げられる。特に、ＳｎＣｌ2・２Ｈ2Ｏは市販されており、最も一般的に用いられ得る。 Examples of the divalent inorganic tin salt used in the method of the present invention include tin (II) halides such as tin fluoride, tin chloride, tin bromide and tin iodide; KSnF 3 , KSnI 3 , K 2 SnBr 4 , Examples thereof include halogeno salts such as K 4 SnCl 6 and K 4 SnBr 6 . In particular, SnCl 2 .2H 2 O is commercially available and can be used most commonly.
本発明の方法に用いられるｄ−ブロック金属のアルコキシドにおいて、ｄ−ブロック金属は、チタン(IV)およびジルコニウム(IV)からなる群より選択される。これらの金属のうち、触媒活性が高い生成物が得られる点で、チタン(IV)が最も好ましい。また、アルコキシドの種類は、特に限定されないが、１価の低級アルコールのアルコキシドが好ましい。例えば、メトキシド、エトキシド、ｎ−プロポキシド、ｉ−プロポキシド、ｎ−ブトキシド、ｓｅｃ−ブトキシド、ｔ−ブトキシドなどが挙げられる。ｄ−ブロック金属のアルコキシドとしては、具体的には、チタニウム(IV)ｎ−ブトキシド、チタニウム(IV)エトキシドなどが挙げられる。 In alkoxides d- block metal used in the method of the present invention, d- block metal is selected from the group consisting of titanium (IV) Contact and zirconium (IV). Of these metals, titanium (IV) is most preferable because a product having high catalytic activity is obtained. The type of alkoxide is not particularly limited, but an alkoxide of a monovalent lower alcohol is preferable. Examples thereof include methoxide, ethoxide, n-propoxide, i-propoxide, n-butoxide, sec-butoxide, t-butoxide and the like. The alkoxide d- block metal, specifically titanium (IV) n-butoxide, and etc. Titanium (IV) ethoxide.
本発明の方法においては、原料である上記の２価の無機スズ塩とｄ−ブロック金属のアルコキシドとを、アルカリ条件下で混合し、水熱処理する。 In the method of the present invention, the above-mentioned divalent inorganic tin salt as a raw material and an alkoxide of a d-block metal are mixed under alkaline conditions and hydrothermally treated.
通常、２価の無機スズ塩とｄ−ブロック金属のアルコキシドとの反応においては、２価の無機スズ塩は水に懸濁させ、一方、ｄ−ブロック金属のアルコキシドはアルコールに溶解して、これらをアルカリ条件下で混合する。反応混合液中のそれぞれの原料の濃度は、これらが十分に混合し得るように適宜決定され得る。２価の無機スズ塩とｄ−ブロック金属のアルコキシドとのモル比は、好ましくは１：３〜３：１、より好ましくは１：１〜２：１、さらに好ましくは３：２である。アルカリ条件にするには、水酸化ナトリウム、水酸化カリウムなどの強アルカリ性水溶液が加えられる。使用するアルカリの量は、原料の２価の無機スズ塩またはｄ−ブロック金属のアルコキシドの量に対して、好ましくは約１．５〜３倍、より好ましくは約２倍である。アルカリの量が少なすぎると、十分な触媒能を有する材料が得られにくい。 Usually, in the reaction of a divalent inorganic tin salt and an alkoxide of a d-block metal, the divalent inorganic tin salt is suspended in water, while the alkoxide of a d-block metal is dissolved in an alcohol. Are mixed under alkaline conditions. The concentration of each raw material in the reaction mixture can be appropriately determined so that they can be sufficiently mixed. The molar ratio of the divalent inorganic tin salt to the d-block metal alkoxide is preferably 1: 3 to 3: 1, more preferably 1: 1 to 2: 1, and even more preferably 3: 2. For alkaline conditions, a strong alkaline aqueous solution such as sodium hydroxide or potassium hydroxide is added. The amount of alkali used is preferably about 1.5 to 3 times, more preferably about 2 times the amount of the raw material divalent inorganic tin salt or d-block metal alkoxide. When the amount of alkali is too small, it is difficult to obtain a material having sufficient catalytic ability.
アルカリ条件下の反応混合物は、次いで水熱処理される。水熱処理とは、高温高圧水の存在下で反応（合成、結晶育成など）させることをいう。本発明の方法においては、上記反応混合物を、オートクレーブなどの耐圧、耐熱、かつ耐食性の容器中に入れ、高温下で攪拌して反応させる。反応温度は、通常１２０℃〜２００℃、好ましくは約１８０℃である。圧力は、０．２〜１．５ＭＰａである。反応時間は、通常１２〜９６時間、好ましくは２４〜７２時間である。 The reaction mixture under alkaline conditions is then hydrothermally treated. Hydrothermal treatment refers to a reaction (synthesis, crystal growth, etc.) in the presence of high-temperature high-pressure water. In the method of the present invention, the reaction mixture is placed in a pressure-resistant, heat-resistant, and corrosion-resistant container such as an autoclave and stirred at a high temperature for reaction. The reaction temperature is usually 120 ° C to 200 ° C, preferably about 180 ° C. The pressure is 0.2 to 1.5 MPa. The reaction time is usually 12 to 96 hours, preferably 24 to 72 hours.
反応終了後、容器内の反応混合物を濾過し、生成物を濾取して回収する。さらに、この生成物を適切な手段で乾燥させることによって、目的の複合材料を得ることができる。この複合材料は、必要に応じて、さらに熱処理または酸洗浄してもよい。 After completion of the reaction, the reaction mixture in the container is filtered, and the product is collected by filtration. Furthermore, the target composite material can be obtained by drying the product by an appropriate means. This composite material may be further subjected to heat treatment or acid cleaning as required.
熱処理は、空気中または高真空下で高温（例えば、約３００℃）にて適切な時間焼成することによって行われ得る。水熱処理で得られた複合材料をさらに焼成することにより、光触媒としての活性が向上され得る。 The heat treatment can be performed by firing at a high temperature (eg, about 300 ° C.) for an appropriate time in air or under a high vacuum. By further firing the composite material obtained by the hydrothermal treatment, the activity as a photocatalyst can be improved.
酸洗浄は、水熱処理で得られた複合材料を、希塩酸、希硫酸などの無機酸で洗浄することによって行う。酸洗浄により、水熱処理で得られた材料中に不純物として含まれているＳｎＯを除去することができる。 The acid cleaning is performed by cleaning the composite material obtained by hydrothermal treatment with an inorganic acid such as dilute hydrochloric acid or dilute sulfuric acid. By the acid cleaning, SnO contained as an impurity in the material obtained by hydrothermal treatment can be removed.
このようにして得られた本発明のスズ／ｄ−ブロック金属複合材料は、５００ｎｍよりも長波長側、好ましくは約６００ｎｍに吸収端を有し、そしてスズとｄ−ブロック金属とをほぼ同程度含む、新規な複合材料である。この新規複合材料は、従来行われている２価のスズ化合物とｄ−ブロック金属アルコキシドとを混合して焼成する方法では得ることができない。水熱処理、すなわち亜臨界状態での反応により、従来の一般的な方法（例えば、焼成など）では得ることができない特殊な結晶構造を有する新規複合材料が得られたと考えられる。また、この新規な複合材料の光吸収能は、ｄ−ブロック金属の種類によって異なる。これは、金属の種類によって、伝導帯の電子エネルギーレベルが異なるためであると考えられる。 The tin / d-block metal composite material of the present invention thus obtained has an absorption edge at a wavelength longer than 500 nm, preferably about 600 nm, and tin and d-block metal are approximately the same. Including new composite materials. This novel composite material cannot be obtained by a conventional method of mixing and baking a divalent tin compound and a d-block metal alkoxide. It is considered that a novel composite material having a special crystal structure that cannot be obtained by a conventional general method (for example, firing) is obtained by hydrothermal treatment, that is, a reaction in a subcritical state. Further, the light-absorbing ability of this novel composite material varies depending on the type of d-block metal. This is thought to be because the electron energy level of the conduction band varies depending on the type of metal.
本発明のスズ／ｄ−ブロック金属複合材料は、光触媒として使用できる。特に、水の分解、すなわち、太陽エネルギーを利用して水から水素を生成するための光触媒として有用である。具体的には、白金助触媒および電子供与犠牲試薬（例えば、メタノール）の存在下で本発明の可視光応答型光触媒を用いると、これらを含有する水に、太陽光あるいは４２０ｎｍより長波長の光を照射することにより、水が分解して水素が発生する。 The tin / d-block metal composite material of the present invention can be used as a photocatalyst. In particular, it is useful as a photocatalyst for water decomposition, that is, to generate hydrogen from water using solar energy. Specifically, when the visible light responsive photocatalyst of the present invention is used in the presence of a platinum promoter and an electron donating sacrificial reagent (for example, methanol), sunlight or light having a wavelength longer than 420 nm is added to water containing these. Irradiation of water decomposes water and generates hydrogen.
（実施例１：スズ／チタン（Sn(II)/Ti(IV)）複合材料の合成）
ナスフラスコに０．２５〜４．０Ｍの種々の濃度の水酸化カリウム水溶液２５ｍＬを入れ、次いで０．２０Ｍのチタニウムｎ−ブトキシドのエタノール溶液２５ｍＬを加えた。さらに、０．３０Ｍの塩化スズ二水和物の水懸濁液２５ｍＬを加えて、数分間攪拌した。このとき、ナスフラスコ内の液体は、薄黄色に懸濁した。次いで、オートクレーブ（１８０℃、１０ｒｐｍ）で４８時間水熱反応を行った。反応終了後、減圧濾過によって生成物を回収し、１１０℃で減圧乾燥させて、結晶性の明るいオレンジ色のSn(II)/Ti(IV)複合材料を得た（約１．５ｇ）。
Example 1: Synthesis of tin / titanium (Sn (II) / Ti (IV)) composite material
An eggplant flask was charged with 25 mL of aqueous potassium hydroxide solution having various concentrations of 0.25 to 4.0 M, and then 25 mL of an ethanol solution of 0.20 M titanium n-butoxide was added. Further, 25 mL of an aqueous suspension of 0.30 M tin chloride dihydrate was added and stirred for several minutes. At this time, the liquid in the eggplant flask was suspended in a light yellow color. Subsequently, the hydrothermal reaction was performed for 48 hours by the autoclave (180 degreeC, 10 rpm). After completion of the reaction, the product was collected by vacuum filtration and dried under reduced pressure at 110 ° C. to obtain a crystalline bright orange Sn (II) / Ti (IV) composite material (about 1.5 g).
得られたSn(II)/Ti(IV)複合材料について、Ｘ線回折（ＸＲＤ）測定を行った。Rigaku製MiniFlex/HRCによって得られた代表的なＸＲＤパターンを図１および２に示す。なお、比較として、酸化スズ（図１）または酸化チタンのアナターゼまたはルチル構造（図２）についてもＸＲＤを測定した。図１のＸＲＤパターンでは、下から順に、合成に使用したＫＯＨ濃度を上昇させた場合のＸＲＤパターンを示しており、最上に示すパターンは、酸化スズ（ＳｎＯ）のＸＲＤパターンである。また、図２においては、下から順に、合成に使用したＫＯＨ濃度が０．６４Ｍおよび０．６６Ｍの場合、酸化チタンアナターゼ構造、およびルチル構造のＸＲＤパターンを示す。 X-ray diffraction (XRD) measurement was performed on the obtained Sn (II) / Ti (IV) composite material. A typical XRD pattern obtained with a Rigaku MiniFlex / HRC is shown in FIGS. For comparison, XRD was also measured for tin oxide (FIG. 1) or anatase or rutile structure of titanium oxide (FIG. 2). The XRD pattern of FIG. 1 shows the XRD pattern when the KOH concentration used for the synthesis is increased in order from the bottom, and the pattern shown at the top is the XRD pattern of tin oxide (SnO). In FIG. 2, when the KOH concentrations used for synthesis are 0.64M and 0.66M, the titanium oxide anatase structure and the XRD pattern of the rutile structure are shown in order from the bottom.
図１および２からわかるように、得られたSn(II)/Ti(IV)複合材料は、２θ＝２６．６°、３５．３°、および５３．８°などに特徴的なピークを有する。このピークは、Ｋ、Ｔｉ、またはＳｎを含む既知のあらゆる化合物のＸＲＤパターンとも一致しなかった。そのため、ＸＲＤでは、Sn(II)/Ti(IV)複合材料の構造を同定できなかった。また、図１から、０．６４Ｍまたは０．６６ＭのＫＯＨ溶液を用いて合成した場合、生成物中にＳｎＯが含まれることがわかった。さらに、図２より、生成物中に酸化チタン（ＴｉＯ2）が全く含まれていないこともわかった。 As can be seen from Figures 1 and 2, the resulting Sn (II) / Ti (IV ) composite, 2 [Theta] = 26.6 °, 35.3 °, characteristic peaks, etc. Contact and 53.8 ° Have. This peak did not match the XRD pattern of any known compound containing K, Ti, or Sn. Therefore, XRD could not identify the structure of the Sn (II) / Ti (IV) composite material. Further, FIG. 1 shows that SnO is contained in the product when synthesized using a 0.64M or 0.66M KOH solution. Further, from FIG. 2, titanium oxide (TiO 2) was also found that not contained at all in the product.
次に、Sn(II)/Ti(IV)複合材料について、紫外可視吸収スペクトルを測定した。なお、比較として、水熱処理を行わなかった試料についてもスペクトルを測定した。Kubelka-Munk変換した紫外可視吸収スペクトルを図３に示す。水熱処理を行った試料の吸収端は、いずれも約５９０ｎｍ（明るいオレンジ色）であり、このことからバンドギャップは２．１ｅＶと推定された。 Next, an ultraviolet-visible absorption spectrum was measured for the Sn (II) / Ti (IV) composite material. For comparison, the spectrum was also measured for a sample that was not subjected to hydrothermal treatment. The UV-visible absorption spectrum after Kubelka-Munk conversion is shown in FIG. The absorption edges of the samples subjected to hydrothermal treatment were all about 590 nm (bright orange), and from this, the band gap was estimated to be 2.1 eV.
さらに、組成を調べるために、上記のSn(II)/Ti(IV)複合材料をさらに０．１Ｍ塩酸で洗浄した試料について、蛍光Ｘ線分析を行った。原料のモル比がＴｉ：Ｓｎ＝２：３であったが、得られた試料の元素成分のモル比は３：２〜１：３であった。このことから、得られた試料は、ＴｉとＳｎとを含む複合材料であることが確認できた。 Further, in order to examine the composition, a fluorescent X-ray analysis was performed on a sample obtained by further washing the above Sn (II) / Ti (IV) composite material with 0.1 M hydrochloric acid. The molar ratio of the raw materials was Ti: Sn = 2: 3, but the molar ratio of the elemental components of the obtained sample was 3: 2 to 1: 3. From this, it was confirmed that the obtained sample was a composite material containing Ti and Sn.
（実施例２：Sn(II)/Ti(IV)複合材料を用いる水素生成反応）
１０ｗｔ％メタノール水溶液７０ｍＬに、０．１９Ｍの塩化白金酸（H2PtCl6）水溶液７９．６μＬを加え（触媒量に対してＰｔは１ｗｔ％相当）、さらに上記実施例１で得られた種々のSn(II)/Ti(IV)複合材料３００ｍｇを加えて懸濁させた。この懸濁液に、アルゴン雰囲気下で、Ｌ−４２フィルター（ＨＯＹＡ製）を装着した３００ＷのＸｅランプ（ＵＳＨＩＯ製）で可視光（＞４２０ｎｍ）を照射した。代表的なSn(II)/Ti(IV)複合材料についての、可視光の照射時間と水素生成量との関係を図４に、そして水素生成速度を表１に示す。
(Example 2: Hydrogen generation reaction using Sn (II) / Ti (IV) composite material)
79.6 μL of 0.19 M chloroplatinic acid (H 2 PtCl 6 ) aqueous solution was added to 70 mL of 10 wt% methanol aqueous solution (Pt is equivalent to 1 wt% with respect to the amount of catalyst), and the various types obtained in Example 1 above were further added. 300 mg of Sn (II) / Ti (IV) composite material was added and suspended. This suspension was irradiated with visible light (> 420 nm) with a 300 W Xe lamp (manufactured by USHIO) equipped with an L-42 filter (manufactured by HOYA) under an argon atmosphere. FIG. 4 shows the relationship between the irradiation time of visible light and the amount of hydrogen generation for a typical Sn (II) / Ti (IV) composite material, and Table 1 shows the hydrogen generation rate.
水熱処理により得られた材料は、水素生成活性を有することがわかった。特に、０．６２Ｍ〜０．６８Ｍの濃度のＫＯＨを用いて水熱処理を行った場合に、より高い水素生成活性を有する材料が得られた。 The material obtained by hydrothermal treatment was found to have hydrogen generation activity. In particular, when hydrothermal treatment was performed using KOH having a concentration of 0.62M to 0.68M, a material having higher hydrogen generation activity was obtained.
（実施例３：水熱処理後の熱処理の検討）
水熱処理により得られた材料について、さらなる活性の向上を目的として、以下のように熱処理を行った。上記実施例１において０．６４ＭのＫＯＨ水溶液を用いる水熱処理により得られたSn(II)/Ti(IV)複合材料を、空気中または高真空下（５×１０-7Ｐａ）で３００℃にて２時間焼成した。焼成後のSn(II)/Ti(IV)複合材料について、ＸＲＤを測定した。焼成前後のＸＲＤパターンを図５に示す。図５からわかるように、熱処理後にはＸＲＤのパターン強度が強くなっていた。また、焼成によっても２θ＝３５．３°および３７．２°付近に見られる水熱処理で特徴的なピークの強度も強くなっており、水熱処理せずに焼成のみによって得られる材料とは異なっていた（データを示さず）。
(Example 3: Examination of heat treatment after hydrothermal treatment)
The material obtained by the hydrothermal treatment was heat-treated as follows for the purpose of further improving the activity. The Sn (II) / Ti (IV) composite material obtained by hydrothermal treatment using 0.64M KOH aqueous solution in Example 1 was heated to 300 ° C. in air or under high vacuum (5 × 10 −7 Pa). And calcined for 2 hours. XRD was measured about the Sn (II) / Ti (IV) composite material after baking. The XRD patterns before and after firing are shown in FIG. As can be seen from FIG. 5, the XRD pattern strength increased after the heat treatment. In addition, the intensity of the characteristic peak in the hydrothermal treatment seen near 2θ = 35.3 ° and 37.2 ° is also increased by firing, which is different from the material obtained only by firing without hydrothermal treatment. (Data not shown).
（実施例４：水熱処理後の酸洗浄の検討）
上記実施例１に記載のように、水熱処理により得られたSn(II)/Ti(IV)複合材料中に、不純物としてＳｎＯが含まれているため、これを除去する目的で、以下のように酸洗浄を行った。上記実施例１において０．６６ＭのＫＯＨ水溶液を用いる水熱処理により得られたSn(II)/Ti(IV)複合材料０．１ｇをナスフラスコにとり、１００ｍＬの０．１Ｍ塩酸を加え、室温にて５時間攪拌した。得られた材料についてＸＲＤを測定した。酸洗浄前後のＸＲＤパターンを、図６に示す。図６から明らかなように、酸洗浄によりＳｎＯは除去された。
(Example 4: Examination of acid cleaning after hydrothermal treatment)
As described in Example 1 above, the Sn (II) / Ti (IV) composite material obtained by hydrothermal treatment contains SnO as an impurity. For the purpose of removing this, the following is performed. Then, acid washing was performed. In the above Example 1, 0.1 g of Sn (II) / Ti (IV) composite material obtained by hydrothermal treatment using 0.66 M KOH aqueous solution was placed in a recovery flask, 100 mL of 0.1 M hydrochloric acid was added, and at room temperature. Stir for 5 hours. XRD was measured about the obtained material. The XRD pattern before and after the acid cleaning is shown in FIG. As apparent from FIG. 6, SnO was removed by the acid cleaning.
（実施例５：水素生成活性の波長依存性の検討）
上記実施例１において０．６４ＭのＫＯＨ水溶液を用いる水熱処理により得られたSn(II)/Ti(IV)複合材料、さらにこの材料を高真空下（５×１０-7Ｐａ）で３００℃にて２時間焼成した試料、ならびに０．１Ｍ塩酸で酸洗浄した試料を用いた。上記実施例２と同様に、各試料３００ｍｇを用い、種々のフィルター（Ｌ４２、Ｙ−４４、Ｙ−５２、およびＲ６０：いずれもＨＯＹＡ製）をそれぞれ装着した３００ＷのＸｅランプで可視光（それぞれ＞４２０ｎｍ、＞４４０ｎｍ、＞５２０ｎｍ、および＞６００ｎｍ）を照射した。また、比較のために、暗所での水素生成も測定した。３００℃で焼成した試料についての可視光の照射時間と水素生成量との関係を図７に、そして各試料の水素生成速度を表２に示す。
(Example 5: Examination of wavelength dependency of hydrogen generation activity)
The Sn (II) / Ti (IV) composite material obtained by hydrothermal treatment using 0.64M KOH aqueous solution in Example 1 above, and this material at 300 ° C. under high vacuum (5 × 10 −7 Pa) A sample calcined for 2 hours and a sample washed with 0.1 M hydrochloric acid were used. As in Example 2 above, 300 mg of each sample was used, and visible light (each>> 300 W Xe lamp equipped with various filters (L42, Y-44, Y-52, and R60: all manufactured by HOYA), respectively. 420 nm,> 440 nm,> 520 nm, and> 600 nm). For comparison, hydrogen production in the dark was also measured. FIG. 7 shows the relationship between the irradiation time of visible light and the amount of hydrogen produced for the sample fired at 300 ° C., and Table 2 shows the hydrogen production rate of each sample.
図７からわかるように、水素の発生は、照射光波長を長くしても見られたが、暗所または吸収端よりも長い波長の照射では見られなかった。したがって、観測された水素生成は、得られた試料の光触媒作用によることが確認された。また、表２からわかるように、酸洗浄した場合も水素生成活性が見られることから、この活性はＳｎＯによるものではないことが明らかとなった。さらに、水熱処理後に焼成を行った試料は、非常に高い水素生成活性を示した。これは、焼成により、結晶性がさらに向上したためと思われる。 As can be seen from FIG. 7, the generation of hydrogen was observed even when the irradiation light wavelength was increased, but was not observed in the irradiation at a wavelength longer than the dark place or the absorption edge. Therefore, it was confirmed that the observed hydrogen production was due to the photocatalytic action of the obtained sample. Further, as can be seen from Table 2, since hydrogen generation activity was observed even when acid cleaning was performed, it was clarified that this activity was not due to SnO. Furthermore, the sample fired after hydrothermal treatment showed very high hydrogen generation activity. This is probably because the crystallinity was further improved by firing.
（実施例６：スズ／ジルコニウム（Sn(II)/Zr(IV)）、スズ／ニオブ（Sn(II)/Nb(V)）、およびスズ／タンタル（Sn(II)/Ta(V)）複合材料の合成）
ジルコニウムｎ−ブトキシド、ニオブエトキシド、およびタンタルエトキシド、および０．６０〜１．２０ＭのＫＯＨ水溶液を用いて、上記実施例１においてSn(II)/Ti(IV)複合材料を合成した場合と同様の手順で、Sn(II)/Zr(IV)、Sn(II)/Nb(V)、およびSn(II)/Ta(V)の試料をそれぞれ合成した。これらの試料はいずれも結晶性を有していた。これらについて、ＸＲＤを測定した。それぞれのＸＲＤパターンを図８に示す。
(Example 6: Tin / zirconium (Sn (II) / Zr (IV)), tin / niobium (Sn (II) / Nb (V)), and tin / tantalum (Sn (II) / Ta (V)) Synthesis of composite materials)
In the case where the Sn (II) / Ti (IV) composite material was synthesized in Example 1 using zirconium n-butoxide, niobium ethoxide, and tantalum ethoxide, and a 0.60 to 1.20 M aqueous KOH solution, and Samples of Sn (II) / Zr (IV), Sn (II) / Nb (V), and Sn (II) / Ta (V) were synthesized in the same procedure. All of these samples had crystallinity. For these, XRD was measured. Each XRD pattern is shown in FIG.
Sn(II)/Zr(IV)のＸＲＤパターンでは、２θ＝３８°付近に特徴的なピークが見られた。しかし、他のピークはＳｎ2Ｏ3のパターンならびにジルコニウムｎ−ブトキシドを加えなかった試料とほぼ一致していた。Sn(II)/Nb(V)のＸＲＤパターンについては、パイロクロア型のＳｎ2Ｎｂ2Ｏ7 にほぼ帰属できた。したがって、本実施例の条件でのこれらの複合材料の生成率はあまり良好ではないと思われる。 In the XRD pattern of Sn (II) / Zr (IV), a characteristic peak was observed around 2θ = 38 °. However, the other peaks were almost consistent with the Sn 2 O 3 pattern and the sample without zirconium n-butoxide. The XRD pattern of the Sn (II) / Nb (V ), was almost attributable to Sn 2 Nb 2 O 7 pyrochlore type. Therefore, the production rate of these composite materials under the conditions of this example seems not very good.
次に、これらの試料について、紫外可視吸収スペクトルを測定した。Kubelka-Munk変換した紫外可視吸収スペクトルを図９に示す。いずれの試料も、可視光領域に吸収端を有していた。 Next, an ultraviolet-visible absorption spectrum was measured for these samples. The UV-visible absorption spectrum after Kubelka-Munk conversion is shown in FIG. All samples had an absorption edge in the visible light region.
（実施例７：Sn(II)/Zr(IV)、Sn(II)/Nb(V)、およびSn(II)/Ta(V)複合材料を用いる水素生成反応）
上記実施例２と同様の手順で、上記実施例６で得た各試料の懸濁液を調製した。これらの懸濁液に、アルゴン雰囲気下で、Ｌ−４２フィルターを装着したまたはフィルターなしで３００ＷのＸｅランプで光を照射した。水素生成速度を表３に示す。
(Example 7: Hydrogen production reaction using Sn (II) / Zr (IV), Sn (II) / Nb (V), and Sn (II) / Ta (V) composite materials)
A suspension of each sample obtained in Example 6 was prepared in the same procedure as in Example 2. These suspensions were irradiated with a 300 W Xe lamp with or without an L-42 filter under an argon atmosphere. Table 3 shows the hydrogen production rate.
水熱処理により得られた各試料は、Sn(II)/Ti(IV)複合材料よりも弱いが、水素生成活性を有することがわかった。これらのことから、Sn(II)/Zr(IV)、Sn(II)/Nb(V)、およびSn(II)/Ta(V)複合材料については、収率および触媒活性を上昇させるための合成条件の検討の必要があると思われる。 Each sample obtained by hydrothermal treatment was weaker than the Sn (II) / Ti (IV) composite material, but was found to have hydrogen generation activity. From these, Sn (II) / Zr (IV), Sn (II) / Nb (V), and Sn (II) / Ta (V) composite materials are used to increase yield and catalytic activity. It seems necessary to examine the synthesis conditions.
本発明のスズ／ｄ−ブロック金属複合材料からなる可視光吸収型光触媒は、水素生成反応に高い活性を示す。そのため、太陽エネルギーまたは可視光を利用した水分解、すなわち、水素エネルギー製造システムへ応用が可能である。あるいは、太陽光によって有害物質を分解する環境浄化システムへの応用も考えられる。さらに、本発明による複合材料の合成方法は、種々の元素を原料として利用できるため、これまでに確認されてない新規な光触媒を合成できる可能性がある。 The visible light absorption type photocatalyst comprising the tin / d-block metal composite material of the present invention exhibits high activity in the hydrogen generation reaction. Therefore, it can be applied to water splitting using solar energy or visible light, that is, a hydrogen energy production system. Alternatively, application to an environmental purification system that decomposes harmful substances with sunlight is also conceivable. Furthermore, since the composite material synthesis method according to the present invention can use various elements as raw materials, there is a possibility that a novel photocatalyst that has not been confirmed so far can be synthesized.
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