JP4194833B2 - Photocatalyst composite powder with visible light response - Google Patents
Photocatalyst composite powder with visible light response Download PDFInfo
- Publication number
- JP4194833B2 JP4194833B2 JP2002373362A JP2002373362A JP4194833B2 JP 4194833 B2 JP4194833 B2 JP 4194833B2 JP 2002373362 A JP2002373362 A JP 2002373362A JP 2002373362 A JP2002373362 A JP 2002373362A JP 4194833 B2 JP4194833 B2 JP 4194833B2
- Authority
- JP
- Japan
- Prior art keywords
- bismuth vanadate
- acid
- type
- powder
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000000843 powder Substances 0.000 title claims description 64
- 239000002131 composite material Substances 0.000 title claims description 30
- 239000011941 photocatalyst Substances 0.000 title description 32
- 230000004298 light response Effects 0.000 title 1
- 229910052797 bismuth Inorganic materials 0.000 claims description 87
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 85
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 83
- 230000001699 photocatalysis Effects 0.000 claims description 45
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 27
- 239000004065 semiconductor Substances 0.000 claims description 24
- 239000011248 coating agent Substances 0.000 claims description 13
- 238000000576 coating method Methods 0.000 claims description 13
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 7
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 7
- 229910001930 tungsten oxide Inorganic materials 0.000 claims description 7
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 7
- 230000004043 responsiveness Effects 0.000 claims description 3
- 239000002253 acid Substances 0.000 description 42
- 239000000243 solution Substances 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 32
- 238000012360 testing method Methods 0.000 description 30
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 239000000126 substance Substances 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 12
- 239000012670 alkaline solution Substances 0.000 description 10
- 239000013078 crystal Substances 0.000 description 10
- -1 silane compound Chemical class 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 9
- 229960000907 methylthioninium chloride Drugs 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 150000002894 organic compounds Chemical class 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000013032 photocatalytic reaction Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005562 fading Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- XPFVYQJUAUNWIW-UHFFFAOYSA-N furfuryl alcohol Chemical compound OCC1=CC=CO1 XPFVYQJUAUNWIW-UHFFFAOYSA-N 0.000 description 3
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 2
- 235000011054 acetic acid Nutrition 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 229940036348 bismuth carbonate Drugs 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- 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 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 229920002678 cellulose Polymers 0.000 description 2
- 235000010980 cellulose Nutrition 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 2
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- BQFYGYJPBUKISI-UHFFFAOYSA-N potassium;oxido(dioxo)vanadium Chemical compound [K+].[O-][V](=O)=O BQFYGYJPBUKISI-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- IHIXIJGXTJIKRB-UHFFFAOYSA-N trisodium vanadate Chemical compound [Na+].[Na+].[Na+].[O-][V]([O-])([O-])=O IHIXIJGXTJIKRB-UHFFFAOYSA-N 0.000 description 2
- 229910001935 vanadium oxide Inorganic materials 0.000 description 2
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 description 2
- CUXYLFPMQMFGPL-UHFFFAOYSA-N (9Z,11E,13E)-9,11,13-Octadecatrienoic acid Natural products CCCCC=CC=CC=CCCCCCCCC(O)=O CUXYLFPMQMFGPL-UHFFFAOYSA-N 0.000 description 1
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- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
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- 125000003277 amino group Chemical group 0.000 description 1
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- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 235000003704 aspartic acid Nutrition 0.000 description 1
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Landscapes
- Catalysts (AREA)
Description
【０００１】
【発明の属する技術分野】
本発明は、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを用いた、耐薬品性及び耐候性に優れる、可視光応答性を有する光触媒複合粉体に関するものである。
【０００２】
【従来技術】
地球規模で環境問題が問われている現在の社会状況との関連から、光触媒技術が大変注目されている。
特に、酸化チタン（ＴｉＯ２）等の光触媒技術の研究開発及び実用化がなされており、その抗菌性、防汚性、脱臭性等の性能を活かし、様々な用途で用いられている。
【０００３】
しかしながら、酸化チタン等の光触媒反応において利用できる光としては、紫外光領域に限られており、エネルギーの有効利用、および屋内での利用を実現するには、可視光領域でも利用できる光触媒が望まれている。
また、酸化チタン等の光触媒の色彩は、白色のものが多く色彩性に乏しいため、様々な用途で多様なニーズに応えるためには、色彩に富む光触媒の開発が望まれている。
【０００４】
【発明が解決しようとする課題】
可視光領域でも高い光触媒活性を示し、さらに彩度の高い色彩を有するものとして、例えば、バナジン酸ビスマス等が挙げられる。バナジン酸ビスマスには、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型、Ｄｒｅｙｅｒｉｔｅ型、及びＰｕｃｈｅｒｉｔｅ型と呼ばれる３つの結晶構造が存在し、このうちＣｌｉｎｏｂｉｓｖａｎｉｔｅ型結晶構造を有するバナジン酸ビスマスは、彩度の高い黄色を有し、可視光領域下で高い光触媒活性を有することが知られている。（例えば、非特許文献１等）
しかしながら、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型結晶構造を有するバナジン酸ビスマスは酸化チタンと比べて耐薬品性、及び耐候性に劣るという問題があった。
【０００５】
【非特許文献１】
Ｓ．Ｔｏｋｕｎａｇａ、Ｈ．Ｋａｔｏ、Ａ．Ｋｕｄｏ、「ジャーナル オブ アメリカン ケミカル ソサエティ（Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．）」、第１２１号、１９９９年、ｐ．１１４５９−１１４６７
【０００６】
【課題を解決するための手段】
本発明の目的は、可視光領域でも高い光触媒活性を示し、彩度の高い色彩を有し、かつ優れた耐薬品性及び耐候性を有する光触媒複合粉体を提供するものである。
【０００７】
本発明は上記の問題点を解決するために、鋭意研究を重ねた結果、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする粒子表面に、特定の重量比率で酸化物半導体を被覆してなる光触媒複合粉体が、可視光領域でも高い光触媒活性を示し、彩度の高い色彩を有し、かつ優れた耐薬品性及び耐候性を有することを見出し、本発明の完成に至った。
【０００８】
即ち本発明は、以下の特徴を有するものである。
１．（Ａ）Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを５０重量％以上有し、粒子径が０．０１〜１００μｍである粒子表面に、（Ｂ）酸化チタン、酸化タングステン、または酸化ジルコニウムから選ばれる少なくとも１種以上の光触媒活性を有する酸化物半導体が被覆され、
その被覆量が（Ａ）成分１００重量部に対し（Ｂ）成分０．１〜２５重量部であり、粒子径が０．１〜１００μｍであることを特徴とする可視光応答性を有する光触媒複合粉体。
【０００９】
【発明の実施の形態】
以下、本発明をその実施の形態に基づき詳細に説明する。
【００１０】
（光触媒複合粉体）
本発明の光触媒複合粉体は、可視光下で光触媒活性を示すＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする粒子（以下「（Ａ）成分」ともいう）表面に酸化物半導体（以下「（Ｂ）成分」ともいう）が被覆されたものである。（Ａ）成分は可視光領域で光触媒活性を有することが必須である。また、（Ｂ）成分は、導電性を有するもので、光触媒活性を有していなくてもよいが、光触媒活性を有しているものが好ましい。
【００１１】
本発明の光触媒複合粉体表面に有害物質が吸着された場合、可視光領域の波長を有する光が（Ａ）成分まで到達すると、（Ａ）成分の光触媒作用で生じた電子（あるいは正孔）が、（Ｂ）成分を通して光触媒複合粉体表面まで移動することができるために、（Ｂ）成分が可視光領域で光触媒活性を有さない場合でも、光触媒複合粉体表面において光触媒反応により有害物質を分解することができる。また、（Ｂ）成分が被覆されていることで、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス単独で用いる場合よりも、耐薬品性に優れた光触媒複合粉体を得ることができる。
【００１２】
さらに、本発明の効果を阻害しない程度に、光触媒複合粉体の表面に、リン酸塩（好ましい例としてハイドロキシアパタイト）、酸化ケイ素、シラン化合物等の光触媒反応によって分解されない化合物（さらに好ましくは多孔質である化合物）を被覆することもできる。このような化合物を被覆することにより、さらに耐薬品性に優れた光触媒複合粉体を得ることができるため好ましい。
【００１３】
本発明の光触媒複合粉体は、粒子径が通常０．１〜１００μｍ（好ましくは０．２〜１０μｍ）であるものが望ましい。このような範囲にあることによって、塗料、繊維等の支持体に用いた場合、着色力と隠蔽力が大きく、分散しやすい。さらに本発明の光触媒複合粉体は、彩度の高い色彩を有しているため、屋外だけでなく屋内等の美観性を要求される部材での使用に適した光触媒複合体粉体としても使用することができる。
【００１４】
（Ａ）成分
本発明の（Ａ）成分は、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスが５０重量％以上、好ましくは８０重量％以上、さらに好ましくは９０重量％以上含有するものである。
Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスは可視光領域でも高い光触媒活性を有し、彩度の高い黄色を有する成分である。このようなＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスは、一般式：ＢｉＶＯ４、で示される物質であり、本発明の効果を阻害しない程度に、Ｄｒｅｙｅｒｉｔｅ型及びＰｕｃｈｅｒｉｔｅ型バナジン酸ビスマスが含まれていてもよい。また、本発明の効果を阻害しない程度に、Ｍｇ、Ｃａ、Ｓｒ、Ｂａ、Ｔｉ、Ｍｎ、Ｆｅ、Ｃｏ、Ｎｉ、Ｃｕ、Ｚｎ、Ｙ、Ｚｒ、Ｍｏ、Ａｌ、Ｓｉ、Ｇａ、Ｇｅ等の金属元素で一部置換されていてもよいし、そのような金属元素を含む化合物で複合されていてもよい。
【００１５】
（Ａ）成分の粒子形状、粒子径、粒子径分布等は用途により適宜設定することができる。粒子形状としては、板状、針状、粒状、球状等の形状を用いることができる。粒子径は、０．０１〜１００μｍ（好ましくは０．１〜１０μｍ）であるものが望ましい。
【００１６】
（Ｂ）成分
本発明の（Ｂ）成分は、（Ａ）成分表面に被覆し用いるもので、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスの可視光領域での光触媒性能を維持しながら、耐酸性及び耐薬品性を付与するものである。
このような（Ｂ）成分としては、特に限定されないが、例えば、酸化チタン、酸化タングステン、酸化ジルコニウム、酸化鉄、酸化すず、酸化モリブデン、酸化バナジウム、酸化マンガン、酸化コバルト等から選ばれる少なくとも１種または２種以上を混合して用いることができる。
【００１７】
特に酸化チタン、酸化タングステン、酸化ジルコニウムを用いた場合、それ自体にも優れた光触媒活性を有するため、より優れた光触媒活性を有する光触媒複合粉体が得られるため、望ましい。
本発明では特に、酸化チタンを用いることが好ましく、ルチル型酸化チタン、アナターゼ型酸化チタン、及びアモルファス型酸化チタンの中から適宜、１種以上選択することができる。特に高い光触媒活性を得るためには、高い光触媒活性を有するアナターゼ型酸化チタンを用いることが望ましい。
【００１８】
（Ｂ）成分の被覆量としては、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする粒子１００重量部に対して、酸化物半導体０．１〜２５重量部、好ましくは０．１〜２０重量部、さらに好ましくは０．２〜１５重量部である。酸化物半導体の被覆量が０．１重量部より少ない場合には、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスの耐酸性と耐薬品性が効果的に改善されない。一方、２５重量部よりも多い場合には、可視光領域下での光触媒活性が抑制され、また、彩度の高い色彩が発現しにくくなる。
また、酸化物半導体の被覆状態としては、最終的に、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする粒子の表面全体を被覆してもよいし、また粒子の一部が被覆されていない状態でもよい。また、粒子の内部に酸化物半導体が存在してもよい。
【００１９】
（光触媒複合粉体の製造方法）
本発明の光触媒複合粉体は、（イ）Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粒子に酸化物半導体を被覆して製造することもできるし、また、所望により、（ロ）熱処理等によりＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに変化する前駆体粒子（例えば、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマス等）に酸化物半導体を被覆し、熱処理等を施すことで製造することもできる。
酸化物半導体を被覆する方法としては、特に限定されず、公知の方法を用いることができる。例えば、ゾル−ゲル法、スパッタリング法等を用いることができる。
【００２０】
Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス、またはその前駆体であるＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマス等を主成分とする粒子は公知の製造方法で製造すればよい。
Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマス粉体を製造する方法としては、例えば、Ｂｉ化合物とＶ化合物を含む酸溶液に、アルカリ溶液を加えることによって製造する方法等が挙げられる。
Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体を製造する方法としては、Ｂｉ化合物とＶ化合物を含む酸溶液に、アルカリ溶液を加えることによって析出したＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマス粉体をｐＨが３未満である溶液中で熟成して製造する方法、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマス粉体を２５０℃以上で熱処理して製造する方法、Ｂｉ化合物とＶ化合物の混合物を熱処理して得られたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス焼結体を必要に応じて、粉砕して製造する方法等が挙げられる。
【００２１】
本発明では、特に、Ｂｉ化合物とＶ化合物を含む酸溶液に、アルカリ溶液を加えることによって析出したＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマス粉体に、ゾル状の酸化物半導体を被覆して熱処理して製造する方法、または、Ｂｉ化合物とＶ化合物を含む酸溶液に、アルカリ溶液を加えることによって析出したＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマス粉体を室温で熟成（あるいは２５０℃以上で熱処理）して得られるＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体にゾル状の酸化物半導体を被覆した後、所望により熱処理することにより、光触媒複合粉体を製造する方法等が望ましい。
このような方法で製造することにより、（Ａ）成分、及び光触媒複合粉体の粒径や形状を制御することが容易であり、また粉砕等の工程を必要とすることなく微粒子を製造することができるために、好ましい。
以下にその詳細を記述する。
【００２２】
本発明において使用するＢｉ化合物とＶ化合物を含む酸溶液は、Ｂｉ化合物とＶ化合物を硝酸または酢酸に溶解して調整することができる。酸溶液は、好ましくはｐＨ１以下、さらに好ましくはｐＨ０．５以下、より好ましくはｐＨ０以下とする。
【００２３】
Ｂｉ化合物とＶ化合物を含む酸溶液に、アルカリ溶液を加えることによって得られるＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマスを製造する場合には、Ｂｉ化合物とＶ化合物を含む酸溶液中のＢｉ／Ｖのモル比は特に限定されない。
Ｂｉ化合物とＶ化合物を含む酸溶液に、アルカリ溶液を加えることによって得られるＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマスを室温で熟成してＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを製造する場合には、酸溶液中のＢｉ／Ｖのモル比としては、ＢｉとＶのモル比が０．１≦Ｂｉ／Ｖ≦１．１（好ましくは０．２≦Ｂｉ／Ｖ≦１．０）とすることが望ましい。このようなモル比の溶液を用いることにより、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする生成物を効率的に作製することができる。溶液中のＢｉ／Ｖ比がこのような範囲よりも小さい場合には、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス以外の成分を主成分となる生成物が生じるため、本発明の目的とする、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする生成物を効率的に製造することができない。溶液中のＢｉ／Ｖ比がこのような範囲よりも大きい場合には、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスを主成分とする生成物が安定になり、本発明の目的とする、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする生成物を得ることができない。
【００２４】
Ｂｉ化合物としては、例えば、水酸化ビスマス、硝酸ビスマス、硝酸ビスマス・五水和物、塩基性硝酸ビスマス、炭酸ビスマス、塩基性炭酸ビスマス、酸化ビスマス、硫酸ビスマス、塩基性硫酸ビスマス、塩化ビスマス、クエン酸ビスマス、オキシ塩化ビスマス、ヨウ化ビスマス、２−エチルヘキサン酸ビスマス、ナフテン酸ビスマス、ジサリチル酸ビスマス等が挙げられ、特に硝酸ビスマス、酸化ビスマスを好適に用いることができる。
【００２５】
Ｖ化合物としては、塩化バナジウム、酸化バナジウム、酸化硫酸バナジウム、しゅう酸バナジウム、酸化バナジウムアセチルアセテート、メタバナジン酸ナトリウム、オルトバナジン酸ナトリウム等のバナジン酸ナトリウム、バナジン酸カリウム、バナジン酸アンモニウム等が挙げられ、特にメタバナジン酸ナトリウム、オルトバナジン酸ナトリウム、バナジン酸カリウム、バナジン酸アンモニウムを好適に用いることができる。
【００２６】
アルカリ溶液としては、水酸化カリウム、水酸化ナトリウム、炭酸カリウム、炭酸ナトリウム、炭酸水素カリウム、炭酸水素ナトリウム、アンモニア、尿素等の溶液を好適に用いることができる。
Ｂｉ化合物とＶ化合物を含む酸溶液とアルカリ溶液の混合は、バッチ式でも連続式でも行うことができる。溶液の混合は完全な攪拌下で行うことが好ましく、必要があれば高乱流下、例えば流通反応装置や混合ノズルを用いて、必要があれば高性能攪拌機付きの装置内で行う。
水溶性のＢｉ化合物とＶ化合物を含む酸溶液とアルカリ溶液の混合は、１０〜１００℃、好ましくは２０〜４０℃で行われる。
【００２７】
前記の酸溶液とアルカリ溶液のｐＨは、例えば混合後に得られる懸濁液のｐＨが３、さらに好ましくは１を超えないように調整する。
【００２８】
特に、アルカリ溶液を加える際に、さらに、水溶性有機化合物を添加することにより、分散性と粒子径の均一性に優れたバナジン酸ビスマスを製造することができるために、特に好ましい。このような効果を有する水溶性有機化合物としては、アルコール類、ポリオール類、ケトン類、ポリエーテル類、エステル類、カルボン酸類、ポリカルボン酸類、セルロース類、糖類、スルホン酸類、アミノ酸類、アミン類であって、より具体的にはメタノール、エタノール、プロパノール、ブタノール、ペンタノール、ヘキサノール等の脂肪族アルコール、エチレングリコール、プロパンジオール、ブタンジオール、グルセリン、ポリエチレングリコール、ポリプロピレングリコール等の脂肪族多価アルコール、フェノール、カテコール、クレゾール等の芳香族アルコール、フルフリルアコール等の複素環を有するアルコール類、アセトン、メチルエチルケトン、アセチルアセトン等のケトン類、エチルエーテル、テトラヒドロフラン、ジオキサン、ポリオキシアルキレンエーテル、エチレンオキサイド付加物、プロピレンオキサイド付加物等のエーテルあるいはポリエーテル類、酢酸エチル、アセト酢酸エチル、グリシンエチルエステル等のエステル類、蟻酸、酢酸、プロピオン酸、ブタン酸、酪酸、蓚酸、マロン酸、クエン酸、酒石酸、グルコン酸、サリチル酸、安息香酸、アクリル酸、マレイン酸、グリセリン酸、エレオステアリン酸、ポリアクリル酸、ポリマレイン酸、アクリル酸ーマレイン酸コポリマー等のカルボン酸、ポリカルボン酸、あるいはヒドロキシカルボン酸やその塩類、カルボキシメチルセルロース類、グルコース、ガラクトース等の単糖類、蔗糖、ラクトース、アミロース、キチン、セルロース等の多糖類、アルキルベンゼンスルホン酸、パラトルエンスルホン酸、アルキルスルホン酸、α−オレフィンスルホン酸、ポリオキシエチレンアルキルスルホン酸、リグニンスルホン酸、ナフタレンスルホン酸等のスルホン酸類やその塩類、グリシン、グルタミン酸、アスパラギン酸、アラニン等のアミノ酸、モノエタノールアミン、ジエタノールアミン、トリエタノールアミン、ブタノールアミン等のヒドロキシアミン類、トリメチルアミノエチルアルキルアミド、アルキルピリジニウム硫酸塩、アルキルトリメチルアンモニウムハロゲン化物、アルキルベタイン、アルキルジエチレントリアミノ酢酸等を例とし挙げることができる。
これら水溶性有機化合物の中でも水酸基、カルボキシル基及びアミノ基の何れか一種或いは二種以上の官能基を有する水溶性有機化合物が好ましい。これらは単独又は２種以上のものを混合して共存させる事もできる。アルカリ溶液を加えることによって沈澱を作製する反応時に存在する水溶性有機化合物は、反応により析出するＣｌｉｎｏｂｉｓｖａｎｉｔｅ型又はＤｒｅｙｅｒｉｔｅ型のバナジン酸ビスマスの表面に吸着して粒子の成長を制御しているものと思われ、結果として結晶形状や平均粒子径等の結晶性が制御できる。
【００２９】
水溶性有機化合物は、Ｂｉ化合物とＶ化合物を含む酸溶液中に約０．００１重量％〜約１０重量％の範囲で共存させるのが好ましく、その量は所望粒径と粒径分布等により決定される。
【００３０】
本発明においては、アルカリ溶液を加えることによりＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマスが析出した後、さらに懸濁液を撹拌して熟成することにより、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスの結晶性や形状、表面性状を改善するのに有効である。このような撹拌は０．１〜６時間、好ましくは０．５〜３時間、反応温度またはそれより低い温度にて行うことが好ましい。
【００３１】
また所望により、撹拌をさらに長時間継続することにより、懸濁液中でＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマスがＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに変化するために、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス製造することができる。このような撹拌は６〜７２時間、好ましくは１０〜６０時間、室温またはそれより低い温度にて行うことが好ましい。
【００３２】
懸濁液は、次いで固液分離し、洗浄、乾燥する。このような操作により、溶液中に残存する不純物を除去することができるため、活性の高い光触媒複合粉体を作製することができ、望ましい。
【００３３】
Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスにゾル状の酸化物半導体を被覆した場合、２６０℃以上の温度で熱処理することにより、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスがＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに変化するので、本発明の目的である光触媒複合粉体を製造することができる。
また、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスにゾル状の酸化物半導体を被覆することによっても、本発明の目的である光触媒複合粉体を製造することができる。このような場合、所望により所定の温度で熱処理を加えてもよい。
Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマス、あるいはＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに、ゾル状の酸化物半導体を被覆した後、所定の温度で熱処理を加えることにより、熱処理温度に応じて酸化物半導体の結晶形態を制御することができる。上述したように、ゾル状の酸化物半導体を被覆したＤｒｅｙｅｒｉｔｅ型バナジン酸ビスマスを用いた場合には、酸化物半導体の結晶形態の変化に併行して、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスがＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに変化する。
具体的には、酸化物半導体としてゾル状の酸化チタンを被覆した場合において、熱処理温度に応じて酸化チタンの結晶形態を、ゾル状酸化チタン、アナターゼ型酸化チタン、ルチル型酸化チタン等の中から選択して作製することができる。これらの酸化物半導体の結晶形態は目的とする光触媒複合粉体の彩度、光触媒活性等に応じて選択すれば良く、例えば、特に光触媒能の高い光触媒複合粉体を得るためには、光触媒活性の高い結晶形態（例えばアナターゼ型酸化チタン）を選択すればよい。
【００３４】
このときの熱処理は、空気中、または酸化雰囲気で行われることが好ましい。また、熱処理時の温度は、選択する酸化物半導体の結晶形態に応じて適宜選択すれば良い。
Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスに酸化物半導体を被覆した場合、２６０℃以上であることが好ましい。２６０℃より低い温度では、Ｄｒｅｙｅｒｉｔｅ型バナジン酸ビスマスからＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスの変化が有効に生じない。また、熱処理温度の上限は限定されないが、通常８００℃以下であれば、光触媒複合粉体同士の焼結による粒成長が抑制され、光触媒活性の高い光触媒複合粉体を得ることができる。
【００３５】
【実施例】
以下に実施例及び比較例を示し、本発明の特徴をより明確にするが、本発明はこの実施例に限定されない。
【００３６】
（実施例１）
（ゾル状酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス）
Ｂｉ(ＮＯ３)３・５Ｈ２Ｏ ４６．５ｇと、Ｎａ３ＶＯ４ ２３．２ｇを１Ｎ硝酸３．２ｌに溶解し、エチレングリコール５５．５ｇを加えた。攪拌しながら、１Ｎ炭酸ナトリウム２．０ｌを滴下すると沈澱を析出した。このとき懸濁液のｐＨは１未満であった。沈澱が析出した後、１２時間攪拌を続けて熟成した。濾過、洗浄した後１１０℃で乾燥して、粉体を得た。
得られた粉体をＸ線回折（ＸＲＤ）パターンを測定したところ、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスのＸＲＤパターンとよく一致したことから、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスが生成したことを確認した。
このようにして得られたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体１０ｇをチタンブトキシド１０ｇ：エタノール２００ｇ：３０％過酸化水素水５ｇからなる溶液に加えて懸濁液とし、攪拌しながら６０℃で３時間加熱し、ろ過、洗浄した後１１０℃で乾燥して、鮮やかな黄色を有する、粉体を得た。
得られた粉体をＸ線回折（ＸＲＤ）パターンを測定したところ、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに由来するＸＲＤパターンと、アモルファス状のＸＲＤパターンを成分としていることから、ゾル状酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体が生成したことを確認した。
【００３７】
（光触媒活性試験）
可視光領域下での光触媒活性の評価は、メチレンブルー溶液の分解試験で行った。実施例１で得られた粉体０．５ｇを１ｍｇ／lメチレンブルー溶液０．１ｌとともに、ガラス容器に密封した。このガラス容器に、太陽光に近いスペクトル分布を有する蛍光灯（１８Ｗのトルーライト、米ライトソーシズ社製）を用い、蛍光灯とガラス容器の間に３８０ｎｍ以下の紫外光を遮断するアクリル板（厚さ：５．０ｍｍ）を挟むことによって、選択的に可視光を２４時間照射し、メチレンブルー溶液の退色の程度を観察した。
評価は、○：無色透明になった。△：退色が起こったが、無色とはならなかった、×：退色が起こらなかった、とし、表１に示した。
表１に示すように、メチレンブルー溶液が退色して溶液が無色になり、可視光領域で優れた光触媒活性を有することが確認できた。
【００３８】
【表１】
（耐酸性試験）
耐酸性試験を以下のようにして行った。実施例１で得られた粉体１０ｗｔ％、アクリル樹脂（固形分５０％）８０ｗｔ％及びシンナー１０ｗｔ％を混合し、ガラス板に０．２５ｍｍの厚みで塗布、７日間養生し、試験体を得た。さらに、この試験体を１０％硫酸中に２４時間浸漬した。耐酸性試験では、色差計（ＣＭ−３７００ｄ、ミノルタ株式会社製）を用いて硫酸に浸漬する前後の色差を測定することによって評価した。
耐酸性試験結果を表２に示す。表２に示すように、硫酸に浸漬する前後の色相の変化が小さく、耐酸性に優れていた。
【００４０】
【表２】
（実施例２）
（アナターゼ型酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス）
実施例１で得られたゾル状の酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体を、さらに空気中で、４００℃で１時間熱処理することにより、鮮やかな黄色を有する粉体を得た。
得られた粉体のＸ線回折（ＸＲＤ）パターンを測定したところ、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに由来するＸＲＤパターンと、アナターゼ型酸化チタンのＸＲＤパターンを成分としていることから、アナターゼ型酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体が生成したことを確認した。
実施例１と同様の光触媒活性試験、耐酸性試験を行なった。
光触媒活性試験の結果を表１に示す。メチレンブルー溶液が退色し、可視光領域下での光触媒活性を有することを確認した。
耐酸性試験結果を表２に示す。実施例１と同様に、耐酸性試験前後の色相の変化が小さく、耐酸性に優れていた。
【００４２】
（実施例３）
（酸化タングステンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス）
実施例１で得られたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体１０ｇをタングステン酸アンモニウム１０ｇ：蒸留水２００ｇからなる溶液に加えて懸濁液とし、攪拌しながら１００℃で加熱し、溶媒を除去した後４００℃で２時間熱処理し、鮮やかな黄色を有する粉体を得た。
得られた粉体のＸ線回折（ＸＲＤ）パターンを測定したところ、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに由来するＸＲＤパターンと、酸化タングステンのＸＲＤパターンを成分としていることから、酸化タングステンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体が生成したことを確認した。
実施例１と同様の光触媒活性試験、耐酸性試験を行なった。
光触媒活性試験の結果を表１に示す。メチレンブルー溶液が退色し、可視光領域下での光触媒活性を有することを確認した。
耐酸性試験結果を表２に示す。実施例１と同様に、耐酸性試験前後の色相の変化が抑制され、耐酸性に優れていた。
【００４３】
（実施例４）
（酸化ジルコニウムにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス）
実施例１で得られたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体１０ｇをジルコニウムプロポキシド１０ｇ：エタノール２００ｇ：３０％過酸化水素水５ｇからなる溶液に加えて懸濁液とし、攪拌しながら６０℃で３時間加熱し、ろ過、洗浄して得られた粉体を、１１０℃で乾燥した後、さらに４００℃で２時間熱処理し、鮮やかな黄色を有する粉体を得た。
得られた粉体のＸ線回折（ＸＲＤ）パターンを測定したところ、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに由来するＸＲＤパターンと、酸化ジルコニウムのＸＲＤパターンを成分としていることから、酸化ジルコニウムにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体が生成したことを確認した。
実施例１と同様の光触媒活性試験、耐酸性試験を行なった。
光触媒活性試験の結果を表１に示す。メチレンブルー溶液が退色し、可視光領域下での光触媒活性を有することを確認した。
耐酸性試験結果を表２に示す。実施例１と同様に、耐酸性試験前後の色相の変化が抑制され、耐酸性に優れていた。
【００４４】
（比較例１）
（Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体）
実施例１で得られたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体を用いて、実施例１と同様の光触媒活性試験、耐酸性試験を行なった。
光触媒活性試験の結果を表１に示す。メチレンブルー溶液が退色し、可視光領域下での光触媒活性を有することを確認した。
耐酸性試験の結果を表２に示す。色相変化が大きく、耐酸性に劣る結果が得られた。
【００４５】
（比較例２）
（アナターゼ型酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス）
実施例１で得られたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体１０ｇに対して、チタンブトキシド５００ｇを加えた以外は、実施例１と同様にして、淡い黄色を有する粉体を得た。
得られた粉体のＸ線回折（ＸＲＤ）パターンを測定したところ、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスに由来するＸＲＤパターンと、アモルファス状物質のＸＲＤパターンを成分としていることから、アモルファス型酸化チタンにより被覆されたＣｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマス粉体が生成したことを確認した。
実施例１と同様の光触媒活性試験、耐酸性試験を行なった。
光触媒活性試験の結果を表１に示す。メチレンブルー溶液は退色せず、可視光領域下での光触媒活性を有しないことを確認した。
【００４６】
【発明の効果】
本発明は、Ｃｌｉｎｏｂｉｓｖａｎｉｔｅ型バナジン酸ビスマスを主成分とする粒子表面に、酸化物半導体が特定の重量比率で被覆されてなる光触媒複合粉体である。本発明の光触媒複合粉体は、可視光領域でも高い光触媒活性を示し、無公害であり、彩度の高い黄色を有し、かつ優れた耐薬品性及び耐候性を有している。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a photocatalyst composite powder having excellent visible light responsiveness and excellent chemical resistance and weather resistance, using Clinobisvanite type bismuth vanadate.
[0002]
[Prior art]
Photocatalytic technology is attracting a great deal of attention because of its relationship with the current social situation where environmental problems are being sought on a global scale.
In particular, titanium oxide (TiO 2 R & D and practical application of photocatalytic technologies such as anti-bacterial, anti-fouling and deodorizing properties are being used for various purposes.
[0003]
However, the light that can be used in photocatalytic reactions such as titanium oxide is limited to the ultraviolet light region, and a photocatalyst that can also be used in the visible light region is desired to realize effective use of energy and indoor use. ing.
In addition, since the color of photocatalysts such as titanium oxide is mostly white and poor in color, development of a photocatalyst rich in color is desired in order to meet various needs in various applications.
[0004]
[Problems to be solved by the invention]
Examples of those that exhibit high photocatalytic activity even in the visible light region and have a high chroma color include bismuth vanadate. Bismuth vanadate has three crystal structures called Clinobisvante type, Dryerite type, and Pucherite type. Among them, bismuth vanadate having a Clinobisvante type crystal structure has a high chroma yellow and has a visible light region. Under high photocatalytic activity is known. (For example, Non-Patent Document 1 etc.)
However, bismuth vanadate having a Clinobisvanite type crystal structure has a problem that it is inferior in chemical resistance and weather resistance as compared with titanium oxide.
[0005]
[Non-Patent Document 1]
S. Tokunaga, H .; Kato, A.A. Kudo, “Journal of American Chemical Society” (J. Am. Chem. Soc.), No. 121, 1999, p. 11459-11467
[0006]
[Means for Solving the Problems]
An object of the present invention is to provide a photocatalyst composite powder that exhibits high photocatalytic activity even in the visible light region, has high chroma, and has excellent chemical resistance and weather resistance.
[0007]
In order to solve the above-mentioned problems, the present invention has been made through extensive research. As a result, a photocatalyst composite powder obtained by coating an oxide semiconductor at a specific weight ratio on the surface of a particle mainly composed of Clinobisvantite bismuth vanadate. The present inventors have found that the body exhibits high photocatalytic activity even in the visible light region, has a highly saturated color, and has excellent chemical resistance and weather resistance, leading to the completion of the present invention.
[0008]
That is, the present invention has the following features.
1. (A) Clinobisvante type bismuth vanadate having 50% by weight or more and a particle diameter of 0.01 to 100 μm (B) on the particle surface At least one photocatalytic activity selected from titanium oxide, tungsten oxide, or zirconium oxide Coated with oxide semiconductor,
The coating amount is 0.1 to 25 parts by weight of component (B) with respect to 100 parts by weight of component (A), The particle size is 0.1-100 μm A photocatalyst composite powder having visible light responsiveness.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail based on the embodiments.
[0010]
(Photocatalyst composite powder)
The photocatalyst composite powder of the present invention has an oxide semiconductor (hereinafter referred to as “(B)”) on the surface of particles (hereinafter also referred to as “component (A)”) mainly composed of Clinobisvanite-type bismuth vanadate that exhibits photocatalytic activity under visible light. (Also referred to as “component”). It is essential that the component (A) has a photocatalytic activity in the visible light region. Moreover, (B) component has electroconductivity and does not need to have photocatalytic activity, but what has photocatalytic activity is preferable.
[0011]
When harmful substances are adsorbed on the surface of the photocatalyst composite powder of the present invention, when light having a wavelength in the visible light region reaches the (A) component, electrons (or holes) generated by the photocatalytic action of the (A) component However, since it can move to the surface of the photocatalyst composite powder through the component (B), even if the component (B) does not have a photocatalytic activity in the visible light region, the photocatalytic reaction causes a harmful substance by the photocatalytic reaction. Can be disassembled. In addition, since the component (B) is coated, a photocatalyst composite powder having superior chemical resistance can be obtained as compared with the case where the Clinobisvante type bismuth vanadate is used alone.
[0012]
Furthermore, a compound that is not decomposed by a photocatalytic reaction such as phosphate (hydroxyapatite as a preferred example), silicon oxide, silane compound, etc. (more preferably porous) on the surface of the photocatalyst composite powder to such an extent that the effect of the present invention is not impaired. It is also possible to coat a compound which is Coating such a compound is preferable because a photocatalyst composite powder having further excellent chemical resistance can be obtained.
[0013]
The photocatalyst composite powder of the present invention desirably has a particle size of usually 0.1 to 100 μm (preferably 0.2 to 10 μm). By being in such a range, when used for a support such as a paint or fiber, the coloring power and the hiding power are large and are easily dispersed. Furthermore, since the photocatalyst composite powder of the present invention has a highly saturated color, it is also used as a photocatalyst composite powder suitable for use not only outdoors but also in members that require aesthetics such as indoors. can do.
[0014]
(A) component
The component (A) of the present invention contains 50% by weight or more, preferably 80% by weight or more, and more preferably 90% by weight or more of Clinobisvantite type bismuth vanadate.
Clinobisvanite-type bismuth vanadate is a component having high photocatalytic activity even in the visible light region and having a high yellow color. Such Clinobisvanite-type bismuth vanadate has a general formula: BiVO 4 , And may contain Dreyerite-type and Pucherite-type bismuth vanadate to an extent that does not inhibit the effects of the present invention. In addition, metals such as Mg, Ca, Sr, Ba, Ti, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Mo, Al, Si, Ga, and Ge to the extent that the effects of the present invention are not hindered. It may be partially substituted with an element, or may be compounded with a compound containing such a metal element.
[0015]
The particle shape, particle size, particle size distribution, etc. of the component (A) can be appropriately set depending on the application. As the particle shape, a plate shape, a needle shape, a granular shape, a spherical shape or the like can be used. The particle diameter is desirably 0.01 to 100 μm (preferably 0.1 to 10 μm).
[0016]
(B) component
The component (B) of the present invention is used by coating the surface of the component (A) and imparts acid resistance and chemical resistance while maintaining the photocatalytic performance in the visible light region of Clinobisvante type bismuth vanadate. is there.
The component (B) is not particularly limited, but for example, at least one selected from titanium oxide, tungsten oxide, zirconium oxide, iron oxide, tin oxide, molybdenum oxide, vanadium oxide, manganese oxide, cobalt oxide, and the like. Or 2 or more types can be mixed and used.
[0017]
In particular, when titanium oxide, tungsten oxide, or zirconium oxide is used, it itself has excellent photocatalytic activity, so that a photocatalyst composite powder having more excellent photocatalytic activity can be obtained, which is desirable.
In the present invention, it is particularly preferable to use titanium oxide, and one or more can be appropriately selected from rutile type titanium oxide, anatase type titanium oxide, and amorphous type titanium oxide. In order to obtain particularly high photocatalytic activity, it is desirable to use anatase-type titanium oxide having high photocatalytic activity.
[0018]
As the coating amount of the component (B), 0.1 to 25 parts by weight of an oxide semiconductor, preferably 0.1 to 20 parts by weight, with respect to 100 parts by weight of particles mainly composed of Clinobisvante type bismuth vanadate, Preferably it is 0.2-15 weight part. When the amount of oxide semiconductor coating is less than 0.1 parts by weight, the acid resistance and chemical resistance of Clinobisvanite type bismuth vanadate are not effectively improved. On the other hand, when the amount is more than 25 parts by weight, the photocatalytic activity under the visible light region is suppressed, and a color with high saturation is hardly exhibited.
In addition, the oxide semiconductor may be finally coated on the entire surface of the particle mainly composed of Clinobisvante bismuth vanadate, or may be in a state where a part of the particle is not coated. . In addition, an oxide semiconductor may be present inside the particle.
[0019]
(Method for producing photocatalyst composite powder)
The photocatalyst composite powder of the present invention can be produced by coating (i) Clinobisvantite type bismuth vanadate particles with an oxide semiconductor, and (b) Clinobisvantite type bismuth vanadate by heat treatment or the like, if desired. It can also be produced by coating a changing precursor particle (for example, Dreyerite type bismuth vanadate) with an oxide semiconductor and performing a heat treatment or the like.
A method for coating the oxide semiconductor is not particularly limited, and a known method can be used. For example, a sol-gel method, a sputtering method, or the like can be used.
[0020]
The particles mainly composed of Clinobisvantite-type bismuth vanadate or its precursor, Dreyerite-type bismuth vanadate, may be produced by a known production method.
Examples of the method for producing Dreyerite-type bismuth vanadate powder include a method of producing an acid solution containing a Bi compound and a V compound by adding an alkaline solution.
As a method for producing Clinobisvanite-type bismuth vanadate powder, a dryryite-type bismuth vanadate powder precipitated by adding an alkaline solution to an acid solution containing a Bi compound and a V compound is used in a solution having a pH of less than 3. A method of aging and manufacturing, a method of manufacturing by heat-treating Dreyerite-type bismuth vanadate powder at 250 ° C. or higher, and a Clinobisvanite-type bismuth vanadate sintered body obtained by heat-treating a mixture of Bi compound and V compound are required. Depending on the method, a method of pulverizing and manufacturing can be mentioned.
[0021]
In the present invention, in particular, a method in which a dry oxide bismuth vanadate powder deposited by adding an alkaline solution to an acid solution containing a Bi compound and a V compound is coated with a sol-like oxide semiconductor and heat-treated. Alternatively, Clinobisvanite-type bismuth vanadate obtained by aging (or heat-treating at 250 ° C. or higher) a Dreyerite-type bismuth vanadate powder precipitated by adding an alkaline solution to an acid solution containing a Bi compound and a V compound. A method of producing a photocatalyst composite powder by coating a powder with a sol-shaped oxide semiconductor and then heat-treating it as desired is desirable.
By producing in this way, it is easy to control the particle size and shape of the component (A) and the photocatalyst composite powder, and produce fine particles without requiring a step such as pulverization. Is preferable.
The details are described below.
[0022]
The acid solution containing Bi compound and V compound used in the present invention can be prepared by dissolving Bi compound and V compound in nitric acid or acetic acid. The acid solution is preferably pH 1 or less, more preferably pH 0.5 or less, and more preferably pH 0 or less.
[0023]
When producing Dryryite-type bismuth vanadate obtained by adding an alkaline solution to an acid solution containing Bi compound and V compound, the molar ratio of Bi / V in the acid solution containing Bi compound and V compound is particularly It is not limited.
In the case of producing Clinobisvanite-type bismuth vanadate by aging Dreyerite-type bismuth vanadate obtained by adding an alkaline solution to an acid solution containing a Bi compound and a V compound at room temperature, Bi / V of Bi / V in the acid solution is produced. The molar ratio of Bi and V is preferably 0.1 ≦ Bi / V ≦ 1.1 (preferably 0.2 ≦ Bi / V ≦ 1.0). By using a solution having such a molar ratio, it is possible to efficiently produce a product having Cinobisvanite type bismuth vanadate as a main component. When the Bi / V ratio in the solution is smaller than the above range, a product mainly composed of components other than Clinobisvantite-type bismuth vanadate is produced. Therefore, the Clinobisvantite-type bismuth vanadate, which is the object of the present invention, is produced. Cannot be produced efficiently. When the Bi / V ratio in the solution is larger than the above range, the product mainly composed of Dryerite type bismuth vanadate becomes stable, and the Clinobisvanite type bismuth vanadate, which is the object of the present invention, is mainly used. A product as a component cannot be obtained.
[0024]
Examples of the Bi compound include bismuth hydroxide, bismuth nitrate, bismuth nitrate pentapentahydrate, basic bismuth nitrate, bismuth carbonate, basic bismuth carbonate, bismuth oxide, bismuth sulfate, basic bismuth sulfate, bismuth chloride, and citrate. Bismuth acid bismuth, bismuth oxychloride, bismuth iodide, bismuth 2-ethylhexanoate, bismuth naphthenate, bismuth disalicylate and the like can be mentioned, and bismuth nitrate and bismuth oxide can be particularly preferably used.
[0025]
Examples of the V compound include vanadium chloride, vanadium oxide, vanadium sulfate, vanadium oxalate, vanadium oxide acetyl acetate, sodium metavanadate, sodium orthovanadate and the like, sodium vanadate, potassium vanadate, ammonium vanadate, and the like. In particular, sodium metavanadate, sodium orthovanadate, potassium vanadate, and ammonium vanadate can be suitably used.
[0026]
As the alkaline solution, a solution of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate, ammonia, urea or the like can be suitably used.
The mixing of the acid solution containing the Bi compound and the V compound and the alkali solution can be performed either batchwise or continuously. The mixing of the solution is preferably carried out under complete stirring. If necessary, it is carried out in a highly turbulent flow, for example, using a flow reactor or a mixing nozzle, and if necessary, in a device equipped with a high-performance stirrer.
The mixing of the acid solution containing the water-soluble Bi compound and the V compound and the alkali solution is performed at 10 to 100 ° C, preferably 20 to 40 ° C.
[0027]
The pH of the acid solution and the alkali solution is adjusted so that, for example, the pH of the suspension obtained after mixing does not exceed 3, more preferably 1.
[0028]
In particular, when adding an alkaline solution, bismuth vanadate excellent in dispersibility and uniformity in particle diameter can be produced by adding a water-soluble organic compound, which is particularly preferable. Water-soluble organic compounds having such effects include alcohols, polyols, ketones, polyethers, esters, carboxylic acids, polycarboxylic acids, celluloses, saccharides, sulfonic acids, amino acids, and amines. More specifically, aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol, aliphatic polyhydric alcohols such as ethylene glycol, propanediol, butanediol, glycerin, polyethylene glycol, polypropylene glycol, Aromatic alcohols such as phenol, catechol and cresol, alcohols having a heterocyclic ring such as furfuryl alcohol, ketones such as acetone, methyl ethyl ketone and acetylacetone, ethyl ether, tetrahydrofuran, di Ethers or polyethers such as xanthone, polyoxyalkylene ether, ethylene oxide adduct, propylene oxide adduct, esters such as ethyl acetate, ethyl acetoacetate, glycine ethyl ester, formic acid, acetic acid, propionic acid, butanoic acid, butyric acid Carboxylic acids such as oxalic acid, malonic acid, citric acid, tartaric acid, gluconic acid, salicylic acid, benzoic acid, acrylic acid, maleic acid, glyceric acid, eleostearic acid, polyacrylic acid, polymaleic acid, acrylic acid-maleic acid copolymer, Polycarboxylic acids, or hydroxycarboxylic acids and salts thereof, carboxymethylcelluloses, monosaccharides such as glucose and galactose, polysaccharides such as sucrose, lactose, amylose, chitin, and cellulose, alkylbenzenesulfonic acid, paratoluene Sulfonic acids such as sulfonic acid, alkyl sulfonic acid, α-olefin sulfonic acid, polyoxyethylene alkyl sulfonic acid, lignin sulfonic acid, naphthalene sulfonic acid, and salts thereof, amino acids such as glycine, glutamic acid, aspartic acid, alanine, monoethanolamine Examples thereof include hydroxyamines such as diethanolamine, triethanolamine and butanolamine, trimethylaminoethylalkylamide, alkylpyridinium sulfate, alkyltrimethylammonium halide, alkylbetaine, and alkyldiethylenetriaminoacetic acid.
Among these water-soluble organic compounds, water-soluble organic compounds having any one or two or more functional groups of a hydroxyl group, a carboxyl group, and an amino group are preferable. These may be used alone or in combination of two or more. The water-soluble organic compounds present during the reaction for producing a precipitate by adding an alkaline solution are considered to be adsorbed on the surface of Clinobisvanite-type or Dryerite-type bismuth vanadate precipitated by the reaction to control particle growth. As a result, crystallinity such as crystal shape and average particle diameter can be controlled.
[0029]
The water-soluble organic compound is preferably allowed to coexist in the acid solution containing Bi compound and V compound in the range of about 0.001% by weight to about 10% by weight, and the amount is determined by the desired particle size and particle size distribution, etc. Is done.
[0030]
In the present invention, after adding Dryerite type bismuth vanadate by adding an alkaline solution, the suspension is further stirred and aged to improve the crystallinity, shape, and surface properties of Dryerite type bismuth vanadate. It is effective. Such stirring is preferably performed for 0.1 to 6 hours, preferably 0.5 to 3 hours, at the reaction temperature or lower.
[0031]
Further, if desired, by continuing the stirring for a longer time, the Dreyerite-type bismuth vanadate is changed into the Clinobisvanite-type bismuth vanadate in the suspension, so that the Clinobisvanite-type bismuth vanadate can be produced. Such stirring is preferably performed at room temperature or lower for 6 to 72 hours, preferably 10 to 60 hours.
[0032]
The suspension is then separated into solid and liquid, washed and dried. By such an operation, impurities remaining in the solution can be removed, so that a highly active photocatalyst composite powder can be produced, which is desirable.
[0033]
When a sol-like oxide semiconductor is coated on Dreyerite-type bismuth vanadate, the heat treatment is performed at a temperature of 260 ° C. or higher, so that Dreyerite-type bismuth vanadate changes to Clinobisvanite-type bismuth vanadate. A photocatalyst composite powder can be produced.
Moreover, the photocatalyst composite powder which is the object of the present invention can also be produced by coating a sol-like oxide semiconductor on Clinobisvanite type bismuth vanadate. In such a case, heat treatment may be performed at a predetermined temperature as desired.
The crystal form of the oxide semiconductor is controlled in accordance with the heat treatment temperature by applying a heat treatment at a predetermined temperature after coating the sol-like oxide semiconductor on Dreyerite type bismuth vanadate or Clinobisvanite type bismuth vanadate. Can do. As described above, when the Dryerite type bismuth vanadate coated with a sol-shaped oxide semiconductor is used, the Dryerite type bismuth vanadate is converted into a Clinobisvanite type bismuth vanadate in parallel with the change in the crystal form of the oxide semiconductor. To change.
Specifically, when sol-like titanium oxide is coated as an oxide semiconductor, the crystal form of titanium oxide is selected from sol-like titanium oxide, anatase-type titanium oxide, rutile-type titanium oxide, etc. according to the heat treatment temperature. It can be made by selecting. The crystal form of these oxide semiconductors may be selected according to the saturation and photocatalytic activity of the target photocatalyst composite powder. For example, in order to obtain a photocatalyst composite powder having particularly high photocatalytic activity, the photocatalytic activity A high crystal form (for example, anatase type titanium oxide) may be selected.
[0034]
The heat treatment at this time is preferably performed in air or in an oxidizing atmosphere. In addition, the temperature at the time of heat treatment may be appropriately selected depending on the crystal form of the oxide semiconductor to be selected.
When Dryerite type bismuth vanadate is coated with an oxide semiconductor, the temperature is preferably 260 ° C. or higher. At a temperature lower than 260 ° C., the change of Cryobisvandite type bismuth vanadate from Dreyerite type bismuth vanadate does not effectively occur. Moreover, although the upper limit of the heat treatment temperature is not limited, if it is usually 800 ° C. or lower, grain growth due to sintering of the photocatalyst composite powder is suppressed, and a photocatalyst composite powder having high photocatalytic activity can be obtained.
[0035]
【Example】
Examples and Comparative Examples are shown below to clarify the features of the present invention, but the present invention is not limited to these Examples.
[0036]
(Example 1)
(Clinobisvanite type bismuth vanadate coated with sol-like titanium oxide)
Bi (NO 3 ) 3 ・ 5H 2 46.5 g of O and Na 3 VO 4 23.2 g was dissolved in 3.2 liters of 1N nitric acid, and 55.5 g of ethylene glycol was added. While stirring, 2.0 l of 1N sodium carbonate was added dropwise to precipitate. At this time, the pH of the suspension was less than 1. After precipitation, the mixture was aged by continuing stirring for 12 hours. Filtration and washing were followed by drying at 110 ° C. to obtain a powder.
When the X-ray diffraction (XRD) pattern of the obtained powder was measured, it was in good agreement with the XRD pattern of Clinobisvantite-type bismuth vanadate. Thus, it was confirmed that Clinobisvantite-type bismuth vanadate was produced.
10 g of the thus obtained Clinobisvanite-type bismuth vanadate powder is added to a solution of 10 g of titanium butoxide: 200 g of ethanol: 5 g of 30% hydrogen peroxide solution, and heated at 60 ° C. for 3 hours with stirring. After filtration, washing and drying at 110 ° C., a powder having a bright yellow color was obtained.
When the X-ray diffraction (XRD) pattern of the obtained powder was measured, it was coated with sol-like titanium oxide because it contained an XRD pattern derived from Clinobisvantite-type bismuth vanadate and an amorphous XRD pattern. It was confirmed that Clinobisvante type bismuth vanadate powder was produced.
[0037]
(Photocatalytic activity test)
Evaluation of the photocatalytic activity under the visible light region was performed by a decomposition test of a methylene blue solution. 0.5 g of the powder obtained in Example 1 was sealed in a glass container together with 0.1 l of a 1 mg / l methylene blue solution. In this glass container, an acrylic plate (thickness of 380 nm or less) is used between the fluorescent lamp and the glass container using a fluorescent lamp (18 W Trulite, manufactured by Light Sources Inc., USA) having a spectral distribution close to that of sunlight. : 5.0 mm) was selectively irradiated with visible light for 24 hours, and the degree of fading of the methylene blue solution was observed.
The evaluation was ○: colorless and transparent. Δ: Fading occurred but not colorless, x: Fading did not occur, and are shown in Table 1.
As shown in Table 1, the methylene blue solution faded and the solution became colorless, and it was confirmed that the solution had excellent photocatalytic activity in the visible light region.
[0038]
[Table 1]
(Acid resistance test)
The acid resistance test was conducted as follows. 10 wt% of the powder obtained in Example 1, 80 wt% of acrylic resin (solid content 50%) and 10 wt% of thinner were mixed, applied to a glass plate with a thickness of 0.25 mm, and cured for 7 days to obtain a test specimen. It was. Furthermore, this test body was immersed in 10% sulfuric acid for 24 hours. In the acid resistance test, the color difference (CM-3700d, manufactured by Minolta Co., Ltd.) was used to measure the color difference before and after being immersed in sulfuric acid.
The acid resistance test results are shown in Table 2. As shown in Table 2, the change in hue before and after immersion in sulfuric acid was small, and the acid resistance was excellent.
[0040]
[Table 2]
(Example 2)
(Clinobisvanite type bismuth vanadate coated with anatase type titanium oxide)
The Clinobisvanite-type bismuth vanadate powder coated with the sol-like titanium oxide obtained in Example 1 was further heat-treated at 400 ° C. for 1 hour in air to obtain a powder having a bright yellow color. .
When the X-ray diffraction (XRD) pattern of the obtained powder was measured, it was coated with anatase-type titanium oxide because it contains the XRD pattern derived from Clinobisvantite-type bismuth vanadate and the XRD pattern of anatase-type titanium oxide as components. It was confirmed that the produced Clinobisvanite-type bismuth vanadate powder was produced.
The same photocatalytic activity test and acid resistance test were conducted as in Example 1.
The results of the photocatalytic activity test are shown in Table 1. It was confirmed that the methylene blue solution faded and had photocatalytic activity in the visible light region.
The acid resistance test results are shown in Table 2. Similar to Example 1, the change in hue before and after the acid resistance test was small, and the acid resistance was excellent.
[0042]
(Example 3)
(Clinobisvanite type bismuth vanadate coated with tungsten oxide)
After adding 10 g of Clinobisvante type bismuth vanadate powder obtained in Example 1 to a solution composed of 10 g of ammonium tungstate: 200 g of distilled water, the suspension was heated to 100 ° C. with stirring to remove the solvent, and then 400 Heat treatment was performed at 0 ° C. for 2 hours to obtain a powder having a bright yellow color.
When the X-ray diffraction (XRD) pattern of the obtained powder was measured, the XRD pattern derived from Clinobisvantite-type bismuth vanadate and the XRD pattern of tungsten oxide were used as components, so that the Clinobisvantite-type coated with tungsten oxide was used. It was confirmed that bismuth vanadate powder was produced.
The same photocatalytic activity test and acid resistance test were conducted as in Example 1.
The results of the photocatalytic activity test are shown in Table 1. It was confirmed that the methylene blue solution faded and had photocatalytic activity in the visible light region.
The acid resistance test results are shown in Table 2. As in Example 1, the change in hue before and after the acid resistance test was suppressed, and the acid resistance was excellent.
[0043]
Example 4
(Clinobisvanite-type bismuth vanadate coated with zirconium oxide)
10 g of Clinobisvanite-type bismuth vanadate powder obtained in Example 1 was added to a solution consisting of 10 g of zirconium propoxide: 200 g of ethanol: 5 g of 30% hydrogen peroxide, and the mixture was stirred at 60 ° C. for 3 hours. The powder obtained by heating, filtering and washing was dried at 110 ° C. and then heat-treated at 400 ° C. for 2 hours to obtain a powder having a bright yellow color.
When the X-ray diffraction (XRD) pattern of the obtained powder was measured, the XRD pattern derived from Clinobisvantite-type bismuth vanadate and the XRD pattern of zirconium oxide were used as components, so that the Clinobisvantite-type coated with zirconium oxide was used. It was confirmed that bismuth vanadate powder was produced.
The same photocatalytic activity test and acid resistance test were conducted as in Example 1.
The results of the photocatalytic activity test are shown in Table 1. It was confirmed that the methylene blue solution faded and had photocatalytic activity in the visible light region.
The acid resistance test results are shown in Table 2. As in Example 1, the change in hue before and after the acid resistance test was suppressed, and the acid resistance was excellent.
[0044]
(Comparative Example 1)
(Clinobisvante type bismuth vanadate powder)
Using the Clinobisvantite bismuth vanadate powder obtained in Example 1, the same photocatalytic activity test and acid resistance test as in Example 1 were conducted.
The results of the photocatalytic activity test are shown in Table 1. It was confirmed that the methylene blue solution faded and had photocatalytic activity in the visible light region.
The results of the acid resistance test are shown in Table 2. The result was inferior in acid resistance with a large hue change.
[0045]
(Comparative Example 2)
(Clinobisvanite type bismuth vanadate coated with anatase type titanium oxide)
A powder having a pale yellow color was obtained in the same manner as in Example 1 except that 500 g of titanium butoxide was added to 10 g of Clinobisvante type bismuth vanadate powder obtained in Example 1.
When the X-ray diffraction (XRD) pattern of the obtained powder was measured, it was coated with amorphous titanium oxide because it contained the XRD pattern derived from Clinobisvanite-type bismuth vanadate and the XRD pattern of an amorphous substance. It was confirmed that Clinobisvante type bismuth vanadate powder was produced.
The same photocatalytic activity test and acid resistance test were conducted as in Example 1.
The results of the photocatalytic activity test are shown in Table 1. It was confirmed that the methylene blue solution did not fade and had no photocatalytic activity in the visible light region.
[0046]
【The invention's effect】
The present invention is a photocatalyst composite powder in which an oxide semiconductor is coated at a specific weight ratio on the surface of a particle mainly composed of Clinobisvante bismuth vanadate. The photocatalyst composite powder of the present invention exhibits high photocatalytic activity even in the visible light region, is non-polluting, has a highly saturated yellow color, and has excellent chemical resistance and weather resistance.
Claims (1)
その被覆量が（Ａ）成分１００重量部に対し（Ｂ）成分０．１〜２５重量部であり、粒子径が０．１〜１００μｍであることを特徴とする可視光応答性を有する光触媒複合粉体。(A) At least one selected from (B) titanium oxide, tungsten oxide, or zirconium oxide on the particle surface having a Clinobisvante-type bismuth vanadate of 50 wt% or more and a particle diameter of 0.01 to 100 μm An oxide semiconductor having photocatalytic activity is coated,
The photocatalytic composite having visible light responsiveness, characterized in that the coating amount is 0.1 to 25 parts by weight of component (B) with respect to 100 parts by weight of component (A) and the particle diameter is 0.1 to 100 μm. powder.
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| CN100398201C (en) * | 2006-02-23 | 2008-07-02 | 上海交通大学 | Bismuth vanadate supported cobalt oxide composite photocatalyst and preparation method thereof |
| CN100460067C (en) * | 2006-02-23 | 2009-02-11 | 上海交通大学 | Bismuth vanadate composite photocatalyst loaded with nickel oxide, its preparation method and application |
| RU2556207C2 (en) * | 2010-04-16 | 2015-07-10 | Трайбахер Индустри Аг | Catalyst composition for selective catalytic reduction of exhaust gas |
| JP5892478B2 (en) * | 2013-06-20 | 2016-03-23 | Toto株式会社 | BiVO4 particles and method for producing the same |
| JP6048752B2 (en) * | 2013-06-28 | 2016-12-21 | 国立研究開発法人産業技術総合研究所 | Visible light responsive composition and photoelectrode, photocatalyst, and photosensor using the same |
| CN106745474B (en) * | 2017-01-20 | 2020-06-30 | 上海交通大学 | Preparation method of visible light response tungsten trioxide-bismuth vanadate heterojunction thin film electrode |
| JP7292703B2 (en) * | 2019-01-09 | 2023-06-19 | 学校法人 龍谷大学 | Method for producing visible-light-responsive bismuth vanadate |
| JP7461635B2 (en) * | 2020-03-23 | 2024-04-04 | 学校法人 龍谷大学 | Structure and manufacturing method thereof |
| JP2024010721A (en) * | 2022-07-13 | 2024-01-25 | 国立研究開発法人産業技術総合研究所 | Photocatalyst and its production method, and oxygen production method and hydrogen production method using photocatalyst |
| CN116328843B (en) * | 2022-12-29 | 2024-08-23 | 广西民族大学 | A heterogeneous photocatalyst and its preparation method and application |
| CN120717510B (en) * | 2025-08-27 | 2025-11-28 | 成都先进金属材料产业技术研究院股份有限公司 | High-purity vanadium oxide electrode and preparation method thereof |
| CN120790061B (en) * | 2025-09-15 | 2025-12-05 | 湖北民腾新材料科技有限公司 | Device for continuously producing isooctyl thioglycolate and preparation method |
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