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TW200940165A - Visible light-responsive photocatalyst and method for producing the same - Google Patents

Visible light-responsive photocatalyst and method for producing the same Download PDF

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Publication number
TW200940165A
TW200940165A TW097112442A TW97112442A TW200940165A TW 200940165 A TW200940165 A TW 200940165A TW 097112442 A TW097112442 A TW 097112442A TW 97112442 A TW97112442 A TW 97112442A TW 200940165 A TW200940165 A TW 200940165A
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Taiwan
Prior art keywords
titanium oxide
visible light
photocatalyst
compound
oxide
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TW097112442A
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Chinese (zh)
Inventor
Yasuhiro Masaki
Katsuhiro Nishihara
Takashi Doi
Rie Katsui
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Sumitomo Metal Ind
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Priority claimed from JP2008074011A external-priority patent/JP5157561B2/en
Application filed by Sumitomo Metal Ind filed Critical Sumitomo Metal Ind
Publication of TW200940165A publication Critical patent/TW200940165A/en

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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • B01D53/885—Devices in general for catalytic purification of waste gases
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/18—Arsenic, antimony or bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • B01J37/033—Using Hydrolysis
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/80—Type of catalytic reaction
    • B01D2255/802—Photocatalytic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • B01J35/45—Nanoparticles

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
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  • Dispersion Chemistry (AREA)
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Abstract

It is intended to provide a titanium oxide photocatalyst and a photocatalytic functional member which can exhibit a high photocatalytic activity under visible light irradiation and can be mass-produced. A visible light-responsive photocatalyst having bismuth enriched on the surface thereof is obtained by mixing a bismuth compound with titanium oxide and baking the resulting mixture to allow titanium oxide to carry bismuth. Further, when bismuth in a bismuth oxide is contained as low-dimensional bismuth, a visible light-responsive photocatalyst with a higher activity is obtained. When the titanium oxide contains at least one element selected from Si, Zr, Al, W, Mo, Mg, Hf and B, an effect of the Bi compound on increasing the visible light-responsive photocatalytic activity is further enhanced. The atomic ratio of Bi/Ti is preferably set to 0.0001 or more and 10 or less. The effect of carrying of the low-dimensional bismuth oxide on increasing photocatalyst can be applied also to a commercially available titanium oxide photocatalyst.

Description

200940165 九、發明說明 【發明所屬之技術領域】 本發明係關於不僅照射紫外線，即使照射可見光亦可 發揮光觸媒作用之可見光應答型光觸媒與其製造方法。 【先前技術】 氧化鈦所示之光觸媒作用被應用於防臭、抗菌、防污 〇 等各式各樣的環境淨化技術。一般使用作爲光觸媒之銳鈦 礦型氧化鈦的帶間隙爲約3.2eV，接受波長約3 80nm之更 短波長紫外線而進行反應，故於運作上必須以紫外線。因 此，利用此光觸媒上，具有設置環境、用途等受到限定的 問題點。 若太陽光線和室內光中存在許多的可見光可利用作爲 光觸媒的能量源，則可在各式各樣場所利用光觸媒。蒙此 想法，近年來極力發展經由可見光之照射表現出光觸媒活 〇 性的可見光應答型光觸媒的開發。 具有可見光觸媒活性的光觸媒具有下述物質。 (1 )氧化鈦中含有氮的氮型（例如，Chem. Phys. Lett 123 ( 1986) 126-128 ;日本化學會誌、1986 ( 8) 、pi〇84 、及 WO 0 1 /0 1 0552 ); (2 )於氧化鈦中導入氧缺陷的氧缺陷型（例如，特開 2001-205103 號公報）； (3)令氧化鈦中含有其他金屬（離子）、或組合金屬氧 化物的金屬摻混型。 -5- 200940165 (3)之金屬摻混型之例可提案如下所述般之各式各 樣者。 於特開平9-262482號公報中，揭示將銳或鉻予以離 子注入的氧化鈦。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a visible light responsive photocatalyst which is capable of exhibiting a photocatalytic action even when irradiated with visible light, and a method for producing the same. [Prior Art] The photocatalytic action shown by titanium oxide is applied to various environmental purification technologies such as deodorization, antibacterial, and antifouling. Generally, an anatase type titanium oxide as a photocatalyst is used in a band gap of about 3.2 eV, and a short-wavelength ultraviolet light having a wavelength of about 3 80 nm is used for the reaction. Therefore, it is necessary to use ultraviolet rays in operation. Therefore, there is a problem in that the photocatalyst is limited in terms of setting environment and use. If there are many visible light in the sun and indoor light, and the energy source as a photocatalyst can be used, the photocatalyst can be used in various places. In view of this, in recent years, the development of visible light-responsive photocatalysts that exhibit photocatalytic activity through visible light has been vigorously developed. Photocatalysts having visible light catalyst activity have the following materials. (1) A nitrogen type containing nitrogen in titanium oxide (for example, Chem. Phys. Lett 123 (1986) 126-128; Nippon Chemist, 1986 (8), pi〇84, and WO 0 1 /0 1 0552) (2) An oxygen-deficient type in which oxygen deficiency is introduced into titanium oxide (for example, JP-A-2001-205103); (3) a metal in which titanium oxide contains other metals (ions) or metal oxides in combination type. -5- 200940165 (3) Examples of metal blending types can be proposed as follows. In Japanese Laid-Open Patent Publication No. Hei 9-262482, titanium oxide in which sharp or chromium is ion-implanted is disclosed.

於 Chem. Commun. 2001，2718-2719 中，報導含有 V 、Cr、Nb、Mo等過渡金屬之具有可見光活性的氧化鈦。 於特開2004-43282號公報中，揭示令各式各樣的金 屬化合物與鈦化合物以溶解狀態混合，並以氫氧化物型式 共沈後，將沈澱物煅燒之具有可見光活性之氧化鈦的製造 方法。 特開2004-275999號公報所記載之具有可見光活性的 光觸媒爲由含有 Si、Ti、V、Sn、Sb、W、Nb、Bi、P、 Mo、Cs、Ge、As、Ce等中選出之金屬化合物的氧化鈦所 構成。此光觸媒爲以包含令氧化鈦或其前驅物以含有金屬 鹵化物之氣體接觸的方法所製造。 另一方面，於 J. Mat. Sci. Lett. 21，2002，1 65 5 -1 656中，報導關於以含有鉍令氧化鈦系光觸媒之紫外線活 性的增進效果與吸收光譜的長波長化。更且，最近於Mat. Lett·，60，2 006，1296- 1305中，報導關於以氧化鈦、氧 化鉍之各種前驅物型式分別將鈦醇鹽和氯化鉍於液體中混 合所製作之鉍予以添加之氧化鈦之紫外線的分解活性、超 親水性。 〔專利文獻1〕特開2001-205103號公報 〔專利文獻2〕特開平9-262482號公報 200940165 〔專利文獻3〕特開2004-43282號公報 〔專利文獻4〕特開2004-275999號公報 〔專利文獻 5〕WO 01/010552 〔非專利文獻 1〕Chem. Phys. Lett 123 ( 1986) 126- 128 〔非專利文獻2〕日本化學會誌，1986(8) ，ρ·1084 〔非專利文獻 3〕Chem· Commun. 2001，2718-2719 ❹ 〔非專利文獻 4〕J. Mat. Sci. Lett. 21，2002，1 65 5 · 1656 〔非專利文獻 5〕Mat. Lett·, 60，2006，1296-1305 【發明內容】 (發明所欲解決之課題） 具有上述可見光應答性之氧化鈦系光觸媒不論爲氮型 、氧缺陷型、金屬摻混型之任一者，於可見光照射下的活 〇 性不能稱爲高。又，於其中，製造上多需要離子注入裝置 和濺鍍裝置，亦具有無法朝向量產的其他問題。 本發明爲提供可表現優良之可見光觸媒活性的光觸媒 、和簡便且適於量產之其製造方法。 (解決課題之手段） 若根據本發明，經由表面擔載特定鉍化合物之氧化鈦 所構成的可見光應答型光觸媒則可解決上述課題。 本發明之可見光應答型光觸媒爲根據下述（])〜（3 -7- 200940165 )之發現而完成。 (1 )較佳爲於含有銳鈦礦型結晶之氧化鈦表面擔載鉍氧 化物，且鉍的含有形態爲於氧化鈦的表面濃化，較佳爲進 一步令氧化物型式含有之鉍爲以混合原子價狀態，即一部 分之鉍爲二價（Bi2+ )以下的低次原子價狀態，全體爲以 BiOx ( x<1.5 )所示之低次氧化物狀態擔載之高活性的可 見光應答型光觸媒。 0 (2)加上，光觸媒爲含有矽、锆、鋁等之其他元素，較 佳爲令母體之氧化鈦中含有之極高活性的可見光應答型光 觸媒。 (3)上述（1)之可見光應答型光觸媒爲於氧化鈦或其固 體狀前驅物中，混合BiOX ( X=鹵素離子、硝酸離子、有 機酸離子、氫氧化物離子等之陰離子）或鹵化鉍等之鉍化 合物後，將混合物煅燒則可簡便製造。製造上述（2 )之 光觸媒上，令氧化鈦中預先含有矽、鋁、錐等元素之化合 〇 物，或在氧化鈦與鉍混合物混合時共存其他元素之化合物 亦可。 如前述般，自以往亦有經由在氧化鈦中追加、含有含 鉍金屬元素令可見光活性表現的報告例。但是，就本發明 者等人所知’如本發明般對於具有光觸媒活性之氧化鈦、 較佳爲銳鈦礦型氧化鈦，擔載鉍氧化鈦，結果令氧化鈦表 面之鉍濃化，更且鉍氧化物中之鉍爲以含有低次鉍之狀態 擔載’變成具有優良之可見光應答活性的光觸媒的發現則 爲未知。 -8 - 200940165 1側面觀中，本發明爲於表面擔載鉍氧化物之氧化鈦 所構成的可見光應答型光觸媒，含有表面之鉍濃化、更佳 爲鉍氧化物中之鉍爲混合原子價狀態，即低次之鉍，且全 體以BiOx(x<l_5)表示爲其特徵之氧化鈦系可見光應答 型光觸媒。 此處，「氧化鈦」可爲二氧化鈦、氧缺陷型氧化鈦、 及含有Ti及Ο以外之其他元素（例如，氮、碳、硫、其 0 他金屬元素）之氧化鈦的任一者均可。其他元素之存在形 態可爲下述任一種： (1 )如鈦酸金屬鹽般與氧化鈦以一定比率化合形成複合 氧化物（其他元素爲金屬之情形）、 (2 )以氧化鈦結晶晶格之佔有〇或Ti位置之摻混元素型 式於氧化鈦中含有、 (3 )與氧化鈦以不定比率微視性均勻混合。 所謂「擔載」鉍氧化物，係意指鉍氧化物爲於氧化鈦 φ 表面具有任何鍵結附著。又，鉍於表面上濃化，係意指鉍 濃度於氧化鈦的表面，比內部更加變高。此鉍氧化物之擔 載和表面之鉍濃化，例如，經由將氧化鈦以XPS予以表面 分析則可加以確認。即，若根據XPS所求出之氧化鈦表面 的Bi濃度，比此氧化鈦之化學分析所求出之氧化鈦全體 的Bi濃度更高，則意指鉍於表面被濃化，且被擔載於表 面。本發明中，表面之Bi濃度爲比Bi之化學分析値（其 爲表示氧化鈦全體中之平均Bi濃度）至少更高2.0倍之 情形稱爲「濃化」。 -9- 200940165 本發明中，鉍於氧化鈦表面以氧化物型式擔載，較佳 爲再令此鉍爲混合原子價狀態’即’全體以Bi〇x ( Χ<1·5 )所示之含有低次（二價以下）鉍氧化物的狀態。鉍以此 低次氧化物狀態於氧化鈦表面擔載’例如’亦可經由XPS 將氧化鈦表面分析加以確認。 所謂「氧化鈦系可見光應答型光觸媒」，係意指利用 氧化鈦所示之光觸媒機能的可見光應答型光觸媒。氧化鈦 Q 並非必定爲光觸媒的主成分。 本發明之可見光應答型光觸媒爲包含下述之態樣： •前述鉍氧化物爲被覆氧化鈦之至少一部分表面； •光觸媒中所含之Bi與Ti的原子比（Bi/Ti )爲0.001以 上，1.0以下； •光觸媒以XAFS解析時之鉍原子周圍的動徑分佈波峰比 R (第二波峰/第一波峰之比）爲〇.4以下； •前述動徑分佈波峰比R爲0.15以下； Φ •光觸媒爲含有矽、錆、鋁、鎢、鉬、鎂、鈴'及硼中選 出至少一種之元素M; •光觸媒中之前述元素Μ的含量（含有二種以上元素之情 形爲合I十量）爲相對於Ti之原子比（M/Ti)爲0.0001以 上，未達1 · 0之份量： •前述元素Μ爲於氧化鈦中含有； •氧化欽爲至少部分性結晶質，其結晶之主要結晶型爲銳 鈦礦型。 ，係意指元素Μ 所謂元素Μ爲「於氧化鈦中含有 -10- 200940165 爲於氧化欽以分子程度混合’例如，被倂入氧化鈦的結晶 構造內外（例如’晶格點之Ti經Μ取代，於結晶粒子界 面存在Μ等）。另一方面，光觸媒爲含有元素Μ，係爲元 素Μ如上述於氧化鈦中含有之情形，加上亦包含元素μ 爲與氧化鈦以物理性混合狀態之情形、和元素Μ爲被覆氧 化鈦之表面、或於表面上擔載之情形。 由另外之態樣’本發明爲包含將氧化鈦或其固體狀前 Q 驅物與鉍化合物，較佳以Bi/Ti之原子比爲0.001〜〗·〇以 下之比例混合的步驟’和將所得之混合物煅燒取得表面擔 載前述鉍氧化物之氧化鈦的煅燒步驟爲其特徵之前述氧化 鈦系可見光應答型光觸媒的製造方法。 此製造方法爲包含下述之態樣： •前述熘燒步驟，於煅燒所得產物之X射線繞射圖型中以 銳鈦礦型氧化鈦爲主之階段停止； •前述煅燒步驟中之煅燒溫度爲50〜800°C ; 〇 •鉍化合物爲BiOX ( X=鹵素離子 '硝酸離子、氫氧化離 子、有機離子）、鹵化鉍、硝酸鉍、硫酸鉍、及硫化鉍中 選出至少一種； •氧化鈦或其固體狀前驅物爲含有矽、銷、鋁、鎢、鉬、 鎂、飴及硼中選出至少一種之元素M; •於混合步驟中，混合氧化鈦或其固體狀前驅物和鉍化合 物，加上矽化石物、锆化合物、鋁化合物、鎢化合物、鉬 化合物 '鎂化合物、飴化合物及硼化合物中選出至少一種 之化合物； -11 - 200940165 •所混合化合物中之至少一者爲分散液狀態的氧化物。 本發明爲再包含下述之多樣形態： •基材表面具有上述可見光應答型光觸媒爲其特徵之光觸 媒機能構件。 •液體介質中含有分散狀態之氧化鈦和分散或溶解狀態之 鉍化合物爲其特徵之可見光應答型光觸媒形成用分散液。 •於液體介質中含有分散之上述可見光應答型光觸媒爲其 D 特徵之光觸媒分散液。 •於液體介質中含有分散狀態之氧化鈦和分別分散或溶解 狀態之鉍化合物及黏合劑爲其特徵之可見光應答型光觸媒 塗敷液。 •於液體介質中含有上述可見光應答型光觸媒和黏合劑， 且光觸媒之含量爲根據不揮發成分之合計量以5〜95質量％ 爲其特徵之可見光應答型光觸媒塗敷液。 •將前述分散液或前述塗敷液塗佈至基材後，施以熱處理 〇 爲其特徵之光觸媒機能構件的製造方法。 •由秘化合物所構成爲其特徵之氧化鈦系光觸媒的可見光 應答活性增進劑。 (發明之效果） 若根據本發明’較佳爲於至少部分含有銳鈦礦結晶之 氧化欽表面’擔載鉍氧化物，令其在氧化鈦的表面濃化， 更佳爲以氧化物型式含有之鉍爲以混合原子價狀態，即一 部分之鉍爲以二價（Bi2+ )以下之低次狀態，全體以Bi〇x -12- 200940165 (χ<1 .5 )所示之氧化物狀態下令氧化鈦擔載鉍，則可確 實提供具有優良之可見光應答性的可見光應答型光觸媒。 原料之氧化鈦爲不具有可見光應答性，例如，爲銳鈦 礦型氧化鈦亦可。此情形亦可根據本發明取得具有高可見 光活性的可見光應答型光觸媒。於原料本來具有可見光應 答性之氧化鈦之情形中，根據本發明可顯著提高其可見光 觸媒活性。 ❹ 【實施方式】 本發明之可見光應答型光觸媒，爲於至少應答紫外線 且具有光觸媒活性的氧化鈦表面，將氧化物狀態之鉍，以 表面濃化般擔載，如此光觸媒可獲得可見光應答性。光觸 媒中之全部鉍氧化物並非必須擔於氧化鈦（即，附著至表 面），一部分的鉍氧化物未擔載地單與氧化鈦以混合狀態 下存在亦可，或者於氧化鈦中含有亦可。但是，鉍必須以 〇 氧化物型式於氧化鈦表面上濃化。較佳爲令鉍以氧化物型 式被覆氧化鈦的至少一部分表面。 本發明之可見光應答型光觸媒表現可見光活性（可見 光應答性）的機構於目前雖未闌明，但認爲係經由氧化鈦 與其表面濃化之鉍的氧化物，較佳爲與含有低次鉍之氧化 物（BiOx : χ<1·5 )的相互作用所產生之新的遷移型式令 可見光被吸收，且生成的載體爲經由氧化鈦（較佳爲銳鈦 礦）與低次鉍氧化物之參與而有效地電荷分離，且令可見 光活性被表現或強化。 -13- 200940165 氧化鈦可利用各式各樣的物質。 具有銳鈦礦構造之結晶質氧化鈦的氧 面而言爲佳。較佳爲於銳鈦礦型之氧 、氫、碳、過渡金屬、硫等賦予可見 。其中，若使用經由氮摻混（含有氮 性的銳鈦礦型氧化鈦，則可取得高可 佳。即使不具有可見光應答性之通常 U 示可見光應答型光觸媒特性之氧化鈦 發明於氧化鈦表面，令鉍濃化般，較 化物型式擔載，則可取得具有高可見 令氧化鈦擔載鉍氧化物的詳細彳 XAFS(X射線吸收微細構造）解析構 鈦亦具有部分作成新化合物的可能性 微細之氧化物微粒子型式於氧化鈦表 鉍氧化物以XPS等之表面分析，取得 〇 的三價（Bi3+)，爲包含低次之二價 )、零價（B。）之混合原子價狀態 化物（BiOx: χ<1·5)，提示於鉍周 性的結果。又，鉍對於全體氧化鈦幾 且氧化鈦爲維持原來的結晶構造（例 由各種元素分析，可知本觸媒中 鉍於氧化鈦中的鉍濃度，以表面爲壓 非進入氧化鈦骨架等內部，而於表 。其與氧化鈦表面之ΟΗ基爲經由 但是，至少部分含有 化鈦，就觸媒活性方 化鈦中，摻混氮、氟 光應答性者亦可利用 )而賦予可見光應答 見光觸媒性能，故爲 的氧化鈦，或者於顯 之情形，亦可根據本 佳以含有低次鉍之氧 光活性的光觸媒。 _造仍爲未明。根據 ;造，認爲鉍爲與氧化 。但是，判定鉍爲以 面擔載的狀態爲佳。 1鉍離子並非僅爲通常 (Bi2+ )、一價（Bi1 ，即全體以低次之氧 圍存在氧缺損之可能 乎完全不造成影響， 如，銳鈦礦）。 以氧化物型式擔載之 倒性高於全體，鉍並 上以氧化物狀態濃化 ί氧化物的存在而減少 -14- 200940165 的FT-IR結果亦一般。表面存在許多（高濃度之）鉍之氧 化物與銳鈦礦氧化鈦之相互作用變強，產生新的可見光吸 收遷移。可見光吸收後，原本電荷分離效率高之銳鈦礦結 晶與鉍之低次氧化物間有效率引起載體的移動，其結果取 得高可見光活性之物質。 令BiOX (X爲硝酸離子、氯離子、羥基離子等之陰 離子）和鹵化鉍、硝酸鉍所示之鉍化合物與氧化鈦或固體 Q 狀前驅物接觸，視需要加以熱處理令氧化鈦擔載之鉍氧化 物，已知效果最大。 本發明之可見光應答型光觸媒中，若令本來之氧化鈦 中含有矽、鋁、鉻等之至少一種的元素Μ，則易取得理想 之構造，故造成更加優良的可見光活性和高性能安定性。 元素Μ的職務有許多，其一者爲在氧化鈦之煅燒時，抑制 結晶轉移，維持原本的結晶構造，較佳爲銳鈦礦構造，並 且可高度維持氧化鈦的比表面積。另一方面，於氧化鈦中 〇 含有，令表面狀態變化，提高表面濕潤性，更且增加固體 酸點。如此於製造時令鉍化合物易與氧化鈦（表面）反應 ，促進由鉍化合物變化成微細的鉍氧化物，更且往氧化鈦 表面部分結合之低配位構造等之低次氧化狀態的鉍氧化物 變化。 更且，重要之發現爲氧化鈦擔載鉍化合物後之可見光 吸收，於不含有元素Μ，或適切範圍外之情形，則頗多變 強至長波長爲止。相對地，若令氧化鈦預先含有適切範圍 份量之元素Μ，則鉍化合物擔載後之可見光吸收爲位於較 -15- 200940165 短波長側，且強度亦非如此強。由此情事認爲，氧化鈦中 元素Μ的主要職務亦爲有效抑制氧化鈦與鉍化合物之間的 固體反應（例如於氧化鈦晶格中倂入鉍等）。 關於以鉍化合物增強可見光應答型光觸媒活性，本發 明者等人再取得下述之發現。 含有鉍之氧化鈦所構成之可見光應答型光觸媒的活性 ’關係於氧化鈦中所含之鉍構造，以xafs(x射線吸收 Q 微細構造）觸析所闡明之氧化鈦中所含的鉍原子的排列方 式’即，根據原子相關性而令活性變化。具體而言，光觸 媒以XAFS解析時之鉍原子周圍的動徑分佈波峰比R (第 2波峰/第1波峰）爲0.4以下，則可見光活性變高。動徑 分佈波峰比R較佳爲0.15以下。鉍氧化物若於氧化鈦表 面存在2層以上’則所存在的第2波峰小，意指鉍氧化物 (BiOx: x<1.5)爲於氧化鈦表面以接近單層狀態擔載。 於適當態樣中，本發明之可見光應答型光觸媒爲以含 〇 有銳鈦礦型結晶之氧化鈦（或其固體狀前驅物）作爲原料 ，並於其中擔載鉍氧化物。氧化鈦中之鉍爲於氧化鈦的表 面濃化，更佳爲以氧化物型式含有之鉍爲以混合原子價狀 態，即含有二價（Bi2+)以下之低次鉍，且全體以BiOx ( x< 1.5 )表示之低次氧化物狀態下擔載爲重要的。 擔載狀態可爲低次鉍氧化物於銳鈦礦型氧化鈦表面以 微粒子狀附著，或者於表面配位之狀態，或者被覆氧化鈦 表面或以單層狀之被覆等。較佳之擔載爲令含有低次祕的 鉍氧化物，被覆氧化鈦之至少一部分的狀態。於擔載之鉍 -16- 200940165 氧化物與氧化鈦的界面附近亦可發生部分固溶 化合物等。於氧化鈦表面擔載鉍氧化物、及經 覆之情事，可根據SEM (掃描型電子顯微鏡） 富利葉轉換紅外線分光光度法）、各種吸脫黏 如，氨TPD〈升溫脫離氣體分析〉法、BAT法 氨滴定法〉）等加以確認。 以鉍氧化物型式於氧化鈦表面擔載的鉍， 0 鈦內部於其表面上存在許多，即，必須令表面 濃化，經由令鉍化合物與氧化鈦於其表面擴散 與表面選擇性反應（避免與全體反應）則可最 成。 關於此鉍的表面濃化，經由將XPS所求出 深度數nm以下）的鉍含量，與表面觸媒粒子 度之氧化鈦的化學分析所求出的鉍含量予以比 。所謂化學分析係爲令觸媒暫時溶解，測定此 〇 之離子量的方法，分析中使用ICP-MASS和發 代替化學分析，以濺鍍或蝕刻削除氧化鈦之 Si〇2換算爲l〇nm以上，較佳爲20nm以上） 出之鉍含量作爲比較對象亦可。或者，如後述 ，令Bi的裝入量近似氧化鈦中之Ni量亦可。 本發明之光觸媒中，以XPS所測定之氧化 濃度，比濺鍍等除去表層後所測定之深部鉍濃 析所測定之鉍濃度更高。具體而言以XPS所定 表層濃度（at% )爲化學分析値的2倍以上。 和生成新的 鉍氧化物被 、FT-IR ( 熱分析（例 〈苯甲醛一 必須比氧化 濃化。鉍的 般混合，並 爲簡單地達 之極表層（ 全體之鉍濃 較則可確認 溶液中所含 光分析等。 表層後（以 以XPS所求 般，視情況 鈦表層的鉍 度或化學分 量分析之鉍 與濺鍍等削 200940165 除表層時之濃度相比較之情形，使用至少除去2 Onm以上 厚度之表層後所測定的濃度，且表層的鉍濃度若爲濺鍍後 濃度之1 .5倍以上，較佳爲2倍以上即可。 鉍氧化物若具有Bi-Ο鍵即可，但鉍以混合原子價狀 態，即含有2價（Bi2+)以下之低次鉍，且全體以Bi〇x ( x< 1 · 5 )所示之含有低次氧化物狀態擔載爲佳。具體而言 可列舉超微粒子狀、具有氧缺損和不飽和鍵者、或於氧化 0 鈦之表面具有配位構造者等。Bi3 +所構成之鉍化合物，例 如氧化鉍（Bi203 )、鈦酸鉍（Bi3Ti4012 )和鉍羥基氧化 物（BiOX、X=鹵素離子、硝酸離子等之酸陰離子、氫氧 化物離子、有機酸離子）等爲部分含有亦可，且氧化鈦表 面存在之鉍氧化物全體以BiOx : x<〗.5表示即可。 最簡單判斷BiOx ( x<1.5 )上，本發明之氧化鈦系光 觸媒以XPS分析所得之Bi-4f內殻準位光譜圖爲具有 (a) 165 〜162.5eV 及 1 5 9 - 7 〜1 5 7 · 2 e V、 Q ( b) 163〜161eV 及 157.7~155.7eV、及 (c) 162.5~160eV 及 1 5 7.2〜154.7eV、 各範圍位置之三組對波峰中之至少二組對波峰爲佳。 若根據 Journal of Electron Spectroscopy and Related Phenomena，25 ( 1982) 181-189，於氧化鈦系光觸媒之In Chem. Commun. 2001, 2718-2719, visible light-active titanium oxide containing a transition metal such as V, Cr, Nb or Mo is reported. Japanese Laid-Open Patent Publication No. 2004-43282 discloses the production of visible light-active titanium oxide in which various metal compounds and titanium compounds are mixed in a dissolved state and coprecipitated in a hydroxide form to freeze the precipitate. method. The photocatalyst having visible light activity described in JP-A-2004-275999 is a metal selected from the group consisting of Si, Ti, V, Sn, Sb, W, Nb, Bi, P, Mo, Cs, Ge, As, Ce, and the like. The compound is composed of titanium oxide. The photocatalyst is produced by a method comprising contacting a titanium oxide or a precursor thereof with a gas containing a metal halide. On the other hand, in J. Mat. Sci. Lett. 21, 2002, 1 65 5 -1 656, the effect of promoting the ultraviolet light activity of the photocatalyst containing a cerium oxide-based photocatalyst and the long wavelength of the absorption spectrum are reported. Furthermore, recently, in Mat. Lett., 60, 2 006, 1296-1305, it is reported that titanium alkoxide and barium chloride are mixed in a liquid in various precursor forms of titanium oxide and cerium oxide. The decomposition activity and superhydrophilicity of ultraviolet rays of titanium oxide to be added. [Patent Document 1] Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. 2004-275. Patent Document 5] WO 01/010552 [Non-Patent Document 1] Chem. Phys. Lett 123 (1986) 126-128 [Non-Patent Document 2] Japanese Society of Chemistry, 1986 (8), ρ·1084 [Non-Patent Document 3 Chem. Commun. 2001, 2718-2719 〔 [Non-Patent Document 4] J. Mat. Sci. Lett. 21, 2002, 1 65 5 · 1656 [Non-Patent Document 5] Mat. Lett·, 60, 2006, 1296 [Review of the Invention] (Problems to be Solved by the Invention) The titanium oxide-based photocatalyst having the above visible light responsiveness is active under visible light irradiation regardless of any of a nitrogen type, an oxygen deficiency type, and a metal mixed type. Can't be called high. Further, among them, an ion implantation apparatus and a sputtering apparatus are often required for manufacturing, and there are other problems that cannot be mass-produced. The present invention provides a photocatalyst capable of exhibiting excellent visible light catalyst activity, and a method for producing the same which is simple and suitable for mass production. (Means for Solving the Problem) According to the present invention, the above-mentioned problem can be solved by a visible light responsive photocatalyst comprising a titanium oxide having a specific ruthenium compound supported on its surface. The visible light responsive photocatalyst of the present invention is completed according to the findings of ()) to (3-7-200940165) below. (1) Preferably, the cerium oxide is supported on the surface of the titanium oxide containing the anatase crystal, and the cerium is contained in the form of a concentrated surface of the titanium oxide, and it is preferred that the oxide type is further contained in the oxide type. The mixed valence state, that is, a part of the enthalpy is a low-order valence state of divalent (Bi2+) or less, and all of them are high-activity visible light-responsive photocatalysts supported by a lower-oxide state represented by BiOx (x<1.5). . 0 (2) In addition, the photocatalyst is an element containing cerium, zirconium, aluminum or the like, and is preferably a highly active visible light responsive photocatalyst contained in the titanium oxide of the matrix. (3) The visible light responsive photocatalyst according to (1) above, in which titanium oxide or a solid precursor thereof is mixed with BiOX (X = anion such as a halogen ion, a nitrate ion, an organic acid ion or a hydroxide ion) or a ruthenium halide After the ruthenium compound is obtained, the mixture can be easily produced by calcining the mixture. In the photocatalyst of the above (2), a compound which contains an element such as cerium, aluminum or a cone in advance in the titanium oxide or a compound in which another element is present when the titanium oxide and the cerium mixture are mixed may be used. As described above, there have been reports of the appearance of visible light activity by adding a cerium-containing metal element to titanium oxide. However, as known to the inventors of the present invention, as described in the present invention, titanium oxide having photocatalytic activity, preferably anatase-type titanium oxide, is supported by titanium oxide, and as a result, the surface of the titanium oxide is concentrated. Further, it is unknown that the ruthenium in the ruthenium oxide is a photocatalyst which is loaded with a low-order enthalpy and becomes excellent in visible light responsiveness. -8 - 200940165 1 In the side view, the present invention is a visible light responsive photocatalyst comprising titanium oxide supported on a surface of cerium oxide, which contains a cerium thickening on the surface, and more preferably a cerium oxide in the cerium oxide is a mixed valence. The state, that is, the low-order enthalpy, and the entire titanium oxide-based visible light-responsive photocatalyst characterized by BiOx (x < l_5). Here, "titanium oxide" may be any of titanium dioxide, oxygen-deficient titanium oxide, and titanium oxide containing other elements other than Ti and antimony (for example, nitrogen, carbon, sulfur, or other metal elements thereof). . The other elements may be in the form of any one of the following: (1) as a metal titanate, combined with titanium oxide to form a composite oxide at a certain ratio (in the case where other elements are metals), (2) a crystal lattice of titanium oxide The blended element pattern of the ruthenium or Ti site is contained in the titanium oxide, and (3) is uniformly mixed with the titanium oxide at an indefinite ratio. By "supporting" cerium oxide, it is meant that the cerium oxide has any bond adhesion to the surface of the titanium oxide φ. Further, the concentration of lanthanum on the surface means that the concentration of lanthanum is higher on the surface of the titanium oxide than in the interior. The support of the ruthenium oxide and the concentration of ruthenium on the surface can be confirmed, for example, by surface analysis of titanium oxide by XPS. In other words, when the concentration of Bi on the surface of the titanium oxide determined by XPS is higher than the concentration of Bi in the entire titanium oxide obtained by chemical analysis of the titanium oxide, it means that the surface is concentrated and supported. On the surface. In the present invention, the Bi concentration on the surface is at least 2.0 times higher than the chemical analysis Bi of Bi (which is an average Bi concentration in the entire titanium oxide), and is referred to as "concentration". -9- 200940165 In the present invention, the ruthenium is supported on the surface of the titanium oxide in an oxide type, and it is preferred that the ruthenium is in a mixed valence state, that is, the whole is represented by Bi〇x (Χ<1·5). Contains a low-order (divalent or lower) cerium oxide state.铋 The surface of the titanium oxide is supported on the surface of the titanium oxide in the low-order oxide state. For example, the surface of the titanium oxide can be confirmed by XPS. The "titanium oxide-based visible light-responsive photocatalyst" means a visible light-responsive photocatalyst that utilizes a photocatalytic function of titanium oxide. Titanium oxide Q is not necessarily the main component of photocatalyst. The visible light responsive photocatalyst of the present invention comprises the following aspects: • the cerium oxide is at least a part of the surface of the coated titanium oxide; • the atomic ratio (Bi/Ti) of Bi and Ti contained in the photocatalyst is 0.001 or more. 1.0 or less; • The photocatalyst has a dynamic wave distribution peak ratio R (the ratio of the second peak/first peak) around the helium atom in the XAFS analysis is 〇.4 or less; • The above-described dynamic path distribution peak ratio R is 0.15 or less; • The photocatalyst is an element M containing at least one selected from the group consisting of ruthenium, osmium, aluminum, tungsten, molybdenum, magnesium, lanthanum and boron; • the content of the aforementioned element Μ in the photocatalyst (in the case of two or more elements, ) is an atomic ratio (M/Ti) with respect to Ti of 0.0001 or more and less than 1 · 0 parts: • The aforementioned element Μ is contained in titanium oxide; • Oxide is at least partially crystalline, and its crystallization is mainly The crystalline form is anatase. , means the element Μ The so-called element Μ is “containing -10-200940165 in titanium oxide, and is mixed with molecular weight in oxidation. For example, it is incorporated into the crystal structure of titanium oxide (for example, 'Ti lattice point of the lattice point Instead, there is a ruthenium or the like at the interface of the crystal particles. On the other hand, the photocatalyst contains an elemental lanthanum, and is an element such as the above-mentioned oxide contained in the titanium oxide, and the element μ is also physically mixed with the titanium oxide. And the case where the element Μ is coated on the surface of the titanium oxide or supported on the surface. In another aspect, the invention includes the titanium oxide or the solid precursor Q-switch thereof and the ruthenium compound, preferably The step of mixing the ratio of the atomic ratio of Bi/Ti to 0.001 to 〇·〇 and the calcination step of calcining the obtained mixture to obtain the titanium oxide having the surface of the above-mentioned cerium oxide is characterized by the above-mentioned titanium oxide-based visible light responsive type. A method for producing a photocatalyst. The manufacturing method comprises the following aspects: • The calcination step, the main step of anatase-type titanium oxide in the X-ray diffraction pattern of the product obtained by calcination The calcination temperature in the calcination step is 50 to 800 ° C; the 〇•铋 compound is BiOX (X=halide ion 'nitrate ion, hydroxide ion, organic ion), antimony halide, antimony nitrate, barium sulfate, and Selecting at least one of strontium sulfide; • titanium oxide or a solid precursor thereof is an element M containing at least one selected from the group consisting of ruthenium, pin, aluminum, tungsten, molybdenum, magnesium, lanthanum and boron; • in the mixing step, mixing the titanium oxide Or a solid precursor and a cerium compound, and a compound selected from the group consisting of a cerium fossil, a zirconium compound, an aluminum compound, a tungsten compound, a molybdenum compound 'magnesium compound, a cerium compound, and a boron compound; -11 - 200940165 At least one of the compounds is an oxide in a dispersion state. The present invention further includes various forms as follows: • A photocatalytic functional member having the above-mentioned visible light responsive photocatalyst as a surface of the substrate. • The liquid medium contains a dispersed state. The titanium oxide and the ruthenium compound in a dispersed or dissolved state are characterized by a visible light-responsive photocatalyst-forming dispersion. The photocatalyst dispersion containing the above-mentioned visible light responsive photocatalyst is a D-characteristic dispersion. The visible light responsive photocatalyst characterized by containing titanium oxide in a dispersed state and a bismuth compound and a binder dispersed or dissolved in a liquid medium. In the liquid medium, the visible light responsive photocatalyst and the binder are contained, and the photocatalyst is a visible light responsive photocatalyst coating liquid characterized by a total amount of nonvolatile components of 5 to 95% by mass. After the dispersion liquid or the coating liquid is applied to a substrate, a method of producing a photocatalytic functional member characterized by heat treatment is applied. • The visible light responsive activity of the titanium oxide photocatalyst characterized by the secret compound is improved. (Effect of the Invention) According to the present invention, it is preferred that the cerium oxide-supporting cerium oxide at least partially contains anatase crystals is concentrated on the surface of the titanium oxide, more preferably as an oxide. The formula contains a mixed valence state, that is, a part of the enthalpy is a low-order state of divalent (Bi2+) or less. In all Bi〇x -12- 200940165 (χ < 1 .5) ordered state shown in the titanium oxide-supported bismuth, may indeed provide a visible light response type photocatalyst having an excellent responsiveness of the visible light. The titanium oxide of the raw material has no visible light responsiveness, and may be, for example, anatase type titanium oxide. In this case, a visible light responsive photocatalyst having high visible light activity can also be obtained according to the present invention. In the case where the raw material originally has visible light responsive titanium oxide, its visible light catalyst activity can be remarkably improved according to the present invention. [Embodiment] The visible light-responsive photocatalyst of the present invention is a surface of a titanium oxide which is responsive to ultraviolet light and has photocatalytic activity, and is supported by a surface-concentrated oxide in an oxide state, whereby the photocatalyst can obtain visible light responsiveness. All of the cerium oxide in the photocatalyst does not have to be supported on the titanium oxide (that is, adhered to the surface), and a part of the cerium oxide is not supported, and the titanium oxide may be present in a mixed state, or may be contained in the titanium oxide. . However, niobium must be concentrated on the surface of the titanium oxide in the form of niobium oxide. Preferably, the crucible is coated with at least a portion of the surface of the titanium oxide in an oxide form. The mechanism for exhibiting visible light activity (visible light responsiveness) of the visible light responsive photocatalyst of the present invention is not described at present, but it is considered to be an oxide of cerium which is concentrated on the surface of titanium oxide and is preferably low in bismuth. The new migration pattern produced by the interaction of the oxide (BiOx: χ<1·5) causes visible light to be absorbed, and the resulting carrier is involved in the passage of titanium oxide (preferably anatase) and low-order cerium oxide. The charge is effectively separated and the visible light activity is expressed or enhanced. -13- 200940165 Titanium oxide can be used in a wide variety of materials. The oxygen phase of the crystalline titanium oxide having an anatase structure is preferred. Preferably, the anatase type oxygen, hydrogen, carbon, transition metal, sulfur, etc. are imparted. Among them, if nitrogen-containing anatase-type titanium oxide is used, it is possible to obtain high-quality. Even if it does not have visible light responsiveness, the titanium oxide which is generally characterized by visible light-responsive photocatalyst is invented on the surface of titanium oxide. The 彳XAFS (X-ray absorbing fine structure) analytic structure titanium with high visible titanium oxide supported cerium oxide can also be partially made into a new compound. The fine oxide fine particle type is analyzed on the surface of XPS or the like by the surface oxide of titanium oxide to obtain a trivalent (Bi3+) of ruthenium, which is a mixed valence state product containing a low-order divalent) and a zero-valent (B.). (BiOx: χ <1·5), suggesting a rounded result. In addition, in the case of the titanium oxide, the titanium oxide is maintained in the original crystal structure (for example, analysis of various elements, it is understood that the concentration of germanium in the titanium oxide in the catalyst is not contained in the titanium oxide skeleton on the surface. In addition, the ruthenium group on the surface of the titanium oxide is passed through, but at least partially contains titanium, and in the catalytically active titanium compound, nitrogen or fluorine responsiveness can also be utilized to impart visible light response to the photocatalyst. The performance is such that, in the case of titanium oxide, or in the case of light, it is also preferable to use a photocatalyst containing a low photo-catalytic activity of oxygen. _ is still unclear. According to ; made, think that 铋 is with oxidation. However, it is preferable to determine that the 铋 is carried by the surface. The 1 铋 ion is not only the usual (Bi2+), monovalent (Bi1, that is, the oxygen deficiency in the whole low-order oxygen may have no effect at all, such as anatase). The pour resistance of the oxide type is higher than that of the whole, and the FT-IR results of the -14-200940165 are also generally reduced by the concentration of the oxide in the oxide state. There are many (highly concentrated) cerium oxides on the surface that interact with anatase titanium oxide to produce new visible light absorption and migration. After absorption by visible light, the efficiency of the carrier is caused by the efficiency of the carrier between the anatase crystal having a high charge separation efficiency and the lower oxide of ruthenium, and as a result, a substance having high visible light activity is obtained. BiOX (X is an anion such as nitrate ion, chloride ion or hydroxyl ion) and ruthenium compound represented by ruthenium halide or ruthenium nitrate are contacted with titanium oxide or a solid Q precursor, and heat treated to carry the titanium oxide if necessary. Oxides are known to have the greatest effect. In the visible light-responsive photocatalyst of the present invention, if the original titanium oxide contains at least one element of cerium, aluminum, chromium or the like, the desired structure is easily obtained, resulting in more excellent visible light activity and high performance stability. There are many duties of elemental ruthenium, one of which is to suppress crystal transfer during the calcination of titanium oxide, to maintain the original crystal structure, preferably an anatase structure, and to maintain the specific surface area of titanium oxide. On the other hand, yttrium is contained in the titanium oxide to change the surface state, improve the surface wettability, and increase the solid acid point. In this way, the ruthenium compound is easily reacted with titanium oxide (surface) at the time of production, and the ruthenium oxidation of the low-order oxidation state, such as a low-coordination structure in which the ruthenium compound is changed to a fine ruthenium oxide, and the surface of the titanium oxide is partially bonded to the surface of the titanium oxide is promoted. Changes in things. Further, it has been found that the absorption of visible light by the titanium oxide-supporting ruthenium compound is enhanced to a long wavelength even when the element ruthenium is not contained or the range is outside the range. In contrast, if the titanium oxide is preliminarily contained in an appropriate amount of elemental cerium, the visible light absorption after the ruthenium compound is supported is located on the shorter wavelength side of -15-200940165, and the intensity is not so strong. From this point of view, the main role of the element bismuth in titanium oxide is to effectively suppress the solid reaction between the titanium oxide and the cerium compound (for example, injecting cerium into the titanium oxide crystal lattice, etc.). With regard to enhancing the visible light responsive photocatalytic activity with a ruthenium compound, the present inventors have further obtained the following findings. The activity of the visible light-responsive photocatalyst composed of titanium oxide containing ruthenium is related to the ruthenium structure contained in the titanium oxide, and the ruthenium atom contained in the titanium oxide clarified by xafs (x-ray absorption Q fine structure) The arrangement 'that is, the activity changes according to the atomic correlation. Specifically, when the photocatalyst has a dynamic path distribution peak ratio R (second peak/first peak) around the helium atom in the XAFS analysis, the visible light activity is high. The dynamic path distribution peak ratio R is preferably 0.15 or less. When the cerium oxide is present in two or more layers on the surface of the titanium oxide, the second peak is small, which means that the cerium oxide (BiOx: x < 1.5) is supported on the surface of the titanium oxide in a state close to a single layer. In a suitable aspect, the visible light responsive photocatalyst of the present invention contains titanium oxide (or a solid precursor thereof) containing iridium anatase crystals as a raw material, and supports cerium oxide therein. The cerium in the titanium oxide is concentrated on the surface of the titanium oxide, and more preferably in the form of a mixed valence, that is, a lower enthalpy of divalent (Bi2+) or less, and all of the bismuth (Bi2+) 1.5) indicates that loading is important in the low-order oxide state. The supported state may be a low-order cerium oxide adhered to the surface of the anatase-type titanium oxide in the form of fine particles, or in a state of surface coordination, or coated on the surface of the titanium oxide or coated in a single layer. Preferably, the support is a state in which at least a part of the titanium oxide is coated with a low-order cerium oxide. After the load is carried out -16- 200940165 Some solid solution compounds may also occur in the vicinity of the interface between the oxide and the titanium oxide. According to SEM (Scanning Electron Microscope) Fourier Transform Infrared Spectrophotometry, various kinds of adsorption and desorption, ammonia TPD (heating and desorption gas analysis) method , BAT method ammonia titration method >), etc. to confirm. The ruthenium oxide type supported on the surface of titanium oxide, there is a lot of ruthenium on the surface of the titanium oxide, that is, the surface must be concentrated, and the surface of the ruthenium compound and titanium oxide are selectively diffused and surface-selectively reacted (avoiding Reacting with the whole) is the best. The surface concentration of the crucible is compared with the niobium content obtained by chemical analysis of titanium oxide having a surface catalyst particle degree by the amount of niobium obtained by XPS. The chemical analysis system is a method for temporarily dissolving a catalyst, and measuring the amount of ions in the crucible. In the analysis, ICP-MASS and hair are used instead of chemical analysis, and Si〇2 is removed by sputtering or etching to convert titanium oxide into l〇nm or more. The content of ruthenium is preferably 20 nm or more. Alternatively, as will be described later, the amount of Bi added may be approximated to the amount of Ni in the titanium oxide. In the photocatalyst of the present invention, the oxidized concentration measured by XPS is higher than the enthalpy concentration measured by deep enthalpy concentration measured after the surface layer is removed by sputtering or the like. Specifically, the surface layer concentration (at%) determined by XPS is twice or more that of the chemical analysis. And the formation of a new cerium oxide, FT-IR (thermal analysis (for example, benzaldehyde must be more concentrated than oxidizing. 铋 铋 , , , , , , , , , , , , , , , , , , , , , , , , , 简单 简单 简单 简单 简单The light analysis included in the surface. After the surface layer (as in the case of XPS, the analysis of the thickness or chemical component of the titanium surface layer as appropriate, and the sputtering of the surface layer of 200940165 in addition to the surface layer, the use of at least 2 The concentration measured after the surface layer of the thickness of Onm or more, and the concentration of the surface layer is 1.5 times or more, preferably 2 times or more, of the concentration after sputtering. If the cerium oxide has a Bi-Ο bond, However, it is preferable to carry a low-order enthalpy in a mixed valence state, that is, a low-order enthalpy of a divalent (Bi2+) or less, and all of them are supported by a low-oxide state represented by Bi〇x (x<1·5). The examples include ultrafine particles, oxygen-deficient and unsaturated bonds, or a coordination structure on the surface of oxidized titanium. Bismuth compounds such as bismuth oxide (Bi203) and barium titanate (Bi3Ti4012) And bismuth oxyhydroxide (BiOX, X = halogen ion) An acid anion such as a nitrate ion, a hydroxide ion or an organic acid ion may be partially contained, and the entire cerium oxide present on the surface of the titanium oxide may be represented by BiOx : x < 〖. 5. The simplest determination of BiOx (x<1.5), the Bi-4f inner shell level spectrum obtained by XPS analysis of the titanium oxide photocatalyst of the present invention has (a) 165 to 162.5 eV and 1 5 9 - 7 to 1 5 7 · 2 e V, Q (b) 163~161eV and 157.7~155.7eV, and (c) 162.5~160eV and 1 5 7.2~154.7eV, at least two of the three sets of peaks in each range are better for the peaks. Journal of Electron Spectroscopy and Related Phenomena, 25 (1982) 181-189, in the photocatalyst of titanium oxide

Bi-4f內殼準位爲基準的 XPS光譜圖中，位於（a ) 165〜162.5eV及 159.7〜157.2eV各範圍的波峰爲歸屬於 Bi3+ ( Bi 2 0 3 )之各 Bi-4f 5/2 狀態及 Bi-4f 7/2 狀態，位於 (c) 162.5〜160eV及157.2〜]54.7各範圍的波峰爲歸屬於 -18 -In the XPS spectrum of the Bi-4f inner shell level reference, the peaks at each of (a) 165~162.5eV and 159.7~157.2eV are each Bi-4f 5/2 attributed to Bi3+ (Bi 2 0 3 ). State and Bi-4f 7/2 state, located in (c) 162.5~160eV and 157.2~]54.7 peaks of each range are attributed to -18 -

200940165200940165

Bi° (金屬Bi)之各Bi-4f 5/2狀態及Bi ，除了上述文獻，加上若根據Chemistry (1996 ) ’ P 1 287- 1 29 1，則位於（b 157.7〜155.76乂各範圍的波峰爲歸屬於 Bi-4f 5/2狀態及Bi-4f 7/2狀態。由其戶J 之Bi-4f 5/2狀態和Bi-4f 7/2狀態之藥 5 .3 ( ±0· 1 ) eV。 因此，上述XPS光譜圖爲具有位於 各範圍之三組對波峰中之至少二組對波Μ 明之氧化鈦系光觸媒中，氧化鈦中所含的 三價鉍（Bi3+ )，且至少部分爲以二價（ (BiG )之狀態，即，相比於三價爲低次 狀態存在。若成爲此低次鉍狀態，推測赛 光觸媒性能。 更且，前述光譜圖更佳爲下列任一者 (1 )具有前述（a) 、（ b)及（c) (2)前述（a) 、 （ b) 、 (c)之名 面積分別爲 a、b、c， （ b + c ) /a的波 0.1 5以上； 本發明之可見光應答型光觸媒若含窄 、鎵、銦、鋅、鋰、鈉、鉀、鉋、鉚、窮 鈮、鉬、鋇、緦、鈣、鎢中選出至少—種 可提高可見光觸媒活性。 此等元素爲維持氧化鈦的銳鈦礦構這 -4f 7/2狀態。又 of Materials，8 )163〜161eV 及 Bi2+ ( BiO )之各 〒得知般，各組中 f波峰的能量差爲 上述（a) ~(c) 〖，係意指於本發 J鉍不僅爲通常的 Bi2+)及/或0價 (低原子價）的 €現出優良的可見 之三組的波峰； r組對波峰的合計 峰面積比之値爲 『矽、鍺、硼、鋁 t、钪、鍩、鉛、 I之其他元素，則 ΐ ’且具有其比表 -19- 200940165 面積比非添加時維持更高之特徵。又，亦達到提高氧 表面之濕潤性，或者於表面提供固體酸點之作用。特 經由Μ添加令強度、份量均被強化的固體酸點，使得 合物於氧化鈦表面中易被分解，易變成微細之低次鉍 物（BiOx(x<l.5)的狀態。又，於光觸媒製造中的 步驟中，即使低溫亦可進行微細化，故於氧化鈦之基 晶構造內難倂入超過必要的Bi，亦具有維持高活性的 ❹ 其中，亦以矽、銷、鋁、鎢、鉬、鎂、鈴、及硼 生更高的活性，故爲佳。因此，較佳的可見光應答型 媒爲含有此等至少一種元素。 其他元素（M)於光觸媒中的存在形態，爲於氧 中以氧化物型式擔載（往表面的附著或被覆）、和於 鈦中含有之任一者均可。於氧化鈦中含有，可爲氧化 Ti網絡的金屬取代，和與氧化鈦之化合形成複合氧化 G 任一者均可。又，擔載後令上述金屬元素移行至鉍化 中，令其含有亦可。但，於取得更高活性上，令氧化 含有此等元素爲佳。關於氧化鈦中所含有的元素，由 面、費用面、易操作度等而言，以矽爲最佳。 本發明之可見光應答型光觸媒中的氧化鈦，含有 —部分採用銳鈦礦構造的氧化鈦爲非常佳。可利用二 鈦（Ti〇2 )及鈦酸緦等之具有Ti〇3單位的氧化鈦。 化鈦（Ti〇2)之情形，除了銳鈦礦型，亦可加上含有 石型結晶、板鈦礦型結晶和非晶質部分。氧化鈦之結 化鈦 別， 鉍化 氧化 煅燒 本結 效果 因產 光觸 化鈦 氧化 鈦之 物的 合物 鈦中 活性 至少 氧化 二氧 金紅 晶形 -20- 200940165 可根據χ射線繞射圖型加以確認。 如銳鈦礦型氧化鈦般，關於本來僅可吸收紫外線者， 經由摻混氮 '氟 '氫、硫、碳、氫、鉍、及鐵、釩、鉻等 之過渡金屬'及鈾化合物和銀化合物等之貴金屬中選出至 少一種元素，則亦可作成賦予可見光應答性之可見光應答 性的氧化鈦。若對母體之氧化鈦預先賦予可見光應答性， 則經由鉍氧化物擔載，可大幅提高可見光活性。摻混量爲 0 根據摻混元素的種類而異，但只要可賦予可見光應答性， 則摻混量及摻混方法並無特別限定。 可見光應答性氧化鈦之情形，摻混（含有）氮之銳鈦 礦型氧化鈦，由性能面，取得容易度、和活性安定性等方 面而言爲佳。此時之氧化鈦中氮的摻混量爲0.0005質量％ 以上、1 0質量％以下較佳，氮摻混形態可爲NO摻混型、 TiN摻混型、或其混合型之任一者。 本發明之可見光應答型光觸媒中所含有之鉍化合物份 ❹ 量，以光觸媒中所含之鉍與Ti之原子比（Bi/Ti )爲0.001 以上、1.0以下之份量爲佳。鉍量爲此範圍外則可見光觸 媒活性的增進效果低，無法取得充分的可見光觸媒活性。 Bi/Ti原子比的更佳範圍爲受到對象光觸媒反應之種類、 費用等所左右，由反應性（光分解特性、超親水化特性） 之觀點而言，推薦大約〇.〇1以上、〇·30以下。Bi/Ti原子 比可根據本發明觸媒製造時之Bi化合物的裝入量而調整 〇 另一方面，可見光應答型光觸媒爲含有锆、鋁、鎢、 -21 - 200940165 鉬、硼等其他元素Μ時，光觸媒中之其他元素Μ的含量 (含有二種以上元素Μ時爲其合計量）爲相對於光觸媒中 之Ti的原子比（M/Ti )爲0.0001以上、未達1 .0之份量 爲佳，此原子比更佳爲0.001以上、未達0.3。若其他元 素Μ的份量爲此範圍，則擔載鉍化合物令可見光觸媒活性 的增進效果變得更加顯著，取得高活性的可見光應答型光 觸媒。 〇 本發明之可見光應答型光觸媒中，氧化鈦所擔載之鉍 構造係大爲參與活性表現，判定其爲特定之構造時取得高 可見光活性。即’可見光觸媒活性爲以XAF S解析所闡明 ’係根據氧化鈦中所含之鉍原子的排列，即，原子相關而 異。具體而言’若以XAFS法所觀測之鉍原子周圍的動徑 分佈波峰比R (第2波峰/第1波峰）爲〇.4以下之構造， 則成爲顯示高可見光活性的光觸媒。 若簡單說明XAFS法，則對特定原子照射X射線所發 〇 生的光電子’相對於其周邊原子受到散亂或干涉所觀測到 的X射線吸收光譜XAFS (X射線吸收微細構造）光譜， 若以適當之區域進行富利葉轉換，則取得動徑分佈函數。 此函數爲以注目元素作爲中心之電子密度的一次元分佈， 於顯示此極大値之距離中存在任何原子，其強度爲比例於 位置原子的電子密度。若數値性解析此動徑分佈函數，則 取得關於注目元素的構造情報（配位數、原子間距離等） 。測定爲在大氣中、常溫，又以固體、液體、氣體任一種 狀態均無妨。 -22- 200940165 關於上述方法所得之動徑分佈函數，以具體例說明。 XAFS的測定爲使用Si (111) 2結晶氯苯，於X射線能量 之間以1〜6 eV之範圍掃描，並且以穿透法進行。積算時間 爲2〜10秒/點。來自XAFS的動徑分佈爲以下列要領求出 。由所測定之EXAFS光譜，使用加以常數項之Victoreen 式減去背景，並根據Cubic-Spline法估計獨立原子的吸光 度，抽出EXAFS信號。對抽出的EXAFS信號，加以重疊 φ kn ( n = 2 )進行富利葉轉換，導出來自吸收原子之距離函 數動徑構造函數。 圖2爲以如上述之手續，根據XAFS法求出鉍原子周 圍之動徑分佈的結果。首先，參照材料Bi203 (和光純藥 製型（僅含A )爲於其動徑分佈中，於ι·7Α附近具有 最大強度之波峰，於3-4A間具有次高強度之波峰。此等 波峰之位置爲示出由鉍至接近原子爲止的距離。與鉍最接 近之原子’即相當於氧原子間的波峰爲於圖2中之〗.7入 〇 附近的第一波峰，與鉍第二接近之原子，即相當於最接近 之鉍原子間的波峰爲3-4A間的波峰。本發明中以此Bi203 的動徑分佈爲基準（同樣測定），將Bi203 1.7A附近的波 峰視爲第一波峰’ 3 - 4 A間的波峰視爲第二波峰。另外， 考慮測定精確等之影響並將±〇·5Α的誤差列入考慮，決定 指定之波峰，並且規定此各波峰強度。於規定之範圍存在 複數波峰時，或者重疊時，視需要進行波峰分離後，抽出 指定的波峰，並將示出範圍之最大強度的波峰視爲指定波 峰。 -23- 200940165 擔載鉍之氧化鈦之情形，若以上述方法依XAFS法所 觀測之鉍原子周圍的動徑分佈波峰比R (第2波峰/第〗波 峰）爲0.4以下，則可見光應答型酸光觸媒的活性變大。 R較佳爲0.15以下。其意指第二接近原子的存在或然率低 ，即，鉍以極微細分散及/或低配位數之狀態存在。 另外，若光觸媒之Bi/Ti的原子比爲超過1.0，則變 成接近Bi4Ti3012的構造，R値變大，可見光觸媒活性降 0 低。此意指較佳之Bi/Ti原子比爲0.5以下。 其次說明關於本發明之可見光應答型光觸媒的製造方 法。 本發明之可見光應答型光觸媒爲包含將氧化鈦或其固 體狀前驅物與鉍化合物混合之步驟、和將所得混合物煅燒 之步驟。經由煅燒，令氧化鈦之表面擔載鉍氧化物，且鉍 爲於氧化鈦之表面濃化之存在形態。更且，通常，於氧化 鈦表面以氧化物型式擔載的鉍爲以混合原子價狀態，即含 ❹ 有二價（Bi2+)以下之低次鉍，且全體以BiOx ( χ<1·5 ) 表示的氧化物狀態。 煅燒較佳爲於煅燒粉末之X射線繞射圖型中，銳鈦礦 爲主的階段中停止。鉍化合物爲根據上述理由，以Bi/Ti 之原子比爲0.001-1.0以下之比例於氧化鈦或其固體狀前 驅物中混合爲佳。Bi化合物爲經過水解以鉍氧化物型式於 氧化鈦上擔載之情形中，實質上全部Bi爲被氧化鈦所擔 載，故生成觸媒之Bi/Ti原子比亦可近似於氧化鈦（或其 前驅物）與Bi化合物之裝入量所算出之値。 -24- 200940165 原料所用之氧化鈦供給源，並非使用經水解等變成氧 化鈦之液體狀或氣體狀的氧化鈦前驅物（例如鈦醇鹽類和 四氯化鈦）’而爲使用已以氧化鈦或其前驅物之狀態以固 體型式單離的物質。若原料爲非固體狀態，則氧化鈦與鉍 氧化物均勻混合，無法取得鉍氧化物於氧化鈦表面濃化般 擔載之本發明的可見光應答型光觸媒。 所用之氧化鈦中，較佳者爲銳鈦礦型的氧化鈦，更佳 @ 爲單獨以光觸媒型式已可作用的氧化鈦。本觸媒中經由鉍 氧化物利用數種原來之氧化鈦的電子狀態。但，前驅物亦 以固體狀之物質可使用於本製法。固體狀前驅物可列舉例 如，氫氧化鈦、氧化鈦溶膠（鈦並非完全變成氧化物，且 至少部分含有氧化鈦）。 與原料氧化鈦或其固體狀前驅物（以下，單稱爲氧化 鈦）混合的鉍化合物爲接受水解和熱處理而形成鉍氧化物 ，並且以此形態被擔載於氧化鈦爲佳。混合時之鉍化合物 Q 的狀態可爲固相（例，粉末）、液相（例，溶液或分散液 )、氣相之任一者。 氧化鈦與鉍化合物的混合手段可列舉固體混合，使用 液相狀態之鉍化合物的含浸、離子交換、水熱處理、氣相 狀態之鉍化合物的沈澱等各種方法。混合可伴隨攪拌、且 亦可不伴隨攪拌。含浸法爲例如於含有鉍化合物之溶液中 浸入氧化鈦、或將含有鉍化合物之溶液滴至氧化鈦的方法 則可實施。鉍化合物與氧化鈦均爲粉末原料之情形，若以 球磨和混合機等將其混合即可。 -25- 200940165 氧化鈦爲以分散介質型式形成液相，即分散液（包含 溶膠）時，若將此分散液與液相狀態之鉍化合物混合’則 於極小之微粒子上引起混合，故混合均勻，多可取得高活 性的可見光應答型光觸媒。因此，此混合方法爲特佳。但 ，經由使用氧化鈦前驅物之溶膠凝膠法等所得之有機溶劑 基質的超微粒子狀氧化鈦溶膠（數者爲含有水分），即使 導入鉍化合物亦無法取得充分之活性。推測其係於有機溶 0 劑中前驅物的水解不夠充分，並且於氧化鈦表面和內部殘 留阻礙與鉍化合物反應的物質。此時，暫時由溶膠液中將 氧化鈦單離後，施以充分的水解，或再予以煅燒使用作爲 原料爲佳。 混合鉍化合物之氧化鈦的分散液，即，分散狀態之氧 化鈦和包含分散或溶液狀態之氧化鉍化合物的分散液，可 操作作爲本發明之可見光應答型光觸媒形成用之分散液。 若將此分散液就其原樣塗佈至基材，並且進行熱處理，則 φ 可於基材表面形成本發明之可見光應答型光觸媒。又，視 需要加入適當的黏合劑，以製造本發明之光觸媒機能構件 基材之塗敷液型式供使用亦可。特別於水系基質之氧化鈦 分散液中含有鉍化合物者，由光觸媒性能、環境面、費用 方法爲佳。 將鉍化合物與氧化鈦之混合物，視需要乾燥後、煅燒 。煅燒爲於煅燒粉末之X射線繞射圖型中，銳鈦礦型氧化 鈦爲主的階段中停止爲佳。其亦適用於原料氧化鈦爲含有 銳鈦礦型氧化鈦之情形，和不含有之情形之任一者。即使 -26- 200940165 原料爲不含有銳鈦礦型氧化鈦，亦於煨燒中令氧化鈦變成 銳鈦礦，若更加進行煅燒（例如，若煅燒溫度變高、煅燒 過長），則銳鈦礦以外之氧化鈦（例，金紅石）和鉍之氧 化物的結晶生成增加，故可見光觸媒活性降低。 煅燒中具體的熱處理溫度（煅燒溫度）爲8(TC至800 °C，更佳爲200°C至600°C。於此溫度範圍變成最高活性 的可見光應答型光觸媒。於原料爲銳鈦礦氧化鈦，鉍化合 © 物亦爲鉍氧化物之情形中，可採用較低的煅燒溫度。另一 方面，原料爲非銳鈦礦型氧化鈦或氧化鈦之固體前驅物之 情形 '及/或鉍化合物爲非氧化物之情形中，使用生成銳 鈦礦型氧化鈦和鉍氧化物上所必要的煅燒溫度。 煅燒時間（熱處理溫度保持時間）並無特別限定，但 適當爲10分鐘至6小時之範圍。升溫速度無特別限定， 但由光觸媒活性和生產性方面而言以厂C /分鐘以上爲佳。 熱處理之氛圍氣爲空氣、純空氣、氧等之氧化性氛圍 ® 氣、氮和氬等之惰性氛圍氣、或含有氫、氨等之還原性氣 體之還原性氛圍氣的任一者均可，且亦可爲其組合的氛圍 氣。以氧化性氛圍氣煅燒，亦經由氧化鈦與鉍化合物的反 應，令鉍於煅燒中變成低次氧化物（BiOx: χ<1.5)。關 於氛圍氣中之水分量並無限定，但以1 0體積％以下爲佳。 若超過此濃度，則察見熱處理後之光觸媒的比表面積變小 之傾向。 原料中，氧化鈦爲固體狀，於其中所混合的鉍化合物 可爲固相、液相、氣相之任一種狀態。因此，鉍化合物可 -27- 200940165 使用包含鉍的全部化合物。具體而言可列舉BiOX所 羥基鉍化合物、鹵化鉍、硝酸鉍、硫酸鉍、檸檬酸鉍 化鉍、鉍醇鹽、硫化鉍等。羥基鉍化合物可列舉羥基 酸鉍、羥基硝酸鉍（鹼性）、羥基氫氧化鉍、羥基氯 、羥基氟化鉍、羥基碘化鉍、羥基碳酸二鉍、羥基硫 鉍、羥基醋酸鉍、羥基過氯酸鉍、羥基氫氧化鉍、經 酸鉍等。鹵化鉍爲包含（三）氯化鉍、（三）氟化秘 φ 三）碘化鉍、（三）溴化鉍。由此等鉍化合物中選出 或二種以上與氧化鈦混合供使用。以使用如鉍鹽、經 鹽般之受到水解和縮合產生氧化鉍的鉍化合物爲佳。 關於原料之氧化鈦可利用氧化鈦和酞酸緦、及於 含有或摻混氮和碳、過渡金屬、鉑化合物、銀化合物 可見光應答性的氧化鈦和鈦酸緦等。其中亦以摻混氮 化鈦使用於原料，就費用面、觸媒性能面而言爲佳。 混量和摻混形態爲如上述。又，可使用氧化鈦之分罱 〇 特別將氧化鈦溶膠使用於原料，且如上述使用此分i 佳。 如前述，若爲固體狀，則氫氧化物等之氧化鈦前 可使用作爲氧化鈦原料。可使用之前驅物除了氫氧化 外，亦可列舉過氧化鈦、水合氧化鈦等。令固體狀之 鈦前驅物與鉍化合物接觸後的熱處理步驟及/或煅燒 中，因爲氧化鈦前驅物變換成氧化鈦，故取得由擔載 合物之氧化鈦所構成之本發明的可見光應答型光觸媒 情形中，氧化鈦前驅物亦可以分散液（溶膠）之形態 示之 、氧 苯甲 化鉍 酸二 基草 ' ( 一種 基秘 其中 等之 之氧 氮摻 液， 液爲 驅物 物以 氧化 步驟 鉍化 。此 供使 -28- 200940165 原料之氧化鈦亦可爲市售的氧化鈦系可見光應答型光 觸媒。此時，若令此光觸媒根據本發明與鉍化合物接觸， 則可提高其可見光應答光觸媒活性。因此，此時鉍化合物 作用爲可見光應答型光觸媒的活性增進劑。 如前述，使用作爲原料之氧化鈦（包含其固體狀前驅 物）爲含有由矽、鉻、鋁、鎢、鉬、鎂、給、及硼中選出 0 至少一種之元素Μ爲佳" 若氧化鈦爲含有元素Μ，則在與鉍化合物的混合中， 特別於加熱下，令鉍化合物與氧化鈦的接觸適切化，結果 取得高活性的可見光應答型光觸媒。如前述推定元素Μ爲 透過提高氧化鈦的比表面積，提供固體酸點等，促進鉍化 合物的微細擔載。 若於氧化鈦中含有元素Μ的化合物，例如，矽化合物 等，則減少鉍本身被倂入氧化鈦的骨架內，並且易於維持 © 氧化鈦的電子狀態。其結果，推測經由氧化鈦與鉍氧化物 間的相互作用所生成的載體，難以氧化鈦被再結合，結果 變成帶有高活性。矽化合物等爲以可見光吸收物質或鉍化 合物之複合氧化物、和分相之氧化物等之矽氧化物型式倂 入爲最佳。 於上述非專利文獻5中，記載於含有Bi之氧化鈦所 構成的紫外線應答型光觸媒中，添加成爲矽化合物的四乙 基鄰矽酸鹽。但，於文獻中明確記述四乙基鄰矽酸鹽被使 用作爲令已倂入Bi的Ti02光觸媒固定化至玻璃基板的黏 -29- 200940165 合劑，並非影響本發明般之具有可見光應答性之氧化鈦與 鉍化合物的接觸。 令氧化鈦含有前述元素Μ並無限定，但可根據下列三 種方法之任一種進行。 1.以氧化鈦之合成階段，添加含有元素Μ之化合物而含 有； 2 ·合成氧化鈦後，將含有元素Μ之化合物以沈澱法和含 D 浸法等之方法等擔載（氧化鈦之事前處理）； 3.將鉍化合物與氧化鈦混合時，於系中加入含有元素Μ 的化合物。 任一種方法均經由擔載鉍化合物而取得本發明之可見 光應答型光觸媒。於性能上以1之方法取得最高活性之光 觸媒。另一方面，2、3之方法中，例如將市場可取得之紫 外線應答型或可見光應答型之氧化鈦光觸媒使用作爲原料 ，可製造更高活性之光觸媒。 〇 關於上述1之方法，以合成含有矽、锆、鋁、鎢、鉬 、鎂、給、及硼（簡稱爲Μ )之至少一者的氧化鈦舉例說 明。 於四氯化鈦、三氯化鈦、鈦醇鹽、硫酸鈦等之水解性 鈦化合物中加入含有元素Μ的氯化物或醇鹽類等之化合物 。可使用之矽化合物例可列舉四氯化矽、碘化矽、氮化矽 、硝酸矽、硫化矽等之無機矽化合物、及四乙氧基矽烷、 甲基三乙氧基矽烷等之烷氧基矽烷類、醋酸矽、聚矽氧樹 脂類之有機矽化合物、或二氧化矽、二氧化矽膠體。鋁化 -30- 200940165 合物之例可列舉鋁、氯化鋁、氟化鋁、氫氧 、硫酸鋁等之無機鋁化合物、及乙醇鋁、異 機鋁化合物。锆化合物之例可列舉氧化鉻、 氯化鉻、三氯化锆、硝酸锆、硝酸鉻氧化物 無機鉻化合物、及異丙醇锆、乙醯丙酮酸锆 醇鉻等之有機鉻化合物。鎢化合物中，可利 酸鎢等（鉬化合物亦同樣），硼之情形可使 φ 硼、乙醇硼等。含有元素Μ之化合物的添力 比爲0.0001~0.5，較佳爲0·00〗〜0.30之範圍 其後，加入氨水、胺、脲、硫脲等之含 水解，收集析出之沈澱物，所得之固形物以 右煅燒，則可調製含有元素Μ之具有可見光 鈦。又，以水解副生成之鹽難以煅燒蒸發時 化鈦使用氫氧化鈉中和時，副生成的N aC 1 終了後充分水洗，由氯化鈦表面除去鹽，最 〇 活性之可見光應答型光觸媒。又，經由進行 則鈦停留於氫氧化物狀態，亦可取得固體狀 物。 本發明之光觸媒之製造方法中，原料之 見光應答性氧化鈦、及視情形（上述3之方 含有矽、鋁、锆等之元素的化合物中，至少 具有結晶性者爲佳。若至少一種原料爲具有 鉍化合物與氧化鈦混合時的接觸適切化，結 的光觸媒。 化鋁、硝酸鋁 丙醇鋁等之有 氧化鉻膠體、 、硫酸锆等之 、丁醇鉻、乙 用氯化鶴和硫 用硼酸和氯化 □量，以M/Ti 〇 氮化合物進行 200〜700〇C 左 應答性的氧化 (例如將四氯 等），於水解 終變成具有高 不完全煅燒， 的氧化鈦前驅 鉍化合物，可 法之情形）， 一種化合物爲 結晶性，則令 果變成高活性 -31 - 200940165 本發明之可見光應答型光觸媒之形狀可列舉粒狀、纖 維狀、薄膜狀等，且根據用途分開使用爲佳。粒狀之情形 ，粒子爲數nm左右之微粉末至數十微米左右之造粒體， 其大小、形態並無限定。薄膜之情形，一般爲固定於基材 上。 成形爲薄膜和纖維狀等任意形狀時，除了光觸媒粒子 ，期望加上添加黏合劑。經由黏合劑的添加，可增大薄膜 @ 的厚度和纖維徑，並且可提高薄膜和纖維強度、加工性等 〇 以上述方法所製造之本發明的可見光應答型光觸媒亦 可就其原樣以粉末狀態利用。但，由操作面而言，便利令 其附著至基材表面並且以固定化之光觸媒機能構件型式供 利用。 固定化之形態可根據基材的表面形狀和用途等而選擇 ，可例示例如，薄膜狀、粒狀、纖維狀等。基材的種類無 Q 限定，可例示碳鋼、鍍鋼、鉻酸鹽處理鋼、琺瑯、不銹鋼 、鈦、鋁等之金屬材料、陶瓷 '玻璃、陶磁器、石英等之 無機材料、塑膠、樹脂、活性碳等之有機材料。又，彼等 亦可爲複合材料，例如，塗裝鋼板等。 較佳之基材爲將金屬或其表面以光觸媒非分解材料被 覆。全體或表面爲有機材料的基材爲根據光觸媒的氧化力 而惡化或分解，故於此情形中，將基材表面，使用光觸媒 非分解之材料預先被覆。有機材料例如，聚矽氧樹脂亦難 因光觸媒而受到惡化，故雖依據條件而異，但即使未被覆 -32- 200940165 亦可。 基材之形狀亦無特別限定，可爲薄板、厚板、纖維狀 (包含編織物、不織布）、網狀'筒狀等任意形狀。可就 其原樣以製品型式使用之複雜形狀的物體，更且亦可爲已 設置或使用中的物體。基材表面可爲多孔質，且爲緻密質 亦可。 光觸媒機能構件之最一般的製造爲於基材上，塗佈本 Q 發明之可見光應答型光觸媒粒子於溶劑中分散的分散液， 並且令塗膜乾燥則可進行。又，基材上塗佈令此可見光應 答性氧化鈦與鉍化合物於溶劑中分散之可見光應答型光觸 媒形成用分散液，並且令塗膜乾燥則可進行。於上述分散 液中加入適當之黏合劑等添加劑，作成塗敷液後塗佈亦可 。更且’於基材塗佈可見光應答型之氧化鈦後，令鉍化合 物以含浸和CVD等之氣相處理接觸後，視需要加以熱處 理’作成本發明之光觸媒機能構件亦可。 €> 如此’本發明之光觸媒爲於使用可見光應答性氧化鈦 之光觸媒機能構件的製造階段中，令鉍化合物與此氧化鈦 接觸亦可形成。例如，於分散可見光應答性氧化鈦之分散 介質中添加祕化合物，或者形成可見光應答性氧化鈦之皮 膜後’令其接觸鉍化合物的方法。 塗敷液亦可經由本發明之可見光應答型光觸媒單純與 介質及黏合劑充分混合而調製。但，以上述方法所製造之 可見光應答型光觸媒，一般爲平均初級粒子徑爲微細至數 nm至百nm ’非常易凝集，若變成凝集體，則其徑爲大至 -33- 200940165 數十μιη，難於介質中均勻分散。 因此，於本發明之適當態樣中，將可見光應答型光觸 媒之粒子預先於介質中充分分散處理，調製光觸媒粒子的 分散液。利用此分散液，令其中含有黏合劑，調製塗敷液 爲佳。若使用此塗敷液，則可形成更加均句的光觸媒皮膜 ，提高皮膜特性和光觸媒活性。 分散液中之光觸媒的平均粒徑（凝集體之粒徑）爲 φ 500nm以下爲佳。若大於此粒徑，則皮膜特性差，例如剝 離 '密黏性變差，分散液本身的保存安定性降低》光觸媒 的平均粒徑更佳爲3 00nm以下，再佳爲200nm» 令光觸媒粒子分散的液體介質可列舉蒸餾水、離子交 換水、超純水等之水，甲醇 '乙醇、2 -丙醇等之醇類；甲 基乙基酮等之酮類；苯、甲苯、二甲苯等之芳香族烴類等 。其可任意混合使用’但於此情形中使用相互相溶性之溶 劑組合。 © 分散處理爲令光觸媒以固形成分濃度爲數質量％〜50 質量％之範圍般，與介質進行混合爲佳。固形成分濃度爲 此範圍外，則分散性降低。視需要，亦可添加分散劑和解 膠劑。分散劑可例示羰基系、碾系等，解膠劑可例示硝酸 、鹽酸、硫酸等。又，爲了調整pH，亦可添加鹼和酸。 分散處理亦可使用調製塗敷液所慣用之塗料振盪器進 行’例如’以原子磨、使用迴轉刃之剪切、薄膜回旋、超 音波之更強力的分散手段予以實施爲佳。組合利用二種以 上之分散手段亦可。 -34- 200940165 所得之分散液爲含有凝集之粗大粒子時，將其以過濾 或離心除去爲佳。粗大粒子爲於皮膜中易成爲剝離和粉化 的起點。於分散處理後之分散液中加入溶劑，調整固形成 分濃度亦可。 將此分散液就其原樣使用作爲塗敷液，塗佈至基材亦 可。若光觸媒爲平均粒徑5 OOnm以下的微粒子，則即使無 黏合劑亦可形成皮膜，實質上形成僅由光觸媒粒子所構成 Q 的皮膜。但是，就其原樣則令皮膜強度和密黏性低，故於 其上塗佈黏合劑溶液，令光觸媒粒子間含浸黏合劑亦可。 較佳之塗敷液爲於光觸媒和介質，再加上含有黏合劑 。介質亦可與上述分散液所述者相同，以令黏合劑溶解或 乳化般選擇。若於含有上述可見光應答型光觸媒之分散液 中混合黏合劑，調製塗敷液，則可取得光觸媒粒子之分散 性優良、保存安定性良好、可形成光觸媒活性高之皮膜的 塗敷液。 〇 黏合劑之份量爲令生成皮膜中之可見光應答型光觸媒 的含量爲5〜95質量％般調整。光觸媒含量未達5質量％之 皮膜，經由可見光照射幾乎完全未顯示出光觸媒活性。若 皮膜中之光觸媒含量爲超過95質量％，則黏合劑成分過少 且皮膜易剝離。皮膜中之光觸媒含量較佳爲30〜90質量％ ，於充分取得光觸媒活性上，以50質量％以上爲更佳。 黏合劑成分可利用二氧化矽、氧化鋁、氧化鈦、氧化 鎂、氧化锆等之金屬氧化物溶膠（於皮膜中變成凝膠）、 有機矽烷化合物、及聚矽氧樹脂、氟樹脂、胺基甲酸乙酯 -35- 200940165 樹脂、丙烯酸系樹脂等之有機樹脂。經由光觸媒的氧化力 引起黏合劑成分的分解時，期望使用金屬氧化物溶膠和聚 矽氧樹脂、丙烯酸聚矽氧、丙烯酸胺基甲酸乙酯等之難分 解性物質。又，於光觸媒機能構件被要求強加工性和高強 度之情形中，將氟樹脂、丙烯酸系樹脂、胺基甲酸乙酯樹 脂等之有機樹脂於前述難分解性之黏合劑成分中適量添加 ，則可確保所要求的特性。 〇 較佳之黏合劑成分爲二氧化矽（例，矽膠）、有機矽 烷化合物之水解/縮合物、聚矽氧樹脂等之矽化合物。二 氧化矽亦可爲矽酸酯（例，矽酸乙酯）之水解和縮合所生 成的二氧化矽溶膠（膠體二氧化矽）。有機矽烷化合物可 使用具有皮膜形成性之水解性的有機矽烷化合物，例如， 烷氧基矽烷類和矽烷偶合劑。黏合劑成分爲對於介均勻溶 解之型式，且亦可於介質中乳化之乳化液型式。 塗敷液亦可含有上述以外之其他成分。此類其他成分 〇 可列舉非可見光應答型之光觸媒（例，先前之氧化鈦系光 觸媒）、光觸媒爲擔載粒子時之載體。又，亦可於皮膜中 含有著色材（較佳爲無機顏料）和體質顏料等之少量成分 塗敷液之塗佈爲配合塗敷液之性狀和基材之形狀，由 習知的各種方法中選擇。塗佈後，視需要一邊加熱一邊令 塗膜乾燥（視情況進一步硬化）。乾燥（硬化）溫度爲配 合塗敷液之組成（溶劑和黏合劑之種類）、基材之耐熱溫 度等而決定即可。塗敷液爲含有氧化鈦光觸媒之前驅物時 -36- 200940165 ，以前驅物變化成氧化鈦般進行加熱。 基材上所形成含有光觸媒的皮膜厚度爲 佳。若皮膜爲薄於0.1 μιη，則光觸媒的份量 見光照射之光觸媒活性非常低。皮膜的厚度 觸媒性能和費用而適當選擇，但由觸媒性能 媒活性方面而言，更佳爲Ιμιη以上，5μιη以 度的上限並無特別規定’若考慮費用和效果 0 50μιη以下，較佳爲20μπι以下。 本發明之可見光應答型光觸媒和其表面 機能構件’不僅紫外線，於照射波長400nm 線下接觸被處理物質，則可表現光觸媒作用 樣有害物質，附著物質等予以分解、除去、 光觸媒若於作爲分解對象之物質可接觸，且 線的環境下使用即可。光源若爲含有至少一 的波長區域即可，例如，可利用太陽光線、 〇 燈、背光、氙燈、水銀燈等。本發明之光觸 線亦可發揮活性，故光源爲包含可見光和紫 其令光觸媒活性變高。 本發明之可見光應答型光觸媒可處理的 著物可例示甲醛、乙醛、甲苯等之VOC氣 S〇x、Furon等之大氣污染氣體；氨、硫化氫 溴氣；醇類、BTX、酚類等之有機化合物； 氯乙烯、Furon等之有機鹵素化合物；除草 殺蟲劑等之各種農藥；蛋白質和胺基酸等之 0.1 μηΐ以上爲 過少，經由可 爲根據必要之 之安定性和觸 上爲再佳。厚 之飽和，則爲 設置的光觸媒 以上之可見光 ，並將各式各 或者無害化。 可照射可見光 部分可見光線 螢光燈、鹵素 媒即使爲紫外 外光均可，且 有害物質或附 ,體類；ΝΟχ、 、硫醇類等之 三鹵甲烷、三 劑、殺菌劑、 各種生物學的 -37- 200940165 需氧物質；界面活性劑；氰胺化合物、硫化合物等之無機 化合物；各種之重金屬離子；大腸菌、葡萄球菌、綠環菌 等之菌類、黴菌類、藻類等之微生物；油、煙屎、指紋、 雨跡、泥等。 又’本發明之可見光應答型光觸媒爲經由光的照射而 呈現超親水性。表面具有本發明光觸媒的機能構件中，經 由超親水化作用而取得防霧性、防污性、防塵性等。 Ο 〔實施例〕 以下，根據實施例例示本發明。但，實施例並非限制 本發明。實施例中之Bi/Ti、Si/Ti比均爲意指金屬原子比 (實施例1 ) 〔氧化鈦之調製〕 〇 試料No . 1 : 令四氯化鈦以氨水（7質量％ )水解所得之氫氧化鈦 於大氣中，以5 0 0 °C煅燒2小時，取得氧化鈦。此氧化鈦 中之氮量爲0.004質量％。X射線繞射之結果’氧化鈦的 主要結晶構造爲銳鈦礦型。 試料N 〇 . 2 : 除了於四氯化鈦加入四氯化矽（Si/Ti = 0·13)以外’ 以試料No . 1同樣之方法，取得含有矽之氧化鈦。此氧化 -38- 200940165 鈦中的氮量爲0.007質量％。X射線繞射之結果，氧化鈦 爲銳鈦礦型。 〔鉍化合物之調製〕 試料N 〇. 3 : 將氯化鉍溶解於3N-HC1，於所得之溶液中加入氨水 (7質量％)令氯化鉍水解。濾除沈澱所得之白色粉末以 φ 80 °C乾燥，取得根據本發明調製可見光應答型光觸媒所用 的鉍化合物。此化合物於X射線繞射之結果，鑑定爲羥基 氯化鉍。 〔可見光應答型光觸媒之調製〕 試料No.4 : 對於試料No.1之粉末狀氧化鈦，將試料N〇.3之鉍化 合物粉末，以Bi/Ti = 〇.〇9般加入，並於乳鉢中充分混練後 〇 ’將混合物於大氣下以5 0 0。(：煅燒2小時，取得鉍氧化物 被擔載之氧化駄所構成的可見光應答型光觸媒。若採取本 試料的X射線繞射圖型，則主要波峰爲氧化鈦銳鈦礦結晶 之物質。 試料N 〇 . 5 : 除了使用試料Νο·2之含矽可見光應答性氧化鈦以外 以試料Νο·4同樣之方法’製作鉍氧化物被擔載之氧化 鈦所構成的可見光應答型光觸媒。本試料的χ射線繞射結 -39- 200940165 果，氧化鈦爲由銳鈦礦結晶所構成。 試料N 〇. 6 : 於液狀之四氯化鈦水溶液（9.3 wt% ) π B i/Ti = 0.0 9般加入混合後，以氨水（7質量 成之含Bi氫氧化鈦於大氣中以5 00 °C煅燒2 有鉍化合物的氧化鈦。X射線繞射之結果， 0 礦結晶。 試料No.7 : 於液狀之四氯化鈦水溶液（9.3wt%)中 化矽與氯化鉍以 Bi/Ti = 0.09、Si/Ti = 0.13般 以氯水（7質量％ )水解，生成之含Bi氫氧 以5 00°C煅燒2小時，取得含有鉍氧化物和 X射線繞射之結果，氧化鈦爲銳鈦礦結晶。 〇 另外，試料N0.6及7均爲氧化鈦原料 狀或溶解狀態，其爲根據共沈法予以水解製 氧化鈦系光觸媒。 〔FT-IR之測定〕 關於Bi的擔載狀態，係由顯示表面構5 譜中之OH基的伸縮振動波峰強度加以推定 試料2、3、5、7之伸縮振動的波峰強度。 (試料No.3 )和氧化鉍的表面幾乎完全不存 戸將氯化鉍以 % )水解，生 小時，取得含 氧化欽爲銳駄 將液狀之四氯 加入混合後， 化鈦於大氣中 矽之氧化鈦。 與鉍原料爲液 造之比較用的 I之 FT-IR光 。圖1中示出 於羥基氯化鉍 在OH基。另 -40- 200940165 —方面，若鉍氧化物被擔載於氧化鈦之表面，則如試料 No.5所示般，對於母體試料Νο·2之OH基的伸縮振動波 峰強度滅少。另一方面，使用液狀之氧化鈦前驅物與鉍化 合物以共沈法所合成之試料Νο·7的光觸媒中，ΟΗ基幾乎 完全無變化。由此認爲，試料Νο·7之鉍氧化物並非被擔 載於氧化鈦表面，而係主要被倂入氧化鈦內部。係因爲由 氧化鈦前驅物於液中形成氧化鈦時，鉍化合物爲以分子程 Q 度被倂入。本發明之可見光應答型光觸媒中，因爲於原料 使用氧化鈦，故鉍化合物主要於氧化鈦表面反應，故變成 如上述的擔載構造。 〔XPS的測定〕 以下列之條件下進行XPS分析。The Bi-4f 5/2 state of Bi° (metal Bi) and Bi, in addition to the above documents, plus according to Chemistry (1996) 'P 1 287- 1 29 1, are located in the range of b 157.7~155.76乂The peak is attributed to the Bi-4f 5/2 state and the Bi-4f 7/2 state. The Bi-4f 5/2 state of the household J and the Bi-4f 7/2 state of the drug 5. 3 (±0·1) eV. Therefore, the above XPS spectrum is a titania (Bi3+) contained in the titanium oxide in the titanium oxide photocatalyst having at least two of the three pairs of pairs of peaks in each range, and at least a portion It is in the state of divalent ((BiG), that is, it is lower than the trivalent state. If it is in this low-order state, the photocatalytic performance is estimated. Further, the above spectrogram is preferably any of the following (1) having the above-mentioned (a), (b), and (c) (2), the areas of the names (a), (b), and (c) are a, b, c, (b + c ) / a, respectively. The wave of the visible light-responsive photocatalyst of the present invention is at least one selected from the group consisting of narrow, gallium, indium, zinc, lithium, sodium, potassium, planer, riveting, sulphur, molybdenum, niobium, tantalum, calcium and tungsten. Improve visible light catalyst The elements are the -4f 7/2 state of the anatase structure of the titanium oxide, and the energy of the f-peak in each group as known by Materials, 8) 163~161eV and Bi2+ (BiO). The difference is the above (a) ~ (c) 〖, which means that the present J J is not only the usual Bi 2+ ) and/or the zero valence (low valence valence) € shows excellent visible three sets of peaks; The total peak area ratio of the group to the peak is "矽, 锗, boron, aluminum t, 钪, 鍩, lead, I other elements, then ΐ ' and has a ratio of the ratio of Table -19- 200940165 is maintained when not added Higher features. Moreover, it is also effective to increase the wettability of the oxygen surface or to provide a solid acid point on the surface. By adding a solid acid point which is strengthened by strength and weight, the composition is easily decomposed in the surface of titanium oxide, and it is easy to become a fine low-order bismuth (BiOx(x) The state of <l.5). Further, in the step of producing a photocatalyst, even if it is low-temperature, it is possible to refine it. Therefore, it is difficult to absorb more than necessary Bi in the base crystal structure of titanium oxide, and it has a high activity. Aluminum, tungsten, molybdenum, magnesium, bell, and boron produce higher activity, so it is better. Therefore, a preferred visible light responsive medium contains at least one of these elements. The form in which the other element (M) is present in the photocatalyst may be either supported by an oxide type in oxygen (adhesion or coating to the surface) or in titanium. It may be contained in titanium oxide, and may be substituted by a metal of an oxidized Ti network, and may be combined with titanium oxide to form a composite oxidized G. Further, after the loading, the above-mentioned metal element is transferred to the hydrazine, and it may be contained. However, in order to achieve higher activity, it is preferred that the oxidation contains such elements. Regarding the elements contained in the titanium oxide, ruthenium is most preferable in terms of surface, cost, ease of operation, and the like. The titanium oxide in the visible light responsive photocatalyst of the present invention contains titanium oxide partially having an anatase structure. Titanium oxide having Ti〇3 units such as titanium (Ti〇2) and barium titanate can be used. In the case of titanium (Ti〇2), in addition to the anatase type, a stone-type crystal, a brookite-type crystal, and an amorphous portion may be added. Titanium oxide tantalized titanium, bismuth oxide oxidized calcination effect due to the photocatalytic titanium titanium oxide compound titanium active at least oxidized red gold oxide crystal form -20- 200940165 according to χ ray diffraction pattern Confirm it. Like anatase-type titanium oxide, it is a transition metal that mixes nitrogen 'fluorine' hydrogen, sulfur, carbon, hydrogen, helium, and iron, vanadium, chromium, etc., and uranium compounds and silver. When at least one element is selected from a noble metal such as a compound, it is also possible to form a titanium oxide which imparts visible light responsiveness to visible light responsiveness. When the visible light responsiveness is imparted to the titanium oxide of the precursor, the visible light activity can be greatly enhanced by carrying the ruthenium oxide. The blending amount is 0 depending on the type of the blending element, but the blending amount and the blending method are not particularly limited as long as the visible light responsiveness can be imparted. In the case of visible light responsive titanium oxide, it is preferred to blend (containing) nitrogen anatase titanium oxide from the viewpoint of performance, ease of availability, and activity stability. In this case, the amount of nitrogen incorporated in the titanium oxide is preferably 0.0005 mass% or more and 10 mass% or less, and the nitrogen blending form may be any of a NO blend type, a TiN blend type, or a mixed type thereof. The amount of the ruthenium compound contained in the visible light-responsive photocatalyst of the present invention is preferably such that the atomic ratio of ruthenium to Ti (Bi/Ti) contained in the photocatalyst is 0.001 or more and 1.0 or less. When the amount of ruthenium is outside this range, the effect of enhancing the activity of the visible light sensor is low, and sufficient visible light catalyst activity cannot be obtained. A more preferable range of the Bi/Ti atomic ratio is affected by the type and cost of the photocatalytic reaction of the object, and from the viewpoint of reactivity (photodegradation property, superhydrophilic property), it is recommended to be about 〇1 or more, 〇· 30 or less. The Bi/Ti atomic ratio can be adjusted according to the amount of Bi compound in the production of the catalyst of the present invention. On the other hand, the visible light responsive photocatalyst contains zirconium, aluminum, tungsten, -21 - 200940165 molybdenum, boron and other elements. When the content of other elements in the photocatalyst (the total amount of cerium when two or more elements are contained) is 0.0001 or more with respect to the atomic ratio (M/Ti) of Ti in the photocatalyst, the amount of not more than 1.0 is Preferably, the atomic ratio is more preferably 0.001 or more and less than 0.3. When the amount of the other element is in this range, the effect of enhancing the activity of the visible light catalyst is more remarkable by supporting the ruthenium compound, and a highly active visible light responsive photocatalyst is obtained. In the visible light-responsive photocatalyst of the present invention, the 铋 structure supported by titanium oxide greatly participates in the activity, and it is judged that it has a high specific visible light activity when it is a specific structure. That is, the 'visible light catalyst activity is explained by XAF S analysis', which is based on the arrangement of the ruthenium atoms contained in the titanium oxide, that is, the atomic correlation. Specifically, when the dynamic-diameter distribution peak ratio R (second peak/first peak) around the helium atom observed by the XAFS method is 〇.4 or less, it is a photocatalyst exhibiting high visible light activity. If the XAFS method is simply described, the X-ray absorption spectrum XAFS (X-ray absorption fine structure) spectrum observed by the photoelectrons generated by X-ray irradiation of a specific atom with respect to the surrounding atoms is scattered or interfered with. When the appropriate area is used for the Fourier transform, the dynamic path distribution function is obtained. This function is a unitary distribution of electron densities centered on the element of interest, and there is any atom in the distance showing this maximal ,, the intensity of which is proportional to the electron density of the atom at the position. When the dynamic path distribution function is analyzed, the structural information (coordination number, interatomic distance, etc.) about the element of interest is obtained. It is measured in the atmosphere, at room temperature, and in any state of solid, liquid, or gas. -22- 200940165 The dynamic path distribution function obtained by the above method is described by way of a specific example. The XAFS was measured by using Si (111) 2 crystalline chlorobenzene, scanned between X-ray energies in the range of 1 to 6 eV, and carried out by a penetrating method. The accumulated time is 2 to 10 seconds / point. The dynamic path distribution from XAFS is obtained by the following method. From the measured EXAFS spectrum, the background was subtracted using the Victoreen formula of the constant term, and the absorbance of the independent atom was estimated according to the Cubic-Spline method, and the EXAFS signal was extracted. The extracted EXAFS signal is superimposed with φ kn ( n = 2 ) for Fourier transform, and the distance function from the absorbing atom is derived. Fig. 2 shows the results of obtaining the dynamic path distribution around the ruthenium atom by the XAFS method as described above. First, the reference material Bi203 (Wako Pure Chemicals Co., Ltd. only contains A) has a peak of maximum intensity near ι·7Α in its dynamic path distribution, and has a peak of the second highest intensity between 3-4A. The position is shown by the distance from 铋 to the atom. The atom closest to 铋, that is, the peak corresponding to the oxygen atom, is the first peak near the 77 in Fig. 2, and the second peak. The close atom, that is, the peak between the closest helium atoms is a peak between 3-4 A. In the present invention, the peak near Bi203 1.7A is regarded as the reference based on the dynamic diameter distribution of Bi203 (the same measurement). The peak between a peak ' 3 - 4 A is regarded as the second peak. In addition, considering the influence of the accuracy of measurement, etc., and taking into account the error of ±〇·5Α, the specified peak is determined, and the intensity of each peak is specified. When there are complex peaks in the range or overlap, the peaks are extracted as needed, and the peaks showing the maximum intensity of the range are regarded as the designated peaks. -23- 200940165 If the above side When the peak-to-earth ratio R (second peak/peak) around the helium atom observed by the XAFS method is 0.4 or less, the activity of the visible light-responsive acid photocatalyst becomes large. R is preferably 0.15 or less. It is assumed that the second near-atomic atom has a low probability of existence, that is, 铋 is present in a state of extremely fine dispersion and/or low coordination number. Further, if the atomic ratio of Bi/Ti of the photocatalyst exceeds 1.0, it becomes a structure close to Bi4Ti3012. R値 becomes large, and the visible light catalyst activity is lowered to 0. This means that the preferred Bi/Ti atomic ratio is 0.5 or less. Next, a method for producing a visible light responsive photocatalyst according to the present invention will be described. The visible light responsive photocatalyst of the present invention contains a step of mixing titanium oxide or a solid precursor thereof with a ruthenium compound, and a step of calcining the obtained mixture. The surface of the titanium oxide is supported by calcination, and the ruthenium is present on the surface of the titanium oxide. Further, in general, the ruthenium supported on the surface of the titanium oxide in an oxide type is in a mixed valence state, that is, a ruthenium containing bismuth (Bi2+) or less, and all of them are BiOx ( χ <1·5 ) The state of the oxide. Calcination is preferably carried out in the X-ray diffraction pattern of the calcined powder, in the anatase-based stage. The ruthenium compound is preferably mixed with titanium oxide or a solid precursor thereof in an atomic ratio of Bi/Ti of 0.001 to 1.0 or less for the above reasons. In the case where the Bi compound is supported on the titanium oxide by hydrolysis and the ruthenium oxide type, substantially all Bi is supported by the titanium oxide, so that the Bi/Ti atomic ratio of the catalytic catalyst can also be approximated to titanium oxide (or The amount of the precursor and the amount of the Bi compound calculated. -24- 200940165 The titanium oxide supply source used for the raw material is not a liquid or gaseous titanium oxide precursor (for example, titanium alkoxide and titanium tetrachloride) which is converted into titanium oxide by hydrolysis or the like, and is used for oxidation. A state in which the state of titanium or its precursor is isolated in a solid form. When the raw material is in a non-solid state, the titanium oxide and the cerium oxide are uniformly mixed, and the visible light-responsive photocatalyst of the present invention in which the cerium oxide is concentrated on the surface of the titanium oxide cannot be obtained. Among the titanium oxides used, anatase-type titanium oxide is preferred, and more preferably, it is a titanium oxide which has been acted upon by a photocatalyst type alone. In the catalyst, the electronic state of several original titanium oxides is utilized via cerium oxide. However, the precursor is also a solid material which can be used in the present process. The solid precursor may, for example, be a titanium hydroxide or a titanium oxide sol (titanium does not completely become an oxide and at least partially contains titanium oxide). The ruthenium compound mixed with the raw material titanium oxide or a solid precursor thereof (hereinafter, simply referred to as titanium oxide) is formed by subjecting to a titanium oxide by hydrolysis and heat treatment, and is preferably supported on the titanium oxide in this form. The state of the ruthenium compound Q during mixing may be either a solid phase (for example, a powder), a liquid phase (for example, a solution or dispersion), or a gas phase. Examples of the means for mixing the titanium oxide with the cerium compound include various methods such as impregnation with a ruthenium compound in a liquid phase, ion exchange, hydrothermal treatment, and precipitation of a ruthenium compound in a gas phase. Mixing may be accompanied by agitation or without agitation. The impregnation method is, for example, a method in which titanium oxide is impregnated into a solution containing a ruthenium compound, or a solution containing a ruthenium compound is dropped onto titanium oxide. When both the cerium compound and the titanium oxide are powder raw materials, they may be mixed by a ball mill, a mixer or the like. -25- 200940165 Titanium oxide is a liquid phase formed in a dispersion medium type, that is, when the dispersion liquid (including a sol) is mixed with a ruthenium compound in a liquid phase state, mixing is caused on extremely small particles, so that the mixture is uniformly mixed. A highly active visible light responsive photocatalyst can be obtained. Therefore, this mixing method is particularly good. However, the ultrafine particulate titanium oxide sol (which contains water) in an organic solvent matrix obtained by a sol-gel method using a titanium oxide precursor or the like can not sufficiently obtain activity even when a ruthenium compound is introduced. It is presumed that the hydrolysis of the precursor in the organic solvent is insufficient, and a substance which inhibits the reaction with the ruthenium compound remains on the surface and inside of the titanium oxide. In this case, it is preferred that the titanium oxide is temporarily separated from the sol liquid, and then sufficiently hydrolyzed or calcined as a raw material. A dispersion liquid of titanium oxide mixed with a cerium compound, that is, a titanium oxide in a dispersed state and a dispersion liquid containing a cerium oxide compound in a dispersed or dissolved state can be handled as a dispersion liquid for forming a visible light responsive photocatalyst of the present invention. When the dispersion is applied to the substrate as it is and heat-treated, φ can form the visible light-responsive photocatalyst of the present invention on the surface of the substrate. Further, a suitable binder may be added as needed to produce a coating liquid type of the photocatalytic member substrate of the present invention. In particular, those containing a ruthenium compound in a titanium oxide dispersion of an aqueous base are preferred from photocatalyst performance, environmental surface, and cost. A mixture of the cerium compound and titanium oxide is dried as needed and calcined. The calcination is preferably in the X-ray diffraction pattern of the calcined powder, and the anatase-type titanium oxide is mainly stopped in the stage. It is also applicable to the case where the raw material titanium oxide is in the case of containing anatase-type titanium oxide, and is not contained. Even if the raw material of -26-200940165 does not contain anatase-type titanium oxide, the titanium oxide is turned into anatase in the sinter, and if it is further calcined (for example, if the calcination temperature becomes high and the calcination is too long), anatase The crystal formation of titanium oxide (for example, rutile) and niobium oxide other than ore is increased, so that the visible light catalyst activity is lowered. The specific heat treatment temperature (calcination temperature) in the calcination is 8 (TC to 800 ° C, more preferably 200 ° C to 600 ° C. This temperature range becomes the most active visible light responsive photocatalyst. The raw material is anatase oxidation. In the case where titanium or ruthenium is also a ruthenium oxide, a lower calcination temperature may be employed. On the other hand, the raw material is a solid precursor of non-anatase-type titanium oxide or titanium oxide' and/or 铋In the case where the compound is a non-oxide, the calcination temperature necessary for forming anatase-type titanium oxide and niobium oxide is used. The calcination time (heat treatment temperature retention time) is not particularly limited, but is suitably 10 minutes to 6 hours. The temperature rise rate is not particularly limited, but it is preferably C / min or more in terms of photocatalytic activity and productivity. The atmosphere of the heat treatment is an oxidizing atmosphere of air, pure air, oxygen, etc., gas, nitrogen, argon, etc. Any of an inert atmosphere or a reducing atmosphere containing a reducing gas such as hydrogen or ammonia, or a combined atmosphere thereof, calcined in an oxidizing atmosphere, and also passed through titanium oxide. The reaction of a compound of bismuth, bismuth becomes so low order oxides in the calcination (BiOx: χ <1.5). The amount of water in the atmosphere is not limited, but it is preferably 10% by volume or less. When the concentration is exceeded, the tendency of the specific surface area of the photocatalyst after the heat treatment to become small is observed. In the raw material, titanium oxide is a solid, and the ruthenium compound mixed therein may be in any one of a solid phase, a liquid phase, and a gas phase. Therefore, the ruthenium compound can be used in -27-200940165 using all compounds containing ruthenium. Specific examples thereof include a hydroxy hydrazine compound of BiOX, cesium halide, cesium nitrate, cesium sulfate, cesium citrate, decyl alkoxide, cesium sulfide, and the like. Examples of the hydroxy hydrazine compound include bismuth hydroxy acid hydride, hydrazine hydroxy nitrate (basic), hydroxy hydroxyhydroxide, hydroxy chloro, hydrazine hydroxy fluoride, hydroxy cesium iodide, bismuth hydroxycarbonate, hydroxy thiopurine, hydrazine hydroxyacetate, hydroxy group. Barium chlorate, barium hydroxide, acid barium, and the like. The ruthenium halide contains (3) ruthenium chloride, (3) fluorination secret φ 3) cesium iodide, and (3) cesium bromide. Among these, one or more of the ruthenium compounds are mixed with titanium oxide for use. It is preferred to use a ruthenium compound such as a ruthenium salt which is hydrolyzed and condensed by salt to produce ruthenium oxide. As the titanium oxide of the raw material, titanium oxide and strontium ruthenate, and titanium oxide and barium titanate containing or incorporating nitrogen and carbon, a transition metal, a platinum compound, a silver compound, visible light responsiveness, and the like can be used. Among them, the use of titanium nitride is also used for the raw material, and it is preferable in terms of cost surface and catalytic performance. The blending and blending morphology is as described above. Further, it is possible to use a fraction of titanium oxide. Specifically, a titanium oxide sol is used for the raw material, and this is preferably used as described above. As described above, in the case of a solid, a titanium oxide raw material can be used before titanium oxide such as hydroxide. The precursor can be used in addition to hydrogen peroxide, and examples thereof include titanium oxide, titanium oxide hydrate, and the like. In the heat treatment step and/or the calcination after the solid titanium precursor is brought into contact with the ruthenium compound, since the titanium oxide precursor is converted into titanium oxide, the visible light responsive type of the present invention comprising the titanium oxide of the support compound is obtained. In the case of photocatalyst, the titanium oxide precursor may also be in the form of a dispersion (sol), oxybenzoic acid dibasin' (a basic oxygen and nitrogen doping solution, and the liquid is driven to oxidize) The titanium oxide of the raw material of -28-200940165 can also be a commercially available titanium oxide-based visible light-responsive photocatalyst. In this case, if the photocatalyst is brought into contact with the ruthenium compound according to the present invention, the visible light response can be improved. Photocatalyst activity. Therefore, at this time, the ruthenium compound acts as an activity enhancer for a visible light responsive photocatalyst. As described above, titanium oxide (including a solid precursor thereof) as a raw material is used to contain ruthenium, chromium, aluminum, tungsten, molybdenum, Among the magnesium, the dosing, and the boron, it is preferable to select at least one of the elements quot; if the titanium oxide contains the elemental cerium, in the mixing with the cerium compound, When heated, the contact between the cerium compound and the titanium oxide is appropriately changed, and as a result, a highly active visible light responsive photocatalyst is obtained. As described above, the enthalpy of the element is increased to increase the specific surface area of the titanium oxide, thereby providing a solid acid point and the like, and promoting the fine charge of the cerium compound. When a compound containing elemental ruthenium in titanium oxide, for example, a ruthenium compound, is used, the ruthenium itself is reduced in the skeleton of titanium oxide, and the electronic state of TiO 2 is easily maintained. The carrier formed by the interaction between the cerium oxides is difficult to recombine with the titanium oxide, and as a result, the carrier is highly active. The cerium compound or the like is a composite oxide of a visible light absorbing material or a cerium compound, and an oxide of a phase separation or the like. In the above-mentioned Non-Patent Document 5, it is described that tetraethyl phthalate which is a ruthenium compound is added to an ultraviolet ray-responsive photocatalyst comprising titanium oxide containing Bi. It is clearly stated in the literature that tetraethyl orthosilicate is used as a binder for immobilizing Ti02 photocatalyst that has been incorporated into Bi to a glass substrate. 29- 200940165 The mixture does not affect the contact of the visible light responsive titanium oxide with the cerium compound as in the present invention. The titanium oxide contains the aforementioned element cerium without limitation, but may be carried out according to any of the following three methods. In the synthesis stage of titanium, a compound containing elemental ruthenium is added and contained; 2) After synthesizing titanium oxide, the compound containing elemental ruthenium is supported by a precipitation method, a D-containing method, or the like (pretreatment of titanium oxide); When the ruthenium compound is mixed with titanium oxide, a compound containing element ruthenium is added to the system. In any of the methods, the visible light responsive photocatalyst of the present invention is obtained by supporting the ruthenium compound, and the highest activity is obtained by the method of 1. On the other hand, in the methods of 2 and 3, for example, a commercially available ultraviolet ray-responsive or visible light-responsive titanium oxide photocatalyst can be used as a raw material to produce a photocatalyst having higher activity. 〇 In the method of the above 1, a titanium oxide containing at least one of cerium, zirconium, aluminum, tungsten, molybdenum, magnesium, donor, and boron (abbreviated as Μ) is synthesized and exemplified. A compound such as a chloride or an alkoxide containing an elemental ruthenium is added to the hydrolyzable titanium compound such as titanium tetrachloride, titanium trichloride, titanium alkoxide or titanium sulfate. Examples of the ruthenium compound which can be used include an inorganic ruthenium compound such as ruthenium tetrachloride, ruthenium iodide, ruthenium nitride, ruthenium nitrate or ruthenium sulfide, and an alkoxylate such as tetraethoxy decane or methyltriethoxy decane. An organic ruthenium compound based on a decane, a ruthenium acetate or a polysiloxane resin, or a ruthenium dioxide or a ruthenium dioxide colloid. Examples of the aluminizing -30-200940165 compound include an inorganic aluminum compound such as aluminum, aluminum chloride, aluminum fluoride, hydrogen peroxide or aluminum sulfate, and an aluminum ethoxide or an aluminum compound. Examples of the zirconium compound include chromium oxide, chromium chloride, zirconium trichloride, zirconium nitrate, chromium nitrate oxide, inorganic chromium compounds, and organic chromium compounds such as zirconium isopropoxide or chromium zirconium acetoacetate. Among the tungsten compounds, tungsten or the like can be used (the molybdenum compound is also the same), and in the case of boron, φ boron, ethanol boron or the like can be used. The compounding ratio of the compound containing the element cerium is 0.0001 to 0.5, preferably in the range of 0·00 〗 〖0.30. Thereafter, hydrolysis is carried out by adding ammonia, amine, urea, thiourea or the like to collect the precipitate, and the resulting precipitate is obtained. When the solid matter is calcined to the right, visible titanium having an elemental cerium can be prepared. Further, when the salt formed by the hydrolysis is difficult to be calcined and evaporated, when the titanium is neutralized with sodium hydroxide, the by-produced NaC1 is sufficiently washed with water to remove the salt from the surface of the titanium chloride, and the most active visible light-responsive photocatalyst. Further, by carrying out, the titanium stays in the hydroxide state, and a solid can be obtained. In the method for producing a photocatalyst according to the present invention, it is preferable that at least one of the light-responsive titanium oxide as the raw material and the compound containing an element such as cerium, aluminum or zirconium in the above-mentioned three materials have at least crystallinity. The raw material is a photocatalyst which has a contact with a bismuth compound and a titanium oxide, and a photocatalyst which is agglomerated, such as chromic oxide colloid, zirconium sulfate or the like, chromium butoxide, chlorinated crane and the like. The sulfur is boric acid and chlorinated, and the M/Ti 〇 nitrogen compound is subjected to 200~700 〇C left responsive oxidation (for example, tetrachloro, etc.), and finally converted to titanium oxide precursor with high incomplete calcination after hydrolysis. In the case where the compound is crystalline, the compound becomes highly active. 31 - 200940165 The shape of the visible light responsive photocatalyst of the present invention may be, for example, a granular form, a fibrous form, a film form, or the like, and may be used separately depending on the use. It is better. In the case of granules, the particles are granules having a fine powder of about several nm to about several tens of micrometers, and the size and form thereof are not limited. In the case of a film, it is generally fixed to a substrate. When forming into any shape such as a film or a fiber, it is desirable to add a binder in addition to the photocatalyst particles. By adding the binder, the thickness and fiber diameter of the film @ can be increased, and the film and fiber strength, workability, etc. can be improved. The visible light responsive photocatalyst of the present invention produced by the above method can also be in a powder state as it is. use. However, it is convenient for the operating surface to adhere to the surface of the substrate and to be utilized in the form of an immobilized photocatalytic functional member. The form to be immobilized can be selected depending on the surface shape, use, and the like of the substrate, and examples thereof include a film shape, a granular shape, and a fiber shape. The type of the substrate is not limited to Q, and examples thereof include carbon steel, plated steel, chromate-treated steel, niobium, stainless steel, titanium, aluminum, and the like, ceramics, glass, ceramics, quartz, and the like, plastics, resins, and the like. Organic materials such as activated carbon. Further, they may be composite materials such as steel sheets. A preferred substrate is a metal or a surface thereof which is coated with a photocatalyst non-decomposable material. The entire substrate or the substrate whose surface is an organic material is deteriorated or decomposed according to the oxidizing power of the photocatalyst. Therefore, in this case, the surface of the substrate is preliminarily coated with a material which is not decomposed by a photocatalyst. Organic materials such as polyoxyxylene resins are also difficult to deteriorate due to photocatalyst, and therefore vary depending on conditions, but they are not covered -32-200940165. The shape of the substrate is not particularly limited, and may be any shape such as a thin plate, a thick plate, a fibrous shape (including a knitted fabric, a non-woven fabric), or a mesh-like tubular shape. An object of a complex shape that can be used as it is in the form of a product, and may also be an object that has been set or in use. The surface of the substrate may be porous and dense. The most common production of the photocatalytic functional member is to apply a dispersion in which the visible light responsive photocatalyst particles of the present invention are dispersed in a solvent, and to dry the coating film. Further, a dispersion for forming a visible light-responsive photocatalyst in which the visible light-responsive titanium oxide and the cerium compound are dispersed in a solvent is applied to the substrate, and the coating film can be dried. An additive such as a suitable binder may be added to the dispersion to form a coating liquid and then applied. Further, after the visible light-responsive type titanium oxide is applied to the substrate, the ruthenium compound is contacted by vapor phase treatment such as impregnation and CVD, and then heat-treated as needed. Thus, the photocatalyst of the present invention can be formed by bringing a ruthenium compound into contact with the titanium oxide in the production stage of a photocatalytic functional member using visible light responsive titanium oxide. For example, a method in which a secret compound is added to a dispersion medium for dispersing visible light responsive titanium oxide or a film of visible light responsive titanium oxide is formed to be in contact with a ruthenium compound. The coating liquid can also be prepared by simply mixing the visible light responsive photocatalyst of the present invention with a medium and a binder. However, the visible light responsive photocatalyst produced by the above method generally has an average primary particle diameter of from fine to several nm to one hundred nm. It is very easy to aggregate. If it becomes an aggregate, its diameter is as large as -33-200940165 tens of μm It is difficult to disperse evenly in the medium. Therefore, in an appropriate aspect of the present invention, the particles of the visible light responsive photocatalyst are sufficiently dispersed in the medium to prepare a dispersion of the photocatalyst particles. It is preferred to use the dispersion to contain a binder and to prepare a coating liquid. When this coating liquid is used, a more uniform photocatalytic film can be formed to improve film properties and photocatalytic activity. The average particle diameter (particle diameter of the aggregate) of the photocatalyst in the dispersion is preferably φ 500 nm or less. If it is larger than this particle size, the film characteristics are poor, for example, the peeling 'adhesion is deteriorated, and the storage stability of the dispersion itself is lowered. The average particle diameter of the photocatalyst is preferably 300 nm or less, and more preferably 200 nm» Dispersing the photocatalyst particles Examples of the liquid medium include water such as distilled water, ion-exchanged water, and ultrapure water; alcohols such as methanol 'ethanol and 2-propanol; ketones such as methyl ethyl ketone; and aromatics such as benzene, toluene, and xylene. Hydrocarbons and the like. It can be used arbitrarily in combination 'but in this case, a mutually compatible solvent combination is used. © Dispersion treatment is such that the photocatalyst is mixed with a medium in a range of several parts by mass to 50% by mass of the solid content. When the solid content concentration is outside this range, the dispersibility is lowered. Dispersants and debonders may also be added as needed. The dispersing agent may, for example, be a carbonyl group, a milled system or the like, and the debonding agent may, for example, be nitric acid, hydrochloric acid or sulfuric acid. Further, in order to adjust the pH, a base and an acid may be added. The dispersion treatment can also be carried out by using a coating shaker conventionally used for preparing a coating liquid, for example, by atomic grinding, shearing with a rotary blade, film swirling, or a more powerful dispersion means of ultrasonic waves. It is also possible to use a combination of two or more. -34- 200940165 When the obtained dispersion is agglomerated coarse particles, it is preferably removed by filtration or centrifugation. The coarse particles are the starting point for peeling and pulverization in the film. A solvent may be added to the dispersion after the dispersion treatment to adjust the concentration of the solid component. This dispersion may be used as a coating liquid as it is and applied to a substrate. When the photocatalyst is a fine particle having an average particle diameter of 50,000 nm or less, a film can be formed without a binder, and a film of Q only composed of photocatalyst particles is formed. However, as it is, the strength and adhesion of the film are low, so that the adhesive solution is applied thereon to impregnate the photocatalyst particles with the adhesive. Preferred coating solutions are used in photocatalysts and media, plus binders. The medium may be the same as described above for the dispersion to dissolve or emulsifie the binder. When a binder is mixed in the dispersion containing the visible light-responsive photocatalyst to prepare a coating liquid, it is possible to obtain a coating liquid which is excellent in dispersibility of the photocatalyst particles, has good storage stability, and can form a film having high photocatalytic activity. 〇 The amount of the binder is adjusted so that the content of the visible light responsive photocatalyst in the formed film is 5 to 95% by mass. The film having a photocatalytic content of less than 5% by mass showed almost no photocatalytic activity by visible light irradiation. If the photocatalyst content in the film is more than 95% by mass, the binder component is too small and the film is easily peeled off. The photocatalyst content in the film is preferably from 30 to 90% by mass, and more preferably 50% by mass or more, in terms of sufficiently obtaining photocatalytic activity. The binder component may be a metal oxide sol such as cerium oxide, aluminum oxide, titanium oxide, magnesium oxide or zirconium oxide (melting into a film), an organic decane compound, and a polyoxyxylene resin, a fluororesin or an amine group. Ethyl formate-35- 200940165 An organic resin such as a resin or an acrylic resin. When the decomposition of the binder component is caused by the oxidizing power of the photocatalyst, it is desirable to use a metal oxide sol, a polyfluorene resin, a polyacrylonitrile acrylate, or a urethane acrylate. In the case where the photocatalytic functional member is required to have high workability and high strength, an organic resin such as a fluororesin, an acrylic resin or a urethane resin is added in an appropriate amount to the hardly decomposable binder component. The required characteristics are ensured.最好 A preferred binder component is a cerium compound such as cerium oxide (for example, cerium), a hydrolyzate/condensate of an organic decane compound, or a polyoxyxylene resin. The cerium oxide may also be a cerium oxide sol (colloidal cerium oxide) produced by hydrolysis and condensation of a phthalic acid ester (e.g., ethyl decanoate). As the organodecane compound, an organic decane compound having a film-forming hydrolyzability, for example, an alkoxydecane and a decane coupling agent can be used. The binder component is an emulsion type which is uniformly dissolved and which can be emulsified in a medium. The coating liquid may also contain other components than the above. Such other components 〇 may be a non-visible light-responsive photocatalyst (for example, a conventional titanium oxide photocatalyst), and a photocatalyst is a carrier when the particles are supported. Further, it is also possible to apply a coating agent for a small amount of a component such as a coloring material (preferably an inorganic pigment) and an extender pigment to the coating film to match the properties of the coating liquid and the shape of the substrate, and various methods are known. select. After coating, the film is dried while heating as needed (further hardened as appropriate). The drying (hardening) temperature may be determined by the composition of the coating liquid (the type of the solvent and the binder), the heat resistance temperature of the substrate, and the like. When the coating liquid contains a titanium oxide photocatalyst precursor, it is heated from -36 to 200940165, and the precursor is changed to titanium oxide. The thickness of the film containing the photocatalyst formed on the substrate is preferably good. If the film is thinner than 0.1 μm, the photocatalyst is very low in photocatalytic activity when exposed to light. The thickness of the film is appropriately selected depending on the performance and cost of the catalyst. However, from the viewpoint of the activity of the catalyst, it is more preferably Ιμηη or more, and the upper limit of 5 μm is not particularly specified. It is 20 μm or less. The visible light-responsive photocatalyst of the present invention and the surface functional component thereof are not only ultraviolet rays but also contact with the substance to be treated under the irradiation wavelength of 400 nm, thereby exhibiting photocatalytic action-like harmful substances, and adhering substances and the like are decomposed and removed, and the photocatalyst is used as a decomposition target. The substance can be contacted and used in the environment of the line. The light source may have at least one wavelength region, and for example, solar rays, a xenon lamp, a backlight, a xenon lamp, a mercury lamp, or the like can be used. The light-touching wire of the present invention can also be made active, so that the light source contains visible light and violet, which makes the photocatalytic activity high. The visible light-responsive photocatalyst treatable object of the present invention can be exemplified by atmospheric pollutant gases such as VOC gas S〇x and Furon of formaldehyde, acetaldehyde, toluene, etc.; ammonia, hydrogen sulfide bromine gas; alcohols, BTX, phenols, etc. Organic compounds; organic halogen compounds such as vinyl chloride and Furon; various pesticides such as herbicidal insecticides; 0.1 μηΐ or more of proteins and amino acids, etc., which are too small, depending on the necessary stability and touch. good. When the thickness is saturated, it is the visible light above the photocatalyst, and the various types are harmless. It can illuminate the visible light part of the visible light fluorescent lamp, the halogen medium can be ultraviolet light, and the harmful substances or attached substances; trihalomethanes such as bismuth, thiol, etc., three doses, fungicides, various biology -37- 200940165 aerobic substances; surfactants; inorganic compounds such as cyanamide compounds, sulfur compounds; various heavy metal ions; microorganisms such as fungi, fungi, algae, etc.; , smoke, fingerprints, rain, mud, etc. Further, the visible light responsive photocatalyst of the present invention exhibits superhydrophilicity by irradiation with light. In the functional member having the photocatalyst of the present invention on the surface, antifogging property, antifouling property, dustproof property and the like are obtained by superhydrophilization.实施 [Embodiment] Hereinafter, the present invention will be exemplified in accordance with examples. However, the examples are not intended to limit the invention. The ratio of Bi/Ti and Si/Ti in the examples means the atomic ratio of metal (Example 1) [Preparation of titanium oxide] 〇 sample No. 1 : Hydrolysis of titanium tetrachloride by ammonia water (7 mass%) The titanium hydroxide was calcined at 500 ° C for 2 hours in the atmosphere to obtain titanium oxide. The amount of nitrogen in the titanium oxide was 0.004% by mass. The result of X-ray diffraction The main crystal structure of titanium oxide is anatase. Sample N 〇 . 2 : In addition to the addition of ruthenium tetrachloride (Si/Ti = 0·13) to titanium tetrachloride, titanium oxide containing ruthenium was obtained in the same manner as in sample No. 1. This oxidation -38 - 200940165 The amount of nitrogen in the titanium was 0.007% by mass. As a result of X-ray diffraction, titanium oxide is anatase. [Preparation of hydrazine compound] Sample N 〇. 3 : Barium chloride was dissolved in 3N-HC1, and ammonia water (7 mass%) was added to the obtained solution to hydrolyze cesium chloride. The white powder obtained by filtration was dried at φ 80 ° C to obtain a ruthenium compound for modulating a visible light responsive photocatalyst according to the present invention. This compound was identified as hydroxy ruthenium chloride as a result of X-ray diffraction. [Preparation of visible light-responsive photocatalyst] Sample No. 4: For powdered titanium oxide of sample No. 1, a powder of the sample N〇.3 was added as a Bi/Ti = 〇.〇9, and it was added to the mortar. After thorough mixing, 〇 'The mixture is placed in the atmosphere at 500 °. (: A visible light-responsive photocatalyst comprising nickel oxide supported by cerium oxide for 2 hours. When the X-ray diffraction pattern of the sample is taken, the main peak is a titanium oxide anatase crystal. N 〇. 5 : A visible light responsive photocatalyst composed of titanium oxide supported on a cerium oxide was prepared in the same manner as the sample Νο. 4 except for the yttrium-containing visible light responsive titanium oxide of the sample Νο. Xenon ray diffraction junction -39- 200940165 If the titanium oxide is composed of anatase crystals, the sample N 〇. 6 : aqueous solution of titanium tetrachloride in liquid form (9.3 wt%) π B i/Ti = 0.0 9 After the addition and mixing, the titanium oxide of the ruthenium compound was calcined with ammonia water (7 mass of Bi-containing titanium hydroxide in the atmosphere at 500 ° C. X-ray diffraction results, 0 ore crystal. Sample No. 7: In a liquid aqueous solution of titanium tetrachloride (9.3 wt%), ruthenium and ruthenium chloride are hydrolyzed with chlorine water (7 mass%) in the form of Bi/Ti = 0.09 and Si/Ti = 0.13 to form Bi-containing hydrogen. Calcined at 500 ° C for 2 hours to obtain the result of containing cerium oxide and X-ray diffraction, titanium oxide Anatase crystals. In addition, samples N0.6 and 7 are in the form of a raw material or a dissolved state of titanium oxide, which is a photocatalyst which is hydrolyzed by a coprecipitation method. [Measurement of FT-IR] About the loading of Bi In the state, the peak intensity of the stretching vibration of the samples 2, 3, 5, and 7 is estimated from the intensity of the stretching vibration peak of the OH group in the surface spectrum of the display surface. (Sample No. 3) and the surface of the cerium oxide are almost completely absent.戸The ruthenium chloride is hydrolyzed in %), and when it is raw, the titanium oxide containing oxidized chin is added to the liquid, and the titanium oxide is added to the atmosphere, and the titanium oxide is sintered in the atmosphere. FT-IR light of I. Fig. 1 shows that ruthenium oxychloride is on the OH group. In addition, on the surface of the titanium oxide, as shown in the sample No. 5, the yttrium oxide is supported on the surface of the titanium oxide. In general, the intensity of the stretching vibration peak of the OH group of the parent sample Νο. 2 is less. On the other hand, in the photocatalyst of the sample Νο·7 synthesized by the coprecipitation method using a liquid titanium oxide precursor and a ruthenium compound, ΟΗ The base is almost completely unchanged. It is therefore believed that the sample Νο·7 is oxidized. The material is not carried on the surface of the titanium oxide, but is mainly incorporated into the interior of the titanium oxide. Because the titanium oxide precursor forms titanium oxide in the liquid, the cerium compound is incorporated by molecular length Q. In the visible light-responsive photocatalyst, since titanium oxide is used as the raw material, the ruthenium compound mainly reacts on the surface of the titanium oxide, and thus becomes the above-described supporting structure. [Measurement of XPS] XPS analysis was carried out under the following conditions.

使用裝置：掃描型X射線光電子分光分析器 Alback，Fi 公司製 PHI Quantum 2000 〇 使用X射線源：mono-AlKa射線44.8W，17kV 取出角：45° X射線光束徑：約200 μιη φ 中和槍：1 ·〇ν，20mA (倂用Ar +低速離子槍） 能量分解能：以純Ag之Ag3d 5/2波峰（ 368.1eV) 以半値寬約0 · 7 5 e V之條件使用 真空度：約 2.0xl0_8torr 根據XPS分析所得試料Νο·3〜5之Bi-4f內殼準位的 光譜圖示於圖2。本光譜爲未進行濺鍍處理並且測定者， -41 - 200940165 反映氧化鈦最表面的表面狀態。 本發明之Νο·4及5之氧化鈦系光觸媒之Bi-4f內殼準 位的XPS光譜中，除了可歸屬於Bi3 +之（a) 165〜162.5eV 及159.7〜157.2^的波峰以外，具有成爲以0的（1>) 163〜161^及157.7〜155.7^。由此可知鉍爲一部分還原 ，即含有低次鉍的氧化物狀態（BiOx : x<1.5 )。 表1中，合併示出試料4、5、6、7之濺鍍前後以 ξ) XPS分析所得的定量分析値、和觸媒的化學分析値。Ar濺 鍍爲以加速電壓3KV、濺鍍速度3.8nm/分鐘（換算Si02 )之條件進行10分鐘，並由表層濺鍍約38nm。又，化學 分析爲暫時溶解觸媒，並將所得之溶液予以ICP發光分析 所測定之値。 〔表1〕 試料No. 構成 Bi/Ti XPS (最表面） XPS (灘鍍後） 化學分析 4 Bi-Ti02 0.594 0.528 0.092 5 Bi-Si-Ti02 0.311 0.157 0.082 6 Bi-Ti02 0.189 0.092 · 0.133 7 Bi-Si-Ti02 0.159 0.065 0.086 - ΒΪ4Τΐ3〇ΐ2 2.18 0.68 0.33) *試料Νο·4、5爲本發明，Νο·6、7爲比較例 XPS (濺鍍器）爲於約38nm (換算Si02) Ar +濺鍍後測定 裝入値爲製造時之原料階段者之Bi4Ti3012的Bi/Ti比（ 1 - 3 3 )爲由化學式所計算者 由表1，本發明之試料4及5中，關於氧化鈦中所含 -42- 200940165 的Bi ’以XPS測定所示之最表面的Bi/Ti値，比化學分析 値所計算之Bi/Ti値更高2.0倍以上。因此，可知本發明 之觸媒中，以氧化物型式存在的Bi爲於氧化鈦表面濃化 。作爲比較例之試料6、7中，最表面之B i/Ti値雖比化學 分析所算出的Bi/Ti値大，但低於本發明所規定之範圍（2 倍以上）’濃化並不充分。又，以光觸媒型式已知之鈦酸 鉍中’最表面的Bi濃度（Bi/Ti)接近化學式所計算的濃 φ 度，未察見濃度偏差。 〔光觸媒活性之測定（乙醛分解試驗）〕 令試料於蒸餾水中分散後，將此分散液塗佈至40mm 正方的玻璃板’其次以80 °C乾燥，作成光觸媒活性測定用 之試驗片。皮膜附著量爲4 0g/m2。將此試驗片放入石英製 反應小池（cell )中，接續至封閉循環流線（合計內體積 約3.7公升），於系內導入含有20 vol %氧之氮氣所稀釋的 0 乙醛（約 240ρριη-40μηιο1 )。一邊令氣體循環一邊由 250W高壓水銀燈，透過紫外線濾鏡（東芝製L42 )進行 可見光之照射。反應的追蹤爲將乙醛分解生成的二氧化碳 (C02 )濃度，以氣相層析經時性測定而進行。光觸媒活 性爲根據二氧化碳的生成速度予以評價。於以下之實施例 中，光觸媒活性亦以相同方法調查。結果整理示於表2。 -43- 200940165 〔表2〕 試料No. 成分 金屬含有比(at%) 光觸媒活性 鉍化合物 氧化鈦 Bi/Ti M/Ti co2發生速度 (μηιοί) 1 Art 挪 Ti02 0 0 1 2 irrr Μ Si/Ti02 0 0.12 1.1 4 BiOCl Ti02 0.09 0 8.9 5 BiOCl Si/Ti〇2 0.09 0.12 25 6 BiCls TiCl4 0.09 0.12 4 7 B1CI3 SiCU+TiCU 0.09 0.12 11.1 鈦氧化物的煅燒溫度全部爲5 0 0 °C ’混合品（Ν ο . 4、5 )的 〇 煅燒溫度爲500°c ( 2小時） *試料No.4、5爲本發明’ No_l、2、6、7爲比較例 *金屬含有比（at% )爲裝入値 如表2所闡明般，令可見光應答性氧化鈦接觸鉍化合 物（BiOCl)所含有之本發明的可見光應答型光觸媒（ Νο·4及5)，比具有單獨可見光應答性之氧化欽（分別 No.l、2 )，活性高’可知經由擔載鉍氧化物（BiOx : x<1.5)令活性增進。試料Νο·5爲比試料ν〇·4活性高， ❹ 經由S i的添加效果明顯。又，Ν 〇 · 4爲比使用氧化鈦前驅 物之四氯化鈦和氯化秘混合且根據共沈法所製作之比較品 試料Νο·6’活性高2倍以上。含有si的Νο·5，亦相對於 同樣含有Si且以共沈法所製作的Νο.7，顯示2倍以上之 高可見光活性。因此，根據本發明所增進的可見光觸媒活 性爲明顯。Equipment used: Scanning X-ray photoelectron spectrometer Alback, PHI Quantum 2000 manufactured by Fi Corporation 〇 X-ray source: mono-AlKa ray 44.8W, 17kV take-out angle: 45° X-ray beam diameter: about 200 μιη φ Neutralizing gun :1 ·〇ν,20mA (倂Ar + low speed ion gun) Energy decomposing energy: Ag3d 5/2 peak of pure Ag (368.1eV) Use vacuum with a half width of about 0 · 7 5 e V: about 2.0xl0_8torr The spectral diagram of the Bi-4f inner shell level of the sample Νο·3~5 obtained by XPS analysis is shown in Fig. 2. This spectrum is not subjected to sputtering treatment and is measured, -41 - 200940165 reflects the surface state of the outermost surface of titanium oxide. The XPS spectrum of the Bi-4f inner shell level of the titanium oxide photocatalyst of the Νο. 4 and 5 of the present invention has, in addition to the peaks of (a) 165 to 162.5 eV and 159.7 to 157.2^ which are attributed to Bi3 + , Become 0 (1 >) 163~161^ and 157.7~155.7^. From this, it is understood that ruthenium is a partial reduction, that is, an oxide state containing low hypofluorene (BiOx: x < 1.5). In Table 1, the quantitative analysis of the enthalpy of XPS analysis before and after the sputtering of the samples 4, 5, 6, and 7 and the chemical analysis of the catalyst were shown. Ar sputtering was carried out for 10 minutes under the conditions of an acceleration voltage of 3 kV and a sputtering rate of 3.8 nm/min (converted to SiO 2 ), and was sputtered by a surface layer by about 38 nm. Further, chemical analysis was carried out by temporarily dissolving the catalyst, and the obtained solution was subjected to ICP emission analysis. [Table 1] Sample No. Composition Bi/Ti XPS (most surface) XPS (after beach plating) Chemical analysis 4 Bi-Ti02 0.594 0.528 0.092 5 Bi-Si-Ti02 0.311 0.157 0.082 6 Bi-Ti02 0.189 0.092 · 0.133 7 Bi -Si-Ti02 0.159 0.065 0.086 - ΒΪ4Τΐ3〇ΐ2 2.18 0.68 0.33) *The sample Νο·4,5 is the invention, Νο·6,7 is the comparative example XPS (sputter) is about 38nm (converted SiO 2 ) Ar + The Bi/Ti ratio (1 - 3 3 ) of Bi4Ti3012 which was measured after the sputtering was measured in the raw material stage at the time of manufacture was calculated by the chemical formula from Table 1, and in the samples 4 and 5 of the present invention, regarding the titanium oxide. The Bi' of the outer surface of Bi' containing -42- 200940165 is more than 2.0 times higher than the Bi/Ti値 calculated by the chemical analysis. Therefore, it is understood that Bi in the oxide type of the catalyst of the present invention is concentrated on the surface of titanium oxide. In the samples 6 and 7 of the comparative example, the B i / Ti 最 on the outermost surface was larger than the Bi / Ti 算出 calculated by the chemical analysis, but was lower than the range specified in the present invention (2 times or more). full. Further, the Bi concentration of Bi on the outermost surface of the barium titanate known as the photocatalyst type was close to the concentration φ calculated by the chemical formula, and no concentration deviation was observed. [Measurement of photocatalyst activity (acetaldehyde decomposition test)] After dispersing the sample in distilled water, the dispersion was applied to a 40 mm square glass plate, and then dried at 80 ° C to prepare a test piece for photocatalytic activity measurement. The film adhesion amount was 40 g/m2. The test piece was placed in a quartz reaction cell (cell), and then connected to a closed circulation flow line (total volume of about 3.7 liters), and 0 acetaldehyde (about 240 ριηη) diluted with nitrogen gas containing 20 vol% of oxygen was introduced into the system. -40μηιο1 ). The gas is circulated by a 250W high-pressure mercury lamp, and is irradiated with visible light through an ultraviolet filter (L42 manufactured by Toshiba). The reaction was traced to the concentration of carbon dioxide (C02) generated by decomposition of acetaldehyde, and the measurement was carried out by gas chromatography over time. The photocatalytic activity is evaluated based on the rate of generation of carbon dioxide. In the following examples, photocatalytic activity was also investigated in the same manner. The results are shown in Table 2. -43- 200940165 [Table 2] Sample No. Component Metal Content Ratio (at%) Photocatalyst Activity 铋 Compound Titanium Bi/Ti M/Ti co2 Generation Rate (μηιοί) 1 Art Move Ti02 0 0 1 2 irrr Μ Si/Ti02 0 0.12 1.1 4 BiOCl Ti02 0.09 0 8.9 5 BiOCl Si/Ti〇2 0.09 0.12 25 6 BiCls TiCl4 0.09 0.12 4 7 B1CI3 SiCU+TiCU 0.09 0.12 11.1 The calcination temperature of titanium oxide is all 500 °C 'mixture ( ο ο . 4, 5) 〇 calcination temperature is 500 ° c (2 hours) * Sample No. 4, 5 is the invention 'No_l, 2, 6, 7 is a comparative example * metal content ratio (at%) is loaded As shown in Table 2, the visible light responsive photocatalyst (Νο·4 and 5) of the present invention contained in the visible light responsive titanium oxide contact bismuth compound (BiOCl) is more oxidized than the individual having visible light responsiveness (respectively No. 1 and 2), the activity was high, and it was found that the activity was enhanced by supporting the cerium oxide (BiOx: x < 1.5). The sample Νο·5 was higher in activity than the sample ν〇·4, and the effect of adding S via S i was remarkable. Further, Ν 〇 · 4 is twice as high as the activity of the comparative product Νο·6' which is mixed with titanium tetrachloride and chlorinated using a titanium oxide precursor and produced by the coprecipitation method. The Νο·5 containing si also exhibits a high visible light activity of 2 times or more with respect to Νο. 7 which is also contained in Si and produced by the co-precipitation method. Therefore, the visible light catalyst activity enhanced according to the present invention is remarkable.

No.6' Νο.7之試料爲於XPS光譜中，具有全部上述 (a ) ~ ( c )中2組以上的對波峰’察見低次鉍的存在。 但，如表1所示般，以氧化物型式存在表面的Bi濃度（ • 44 · 200940165The sample of No. 6' Νο. 7 has the presence of low-order enthalpy in all of the above-mentioned (a) to (c) pair of peaks in the XPS spectrum. However, as shown in Table 1, the Bi concentration of the surface exists in the oxide type ( • 44 · 200940165)

Bi/Ti)，比全體中之Bi濃度和化學分析所算出之Bi/Ti 稍大，相比於分別對應之本發明觸媒（N 〇. 4和5 )則無大 差別，未察見B i的表面濃化。又，如f T -1R所闡明般， Bi氧化物未被擔載於氧化鈦表面，故無法取得充分的活性 (實施例2) 0 試料No.8〜12: 於四氯化鈦中加入四氯化矽 '氯化銷、氯化鎢或氫氧 化鋁後（M/Ti = 0.03 )，以氨水（7質量％)水解，將所得 之固形物（含Μ化合物之氫氧化鈦），其次於大氣中以 45(TC熘燒2小時，取得含有上述添加元素的氧化鈦。對 於此氧化鈦將實施例1之試料No.3所製作的羥基氯化鉍 粉末以Bi/Ti = 0· 09般加入，於乳鉢中充分混練後，大氣下 以45 0°C煅燒2小時，取得鉍氧化物被擔載之氧化鈦所構 〇 成之本發明的可見光應答型光觸媒。X射線繞射圖型的結 果，氧化鈦爲銳鈦礦型。其活性以實施例1記載之方法測 定之結果整理示於表3。 -45 - 200940165 〔表3〕 試料No. 添加金屬元素 使用金屬化合物 C〇2發生速度(μιηοΐ/h) 8 Si SiCl4 18.1 9 Zr ZrCl4 10.6 10 W WC16 5.6 11 A1 Al(OH)3 12.1 12 Ατττ Μ - 4.8 令添加金屬元素之Ti〇2 (煅燒45 0°C )接觸混合BiOCl ( 實施例1，試料No.3)後’以450°C熱處理 由表3可知，使用於可見光應答性氧化鈦，添加矽、 锆、鎢、鋁等之金屬元素的氧化鈦’經由擔載鉍氧化物令 本發明之可見光應答型光觸媒活性’比未添加之情形（試 料No.12)更大。其中亦以矽的增進效果最大。另外，於 此表所記載之元素以外，將硼、鎂、鈴、鉬等加入可見光 應答性氧化鈦中，亦察見同樣的增進效果。 試料 No. 1 3~2 3 : 於實施例1之試料No.4 (含Si之氧化鈦）中，除了 改變混練後的煅燒溫度以外，以同樣方法調製本發明之可 見光應答性光觸媒。表4中，示出以實施例1記載之方法 所求出的醛分解活性。 -46- 200940165 〔表4〕 試料No· ----- 煅燒溫度fc ) C〇2發生速度 (umol/h) -_ 13 25 1.1 14 80 1.4 —_ 15 200 1.4 __16 300 10.9 __ 17 400 26.9 __ 18 450 19.74 __ 19 500 25 20 550 11.3 --21 600 8.5 22 700 2.6 —_ 800 1.8 試料爲 Si/TiO2(Si/Ti = 0.12、500°C 煅燒 )與BiOCl混合’並以指定溫度於大氣中 熱處理2小時。Bi/Ti = 0.09 擔載鉍氧化物之活性增進作用，比未添加鉍化合物之 可見光應答性氧化鈦（實施例1之試料Νο·2)的活性（ φ 1_1 μπιοΐ/h) ’於煅燒溫度爲25°c下無效果，但經由熱處 理之活性增進效果爲由80 °C開始明確出現。更且於300 °C 至700°C之範圍中顯示出顯著的增進效果，於800°C下亦 可持續效果。 此等觸媒之SEM圖示於圖3，FT-IR光譜中3400cm·1 之波峰（來自OH基伸縮）的強度示於圖4。 由圖3之SEM圖可知，鉍氧化物爲被氧化鈦所擔載 ，更具體而言，被覆氧化鈦之至少一部分表面。若更詳細 說明SEM圖，於混練後僅乾燥之80 °C階段中，若相比於 -47- 200940165 含有母體粒子之氧化鈦（Si-Ti02)，則僅母體粒子本身附 著鉍化合物。若爲3 00 °C，則於母體粒子表面，鉍氧化物 爲以微粒子狀擔載。若煅燒溫度爲500°C，則鉍化合物的 微粒子幾乎完全消失，於600 t下則粒子表面變得平滑， 鉍化合物爲被覆母體粒子之大部分表面。 另一方面，於圖4所示1FT-IR光譜結果中，含母體 Si之氧化鈦及混練後僅乾燥之80°C的狀態下，於3400CHT1 f) 附近察見相當於來自氧化鈦之OH基伸縮的寬波峰。若提 高煅燒溫度，則此OH的波峰慢慢變弱。此等舉動顯示隨 著煅燒溫度上升，鉍化合物爲以鉍氧化物型式被覆母體之 氧化鈦（Si/Ti02 )表面》 此結果亦與前述之SEM的粒子觀察結果一致。由此 等測定結果，判定本發明之可見光應答型光觸媒中，鉍化 合物爲被氧化鈦擔載，更且於被覆氧化鈦表面的至少一部 分下，變成更高活性。 〇 (實施例4 ) 試料No.24〜32 : 除了令氫氧化鈦的煅燒溫度於1 〇 〇〜6 0 0 °C之範圍變化 以外，以實施例1之試料No .2同樣之方法，製作含有矽 之氧化鈦。所製作之氧化鈦，以實施例1之試料No.4同 樣之方法進行與鉍化合物的混練及煅燒（大氣中以5〇(rc 2 小時）’調製氧化鈦擔載鉍氧化物之本發明的可見光應答 性光觸媒。表5中’整理出以前述方法所求出之乙醛的分 -48- 200940165 解活性。 C表5〕 試料No. 鈦氧化物之 煅燒溫度(。。） C〇2發生速度 (μιηοΐ/h) _ 24 100 3.9 25 200 6.3 26 300 7.7 27 350 12.1 — 28 400 16.3 — 29 450 16.3 — 30 500 26.9 _ 31 550 21.4 __ 32 600 18.5 試料爲於BiOCl中混合以指定溫度煅燒的 可見光應答性Si/Ti並以400°C熘燒。 原料之含矽氧化鈦爲經由其製作時的煅燒溫度而令光 觸媒活性變化，且於60(TC附近則煅燒溫度愈高，光觸媒 活性愈高。反映此情事，經由與鉍化合物混合和熱處理擔 載鉍化合物之本發明光觸媒的可見光觸媒活性，亦取得同 樣之結果。 (實施例5 ) 試料No.33〜38 : 相對於實施例1之試料N 〇 · 2之含砂氧化欽，分別添 加作爲鉍化合物的硝酸鉍 '羥基硝酸鉍、羥基氫氧化鉍、 氯化鉍、氧化秘（Bi2〇3 )或羥基醋酸鉍（Bi/Ti = -49- 200940165 0.09~0.11)，充分混練後，於大氣中以450°C或5 00 °C煅 燒2小時，取得由擔載鉍氧化物之氧化鈦所構成之本發明 的可見光應答型光觸媒。X射線繞射圖型之主要波峰爲歸 屬於銳鈦礦型氧化鈦。其可見光活性以前述同樣之方法求 出之結果整理於表6。 〔表6〕 試料No. 鉍化合物 Bi/Ti 煅燒溫度(°c ) co2發生速S (μιηοΐ/h) 33 硝隱[Bi(N03)3] 0.09 450 9.5 34 羥基硝隱[BiO(N03)] 0.09 450 8.7 35 羥基氫氧化鉍[BiO(OH)] 0.09 450 10.9 36 氯化鉍(BiCl3) 0.11 500 12.0 37 氧化鉍(Bi203) 0.09 500 1.3 38 羥基醋酸鉍[BiO(CH3COO)] 0.09 500 10.8 於Si/Ti02接觸，混合上述鉍化合物並以450-500°C熘燒 可知於本發明之可見光應答型光觸媒之製造中，雖然 鉍化合物爲有活性優劣，但若爲含有鉍之化合物則均可利 用。但，若鉍化合物爲安定的氧化物，則活性增進效果小 ，若鉍化合物爲羥基鉍類BiOX ( 鹵素離子、硝酸離子 、氫氧化離子、有機離子）、鹵化鉍或硝酸鉍則效果高。 此外，確認硫酸鉍和硫化鉍亦顯示出高效果。 另一方面，混合之鉍化合物爲氧化欽之試料No.37, 若相比於氧化鈦原料之試料No.2，則可見光觸媒活性稍微 提高，但其提高爲極些微。 -50- 200940165 (實施例6 ) 試料No.39 : 對於市場可取得之粉末狀可見光應答性氧化鈦，將實 施例1之試料No.3所製作之鉍化合物（羥基氯化鉍）以 活性增進劑型式加入（Bi/Ti = 0.09 )後，此乳鉢充分混練 後，於大氣中以500°C煅燒2小時，製作本發明之可見光 應答型光觸媒。X射線繞射圖型之主要波峰爲歸屬於銳鈦 〇 礦型氧化鈦。調查此光觸媒之活性時，相對於原料氧化鈦 之活性（2·6μπι〇1/Ηι·)，與鉍化合物接觸混合，煅燒後之 活性爲增進至5 ·9μηιο1/Hr之2倍以上的活性，可知鉍化合 物爲對於已製造之可見光應答性氧化鈦光觸媒有效作爲活 性增進劑。 試料No.40 : 將試料No.39所用之市售的可見光應答性氧化鈦加入 Ο 〇·1Ν硝酸，充分分散後，將鄰矽酸乙酯以Si/Ti = 0.12般加 入’並攪拌3小時以上。將過濾後所得之粉末乾燥，於大 氣中以500 °C熘燒2小時，取得含有矽之可見光應答性氧 化鈦。對此氧化鈦，以試料No.39同樣之方法將鉍化合物 以活性增進劑型式加入’於大氣中以5 0 0。(：煅燒2小時， 製作本發明之可見光應答型光觸媒。X射線繞射圖型之主 要波峰爲歸屬於銳鈦礦型氧化鈦。 此光觸媒的可見光活性爲8.6μηιο1/Ηι·，相比於試料 Ν〇·39，經由矽之含量令活性更加增進。即，得知將鉍化 -51 - 200940165 合物使用於活性增進劑，且事先施以矽等金屬元素的含有 處理，則可取得更高的增進作用。 試料No.41 : 令實施例1之試料No .2之含Si氧化鈦，使用有機系 分散劑於脫離小水中分散，製作pH 7，固形成分20質量 %的分散液。於此分散液中，加入羥基氯化鉍的水中分散 @ 液（pH7) (Bi/Ti = 〇.〇9)，充分攪拌，製作本發明之可 見光應答型光觸媒形成用分散液。將此分散液於玻璃板塗 佈後（皮膜附著量約40g/m2)，於大氣中以4〇〇°C锻燒2 小時，取得具有本發明之可見光應答型光觸媒層的光觸媒 機能構件。X射線繞射圖型的主要波峰爲歸屬於氧化鈦。 將此光觸媒機能構件以實施例1記載之方法供於乙醛 分解試驗。將使用作爲原料之試料Νο·2的含矽氧化鈦溶 膠同樣塗佈至玻璃構件，並且予以熱處理所製作之光觸媒 〇 機能構件的活性爲2μηι〇1/Η，相對地，本發明之光觸媒機 能構件的活性爲12μιη〇1/Η，於塗佈與鉍化合物接觸所得 之本發明之可見光應答型光觸媒的構件中，確認可見光觸 媒活性爲提高（達成活性增進效果）。 試料Ν 〇. 4 2 : 由試料Νο.39所使用之市售可見光應答性氧化鈦，使 用試料No.41所使用之相同有機系分散劑及脫離子水所調 製的分散液（pH 7、固形成分1〇質量％)中’加入作爲光 -52- 200940165 觸媒活性增進劑的羥基氯化鉍的水中分散液（pH 7 )( Bi/Ti = 0.10)，充分攪拌，製作本發明之可見光應答型光 觸媒形成用分散液。將此分散液直接塗佈至玻璃板（約 40g/m2 )，於大氣中以80°C煅燒2小時，製作具有本發明 之可見光應答型光觸媒層的光觸媒機能構件。 試料No.43 : Q 由試料No.39所使用之市售可見光應答性氧化鈦，使 用試料No.36所使用之相同有機系分散劑及脫離子水所調 製的分散液（pH 7、固形成分10質量％)中，加入矽膠（ Sunotech Ο ) ( Si/Ti = 0.12 )，充分攪拌後，再加入作爲 光觸媒活性增進劑的羥基硝酸鉍的分散液（pH 7 )( Bi/Ti = 0.10)，充分攪拌，製作本發明之可見光應答型光 觸媒形成用分散液。將此分散液直接塗佈至玻璃板（約 40g/m2 )，於大氣中以80°C煅燒2小時，製作具有本發明 〇 之可見光應答型光觸媒層的光觸媒機能構件。X射線繞射 圖型之主要波峰爲歸屬於銳鈦礦型氧化鈦。 將試料No. 42及No. 43所製作之光觸媒機能構件以實 施例1記載之方法供於乙醛分解試驗。其結果，相對於塗 佈原料之可見光應答性氧化鈦溶膠的試料活性（ 1·6μηιο1/ΗΓ)，試料 Ν 〇 · 4 2 爲 2 · 3 μιη ο 1/H r，試料 Ν 〇 · 4 3 爲 4.0μπιο1/ΗΓ之活性。由此可知，本發明之含有鉍化合物的 活性增進劑對於氧化鈦光觸媒的溶膠亦爲有效，更且經由 添加矽（本例爲Si02)，此增進作用變得更高。 -53- 200940165 (實施例7 ) (XAFS測定） 關於含有上述試料Νο·4、No.5的各種光觸媒，以 XAFS法求出鉍原子周圍之動徑分佈波峰比R (第2波峰/ 第1波峰）。測定爲以SPring 8-BL19-B2進行。測定結果 示於表7，以前述方法所求出之光觸媒活性（C02發生速 0 度）亦示出。 表7中，R値不同之試料，於上述試料n〇.4及5及 鈦酸鉍（Bi3Ti4012)及Bi203、及鉍量爲Bi/Ti = 0.30以外 ’以試料No·4同樣之方法所製作的試料No.44，亦示出R 値及光觸媒活性的測定結果。 〔表7〕 試料No. 觸媒 成分 R値 〇)2發生速度 (μιηοΐ/h) 鉍化合物 氧化鈦 - Bi2O3(0： X市售品） . 0.50 4 Bi-Ti02 BiOCl Ti〇2 0.15 8.9 5 Bi-Si-Ti02 BiOCl Si/Ti02 0.03 25.0 44 Bi-Si-Ti02 BiOCl Si/ Ti02 0.20 1.8 - Bi3Ti4012(市售品）1 - 0.48 0.8 如表7之結果所闡明般，若動徑分佈之波峰比R爲 〇.4以下’則示出高可見光觸媒活性。更且可知若波峰比Bi/Ti) is slightly larger than the Bi concentration in the whole and Bi/Ti calculated by chemical analysis, and there is no big difference compared with the corresponding catalysts of the present invention (N 〇. 4 and 5), and no B is observed. The surface of i is concentrated. Further, as described in f T -1R, the Bi oxide was not supported on the surface of the titanium oxide, so that sufficient activity could not be obtained (Example 2). 0 Sample No. 8 to 12: Four was added to titanium tetrachloride. After cesium chloride 'chlorinated pin, tungsten chloride or aluminum hydroxide (M/Ti = 0.03), it is hydrolyzed with ammonia water (7 mass%), and the obtained solid matter (titanium hydroxide containing cerium compound) is secondarily In the air, the titanium oxide containing the above-mentioned additive element was obtained by baking at 45 °C for 2 hours. For this titanium oxide, the bismuth hydroxychloride powder prepared in the sample No. 3 of Example 1 was obtained by Bi/Ti = 0·09. After being sufficiently kneaded in a mortar, it is calcined at 45 ° C for 2 hours in the atmosphere to obtain a visible light-responsive photocatalyst of the present invention in which the cerium oxide is supported by the supported titanium oxide. The X-ray diffraction pattern is obtained. As a result, titanium oxide was anatase type, and the activity thereof was measured by the method described in Example 1. The results are shown in Table 3. -45 - 200940165 [Table 3] Sample No. Adding a metal element using a metal compound C〇2 occurs at a rate (μιηοΐ/h) 8 Si SiCl4 18.1 9 Zr ZrCl4 10.6 10 W WC16 5.6 11 A1 Al(OH)3 12.1 12 Ατττ Μ - 4.8 Adding a metal element Ti〇2 (calcined at 45 ° C) to the mixed BiOCl (Example 1, sample No. 3) and then 'heat treatment at 450 ° C. It can be seen from Table 3 that it is used for visible light responsiveness. In the case of the titanium oxide, the titanium oxide of the metal element such as cerium, zirconium, tungsten or aluminum is added, and the visible light-responsive photocatalyst activity of the present invention is made larger than the case where it is not added (sample No. 12). In addition to the elements described in this table, boron, magnesium, bell, molybdenum, etc. are added to the visible light-responsive titanium oxide, and the same improvement effect is also observed. Sample No. 1 3~ 2 3 : The visible light responsive photocatalyst of the present invention was prepared in the same manner as in the sample No. 4 (titanium containing Si) of Example 1 except that the firing temperature after kneading was changed. The aldehyde decomposition activity determined by the method described in Example 1. -46- 200940165 [Table 4] Sample No. ----- Calcination temperature fc) C〇2 occurrence rate (umol/h) -_ 13 25 1.1 14 80 1.4 —_ 15 200 1.4 __16 300 10.9 __ 17 400 26.9 __ 18 450 19.74 __ 19 500 25 20 550 11.3 --21 600 8.5 22 700 2.6 —_ 800 1.8 The sample is Si/TiO2 (Si/Ti = 0.12, 500 °C calcined) mixed with BiOCl' and heat treated at atmospheric temperature for 2 hours at the specified temperature. . The activity of Bi/Ti = 0.09 supported on cerium oxide is higher than that of visible light responsive titanium oxide (sample Νο. 2 of Example 1) without addition of cerium compound at calcination temperature. There was no effect at 25 ° C, but the activity enhancement effect by heat treatment was clearly started from 80 ° C. It also shows a remarkable improvement in the range of 300 °C to 700 °C, and it also has a sustainable effect at 800 °C. The SEM image of these catalysts is shown in Fig. 3, and the intensity of the peak of 3400 cm·1 (from the OH group stretching) in the FT-IR spectrum is shown in Fig. 4 . As can be seen from the SEM image of Fig. 3, the cerium oxide is supported by titanium oxide, more specifically, at least a part of the surface of the titanium oxide. If the SEM image is described in more detail, in the 80 °C stage which is only dried after kneading, if the parent particle contains titanium oxide (Si-Ti02) as compared with -47-200940165, only the parent particle itself is attached with a ruthenium compound. When it is 300 ° C, the cerium oxide is supported on the surface of the mother particles in the form of fine particles. When the calcination temperature is 500 ° C, the fine particles of the ruthenium compound almost completely disappear, and at 600 t, the surface of the particles becomes smooth, and the ruthenium compound coats most of the surface of the matrix particles. On the other hand, in the 1FT-IR spectrum results shown in Fig. 4, the titanium oxide containing the parent Si and the state of 80 ° C which was dried only after kneading were observed to correspond to the OH group derived from titanium oxide in the vicinity of 3400 CHT1 f). Wide and narrow peaks. If the calcination temperature is raised, the peak of this OH gradually becomes weak. These actions show that the ruthenium compound is a titanium oxide (Si/TiO 2 ) surface coated with a ruthenium oxide type as the calcination temperature rises. This result is also consistent with the SEM particle observation results described above. As a result of the measurement, it was found that in the visible light-responsive photocatalyst of the present invention, the ruthenium compound was supported by titanium oxide and further activated at at least a part of the surface of the coated titanium oxide. 〇 (Example 4) Sample No. 24 to 32: The same procedure as in Sample No. 2 of Example 1 was carried out except that the baking temperature of the titanium hydroxide was changed in the range of 1 〇〇 to 600 ° C. Contains titanium oxide. The produced titanium oxide was kneaded and calcined with a ruthenium compound in the same manner as in sample No. 4 of Example 1, and the present invention was prepared by arranging titanium oxide-supported ruthenium oxide at 5 Torr (rc 2 hours) in the atmosphere. Visible light responsive photocatalyst. In Table 5, 'the acetaldehyde fraction obtained by the above method was decomposed to -48-200940165. C. Table 5] Sample No. Titanium oxide calcination temperature (.) C〇2 occurred Speed (μιηοΐ/h) _ 24 100 3.9 25 200 6.3 26 300 7.7 27 350 12.1 — 28 400 16.3 — 29 450 16.3 — 30 500 26.9 _ 31 550 21.4 __ 32 600 18.5 The sample is mixed in BiOCl and calcined at the specified temperature. The visible light responsive Si/Ti is calcined at 400 ° C. The cerium-containing titanium oxide of the raw material changes the photocatalytic activity through the calcination temperature at the time of production, and the higher the calcination temperature is, the higher the photocatalytic activity is at 60 (about TC). In response to this, the same results were obtained by mixing and heat-treating the visible light catalyst activity of the photocatalyst of the present invention with a ruthenium compound. (Example 5) Sample No. 33 to 38: Samples relative to Example 1 N含···································································································· 200940165 0.09~0.11), after thorough kneading, calcination at 450 ° C or 500 ° C for 2 hours in the atmosphere to obtain a visible light-responsive photocatalyst of the present invention comprising titanium oxide supported on cerium oxide. The main peak of the pattern type is attributed to anatase type titanium oxide. The visible light activity is determined by the same method as described above and is summarized in Table 6. [Table 6] Sample No. 铋 Compound Bi/Ti Calcination temperature (°c ) co2 occurs at a rate of S (μιηοΐ/h) 33 Nitrate [Bi(N03)3] 0.09 450 9.5 34 Hydroxyl nitrate [BiO(N03)] 0.09 450 8.7 35 Hydroxyl hydroxide [BiO(OH)] 0.09 450 10.9 36 bismuth chloride (BiCl3) 0.11 500 12.0 37 bismuth oxide (Bi203) 0.09 500 1.3 38 bismuth hydroxyacetate [BiO(CH3COO)] 0.09 500 10.8 In contact with Si/Ti02, the above ruthenium compound is mixed and tempered at 450-500 °C. It is known that the ruthenium compound is active in the production of the visible light responsive photocatalyst of the present invention. However, if it is a compound containing bismuth can be utilized. However, if the ruthenium compound is a stable oxide, the activity enhancement effect is small, and if the ruthenium compound is hydroxy quinone BiOX (halogen ion, nitrate ion, hydroxide ion, organic ion), cesium halide or lanthanum nitrate, the effect is high. Further, it was confirmed that barium sulfate and barium sulfide also showed high effects. On the other hand, the mixed ruthenium compound was oxidized sample No. 37, and the visible light catalyst activity was slightly improved compared to the sample No. 2 of the titanium oxide raw material, but the increase was extremely small. -50-200940165 (Example 6) Sample No. 39: For the powdery visible light responsive titanium oxide which is commercially available, the ruthenium compound (barium hydroxychloride) produced in sample No. 3 of Example 1 was improved in activity. After the dosage form was added (Bi/Ti = 0.09), the chyle was thoroughly kneaded and then calcined at 500 ° C for 2 hours in the atmosphere to prepare a visible light responsive photocatalyst of the present invention. The main peak of the X-ray diffraction pattern is attributed to anatase 矿 ore type titanium oxide. When investigating the activity of the photocatalyst, it is mixed with the ruthenium compound in contact with the activity of the raw material titanium oxide (2·6μπι〇1/Ηι·), and the activity after calcination is increased to 2 times or more of the activity of 5·9μηιο1/Hr. It is known that the ruthenium compound is effective as an activity enhancer for the visible visible light responsive titanium oxide photocatalyst. Sample No. 40: Commercially available visible light responsive titanium oxide used in sample No. 39 was added to Ο 〇 1 Ν nitric acid, and after sufficiently dispersed, ethyl ortho citrate was added as Si/Ti = 0.12 and stirred for 3 hours. the above. The powder obtained after the filtration was dried, and calcined at 500 °C for 2 hours in the atmosphere to obtain a visible light responsive titanium oxide containing ruthenium. With respect to this titanium oxide, the ruthenium compound was added in the same manner as in the sample No. 39 to the atmosphere at 50,000. (: calcination for 2 hours, the visible light-responsive photocatalyst of the present invention is produced. The main peak of the X-ray diffraction pattern is attributed to anatase type titanium oxide. The visible light activity of the photocatalyst is 8.6 μηιο1/Ηι·, compared to the sample Ν〇·39, the activity is further enhanced by the content of ruthenium. That is, it is known that the use of the bismuth-51 - 200940165 compound in the activity promoter and the prior treatment of the metal element such as ruthenium can be achieved. In the sample No. 41, the Si-containing titanium oxide of the sample No. 2 of Example 1 was dispersed in the detached water using an organic dispersing agent to prepare a dispersion liquid having a pH of 7 and a solid content of 20% by mass. In the dispersion, a liquid (pH 7) (Bi/Ti = 〇.〇9) was dispersed in water containing cesium hydroxychloride, and the mixture was stirred sufficiently to prepare a dispersion for forming a visible light-responsive photocatalyst of the present invention. After the sheet was applied (the film adhesion amount was about 40 g/m 2 ), it was calcined in the air at 4 ° C for 2 hours to obtain a photocatalytic functional member having the visible light responsive photocatalyst layer of the present invention. The X-ray diffraction pattern was obtained. Main peaks are attributable Titanium oxide. The photocatalytic functional member was subjected to an acetaldehyde decomposition test by the method described in Example 1. The ruthenium-containing titanium oxide sol using the sample Νο. 2 as a raw material was similarly applied to a glass member and heat-treated. The photocatalytic functional component has an activity of 2 μηι〇1/Η. In contrast, the photocatalytic functional component of the present invention has an activity of 12 μm 〇 1 /Η, which is coated in the visible light responsive photocatalyst member of the present invention obtained by contacting the ruthenium compound. It is confirmed that the activity of the visible light-sensitive catalyst is improved (the activity-enhancing effect is achieved). Sample Ν 4. 4 2 : Commercially available visible light-responsive titanium oxide used for the sample Νο.39, using the same organic dispersant used in sample No. 41 In the dispersion prepared by deionized water (pH 7, solid content: 1% by mass), 'aqueous dispersion (pH 7 ) added as a photo-52-200940165 catalyst activity enhancer (Bi/) Ti = 0.10), and sufficiently stirred to prepare a dispersion for forming a visible light-responsive photocatalyst of the present invention. This dispersion was directly applied to a glass plate (about 40 g/m 2 ) at atmospheric pressure. The photocatalytic functional member having the visible light responsive photocatalyst layer of the present invention was produced by calcination at 80 ° C for 2 hours. Sample No. 43 : Q Commercially available visible light responsive titanium oxide used in sample No. 39, sample No. 36 was used. In the dispersion of the same organic dispersant and deionized water (pH 7, solid content: 10% by mass), silicone (Sunotech®) (Si/Ti = 0.12) was added, and the mixture was thoroughly stirred and then added. The dispersion of the hydroxy strontium nitrate (pH 7) (Bi/Ti = 0.10) of the photocatalyst activity enhancer was sufficiently stirred to prepare a dispersion for forming a visible light responsive photocatalyst of the present invention. This dispersion was directly applied to a glass plate (about 40 g/m2), and calcined at 80 °C for 2 hours in the air to prepare a photocatalytic functional member having the visible light responsive photocatalyst layer of the present invention. X-ray diffraction The main peak of the pattern is attributed to anatase type titanium oxide. The photocatalytic functional members produced in Sample No. 42 and No. 43 were subjected to an acetaldehyde decomposition test by the method described in Example 1. As a result, the sample activity (1·6μηιο1/ΗΓ) of the visible light-responsive titanium oxide sol coated with the raw material, the sample Ν 〇· 4 2 was 2·3 μηη ο 1/H r , and the sample Ν 〇· 4 3 was 4.0μπιο1/ΗΓ activity. From this, it is understood that the activity enhancer containing the ruthenium compound of the present invention is also effective for the sol of the titanium oxide photocatalyst, and further enhances the effect by adding ruthenium (in this example, SiO 2 ). -53-200940165 (Example 7) (XAFS measurement) With respect to various photocatalysts containing the above-mentioned samples Νο.4 and No. 5, the peak-to-peak ratio R (the second peak / first) around the erbium atom was obtained by the XAFS method. crest). The measurement was carried out with SPring 8-BL19-B2. The measurement results are shown in Table 7, and the photocatalytic activity (C02 occurrence rate 0 degree) obtained by the above method is also shown. In Table 7, samples having different R値 were produced in the same manner as Sample No. 4 except for the above samples n〇.4 and 5, barium titanate (Bi3Ti4012) and Bi203, and the amount of bismuth (Bi/Ti = 0.30). Sample No. 44 also shows the measurement results of R 値 and photocatalytic activity. [Table 7] Sample No. Catalyst component R値〇) 2 generation rate (μιηοΐ/h) 铋 Compound titanium oxide - Bi2O3 (0: X commercial product) . 0.50 4 Bi-Ti02 BiOCl Ti〇2 0.15 8.9 5 Bi -Si-Ti02 BiOCl Si/Ti02 0.03 25.0 44 Bi-Si-Ti02 BiOCl Si/ Ti02 0.20 1.8 - Bi3Ti4012 (commercial product) 1 - 0.48 0.8 As shown in the results of Table 7, if the dynamic diameter distribution peak ratio R It is high in visible light catalyst activity when it is below . Even more, if the peak ratio

〇 . 1 5以下’則具有極高之活性。又，不含有其他元素M 之單獨的氧化鈦’亦在令氧化鈦與鉍化合物混合、煅燒下 ’成爲R値爲0.4以下，相比於母體之氧化鈦顯示出充分 -54- 200940165 的可見光活性。 如此，於含铋之氧化鈦中，令xAFS測定所得之Bi 原子周圍的動徑分佈中波峰之比（第2波峰/第1波峰） 爲〇·4以下，則可提供具有極高可見光活性之可見光應答 型的光觸媒。 【圖式簡單說明】 Q 圖1爲示出實施例1所製作之各種試料的FT_IR光譜 〇 圖2爲示出實施例1所製作之試料No.3~5之Bi-4f內 殼準位的光譜圖。 圖3爲示出實施例3所得之可見光應答型光觸媒試料 的SEM觀察照片。 圖4爲示出整理實施例3所得之可見光應答型光觸媒 試料之FT-IR光譜之3400cm·1吸收値之圖。 φ 圖5爲示出關於實施例7所得之可見光應答型光觸媒 試料’以XAFS法求出試料之鉍周圍的動徑分佈結果。 -55-〇 . 15 or less 'has extremely high activity. Further, the titanium oxide ' alone containing no other element M is also obtained by mixing titanium oxide with a cerium compound and calcining it to have an R 値 of 0.4 or less, and exhibiting a sufficient visible light activity of -54 to 200940165 as compared with the titanium oxide of the precursor. . In the titanium oxide containing ruthenium, the peak ratio (second peak/first peak) in the dynamic path distribution around the Bi atom obtained by xAFS measurement is 〇·4 or less, thereby providing extremely high visible light activity. A visible light responsive photocatalyst. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a FT_IR spectrum showing various samples prepared in Example 1. FIG. 2 is a view showing Bi-4f inner shell levels of Sample Nos. 3 to 5 produced in Example 1. Spectrum. Fig. 3 is a SEM observation photograph showing a visible light responsive photocatalyst sample obtained in Example 3. Fig. 4 is a view showing the 3400 cm·1 absorption enthalpy of the FT-IR spectrum of the visible light responsive photocatalyst sample obtained in Example 3. φ Fig. 5 is a graph showing the results of the dynamic path distribution around the crucible obtained by the XAFS method for the visible light responsive photocatalyst sample obtained in Example 7. -55-

Claims (1)

200940165 # 十、申請專利範圍 1- 一種氧化鈦系可見光應答型光觸媒，其爲由表面 擔載鉍氧化物之氧化鈦所構成的可見光應答型光觸媒，其 特徵爲鉍於表面濃化。 2 ·如申請專利範圍第1項之光觸媒，其中，該鉍氧 化物爲以BiOx(x<1.5)表示。 3- 如申請專利範圍第1項或第2項之可見光應答型 0 光觸媒，其中，該鉍氧化物爲被覆氧化鈦之表面的至少一 部分。 4- 如申請專利範圍第1項~第3項中任一項之可見光 應答型光觸媒，其中，光觸媒中所含之Bi與Ti的原子比 (Bi/Ti )爲 0.001 以上，1 ·〇 以下。 5. 如申請專利範圍第1項〜第4項中任一項之可見光 應答型光觸媒，其中，將光觸媒予以XAFS解析時之鉍原 子周圍的動徑分佈波峰比R (第2波峰/第1波峰之比）爲 ❹ 〇 . 4以下。 6. 如申請專利範圍第5項之可見光應答型光觸媒， 其中，該動徑分佈波峰比R爲0.15以下。 7 .如申請專利範圍第1項~第6項中任一項之可見光 應答型光觸媒，其中，光觸媒爲含有矽、鉻、鋁、鎢、鉬 、鎂、铪、及硼中選出至少一種之元素Μ。 8.如申請專利範圍第7項之可見光應答型光觸媒， 其中光觸媒中之該元素Μ的含量（含有2種以上元素時爲 合計量）爲相對於Ti之原子比（M/Ti )爲0.000 1以上， -56- 200940165 未達1 . 〇之份量。 9 ·如申請專利範圍第7項或第8項 光觸媒，其中’該元素Μ爲含於氧化鈦中 10.如申請專利範圍第1項〜第9項 光應答型光觸媒’其中，氧化鈦爲至少部 結晶的主要結晶型爲銳駄礦。 η · —種如申請專利範圍第1項〜第 @ 氧化鈦系可見光應答型光觸媒的製造方法 將氧化鈦或其固體狀前驅物與鉍化合物混 和將所得到的混合物煅燒，取得表面擔載 化鈦的煅燒步驟。 12. 如申請專利範圍第11項之方法 步驟爲於煅燒所得產物之X射線繞射圖型 化鈦爲主的階段中停止。 13. 如申請專利範圍第11項或第12 ❹ ，該煅燒步驟中之煅燒溫度爲50〜80〇°c。 14. 如申請專利範圍第11項〜第13 法，其中，鉍化合物爲由BiOX ( X=鹵素 、氫氧化離子、有機離子）、鹵化鉍、硝 及硫化鉍中選出至少一種。 15. 如申請專利範圍第11項〜第】4 法，其中，氧化鈦或其固體狀前驅物爲含 鎢、鉬、鎂、鈴及硼中選出至少~種之元 16. 如申請專利範圍第11項〜第！ 5 之可見光應答型 〇 中任一項之可見 分的結晶質，此 1 〇項中任一項之 ，其特徵爲包含 合的混合步驟， 該鉍氧化物之氧 ，其中，該煅燒 中，銳鈦礦型氧 項之方法，其中 項中任一項之方 離子、硝酸離子 酸鉍、硫酸鉍、 項中任〜項之方 有矽、鉻、鋁、 素Μ。 項中任~項之方 -57- 200940165 法’其中，於混合步驟中，將氧化鈦或其固體狀前驅物與 鉍化合物’加上由矽化合物、锆化合物、鋁化合物、鎢化 合物、鉬化合物、鎂化合物、飴化合物及硼化合物中選出 至少一種之化合物予以混合。 17.如申請專利範圍第11項〜第16項中任一項之方 法，其中’被混合化合物中之至少一者爲分散液狀態的氧 化物。 〇 18. —種光觸媒機能構件，其特徵爲於基材表面具有 如申請專利範圍第I項〜第10項中任一項之可見光應答型 光觸媒。 19. 一種可見光應答型光觸媒形成用分散液，其特徵 爲於液體介質中含有分散狀態之氧化鈦和分散或溶解狀態 之鉍化合物。 20. —種光觸媒分散液，其特徵爲含有液體介質中分 散之如申請專利範圍第1項〜第1 0項中任一項之可見光應 〇 答型光觸媒。 21. —種可見光應答型光觸媒塗敷液，其特徵爲於液 體介質中含有分散狀態之氧化鈦和分別分散或溶解狀態之 鉍化合物及黏合劑。 22. —種可見光應答型光觸媒塗敷液，其特徵爲於液 體介質中含有如申請專利範圍第1項~第1 〇項中任一項之 可見光應答型光觸媒和黏合劑，且光觸媒之含量爲根據不 揮發成分之合計量爲5〜95質量％。 23. —種光觸媒機能構件之製造方法’其特徵爲將如 -58- 200940165 申請專利範圍第1 9項或第20項之分散液或如申請專利範 圍第21項或第22項之塗敷液於基材上塗佈後，施以熱處 理。 24. —種氧化鈦系光觸媒之可見光應答活性增進劑， 其特徵爲由鉍化合物所構成。200940165 # X. Patent Application No. 1 - A titanium oxide-based visible light-responsive photocatalyst, which is a visible light-responsive photocatalyst composed of titanium oxide having a surface-supporting cerium oxide, which is characterized in that it is concentrated on the surface. 2. The photocatalyst of claim 1, wherein the bismuth oxide is represented by BiOx (x < 1.5). 3- A visible light responsive type 0 photocatalyst according to claim 1 or 2, wherein the cerium oxide is at least a part of a surface of the coated titanium oxide. The visible light responsive photocatalyst according to any one of the first to third aspects of the invention, wherein the atomic ratio (Bi/Ti) of Bi and Ti contained in the photocatalyst is 0.001 or more and 1 · 〇 or less. 5. The visible light responsive photocatalyst according to any one of the first to fourth aspects of the invention, wherein the photocatalyst has a dynamic peak distribution peak ratio R around the helium atom when XAFS is analyzed (the second peak / the first peak) The ratio is ❹ 〇. 4 or less. 6. The visible light responsive photocatalyst of claim 5, wherein the dynamic path distribution peak ratio R is 0.15 or less. The visible light responsive photocatalyst according to any one of claims 1 to 6, wherein the photocatalyst is an element containing at least one of cerium, chromium, aluminum, tungsten, molybdenum, magnesium, cerium, and boron. Hey. 8. The visible light responsive photocatalyst according to claim 7, wherein the content of the element bismuth in the photocatalyst (the total amount when two or more elements are contained) is 0.000 1 with respect to the atomic ratio (M/Ti) of Ti. Above, -56- 200940165 did not reach 1. The amount of 〇. 9 · For the photocatalyst according to item 7 or item 8 of the patent application, where 'the element is contained in titanium oxide. 10. For the patent range 1 to 9 light-responsive photocatalyst', titanium oxide is at least The main crystalline form of the partial crystal is the sharp ore. η — 种 如 如 第 第 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛 氧化钛Calcination step. 12. The method of claim 11 is to stop in the stage where the X-ray diffraction pattern of the product obtained by calcination is dominant. 13. In the case of claim 11 or 12, the calcination temperature in the calcination step is 50 to 80 ° C. 14. The method of claim 11, wherein the ruthenium compound is at least one selected from the group consisting of BiOX (X = halogen, hydroxide ion, organic ion), ruthenium halide, nitrate, and ruthenium sulfide. 15. The method of claim 11 to 4, wherein the titanium oxide or its solid precursor is at least one selected from the group consisting of tungsten, molybdenum, magnesium, bell and boron. 11 items ~ the first! The crystal of any of the visible light responsive type 〇, any one of the items of the present invention, characterized by comprising a mixing step of the oxygen of the cerium oxide, wherein the calcination is sharp The method of the ilmenite-type oxygen term, wherein any one of the terms, such as a square ion, a cerium nitrate strontium sulphate, a barium sulphate, or any one of the items, has bismuth, chromium, aluminum, and bismuth. In the mixing step, the titanium oxide or its solid precursor and the cerium compound are added to the cerium compound, the zirconium compound, the aluminum compound, the tungsten compound, the molybdenum compound. At least one of the magnesium compound, the cerium compound and the boron compound is selected and mixed. 17. The method of any one of clauses 1 to 16, wherein at least one of the mixed compounds is an oxide in a dispersion state. 〇 18. A photocatalytic functional member characterized by having a visible light responsive photocatalyst according to any one of claims 1 to 10 on the surface of the substrate. A visible light responsive photocatalyst-forming dispersion liquid characterized by containing a titanium oxide in a dispersed state and a ruthenium compound in a dispersed or dissolved state in a liquid medium. 20. A photocatalyst dispersion characterized by containing a visible light-receiving photocatalyst as disclosed in any one of claims 1 to 10 of the patent medium. A visible light responsive photocatalyst coating liquid characterized by containing a titanium oxide in a dispersed state and a bismuth compound and a binder in a dispersed or dissolved state in a liquid medium. 22. A visible light responsive photocatalyst coating liquid characterized by containing a visible light responsive photocatalyst and a binder according to any one of claims 1 to 1 in a liquid medium, and the photocatalyst content is The total amount of the nonvolatile components is 5 to 95% by mass. 23. A method of producing a photocatalytic functional component, characterized by a dispersion of the ninth or twenty-ninth item of the patent application--58-200940165 or a coating liquid according to claim 21 or 22 of the patent application. After coating on the substrate, heat treatment is applied. A visible light responsive activity enhancer for a titanium oxide-based photocatalyst, which is characterized by being composed of a ruthenium compound. -59--59-
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