200540119 伍、 中文發明摘要： 本發明揭示製造含銀二氧化鈦溶膠光觸媒的方法，來提高二氧化鈦光催 化的效果，並揭示其在廢水及廢氣處理上的應用。本發明以四氣化鈦為原 料，先以驗性溶液製成氫氧化鈦，經過多次離心、水洗後，完全去除離子， 再加入雙氧水及銀的鹽類，在70至100°C間，煮一段時間後即可形成穩定 透明的二氧化鈦溶膠，其係奈米級固體粒懸浮在水中，為菱形顆粒，長軸 為十奈米，短轴為四奈米左右，且水溶液為弱酸性或中性，其可直接做為 廢氣及廢水處理的光觸媒，亦可浸鍍在載體上，以日光燈、紫外光燈或太 陽光照射，就具高的活性，可做為廢氣及廢水處理的光觸媒。 陸、 英文發明摘要：200540119 Wu, Chinese Abstract of the Invention: The present invention discloses a method for manufacturing a silver-containing titanium dioxide sol photocatalyst to improve the photocatalytic effect of titanium dioxide and its application in wastewater and waste gas treatment. In the present invention, titanium tetraoxide is used as a raw material, and titanium hydroxide is first prepared from an experimental solution. After several centrifugations and water washing, the ions are completely removed, and then hydrogen peroxide and silver salts are added. The temperature is between 70 and 100 ° C. After cooking for a period of time, a stable and transparent titanium dioxide sol can be formed. Its nano-sized solid particles are suspended in water. They are diamond-shaped particles with a major axis of ten nanometers and a minor axis of about four nanometers. It can be directly used as a photocatalyst for waste gas and wastewater treatment, or it can be immersed on a carrier and irradiated with a fluorescent lamp, ultraviolet light or sunlight. It has high activity and can be used as a photocatalyst for waste gas and wastewater treatment. Lu and English Invention Abstract:
This invention declares the method to produce Ti02 sol which contains silver· The suspended nanosized Ag/Ti〇2 particles with anatase structure in aqueous solution were synthesized by a sol-gd method using Ή〇4 and Ag salt as the precursors. was reacted with aqueous solution of NaOH or NH40H to form Ti(OH)4. Silver salt and hydrogen peroxide was then added. The mixture was then heated in water to form Ag/Ti02 sol. The primary particles were rhombus with the m^jor axis ca. 10 nm and minor axis ca. 4 nm, and was in anatase structure. The sol was excellent in dispersibility and was stable in neutral conditions without causing agglomeration. The transparent adherent Ti02 film on substrates could be obtained through spray-coating or dip-coating. It exhibits strong photoactivity under illuminating by fluorescence light. 【發明所屬之技術領域】 本發明係揭示含銀二氧化鈦溶膠光觸媒之製法，及其在廢水及廢氣處理之應用。其特徵 在以四氯化鈦爲原料，先以鹼性溶液製成氫氧化鈦，經過多次離心、7jC洗後，完全去除 離子，再加入雙氧水及銀的鹽類，在70至100°C間，煮一段時間後即可形成穩定透明的 二氧化鈦溶膠，其係奈米級固體粒懸浮在水中，且水溶液爲弱酸性或中性，其可直接做 爲廢氣及廢水的光觸媒，亦可浸鍍在載體上以日光燈照射，具高的去污活性。本發明亦 揭示Ag/Ti02在廢水及廢氣處理上的應用方法。 【先前技術】 所謂「觸媒」，其實是一種化學物質，在化學上，又被叫做催化劑。觸媒可以促 使化學反應發生，或加速反應的速度。而光觸媒(Photo catalysis)，就是經過光的照射， 200540119 可以促進化學反應的物質。以大家都耳熟能詳的植物光合作用爲例，在光合作用起重 要作用的葉綠素，就可以稱爲光觸媒。 目前可用來作爲光觸媒的物質有二氧化鈦(Ti〇2)等氧化物及CdS等硫化物，其中 二氧化鈦因爲具有強大的氧化還原能力，高化學穩定度及無毒的特性，而最常被使用 來做爲光觸媒的物質。根據工硏院的報告，光觸媒最擅長於處理空氣中極低濃度的有 害化學物質，況且本身不會釋出有害物質，因此是極優異的環境淨化用觸媒。光觸媒 可以產生消臭、殺菌、抗菌、防污和除去有害物質等等功能。 二氧化鈦的結晶構造有正方晶系的高溫金紅石(rutile)型、低溫銳鈦礦(anatase)型及屬 於斜方晶系的板鈦礦(brookite)型3種。其中只有銳鈦礦結構具光觸媒的效果。光催化處 理程序之光分解機制是藉由紫外光或太陽光激發光觸媒，使觸媒產生電子以及電洞，藉 以氧化表面吸附之物質，進而將表面吸附之物質裂化爲小分子。以二氧化鈦爲例，二氧 化鈦反應從照400nm之光波長開始反應(因爲二氧化鈦之能階差約爲3.1eV，而400nm之 光波長大約可提供3.1eV之能量），二氧化鈦吸收光能量產生電子(e-)及電洞(h+)，此電洞 具有相當強之氧化力，可以直接將吸附在物質表面之污染物分子直接氧化使其分解，或 者將吸附於物質表面之水分子氧化爲氫氧自由基（0H)。原本大分子之污染物，經由光 觸 媒照光反應將大分子裂解爲小分子，達到污染物淸除之目的。 數十年來，光觸媒被廣泛地硏究，並逐漸應用在環保、能源、殺菌、自我潔淨等 方面。自1972年’ Fujishma和Honda首次在Nature雜誌上發表Ti02經照光後會分解 7JC產生氏及02後，越來越多人投入1102光催化性質相關的硏究，並致力於各種可能 的改質方法，以提高1102光觸媒的效果。 國內現有之專利仍著重在二氧化鈦製備方法及相關之應用，沒有如本案所用金 屬改質方法的專利。國內目前相關專利列於表1。國外相關專利列於表2。已公開專利 中，未有如本發明所揭示所用雙氧水及添加銀製備銀/二氧化鈦光觸媒的方法。This invention declares the method to produce Ti02 sol which contains silver · The suspended nanosized Ag / Ti〇2 particles with anatase structure in aqueous solution were synthesized by a sol-gd method using Ή〇4 and Ag salt as the precursors. Was reacted with aqueous solution of NaOH or NH40H to form Ti (OH) 4. Silver salt and hydrogen peroxide was then added. The mixture was then heated in water to form Ag / Ti02 sol. The primary particles were rhombus with the m ^ jor axis ca. 10 nm and minor axis ca. 4 nm, and was in anatase structure. The sol was excellent in dispersibility and was stable in neutral conditions without causing agglomeration. The transparent adherent Ti02 film on substrates could be obtained through spray-coating or dip-coating It exhibits strong photoactivity under illuminating by fluorescence light. [Technical Field to which the Invention belongs] The present invention discloses a method for preparing a silver-containing titanium dioxide sol photocatalyst and its application in wastewater and waste gas treatment. It is characterized in that titanium tetrachloride is used as a raw material, firstly, titanium hydroxide is prepared from an alkaline solution, and after several centrifugations and 7jC washing, the ions are completely removed, and then hydrogen peroxide and silver salts are added, at 70 to 100 ° C. After a period of time, a stable and transparent titanium dioxide sol can be formed. The nano-scale solid particles are suspended in water, and the aqueous solution is weakly acidic or neutral. It can be directly used as a photocatalyst for waste gas and wastewater, and can also be immersed. Illuminated by fluorescent lamp on the carrier, it has high decontamination activity. The invention also discloses the application method of Ag / Ti02 in wastewater and waste gas treatment. [Previous technology] The so-called "catalyst" is actually a chemical substance, and chemically, it is also called a catalyst. Catalysts can cause chemical reactions to occur or accelerate the speed of reactions. Photo catalysis is a substance that can promote chemical reactions after light irradiation. Taking the photosynthesis of plants that everyone knows well, chlorophyll, which plays an important role in photosynthesis, can be called photocatalyst. At present, the materials that can be used as photocatalysts are oxides such as titanium dioxide (Ti〇2) and sulfides such as CdS. Among them, titanium dioxide is most commonly used as a material because of its strong redox capacity, high chemical stability, and non-toxic properties. Photocatalyst substance. According to the report of the Institute of Industry and Commerce, photocatalysts are best at treating extremely low concentrations of harmful chemicals in the air, and they do not release harmful substances themselves, so they are excellent catalysts for environmental purification. Photocatalyst can produce functions such as deodorization, sterilization, antibacterial, antifouling and removal of harmful substances. The crystal structure of titanium dioxide includes three types: a high-temperature rutile type, a low-temperature anatase type, and a brookite type that belong to the orthorhombic system. Only the anatase structure has the effect of photocatalyst. The photodecomposition mechanism of the photocatalytic processing program is to excite the photocatalyst by ultraviolet light or sunlight to cause the catalyst to generate electrons and holes, thereby oxidizing substances adsorbed on the surface, and then cracking the substances adsorbed on the surface into small molecules. Taking titanium dioxide as an example, the titanium dioxide reaction starts from the light wavelength of 400nm (because the energy step difference of titanium dioxide is about 3.1eV, and the light wavelength of 400nm can provide about 3.1eV energy), the titanium dioxide absorbs light energy to generate electrons (e- ) And hole (h +), this hole has a fairly strong oxidizing power, which can directly oxidize pollutant molecules adsorbed on the surface of the material to decompose it, or oxidize water molecules adsorbed on the surface of the material to hydroxyl radical (0H). The pollutants of the original macromolecules are cracked into small molecules by photocatalytic light reaction to achieve the purpose of eliminating the pollutants. For decades, photocatalysts have been widely studied and gradually applied to environmental protection, energy, sterilization, and self-cleaning. Since 1972 ', Fujishma and Honda first published in the journal Nature that Ti02 decomposes 7JC and 02 after exposure to light. More and more people have invested in research on the photocatalytic properties of 1102 and are working on various possible modification methods. To improve the effect of 1102 photocatalyst. The existing domestic patents still focus on the preparation method of titanium dioxide and related applications, and there is no patent on the method of metal modification as used in this case. The domestic related patents are listed in Table 1. Related foreign patents are listed in Table 2. In the published patents, there is no method for preparing a silver / titanium dioxide photocatalyst by using hydrogen peroxide and adding silver as disclosed in the present invention.
John T· Yates等人已在Chem· Rev· 1995,95, 735-758中報導了表面金屬改質二氧化鈦的 ° K. Rajeshwar^A^Pure Applied Chemistry, Vol. 73, No. 12, pp. 1849-1860, 2001中亦發現加銀可使二氧化駄還原Cr(VI)爲Cr(m)的效率增加。P. Falaras等人在John T. Yates et al. Reported in Chem. Rev. 1995, 95, 735-758 the surface metal modified titanium dioxide ° K. Rajeshwar ^ A ^ Pure Applied Chemistry, Vol. 73, No. 12, pp. 1849 -1860, 2001 also found that adding silver can increase the efficiency of reduction of Cr (VI) to Cr (m) by thorium dioxide. P. Falaras and others at
Applied Catalysis B: Environmental 42 (2003) ρρ· 187-201 中利用添加銀的二氧化欽薄 膜，來光催化分解甲基橙。Pierre Pichat等人在Photochem. Photobiol· Sci·，2004, 3， pp.142-144中也揭露加銀可增強二氧化鈦去除水中2-chlorophenol的速率。但先前專文 200540119 獻均係以粉末狀大顆粒的二氧化鈦且均係以紫外光爲光源。 本發明以四氯化鈦爲原料，硏究製作透明的奈米含銀二氧化鈦光觸媒穩定懸浮劑 的方法，二氧化鈦爲銳鈦礦結晶，顆粒爲奈米級。四氯化欽水溶液先加入氣水，變成 氫氧化鈦’再加入過氧化氫及銀的鹽類，再在攝氏70-100度下煮若干時間，即可得到 透明奈米含銀二氧化鈦光觸媒懸浮劑。利用X光繞射儀及穿透式電子顯微鏡分析產 物。本發明所得的含銀二氧化鈦爲長條狀的奈米粒子，長軸約10nm、短軸約4nm 〇 將此二氧化鈦粒子溶液以浸漬覆膜方式鍍於玻璃上，可得透明且牢固的二氧化欽薄 膜。以紫外光或曰光燈照射，顯示均有強烈的光催化活性。 一般二氧化鈦在低溫製備時，大多形成非結晶的顆粒，必須在300左右 燒 才會形成銳鈦礦結晶，這麵態的結晶才具有光催化效果，但有些載體，例如一般的 玻璃、皮革、布料等無法耐此高溫，本發明即揭示在製備時即形成銳鈦礦奈米結晶顆 粒，當其塗布在載體後。二氧化鈦薄膜可作爲光觸媒。但一般 塗布的二氧化鈦水溶液均是以院氧化欽爲原料，其價格昂貴，且製作過程複雜。本發 明以較便宜的四氯化鈦爲原料，於低溫下製作含銀且爲銳鈦礦結晶的二氧化鈦水溶 液。 藉由紫外光線照射二氧化鈦觸媒進行光催化反應，可用來分解廢水或飮水中之有 機物質。此光化學反應是屬於非均相之光催化反應，利用具半導體情質的二氧化鈦， 在適當之波長輻射下，將電子由共價帶激發至導電帶，產生電洞及電子，而電洞及電 子與水及氧氣反應生成氫氧自由基及過氧化自由基，而這些自由基可以與有機物質反 應，生成新物質。 光催化反應原理 如圖1所示。半導體物質之外層電子可分爲兩個電子能帶，分別爲共價帶(Valence band) 與傳導帶(Conduction band),兩個能帶之間的能量差稱之爲能帶間隙(band gap) 〇而電子位 於不同之能帶，其移動的能力亦有所不同，若電子位於共價帶，則無法移動；而位於傳 導帶之電子則可在晶格中自由移動。異相光催化觸媒之反應機構。進行光催化反應須先 將觸媒活化，即是外加一能量大於能帶間隙之光源，激發共價帶之電子躍遷至傳導帶， 產生電子與電洞，此時傳導帶的電子可移動至觸媒表面並與吸附在觸媒表面的電子接受 物(electron acceptor,如〇2)發生作用，讓氧分子將傳導帶的電子帶走，形成自由基物質(路 徑C);同樣地，共價帶所產生的電洞，可與吸附在觸媒表面之電子供給物(electrondonor ’ 如表面的OH基、多電子有機物)發生作用(路徑D)，然後再進一步使有機物被氧化(Boucher， 20Ό540119 1995; Litter，1996)。 二氧化鈦可以製作成粉體直接投入廢水中，也可以塗佈於基材表面，藉紫外光的 照射加速分解水和空氣中的有機物質，但是會面臨如何回收粉體及觸媒的表面積能否 完全接受到紫外光的照射等問題。爲了改善這些問題，將二氧化鈦覆成透明薄膜，希 望提高二氧化鈦的暴露面積增加光催化效果。這樣不但能解決上述問題，同時更增加 二氧化鈦光觸媒的用途。 爲了製作二氧化鈦薄膜，近年來發展出幾種主要的製備方法。表面積大的基材，通 常會採用化學氣相沈積法來製作薄膜，其原理利用化學反應，將氣體反應物在反應區域 內生成固態物種，並進一步沈積於載體表面的一種製備技術，基材吸附力要強，必須要 有高溫設備 > 過程複雜。 本發明以較宜的四氯化鈦爲原，於低溫下製作銳鈦礦結晶的二氧化鈦水溶液。 並採用米結晶子懸浮液覆膜法，製備二氧化鈦薄膜，製作透明，穩定懸浮且含銀二 氧化鈦米結晶子薄膜。能在製備時即形成銳鈦礦米結晶顆，當其塗布在載體 後，就需再在高溫鍛燒。 本發明目的係以價格較宜的四氯化鈦爲原，製作含米級二氧化鈦子的水溶 液，以做爲塗布的原，並使塗布後具催效果。此米級二氧化鈦具備銳鈦礦結晶型態， 故須再經高溫鍛燒。此懸浮溶液是穩定，米子會在短時間內聚集、產生澱。 此溶液是中性或弱酸性，故會對載體有腐蝕的現象。 表1 公告號 公告日 專利名稱 1 00581168 2004/03/21 二氧化鈦光觸媒之風扇結構 2 00580116 2004/03/11 二氧化鈦光觸媒電熱器結構 3 00572973 2004/01/21 二氧化鈦顏料及其製造方法，與添加其所成之樹脂 組成物 4 00567092 2003/12/21 金紅石二氧化鈦光觸媒電極之製造方法 5 00561179 2003/11/11 含有二氧化鈦之聚碳酸酯樹脂摻合物 6 00541285 2003/07/11 二氧化鈦粉體之製備技術 7 00539579 2003/07/01 二氧化鈦光觸媒粉體、其製造方法及其應用 8 00535263 2003/06/01 合倂有金紅石二氧化鈦以及其它高K介電質於動態 隨機存取記憶體的深溝槽儲存細胞的方法和^構、 9 00531447 2003/05/11 二氧化鈦矽石之活化方法以及其於利用過 氧化方法之用途 10 00526173 2003/04/01 二氧化鈦顏料及其製造方法 ____ 11 00514554 2002/12/21 以砂聚合物黏著二氧化鈦於不鏽鋼表面之方法 200540119 12 00496908 2002/08/01 作爲罩幕材料之二氧化鈦膜及其移除方法 ~ 13 00487579 2002/05/21 含二氧化鈦微粒之防紫外線化妝品組成物 ^一 14 00482816 2002/04/11 耐光二氧化鈦顏料及倂含此顏料之紙類層合物^' 15 00445285 2001/07/11 二氧化鈦陶瓷塗料及其製法 ~ 16 00438625 2001/06/07 降低粗粒子數之二氧化鈦漿料之製造方法 ^" 17 00429433 2001/04/11 形成二氧化鈦膜之方法追加（一） ~ 18 00428714 2001/04/01 二氧化鈦/紫外光空氣淸淨除濕裝置 ~ 19 00409127 2000/10/21 微粒二氧化鈦一聚矽氧分散體 —^ 20 00406121 2000/09/21 不含基材之小片狀二氧化鈦顏料及其製法 ~ 21 00406120 2000/09/21 小片狀二氧化鈦還原性顏料 ^ 22 00402162 2000/08/11 紫外光/二氧化鈦光氧化裝置 ~ 23 00389942 2000/05/11 形成二氧化鈦膜之方法 ~ 24 00388098 2000/04/21 供記億體應用之高介電質二氧化鈦-氮化矽複合^ 25 00388073 2000/04/21 一種在砷化鎵基板上成長二氧化欽之液相沉積方法 26 00387861 2000/04/21 二氧化鈦的D燒 ~ 27 00383331 2000/03/01 塗覆二氧化鈦粒子的方法 28 00382619 2000/02/21 製造二氧化鈦之方法與裝置 29 00374243 1999/11/11 液相二氧化鈦薄膜的製造方法 30 00371294 1999/10/01 連續無污染液相二氧化鈦之製法 31 00370552 1999/09/21 含有經塗覆二氧化鈦顆粒之金紅石二氧化鈦顔料之 製造方法 32 00363941 1999/07/11 製備銳鈦礦二氧化鈦的方法 33 00350868 1999/01/21 金紅石二氧化鈦及其製法 34 00343223 1998/10/21 以氧化鋁塗佈之無機二氧化鈦色素及其製法 35 00343222 1998/10/21 二氧化鈦色素之處理方法，新穎二氧化鈦色素及其 在造紙之用途 36 00338772 1998/08/21 在混入聚合物時不脫色之經矽烷化的二氧化鈦顏料 37 00316281 1997/09/21 含經還原之二氧化鈦層之干擾顏料其在製備防止僞 造文件及包裝之用途 38 00307742 1997/06/11 製造二氧化鈦產物之方法 39 00292974 1996/12/11 高固體含量二氧化鈦水性泥狀物之製法 40 00290578 1996/11/11 耐久性顏料用二氧化鈦及其製法 200540119 41 00272227 1996/03/11 控制高分子膠乳吸附於二氧化鈦上之方法 42 00265355 1995/12/11 製造二氧化鈦塗膜之方法及製造二氧化鈦粒子方法 43 00221800 1994/03/21 一種製備自由流動之非顏料之二氧化鈦粉末之方法 44 00218888 1994/01/11 聚合物修飾之粒狀二氧化鈦 45 00203630 1993/04/11 二氧化鈦礦石之純化方法 46 00194507 1992/11/11 以覆烷基乙烯酮二聚物於二氧化鈦表面上之改良方 法 47 00190453 1992/09/11 二氧化鈦-氧化鈣系滑動材料之製造方法 48 00180193 1992/03/11 以熱製之二氧化鈦爲底質之緊密體，彼之製法及用 途 49 00177331 1992/01/21 二氧化鈦壓榨物件，彼之製法及用途 50 00172687 1991/11/11 使由流動床式二氧化鈦氯化器排放之一氧化碳量減 少的方法 51 00162402 1991/07/01 針狀導電性二氧化鈦及其製法 52 00157177 1991/05/01 製備顏料二氧化鈦之方法 53 00155753 1991/04/11 針狀二氧化鈦粒子以及彼之製法 54 00155752 1991/04/11 於聚合物添加物之存在下能防止聚合物變色之二氧 化鈦顏料 55 00153574 1991/03/11 變性菝化的二氧化鉻-二氧化欽-氧化釔之陶瓷合金 56 00144912 1990/11/01 二氧化鈦之製法 57 00144911 1990/11/01 耐久性二氧化鈦顏料之製法 58 00135895 1990/06/11 製備二氧化鈦的方法 59 00129750 1990/03/01 二氧化鈦顏料，含有該顏料之電泳塗覆組合物，以 及處理二氧化鈦顏料之方法 60 00125278 1989/12/21 製造二氧化鈦粉的方法 61 00121799 1989/11/01 穩定二氧化鈦及其製造 62 00120387 1989/10/11 二氧化鈦礦的純化方法 63 00118585 1989/09/11 在一表面上形成具有控制之光學厚度的二氧化鈦薄 膜的方法 64 00109264 1989/03/01 淸潔二氧化鈦反應器內之噴射管用之裝置 65 00101372 1988/07/16 塗覆有經氧化硼修飾之二氧化矽的二氧化鈦顏料 66 00101371 1988/07/16 塗覆有鈽陽離子，經選擇之酸陰離子，以及氧化鋁 等之二氧化鈦顏料 200540119 67 00066089 1985/04/01 製造濃二氧化鈦之製法 68 00057275 1984/03/16 二氧化鈦濃體之製法 69 00051044 1983/06/16 二氧化鈦之製法 70 00035302 1981/02/01 形成抗反光二氧化鈦塗層於基質上之方法 71 00031065 1980/07/01 由人造金紅石製造顏料級二氧化鈦及鎰明礬 72 00030641 1980/06/01 二氧化鈦之製法 73 00026289 1979/09/01 二氧化鈦之製造方法 74 00019405 1975/10/01 從未溶解鈦鐵礦廢渣回收二氧化鈦之方法 75 00015939 1974/05/01 改良二氧化鈦之製造法 76 00010942 1972/06/01 具有二氧化鈦與二氧化矽複合氧化膜之半導體裝置 及其製造方法 200540119 表2 PAT. NO. Title 1 6,649,561 T Titania-coated honeycomb catalyst matrix for UV-photocatalytic oxidation of organic pollutants, and process for making 2 6,566,300 T Titania photocatalyst and its preparing method 3 6,455,465 T Photocatalyst coated products and a method for producing a photocatalyst layer 4 6,267,944 T Method of preparing a solution for titania film 5 6,090,489 T Method for photocatalytically hydrophilifying surface and composite material with photocatal^ically hydrophilifiable surface 6 5,707,915 T Photocatalyst sheet and method for producing thereof 7 6.699.577 T Air purification-functioning road and method for purifVing polluted air over road 8 6.627.173 T Doped titanium dioxide 9 6.602.607 T Titanium doxide photocatalvst carrier and process for its production 10 6.576.589 T Method for making anatase tvpe titanium dioxide photocatalvst 11 6.558.553 T Photocatalvst 12 6.524.536 T Enhanced oxidation of air contaminants on an ultra-low density UV-accessible aerogel photocatalvst 13 6.517.804 T Ti02 ultrafine oowder, and process for preparing thereof 14 6.508.941 T Photocatalvtic process 15 6,406.536 T Organic additives for the DreDaration of cementitious compositions with improved constancy of color 16 6.365.545 T Highly functional base material 17 6.315.963 T Method and aooaratus for the enhanced treatment of fluids via photolvtic and photocatalvtic reactions 18 6.306.796 T Photocatalvst, process for producing the same and multifunctional members 19 6.265.341 T Highly functional base material and a method of manufacturing the same 20 6,241,856 T Enhanced oxidation of air contaminants on an ultra-low density UV-accessible aerogel ohotocatalvst 21 6.139,803 T Photocatalvtic air treatment process under room light 22 6,121,191 T Ultrafine metal particle carrvins photocatalvst, highly function material loaded with the photocatalvst, and method of manufacturing them 200540119 23 6,117,229 T Use of organic additives for the preparation of cementitious compositions with improved properties of constancy of color 24 6,024,929 T Fluorescent lamp with a thin film photocatalvst, and method of creating the same 25 5,874.701 T Photocatalvtic air treatment process under room light 【發明內容】 本發明主要適用於去除水中或氣體中的污染物。由於工業製程中會產生高濃度有機 物質的廢水及廢水，不易處理，且不同產業亦會產生各種不同的廢水組成；因此，我們 藉二氧化鈦具光催化的性質，利用其特殊的反應機制，來分解水中的污染物。爲了進一 步提高二氧化鈦光催化的效果，添加適當金屬加以改質，而本發明的重點就在於揭示製 作奈米級含銀二氧化鈦的溶膠（sol)，它以日光燈或紫外光照射，均具有高的光催化效 果。爲鑑定光觸媒的效果，本發明藉由紫外光或曰光燈進行光催化反應，每隔固定時間 取樣量測污染物的濃度。 本發明採用奈米結晶粒子懸浮液覆膜法製備含銀二氧化鈦薄膜，製作出透明，穩 定懸浮且具光催化活性的銀/二氧化鈦奈米結晶粒子溶液。本發明係以價格較便宜的四 氯化鈦爲原料，製作含Ag奈米級二氧化鈦粒子的水溶液，以做爲塗布的原料，並使塗 祖燒。布後具光催化效果。此奈米級二氧化鈦具備銳鈦礦 此懸浮溶液很穩定，奈米粒子超過一年也不會聚集、產生沈澱。此溶液是弱酸性或中 性，不會對載體有腐蝕的現象。 首先將四氯化鈦於5下緩慢加入水中，配成一摩耳濃度（1M )水溶液，再加入30% 氨水或氫氧化鈉，變成氫氧化鈦膠體溶液。此膠體溶液經離心過濾後，再水洗數次， 直到沒有氯離子爲止（以硝酸銀滴定直到沒有白色氯化銀沈澱爲判斷依據）。氫氧化 鈦膠體溶液再加入過氧化氫及銀的鹽類，再以三頸燒瓶上接冷凝管於攝氏60度至100度 間煮一段時間，即可得到奈米含銀二氧化鈦光觸媒懸浮劑。透明的含銀二氧化鈦溶液 可覆膜於玻璃或任何載體上如陶瓷、塑膠片上，可應用於以紫外光或曰光燈做爲光源， 會產生相當高的催化活性。以下爲製作透明含銀二氧化鈦玻璃基材和測量活性的方法。 一、淸洗基材 我們以載玻片作爲基材。未經淸洗的玻璃基材表面可能有油性物質或其它不潔 物，會導致鍍膜不均勻和鍛燒時發生剝落的現象；淸洗玻璃基材是爲了使含銀二氧 化鈦奈米粒子能夠更牢固地附著在玻璃基材上。淸洗基材程序如下： 200540119 L將基材靜置於中性淸潔劑中，以超音波震盪淸洗一小時。 2·以去離子水淸洗基材表面殘留的淸潔劑，並以超音波震盪淸洗一小時。 3·將基材置於氫氧化鈉溶液中，以超音波震盪淸洗一小時。 4·以去離子水淸洗淺留於基材表面上的氫氧化鈉溶液，並以超音波震盪淸洗一小時。 5·將基材置入烘箱中乾燥並保存，以備鍍膜之用。 二、镀膜方法 可採用浸漬覆膜法或噴灑覆膜法。其中浸漬鍍膜進行的步驟如下： h將覆膜液置於拉昇機台上。 2·將玻璃基材固定於拉昇機上。 3·將基材浸入覆膜液中，下降速率爲8cm/min ,並停留30秒。 4·開始拉昇覆膜，上昇速率爲Scm/min 〇 5·覆膜完畢後，置於紫外光燈下照射30分鐘。 6·將薄膜置於烘箱中，於100下乾燥1小時，即完成二氧化鈦一次覆膜工作。 7·製作多層覆膜時，須重複上述各項步驟。 X射ίΐίϋί 分析(XRD) 由於各化合物晶體之組成原子及晶格平面各不相同，故X光以不同入射角度通過 時，將在不同平面上產生不同之繞射強度。二氧化鈦結晶形態有三種，分別爲銳鈦礦 (anatase)、金紅石(rutile)和板鈦礦(brookite)，其中以銳鈦礦最具光化學活性。二氧 化鈦的X射線繞射圖，在2Θ= 25°附近出現波峰，此可作爲判斷生成銳鈦礦結晶的依據。 穿透式電子顯微鏡分析(ΤΕΜ) 本硏究製作ΤΕΜ待測樣品，是從製備完成的二氧化鈦粒子懸浮液中，取2〜3滴， 直接滴在銅網上，接著置入烘箱中，40下乾燥3小時後置於防潮箱內，等待測量。 測量時，ΤΕΜ的加速電壓固定爲160kV。 【實施方式】 fc卜蔽例1 : 觸媒合成方法：含2wt%Ag/Ti02，用含浸法，於120°C烘乾磨粉，於250°C 燒 將ai6g之人81^03溶於適量純水中，倒入5g之Ti02粉末，二氧化鈦爲市售之Degussa 公司，型號爲P-25，含有25%金紅石、75%銳鈦礦，其BET表面積爲56 m2/g 〇 在室溫下充分攪拌混合1小時，於120°C下烘乾，磨粉。然後在空氣中250°C下 200540119 燒2小時。所製得爲含2wt%Ag之二氧化鈦粉末，顏色爲淡灰色。 進行甲烯藍液相光催化反應時，將0.5克觸媒和亞甲烯藍溶液（含10,000ppm 亞甲烯藍）均勻攪拌混合，周圍用波長爲254nm之紫外光或日光燈管照射（2根 10W的燈管），每隔10分鐘取樣，離心後再用分光光度計量測波長爲662nm時的 吸收値，由吸收度變化情形，可判斷亞甲烯藍的消失率。試驗結果發現4小時後之 亞甲烯藍消失24%。 一、 氫氧化鈦水溶液酸鹼値的影響 氫氧化鈦水溶液酸鹼値對於水溶液中二氧化鈦粒子的生成有很大的影響。四氯化鈦極易 水解，可與空氧中的水反應而產生白色的鹽酸氣體，將其溶於水中會發生劇烈水解，使 得溶液酸鹼値降至1以下。因此四氯化鈦與鹼性的氫氧化銨反應後將立刻產生氫氧化鈦 其爲膠性物質。Applied Catalysis B: Environmental 42 (2003) ρρ · 187-201 utilizes a thin film of silver dioxide added with silver to photocatalytically decompose methyl orange. Pierre Pichat et al. Also disclosed in Photochem. Photobiol · Sci ·, 2004, 3, pp.142-144 that the addition of silver can enhance the removal rate of 2-chlorophenol in water by titanium dioxide. However, the previous special article 200540119 proposed that the powders are large particles of titanium dioxide and all use ultraviolet light as the light source. In the present invention, titanium tetrachloride is used as a raw material, and a method for preparing a transparent nano-silver-containing titanium dioxide photocatalyst stable suspending agent is studied. The titanium dioxide is anatase crystal, and the particles are nano-grade. The aqueous solution of tetrachloromethane is firstly added with gas and water to become titanium hydroxide, and then added with hydrogen peroxide and silver salts, and then cooked at 70-100 degrees Celsius for several hours to obtain transparent nano silver-containing titanium dioxide photocatalyst suspension agent. . The products were analyzed using an X-ray diffractometer and a transmission electron microscope. The silver-containing titanium dioxide obtained by the present invention is a long nanometer particle with a long axis of about 10 nm and a short axis of about 4 nm. This titanium dioxide particle solution is plated on glass by dipping and coating to obtain a transparent and strong dioxin. film. Irradiation with ultraviolet light or fluorescent lamp shows strong photocatalytic activity. Generally, when titanium dioxide is prepared at low temperature, most of them form non-crystalline particles, which must be burned at about 300 to form anatase crystals. This state of crystals has a photocatalytic effect, but some carriers, such as general glass, leather, cloth, etc. When it is unable to withstand this high temperature, the present invention discloses that anatase nanocrystalline particles are formed during preparation, and when they are coated on a carrier. Titanium dioxide film can be used as a photocatalyst. However, the generally applied titanium dioxide aqueous solution is based on alumina oxide, which is expensive and has a complicated manufacturing process. The present invention uses a relatively inexpensive titanium tetrachloride as a raw material to produce an aqueous titanium dioxide solution containing silver and anatase crystals at a low temperature. The photocatalytic reaction of titanium dioxide catalyst by irradiating ultraviolet light can be used to decompose organic substances in wastewater or tritium water. This photochemical reaction is a heterogeneous photocatalytic reaction. Using semiconductor-grade titanium dioxide, under appropriate wavelengths of radiation, the electrons are excited from the covalent band to the conductive band to generate holes and electrons. Electrons react with water and oxygen to generate hydroxide radicals and peroxide radicals, and these radicals can react with organic substances to generate new substances. The principle of photocatalytic reaction is shown in Figure 1. The electrons in the outer layer of a semiconductor substance can be divided into two electronic energy bands, namely the covalent band and the conduction band. The energy difference between the two energy bands is called the band gap. 〇The electrons are located in different energy bands, and their ability to move is also different. If the electrons are in the covalent band, they cannot move; while the electrons in the conduction band can move freely in the crystal lattice. Reaction mechanism of heterogeneous photocatalytic catalyst. To perform the photocatalytic reaction, the catalyst must be activated first, that is, an external light source with an energy greater than the energy band gap is used to stimulate the electrons of the covalent band to transition to the conduction band to generate electrons and holes. At this time, the electrons in the conduction band can move to the catalyst. The surface of the medium interacts with an electron acceptor (such as 〇2) adsorbed on the surface of the catalyst, allowing oxygen molecules to take away the electrons of the conduction band to form a radical substance (path C). Similarly, the covalent band The generated holes can interact with electron donors (electrondonor 'such as OH groups on the surface, multi-electron organic matter) adsorbed on the catalyst surface (path D), and then further oxidize the organic matter (Boucher, 20Ό540119 1995; Litter, 1996). Titanium dioxide can be made into powder directly into the waste water, or it can be coated on the surface of the substrate to accelerate the decomposition of organic substances in water and air by the irradiation of ultraviolet light, but it will face how to recover the surface area of the powder and catalyst. Problems such as exposure to ultraviolet light. In order to improve these problems, titanium dioxide is coated into a transparent film, and it is desirable to increase the exposed area of titanium dioxide to increase the photocatalytic effect. This can not only solve the above problems, but also increase the use of titanium dioxide photocatalyst. In order to make titanium dioxide films, several main preparation methods have been developed in recent years. For a substrate with a large surface area, a chemical vapor deposition method is usually used to make a thin film. The principle is to use a chemical reaction to generate a solid species in the reaction area from a gaseous reactant and further deposit it on the surface of the carrier. The substrate is adsorbed. The force must be strong, and high temperature equipment must be available. The process is complicated. In the present invention, an appropriate titanium tetrachloride is used as a raw material to prepare an anatase crystal titanium dioxide aqueous solution at a low temperature. A titanium dioxide thin film is prepared by using a rice crystal suspension coating method to produce a transparent, stable suspended and silver-containing titanium dioxide rice crystal film. Crystals of anatase rice can be formed during preparation. After coating on the carrier, it needs to be calcined at high temperature. The purpose of the present invention is to use titanium tetrachloride as a raw material to prepare an aqueous solution containing rice-grade titanium dioxide particles as a coating raw material, and to make the coating have a catalytic effect. This meter grade titanium dioxide has anatase crystalline form, so it must be calcined at high temperature. This suspension solution is stable, and the rice seeds will aggregate in a short period of time, resulting in precipitation. This solution is neutral or weakly acidic, so it will corrode the carrier. Table 1 Announcement date Patent name 1 00581168 2004/03/21 Titanium dioxide photocatalyst fan structure 2 00580116 2004/03/11 Titanium dioxide photocatalyst electric heater structure 3 00572973 2004/01/21 Titanium dioxide pigment and its manufacturing method Resin composition 4 00567092 2003/12/21 Manufacturing method of rutile titanium dioxide photocatalyst electrode 5 00561179 2003/11/11 Polycarbonate resin blend containing titanium dioxide 6 00541285 2003/07/11 Preparation technology of titanium dioxide powder 7 00539579 2003/07/01 Titanium dioxide photocatalyst powder, manufacturing method and application thereof 8 00535263 2003/06/01 Combined with rutile titanium dioxide and other high-K dielectrics in deep groove storage cells of dynamic random access memory Method and structure, 9 00531447 2003/05/11 activation method of titanium dioxide silica and its use in the use of peroxidation method 10 00526173 2003/04/01 titanium dioxide pigment and manufacturing method thereof ____ 11 00514554 2002/12/21 Method for adhering titanium dioxide to stainless steel surface with sand polymer 200540119 12 00496908 2002/08/01 as cover material Titanium dioxide film and its removal method ~ 13 00487579 2002/05/21 UV-proof cosmetic composition containing titanium dioxide particles ^ -14 00482816 2002/04/11 Lightfast titanium dioxide pigment and paper laminates containing this pigment ^ '15 00445285 2001/07/11 Titanium dioxide ceramic coating and manufacturing method thereof ~ 16 00438625 2001/06/07 Manufacturing method of titanium dioxide slurry with reduced number of coarse particles ^ " 17 00429433 2001/04/11 Added method for forming titanium dioxide film (1) ~ 18 00428714 2001/04/01 Titanium dioxide / ultraviolet air dehumidifier ~ 19 00409127 2000/10/21 Particulate titanium dioxide-polysiloxane dispersion— ^ 20 00406121 2000/09/21 Small sheet without substrate Titanium dioxide pigment and its manufacturing method ~ 21 00406120 2000/09/21 Small flake titanium dioxide reducing pigment ^ 22 00402162 2000/08/11 UV / TiO2 photooxidation device ~ 23 00389942 2000/05/11 Method for forming titanium dioxide film ~ 24 00388098 2000/04/21 High-dielectric titanium dioxide-silicon nitride composite for billions of applications ^ 25 00388073 2000/04/21 A solution of gallium dioxide grown on a gallium arsenide substrate Deposition method 26 00387861 2000/04/21 D burning of titanium dioxide ~ 27 00383331 2000/03/01 Method of coating titanium dioxide particles 28 00382619 2000/02/21 Method and device for manufacturing titanium dioxide 29 00374243 1999/11/11 Liquid titanium dioxide Film manufacturing method 30 00371294 1999/10/01 Continuous non-polluting liquid titanium dioxide manufacturing method 31 00370552 1999/09/21 Manufacturing method of rutile titanium dioxide pigment containing coated titanium dioxide particles 32 00363941 1999/07/11 Preparation of anatase Method of ore titanium dioxide 33 00350868 1999/01/21 Rutile titanium dioxide and preparation method thereof 34 00343223 1998/10/21 Alumina coated inorganic titanium dioxide pigment and preparation method thereof 35 00343222 1998/10/21 Treatment method of titanium dioxide pigment, novel Titanium dioxide pigments and their use in papermaking 36 00338772 1998/08/21 Silanized titanium dioxide pigments that do not discolor when mixed with polymers 37 00316281 1997/09/21 Interference pigments with reduced titanium dioxide layers are prepared to prevent counterfeiting Use of documents and packaging 38 00307742 1997/06/11 Method of manufacturing titanium dioxide products 39 00 292974 1996/12/11 Preparation method of high solid content titanium dioxide aqueous sludge 40 00290578 1996/11/11 Titanium dioxide for durable pigment and preparation method 200540119 41 00272227 1996/03/11 Method for controlling adsorption of polymer latex on titanium dioxide 42 00265355 1995/12/11 Method for manufacturing titanium dioxide coating film and method for manufacturing titanium dioxide particles 43 00221800 1994/03/21 A method for preparing free-flowing non-pigmented titanium dioxide powder 44 00218888 1994/01/11 Polymer-modified granular titanium dioxide 45 00203630 1993/04/11 Purification method of titanium dioxide ore 46 00194507 1992/11/11 Improved method of coating alkyl ketene dimer on titanium dioxide surface 47 00190453 1992/09/11 The titanium dioxide-calcium oxide sliding material Manufacturing method 48 00180193 1992/03/11 Compact body with thermally produced titanium dioxide as the substrate, its manufacturing method and application 49 00177331 1992/01/21 Titanium dioxide pressed article, its manufacturing method and application 50 00172687 1991/11/11 Method for reducing the amount of carbon oxide emitted by a fluidized bed titanium dioxide chlorinator 51 00162402 1991/07/01 Needle shape Conductive titanium dioxide and preparation method thereof 52 00157177 1991/05/01 Method for preparing pigment titanium dioxide 53 00155753 1991/04/11 Needle-shaped titanium dioxide particles and a method for preparing the same 54 00155752 1991/04/11 Prevented by the presence of polymer additives Polymer-colored titanium dioxide pigments 55 00153574 1991/03/11 Modified and aluminized chromium dioxide-ammonium dioxide-yttrium oxide ceramic alloy 56 00144912 1990/11/01 Preparation of titanium dioxide 57 00144911 1990/11/01 Durable titanium dioxide Method for producing pigment 58 00135895 1990/06/11 Method for preparing titanium dioxide 59 00129750 1990/03/01 titanium dioxide pigment, electrophoretic coating composition containing the pigment, and method for treating titanium dioxide pigment 60 00125278 1989/12/21 Manufacture of titanium dioxide powder 61 00121799 1989/11/01 stabilized titanium dioxide and its manufacturing 62 00120387 1989/10/11 purification method of titanium dioxide ore 63 00118585 1989/09/11 method of forming a titanium dioxide film with controlled optical thickness on a surface 64 00109264 1989/03/01 The device for the spray tube in the Titanium dioxide reactor 65 00101372 1988/07/16 Titanium dioxide pigment coated with boron oxide-modified silicon dioxide 66 00101371 1988/07/16 Titanium dioxide pigment coated with scandium cations, selected acid anions, and alumina, etc. 200540119 67 00066089 1985 / 04/01 Method for making concentrated titanium dioxide 68 00057275 1984/03/16 Method for making concentrated titanium dioxide 69 00051044 1983/06/16 Method for making titanium dioxide 70 00035302 1981/02/01 Method for forming anti-reflective titanium dioxide coating on a substrate 71 00031065 1980/07/01 Manufactured pigment-grade titanium dioxide and alum alumina from artificial rutile 72 00030641 1980/06/01 Manufacturing method of titanium dioxide 73 00026289 1979/09/01 Manufacturing method of titanium dioxide 74 00019405 1975/10/01 Undissolved ilmenite Method for recovering titanium dioxide from waste slag 75 00015939 1974/05/01 Improved manufacturing method for titanium dioxide 76 00010942 1972/06/01 Semiconductor device having titanium dioxide and silicon dioxide composite oxide film and manufacturing method 200540119 Table 2 PAT. NO. Title 1 6,649,561 T Titania-coated honeycomb catalyst matrix for UV-photocatalytic oxidation of organic pollutants, an d process for making 2 6,566,300 T Titania photocatalyst and its preparing method 3 6,455,465 T Photocatalyst coated products and a method for producing a photocatalyst layer 4 6,267,944 T Method of preparing a solution for titania film 5 6,090,489 T Method for photocatalytically hydrophilifying surface and composite material with photocatal ^ ically hydrophilifiable surface 6 5,707,915 T Photocatalyst sheet and method for producing thereof 7 6.699.577 T Air purification-functioning road and method for purifVing polluted air over road 8 6.627.173 T Doped titanium dioxide 9 6.602.607 T Titanium doxide photocatalvst carrier and process for its production 10 6.576.589 T Method for making anatase tvpe titanium dioxide photocatalvst 11 6.558.553 T Photocatalvst 12 6.524.536 T Enhanced oxidation of air contaminants on an ultra-low density UV-accessible aerogel photocatalvst 13 6.517.804 T Ti02 ultrafine oowder, and process for preparing them 14 6.508.941 T Photocatalvtic pr ocess 15 6,406.536 T Organic additives for the DreDaration of cementitious compositions with improved constancy of color 16 6.365.545 T Highly functional base material 17 6.315.963 T Method and aooaratus for the enhanced treatment of fluids via photolvtic and photocatalvtic reactions 18 6.306.796 T Photocatalvst, process for producing the same and multifunctional members 19 6.265.341 T Highly functional base material and a method of manufacturing the same 20 6,241,856 T Enhanced oxidation of air contaminants on an ultra-low density UV-accessible aerogel ohotocatalvst 21 6.139,803 T Photocatalvtic air treatment process under room light 22 6,121,191 T Ultrafine metal particle carrvins photocatalvst, highly function material loaded with the photocatalvst, and method of manufacturing them 200540119 23 6,117,229 T Use of organic additives for the preparation of cementitious compositions with improved properties of constancy of color 24 6,024,929 T Fluorescent lamp wi th a thin film photocatalvst, and method of creating the same 25 5,874.701 T Photocatalvtic air treatment process under room light [Abstract] The present invention is mainly applicable to remove pollutants in water or gas. Due to the high concentration of organic substances in the industrial process, wastewater and wastewater are not easy to handle, and different industries also produce various wastewater compositions. Therefore, we take advantage of the photocatalytic properties of titanium dioxide and use its special reaction mechanism to decompose. Contaminants in water. In order to further improve the photocatalytic effect of titanium dioxide, an appropriate metal is added for modification, and the focus of the present invention is to disclose the production of a nano-scale silver-containing titanium dioxide sol, which is illuminated by a fluorescent lamp or ultraviolet light and has high light Catalytic effect. In order to identify the effect of the photocatalyst, the present invention performs photocatalytic reaction by ultraviolet light or light lamp, and samples the concentration of pollutants at regular intervals. The present invention adopts a nanocrystalline particle suspension coating method to prepare a silver-containing titanium dioxide thin film, and prepares a transparent, stable suspended and photocatalytically active silver / titanium dioxide nanocrystalline particle solution. In the present invention, titanium tetrachloride, which is relatively inexpensive, is used as a raw material to prepare an aqueous solution containing Ag nano-scale titanium dioxide particles as a coating raw material, and the coating is baked. Photocatalytic effect after cloth. This nano-sized titanium dioxide has anatase. This suspension solution is very stable, and nano particles will not aggregate and cause precipitation for more than one year. This solution is weakly acidic or neutral and will not corrode the carrier. First, titanium tetrachloride was slowly added to water at a temperature of 5 to prepare a one mol concentration (1M) aqueous solution, and then 30% ammonia water or sodium hydroxide was added to form a titanium hydroxide colloid solution. After the colloidal solution was filtered through centrifugation, it was washed with water several times until there was no chloride ion (titrated with silver nitrate until no white silver chloride precipitated as the basis of judgment). Add titanium hydroxide colloidal solution and add hydrogen peroxide and silver salts, and then use a three-necked flask to connect a condenser to cook at 60 ° C to 100 ° C for a period of time to obtain nano silver-containing titanium dioxide photocatalyst suspension. The transparent silver-containing titanium dioxide solution can be coated on glass or any carrier such as ceramics and plastic sheets. It can be applied to ultraviolet light or fluorescent lamp as a light source, which will produce a relatively high catalytic activity. The following is a method for making a transparent silver-containing titanium dioxide glass substrate and measuring the activity. 1. Washing the substrate We use glass slides as the substrate. The surface of the glass substrate that has not been washed may have oily substances or other impurities, which may cause uneven coating and peeling during calcination. The glass substrate is washed to make the silver-containing titanium dioxide nano particles more secure. Attach to glass substrate. The procedure for rinsing the substrate is as follows: 200540119 L Place the substrate in a neutral detergent and rinse it for one hour with ultrasonic vibration. 2. Rinse the remaining detergent on the surface of the substrate with deionized water and wash it with ultrasonic vibration for one hour. 3. Place the substrate in a sodium hydroxide solution and wash it with ultrasonic vibration for one hour. 4. Rinse the sodium hydroxide solution left on the surface of the substrate with deionized water, and rinse with ultrasonic vibration for one hour. 5. Put the substrate in an oven to dry and save it for coating. 2. Coating method Dipping coating method or spray coating method can be used. The steps for dip coating are as follows: h Place the coating solution on the lifting machine. 2. Fix the glass substrate to the elevator. 3. Immerse the substrate in the coating solution, the falling rate is 8 cm / min, and stay for 30 seconds. 4. Start to pull up the film, the rising rate is Scm / min. 5 · After the film is finished, put it under UV light for 30 minutes. 6. Place the film in an oven and dry it at 100 ° C for 1 hour to complete the primary coating of titanium dioxide. 7. When making a multilayer film, the above steps must be repeated. X-ray analysis (XRD) Because the composition atoms and lattice planes of each compound crystal are different, when X-rays pass through at different angles of incidence, different diffraction intensities will be generated on different planes. There are three crystal forms of titanium dioxide, namely anatase, rutile and brookite. Among them, anatase is the most photochemically active. The X-ray diffraction pattern of titanium dioxide shows a peak around 2Θ = 25 °, which can be used as a basis for judging the formation of anatase crystals. Transmission Electron Microscopy Analysis (TEM) This study is to make a TEM test sample, from the prepared titanium dioxide particle suspension, take 2 ~ 3 drops, directly drop on the copper mesh, and then put it in an oven, 40 times After drying for 3 hours, put it in a moisture-proof box and wait for measurement. During the measurement, the acceleration voltage of the TEM was fixed at 160 kV. [Embodiment] fc example 1: catalyst synthesis method: containing 2wt% Ag / Ti02, impregnation method, baking powder at 120 ° C, burning at 250 ° C, dissolving ai6g of human 81 ^ 03 in an appropriate amount In pure water, pour 5 g of Ti02 powder. Titanium dioxide is commercially available from Degussa, model P-25, contains 25% rutile, 75% anatase, and its BET surface area is 56 m2 / g. 〇 At room temperature Stir well for 1 hour, dry at 120 ° C, and grind. Then burn in air at 250 ° C 200540119 for 2 hours. The prepared titanium dioxide powder containing 2wt% Ag was light gray in color. For liquid phase photocatalytic reaction of methylene blue, 0.5g of catalyst and methylene blue solution (containing 10,000 ppm of methylene blue) are evenly mixed, and the surrounding area is irradiated with ultraviolet light with a wavelength of 254nm or a fluorescent tube (2 10W lamp tube), take samples every 10 minutes, and then use spectrophotometry to measure the absorption 値 at a wavelength of 662nm. From the change of the absorption, the disappearance rate of methylene blue can be judged. The test results found that after 4 hours, methylene blue disappeared by 24%. First, the effect of the acid and alkali of the titanium hydroxide aqueous solution The acid and alkali of the titanium hydroxide aqueous solution have a great influence on the formation of titanium dioxide particles in the aqueous solution. Titanium tetrachloride is extremely easy to hydrolyze, and can react with water in air oxygen to produce white hydrochloric acid gas. When it is dissolved in water, it will undergo severe hydrolysis, which will reduce the pH of the solution to below 1. Therefore, titanium tetrachloride reacts with alkaline ammonium hydroxide to produce titanium hydroxide immediately, which is a colloidal substance.
TiCU + 4NH4〇H — Ti ( OH ) 4 + 4NH/+ 4C1· 我們製備不同酸鹼値的二氧化鈦溶液，觀察酸鹼値對溶液的影響，這裏所指的酸鹼 値是氨水滴定終止時，溶液的酸鹼値。 溶液組成爲Ti〇2 / H202 / H20 = 1 / 2 / 97 (重量比），90°c加熱迴流2小時 製備過程中發現，溶液的酸鹸値愈高，生成的白色氫氧化鈦顆粒愈大；隨著攪拌時 間和水洗過濾次數增加，氫氧化鈦顆粒會逐漸變小，這是發生水解緣故。由實驗可知， 溶液的酸鹼値至少要8以上，才能製備穩定懸浮的二氧化鈦溶液。 二、 過氧化氫與酸鹼値的關係 過氧化氫爲一弱酸溶液，添加至氫氧化鈦水溶液中，可改變水解縮合平衡進行解膠。加 入過氧化氫後，溶液的酸鹸値即開始下降，過一段時間後，酸鹼値又會回升至驗性範圍。 溶液顏色的變化由原先的白色轉爲黃色、黃橙色，進而變成透明均勻的橙紅色溶液。添 加過氧化氧的量愈多，解膠時間愈短，若添加量不足則無法完全解膠，實驗結果見下表。 三、 加熱溫度與加熱時間的影響 加熱溫度對於二氧化鈦微粒的生成有很大的影響。不同的加熱溫度會改變二氧化鈦 成核速率的快慢，可能會影響二氧化鈦的結晶形態。提高加熱溫度可縮短反應時間並增 加結晶速率，但是也會造成二氧化鈦粒子的粒徑成長較快。 加熱時間增長，使得二氧化鈦粒子的結晶性隨之增加，溶液的透光率愈來愈低，這 是因爲二氧化鈦粒子數持續增加，同時結晶粒子的粒徑也持續變大。 11 200540119 爲了瞭解不同加熱溫度製備之二氧化鈦生成物的結晶形態，我們進行χ射線繞射 分析。加熱溫度在70°C以上，均會形成二氧化鈦銳鈦礦結晶；隨著溫度增加，二氧化 鈦粒子的結晶性也會增加。加熱時間愈長，二氧化鈦粒子的結晶性愈高。 隨著加熱時間增加，二氧化鈦粒子的結晶性呈線性增加。加熱16小時後，溶液漸漸不 透明，表示已有大顆粒子產生。繼續加熱會使得二氧化鈦的結晶性持續增加，但是對 於二氧化鈦溶液覆膜於基材後的透光性及黏著性會產生負面影響，因此欲決定最佳製 備二氧化鈦覆膜液條件時，必須有所取捨。加熱溫度對於二氧化鈦微粒的生成有很大 的影響。不同的加熱溫度會改變二氧化鈦成核速率的快慢，可能會影響二氧化鈦的結 晶形態。提高加熱溫度可縮短反應時間並增加結晶速率，但是也會造成二氧化鈦粒子 的粒徑成長較快。 加熱時間增長，使得二氧化鈦粒子的結晶性隨之增加，溶液的透光率愈來愈低， 這是因爲二氧化鈦粒子數持續增加，同時結晶粒子的粒徑也持續變大。 爲了瞭解不同加熱溫度製備之二氧化鈦生成物的結晶形態，我們進行X射線繞射 分析。發現隨著加熱時間增加，二氧化鈦粒子的結晶性呈線性增加。加熱16小時後， 溶液漸漸不透明，表示已有大顆粒子產生。繼續加熱會使得二氧化鈦的結晶性持續增 加，但是對於二氧化鈦溶液覆膜於基材後的透光性及黏著性會產生負面影響。 四、加熱溫度時間對粒徑的影響 過氧鈦溶膠經迴流加熱後，漸漸形成二氧化鈦微結晶粒子懸浮溶液，加熱時間愈長 使得粒子的粒徑變大。 由以上結果可知，本硏究製備的透明銀/二氧化鈦玻璃基材，經紫外光照射後會產 生強烈的光催化活性。經由穿透式電子顯微鏡(TEM)觀察發現，本硏究製備之二氧化 鈦粒子外觀爲長條狀，而非一般的球體狀。我們以TEM觀察粒徑的結果，成功製備的 二氧化鈦納米粒子懸浮液。圖二到圖五爲TEM的觀察結果。 實施例1 在下的冰浴中，將TiCU緩慢滴入蒸餾水中，製成5摩耳濃度（5M)，再以30% 的氨水，緩慢加入前述溶液，並不斷攪拌直到溶液的pH値爲7經過數次離心、7JC洗， 直到氯的濃度低於lOppm，此時再將其加到蒸餾水中，並加入雙氧水（1%)及硝酸銀， 其Ti02/H202/H20的比例爲1/2/97 (重量比），Ag/Ti02的比例爲2/98 (重量比）此溶液 在三頸圓錐瓶內，上接冷凝管於90°C下煮2小時，即可得到奈米級含銀二氧化鈦溶膠。 實施例2 同實施例卜惟加入氨水後的氫氧化鈦水溶液的pH値爲8。 12 200540119 實施例3 同實施例1，惟加入氨水後的氫氧化鈦水溶液的pH値爲9。 實施例4 同實施例1，惟加入氨水後的氫氧化鈦水溶液的pH値爲1。 比較例2 同實施例1，惟加入氨水後的氫氧化鈦水溶液的pH値爲3。 比較例3 同實施例1，惟加入氨水後的氫氧化鈦水溶液的pH値爲4。 比較例4 同實施例1，惟加入氨水後的氫氧化鈦水溶液的pH値爲6。 結果列於表1 ,本發明係在加入氨水後的溶液，其pH値必須是在7以上，才能在後續 的製程中形成含銀二氧化鈦溶膠。 氫氧化鈦溶液的酸鹼値對二氧化鈦的影響。 例子 酸鹼値 最後產物 比較例1 3 沈澱物顆粒太小，無法經由過濾得到白色氫氧化鈦糕狀物 比較例2 4 黃色透明凝膠 比較例3 6 黃色透明凝膠 實施例1 7 24小時後變成黃色透明凝膠 實施例2 8 黃色透明穩定懸浮液 實施例3 9 黃色透明穩定懸浮液 實施例4 10 黃色透明穩定懸浮液 實施例5 同實施例2，惟其中H2〇2m〇2之重量比爲2。 實施例6 同實施例2，惟其中H2〇2m〇2之重量比爲4。 實施例7 同實施例2，惟其中H2〇2m〇2之重量比爲6。 實施例8 同實施例2，惟其中H2〇2m〇2之重量比爲4，TiCb濃度爲lwt%。 實施例9 同實施例4，惟其中H2〇2/Ti〇2之重量比爲2。 13 200540119 實施例ίο 同實施例4，惟其中H2〇2m〇2之重量比爲4。 表五、過氧化氫濃度對於溶液性質的影響 起始溶液 酸鹼値 Ti〇2濃度 (wt. %) H202/Ti〇2 (重量比） 溶液顏色 5 8 1 2 透明橙紅 6 8 1 4 透明橙紅 7 8 1 6 透明橙紅 8 8 2 4 透明橙紅 9 10 1 2 微透明黃 10 10 1 4 透明黃橙TiCU + 4NH4〇H — Ti (OH) 4 + 4NH / + 4C1 · We prepare titanium dioxide solutions with different acid-base ratios and observe the effect of acid-base ratios on the solution. The acid-base ratios referred to here are the solutions when ammonia titration is terminated. Acid and base 値. The composition of the solution was Ti〇2 / H202 / H20 = 1/2/2/97 (weight ratio). It was found that the higher the acid pH of the solution was, the larger the white titanium hydroxide particles were. ; As the stirring time and the number of washing and filtering times increase, the titanium hydroxide particles will gradually become smaller, which is due to hydrolysis. It can be known from experiments that the stable pH of the solution must be at least 8 in order to prepare a stable suspended titanium dioxide solution. Second, the relationship between hydrogen peroxide and acid-base hydrazone Hydrogen peroxide is a weak acid solution, added to the titanium hydroxide aqueous solution, can change the hydrolysis condensation equilibrium for degumming. After the addition of hydrogen peroxide, the pH of the solution began to decrease, and after a period of time, the pH of the solution would return to the experimental range. The color of the solution changed from the original white to yellow, yellow-orange, and then became a transparent and uniform orange-red solution. The more oxygen peroxide is added, the shorter the degumming time. If the added amount is insufficient, the degumming cannot be completed. The experimental results are shown in the table below. Third, the effect of heating temperature and heating time Heating temperature has a great impact on the formation of titanium dioxide particles. Different heating temperatures will change the nucleation rate of titanium dioxide and may affect the crystalline form of titanium dioxide. Increasing the heating temperature can shorten the reaction time and increase the crystallization rate, but it will also cause the particle size of titanium dioxide to grow faster. As the heating time increases, the crystallinity of the titanium dioxide particles increases, and the transmittance of the solution becomes lower and lower. This is because the number of titanium dioxide particles continues to increase, and the particle size of the crystal particles also continues to increase. 11 200540119 In order to understand the crystal morphology of titanium dioxide products prepared at different heating temperatures, we performed X-ray diffraction analysis. If the heating temperature is above 70 ° C, titanium dioxide anatase crystals will be formed; as the temperature increases, the crystallinity of the titanium dioxide particles will also increase. The longer the heating time, the higher the crystallinity of the titanium dioxide particles. As the heating time increases, the crystallinity of the titanium dioxide particles increases linearly. After 16 hours of heating, the solution gradually became opaque, indicating that large particles had been produced. Continued heating will continue to increase the crystallinity of titanium dioxide, but it will negatively affect the light transmittance and adhesion of the titanium dioxide solution after it is coated on the substrate. Therefore, when determining the optimal conditions for the preparation of titanium dioxide coating liquid, some trade-offs must be made. . The heating temperature has a great influence on the formation of titanium dioxide particles. Different heating temperatures will change the nucleation rate of titanium dioxide and may affect the crystalline morphology of titanium dioxide. Increasing the heating temperature can shorten the reaction time and increase the crystallization rate, but it will also cause the particle size of titanium dioxide to grow faster. As the heating time increases, the crystallinity of the titanium dioxide particles increases and the light transmittance of the solution becomes lower and lower. This is because the number of titanium dioxide particles continues to increase and the particle size of the crystal particles also continues to increase. In order to understand the crystal morphology of titanium dioxide products prepared at different heating temperatures, we performed X-ray diffraction analysis. It was found that as the heating time increased, the crystallinity of the titanium dioxide particles increased linearly. After 16 hours of heating, the solution gradually became opaque, indicating that large particles had been produced. Continued heating will continue to increase the crystallinity of titanium dioxide, but it will have a negative impact on the light transmittance and adhesion after the titanium dioxide solution is coated on the substrate. Fourth, the effect of heating temperature and time on the particle size After the peroxytitanium sol is heated under reflux, it gradually forms a suspension solution of titanium dioxide microcrystalline particles. The longer the heating time, the larger the particle size. From the above results, it can be seen that the transparent silver / titanium dioxide glass substrate prepared in the present study has strong photocatalytic activity after being irradiated with ultraviolet light. Observation through a transmission electron microscope (TEM) revealed that the titanium dioxide particles prepared in this study were elongated in appearance, rather than general spheroids. As a result of observing the particle size by TEM, we successfully prepared a titanium dioxide nanoparticle suspension. Figures 2 to 5 show the results of TEM observations. Example 1 In a lower ice bath, TiCU was slowly dropped into distilled water to make a 5 mol concentration (5M), and then the aforementioned solution was slowly added with 30% ammonia water, and continuously stirred until the pH of the solution was 7 Centrifuge and wash at 7JC several times until the concentration of chlorine is lower than 10 ppm. At this time, add it to distilled water, and add hydrogen peroxide (1%) and silver nitrate. The ratio of Ti02 / H202 / H20 is 1/2/97 ( (Weight ratio), Ag / Ti02 ratio is 2/98 (weight ratio). This solution is placed in a three-necked conical flask and connected to a condenser to cook at 90 ° C for 2 hours to obtain a nanometer silver-containing titanium dioxide sol. Example 2 The pH value of the titanium hydroxide aqueous solution after adding ammonia water was 8 as in Example 1. 12 200540119 Example 3 Same as Example 1, except that the pH value of the titanium hydroxide aqueous solution after adding ammonia water was 9. Example 4 The same as Example 1, except that the pH value of the titanium hydroxide aqueous solution after adding ammonia was 1. Comparative Example 2 The same as Example 1, except that the pH value of the aqueous titanium hydroxide solution after adding ammonia was 3. Comparative Example 3 The same as Example 1, except that the pH value of the titanium hydroxide aqueous solution after adding ammonia was 4. Comparative Example 4 The same as Example 1, except that the pH value of the titanium hydroxide aqueous solution after the addition of ammonia water was 6. The results are listed in Table 1. The solution of the present invention after adding ammonia water must have a pH of 7 or higher in order to form a silver-containing titanium dioxide sol in the subsequent process. Effects of the pH of the Titanium Hydroxide Solution on Titanium Dioxide. Example Acid-base final product Comparative Example 1 3 Precipitate particles are too small to obtain white titanium hydroxide cake by filtration Comparative Example 2 4 Yellow transparent gel Comparative example 3 6 Yellow transparent gel Example 1 24 hours later Yellow transparent gel Example 2 8 Yellow transparent stable suspension Example 3 9 Yellow transparent stable suspension Example 4 10 Yellow transparent stable suspension Example 5 Same as Example 2 except that the weight ratio of H2O2m2 Is 2. Example 6 The same as Example 2, except that the weight ratio of H2202m2 was 4. Example 7 The same as Example 2, except that the weight ratio of H2O2m2 was 6. Example 8 is the same as Example 2, except that the weight ratio of H20m2 is 4 and the concentration of TiCb is 1% by weight. Example 9 The same as Example 4, except that the weight ratio of H2O2 / Ti02 was 2. 13 200540119 EXAMPLE Same as Example 4, except that the weight ratio of H2O2m2 is 4. Table 5. The effect of hydrogen peroxide concentration on the properties of the solution. The initial solution acid-base 〇Ti〇2 concentration (wt.%) H202 / Ti〇2 (weight ratio) solution color 5 8 1 2 transparent orange red 6 8 1 4 transparent orange red 7 8 1 6 transparent orange red 8 8 2 4 transparent orange red 9 10 1 2 slightly transparent yellow 10 10 1 4 transparent yellow orange
進行甲烯藍液相光催化反應時，將0.5克觸媒和亞甲烯藍溶液（含10,000ppm亞甲 烯藍）均勻攪拌混合，周圍用波長爲254nm之紫外光或日光燈管照射（2根10W 的燈管），每隔10分鐘取樣，離心後再用分光光度計量測波長爲062nm時的吸收 値，由吸收度變化情形，可判斷亞甲烯藍的消失率。試驗4小時後之亞甲烯藍消失 率如下。 亞甲烯藍消失率（光照射4小時後) 實驗 以紫外光照射 以曰光燈照射 比較例1 24 2 實施例1 100 96 實施例2 100 96 實施例3 100 88 實施例4 100 82 實施例5 100 84 實施例6 100 82 實施例7 100 80 實施例8 100 92 14 200540119 實施例9 100 84 實施例10 100 81 拾、申請專利範圍： 1. 一種製備銀/二氧化鈦觸媒之方法，其步驟包含： 1. 一種製備含銀二氧化鈦溶膠的方法，它是以四氯化鈦，在5°C下加入水中’形成溶液’ 再加入鹼性溶液，使其形成氫氧化鈦膠體溶液，其pH値在7到12的範圍’再加入 雙氧水及銀的鹽類，形成一水溶液，Ti〇2/H202的重量比在1/2到1/10之間’ Ag/Ti02 的重量比在1/99到5/95之間，Ti02/H20的重比在1/200到20/80之間，此溶液再在 60至100°C的範圍內加熱，直到膠體完全消失，即形成含銀二氧化鈦溶膠，固體顆 粒以奈米級分散，穩定懸浮於水中。 2. 如申請專利範圍第1項，其中氫氧化鈦膠體溶液的pH値，最佳是在8與10之間。 3. 如申請專利範圍第1項，其中Ti02/H202的重量比最佳是在1/2到1/4之間。 4. 如申請專利範圍第1項，其中Ag/Ti02的重量比最佳是在1/99到4/96之間。 5·如申請專利範圍第1項，其中Ti02/H20的重量比最佳是在1/200到4/96之間。 6.如申請專利範圍第1項，其中加熱溫度最佳是在80至99°C之間。 7·如申請專利範圍第1項所製得的Ag/Ti02溶膠，直接加入廢水溶液中，再以紫外光、 太陽光或日光燈照射後，可達到分解有機物的方法。 8.如申請專利範圍第1項所製得的Ag/Ti02溶膠，以噴灑或浸漬方法覆膜於任何載體， 如瓷磚、玻璃、纖維布、皮革等，以紫外光、曰光燈或太陽光照射做爲氣體中之有 機物質分解之方法。 9· 一種物質，其係以申請專利範圍第1項的方法製造，它含有Ag/Ti02奈米顆粒懸浮 於水中，其固體含量佔全部重量的0.5至20%，Ag/Ti02重量比爲1/99到4/96之間， 且溶液之pH値爲5到8之間。 15For liquid phase photocatalytic reaction of methylene blue, 0.5g of catalyst and methylene blue solution (containing 10,000 ppm of methylene blue) are evenly mixed, and the surrounding area is irradiated with ultraviolet light or fluorescent tube with a wavelength of 254nm (2 10W lamp tube), take samples every 10 minutes, and then measure the absorption 値 at a wavelength of 062nm by centrifugation, and the disappearance rate of methylene blue can be judged by the change of the absorption. The disappearance rate of methylene blue after 4 hours of the test is as follows. Extinction rate of methylene blue (4 hours after light irradiation) Experiment was irradiated with ultraviolet light and irradiated with a lamp. Comparative Example 1 24 2 Example 1 100 96 Example 2 100 96 Example 3 100 88 Example 4 100 82 Example 5 100 84 Example 6 100 82 Example 7 100 80 Example 8 100 92 14 200540119 Example 9 100 84 Example 10 100 81 Scope of patent application: 1. A method for preparing a silver / titanium dioxide catalyst, its steps Containing: 1. A method for preparing silver-containing titanium dioxide sol, which is based on titanium tetrachloride and added to water to form a solution at 5 ° C, and then an alkaline solution is added to form a colloidal solution of titanium hydroxide. In the range of 7 to 12, 'add hydrogen peroxide and silver salts to form an aqueous solution. The weight ratio of Ti〇2 / H202 is between 1/2 and 1/10.' The weight ratio of Ag / Ti02 is 1/99 to Between 5/95, the weight ratio of Ti02 / H20 is between 1/200 and 20/80, and the solution is heated in the range of 60 to 100 ° C until the colloid completely disappears, that is, a silver-containing titanium dioxide sol is formed. The solid The particles are dispersed at the nanometer level and stably suspended in water. 2. As for the first item in the scope of patent application, the pH of the titanium hydroxide colloidal solution is preferably between 8 and 10. 3. As for the first item in the patent application scope, the weight ratio of Ti02 / H202 is preferably between 1/2 and 1/4. 4. As for the first item in the patent application scope, the weight ratio of Ag / Ti02 is best between 1/99 and 4/96. 5. As the first item in the scope of patent application, the best weight ratio of Ti02 / H20 is between 1/200 and 4/96. 6. According to the first patent application range, the heating temperature is preferably between 80 and 99 ° C. 7. The Ag / Ti02 sol prepared as described in item 1 of the scope of patent application can be directly added to the wastewater solution, and then irradiated with ultraviolet light, sunlight or fluorescent lamp to achieve the method of decomposing organic matter. 8. Ag / Ti02 sol prepared according to item 1 of the scope of patent application, spray or impregnate on any carrier, such as tiles, glass, fiber cloth, leather, etc., with ultraviolet light, fluorescent lamp or sunlight Irradiation is used as a method for the decomposition of organic substances in gases. 9. A substance manufactured by the method in the first patent application scope, which contains Ag / Ti02 nano particles suspended in water, and its solid content accounts for 0.5 to 20% of the total weight, and the Ag / Ti02 weight ratio is 1 / It is between 99 and 4/96, and the pH of the solution is between 5 and 8. 15