541285 A7541285 A7
五、發明説明（1 ) 發明領域 本發明係揭示—種二氧化鈦（丁办）陶究粉體之新穎合 成方法及财法所合成之三氧化鈦粉體。該方法係將含鈦 離子之水溶液加人含有界面活性誠同時含有界面活性劑 與共界面活性劑之有機溶射抑混合或祕，以使該水 溶液分散_有機溶射而形成含鈦軒之—乳膠或顯微 乳膠溶液，再將另一含氫氧根離子之水溶液，依上述方 法，製備成含氫氧根離子之乳膠或顯微乳膠液後，再將上 述含鈦離子及氫氧根離子之乳膠或顯微乳膠溶液混合或攪 拌，隨後經過水熱（hydrothermal)反應處理，以合成二氧 化鈦粉體。本發明方法藉由乳膠或顯微乳膠粒子之控制， 並經由水熱反應，可製付次微米級至奈米級之結晶態二氧 化鈦粉體。 發明背景 經濟部智慧財產局員工消費合作社印製 ---------衣------"訂 (請先閱讀背面之注意事項再填寫本頁) 二氧化鈦陶瓷為重要陶瓷材料之一，廣泛應用於塗料 工業、結構陶瓷、太陽電池及電子陶瓷元件中。電子陶瓷 領域之應用包括積層陶瓷電容、感測器、壓電陶瓷添加劑 等。近年來另一種重視之發展領域為光觸媒材料上。工業 過度的發展使得地球產生溫室效應、氣候異常、臭氧層破 洞等環境危機，使得人們不得不正視這個與日遽增的環保 -4- 本紙張尺度適用中國國家標準（CNS)A4規格（210X297公釐） ^ 541285 A7 B7 五、發明説明（2 ) 經濟部智慧財產局員工消費合作社印製 f適 張 一紙 本 問題。如今環保意識抬頭，地球村的永續發展觀念將是目 前全世界最重要的課題之一，生產與環保相關的「綠色產 品」將成為世界潮流的新趨勢。而「光觸媒Ti〇2」正是目 前相當受到矚目的一種綠色產品。曰本東京大學的藤嶋昭 教授在1972年發現了 Ti〇2的光化學特性，使得丁丨〇2的光 觸媒特性從此受到世人的重視。各國也在近年來陸續發表 了光觸媒Ti〇2的相關產品。Ti〇2早期被用來當作白色顏料 的主要來源，後來Ti〇2的光觸媒效用被發現後，光觸媒的 相關研究便迅速展開。光觸媒顧名思義必須要有光的存在 才可以發揮其功效。光觸媒Ti〇2受到大於Ti〇^^^b(Band gaP)寬度之光線照射之後，電子會從導電帶躍遷至價帶， 因而產生電子_電洞對，其中電子具還原性，電洞具氧化 性，電洞會和风表面的OH·反應生成氧化性很高的〇H 自由基，活潑的OH自由基可以把有機物降解變為 H2〇，因而達到淨化的效果。利用以上原理，光觸媒丁丨〇2 會有「抗菌」、「防污」、「除霧」、「脫臭」、「淨 水」、「抗癌」等特性。二氧化鈦因為具有良好光學活 性、物理與化學性質穩定等優點，所以成為重要光觸媒料。 左Ti〇2粉體的製備過程對於光觸媒的特性有極大影響。 隨著製備方法或製程參㈣不同，不但會影響粉體S子 用中國 — (請先閱讀背面之注意事項再填寫本頁) *訂 541285 A7 B7 五、發明説明（3V. Description of the invention (1) Field of the invention The present invention discloses a novel synthesis method of titanium dioxide (Dingban) ceramic powder and titanium dioxide powder synthesized by financial law. The method is to mix or secrete an aqueous solution containing titanium ions with an organic solvent containing interfacial activity and simultaneously containing a surfactant and a co-surfactant, so as to disperse the aqueous solution and organically spray to form a titanium-containing compound—latex or After the microemulsion solution and another hydroxide ion-containing aqueous solution are prepared into a hydroxide ion-containing latex or a microemulsion according to the above method, the titanium ion and hydroxide ion-containing latex are then prepared. Or the microemulsion solution is mixed or stirred, followed by hydrothermal reaction treatment to synthesize titanium dioxide powder. The method of the present invention can produce sub-micron to nano-sized crystalline titanium dioxide powder through the control of latex or micro-latex particles and through hydrothermal reaction. Background of the Invention Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --------- Clothing ------ " Order (Please read the precautions on the back before filling this page) Titanium dioxide ceramic is an important ceramic material One is widely used in the coating industry, structural ceramics, solar cells and electronic ceramic components. Applications in the field of electronic ceramics include multilayer ceramic capacitors, sensors, and piezoelectric ceramic additives. In recent years, another important development area is photocatalyst materials. Excessive industrial development has caused the earth to produce environmental effects such as the greenhouse effect, climate anomalies, and ozone hole breakouts, making people have to face up to this growing environmental protection. -4- This paper size applies the Chinese National Standard (CNS) A4 specification (210X297). ^) 541285 A7 B7 V. Description of the invention (2) Printed on a paper sheet by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Now that environmental awareness is rising, the concept of sustainable development of the global village will be one of the most important issues in the world. The production of "green products" related to environmental protection will become a new trend in the world. And "Photocatalyst Ti02" is a kind of green product that attracts much attention at present. Professor Fujimaki Akira of the University of Tokyo discovered the photochemical properties of Ti〇2 in 1972, which made Ding O 2's photocatalyst characteristics ever more important. Various countries have also released related products of photocatalyst Ti02 in recent years. In the early days, Ti〇2 was used as the main source of white pigments. Later, after the photocatalytic effect of Ti〇2 was discovered, related research on photocatalysts began quickly. Photocatalyst, as its name implies, requires the presence of light in order to exert its effect. After photocatalyst Ti〇2 is irradiated with light larger than the width of Ti〇 ^^^ b (Band gaP), the electrons will transition from the conductive band to the valence band, thus generating an electron_hole pair, among which the electron is reducing and the hole is oxidizing The pores will react with the OH · on the wind surface to generate highly oxidative 0H radicals. The active OH radicals can degrade organic matter into H2O, thus achieving a purification effect. Utilizing the above principles, photocatalyst D02 has characteristics such as "antibacterial", "antifouling", "defogging", "deodorizing", "purifying water", and "anticancer". Titanium dioxide is an important photocatalyst because of its advantages such as good optical activity and stable physical and chemical properties. The preparation process of the left Ti〇2 powder has a great influence on the characteristics of the photocatalyst. With different preparation methods or process parameters, it will not only affect the powder S. Use China — (Please read the precautions on the back before filling out this page) * Order 541285 A7 B7 V. Description of the invention (3
型態、晶粒大小、晶相、及比表面積等，更會對最終的光 觸媒活有很大t響。過去以利肖火焰熱分解法製備二氧 化鈦知體％，因於高溫火焰中生成了处粉體，故其生成的 產物中含有3G %的金紅石相及7G %的銳鈦翻Ti〇2，無 法製得純相銳鈦礦相Ti〇2，且粒徑大及凝團嚴重，故光觸 媒活性不高。錢轉方法製備錢，但因其水解速 率過快’故容易造成Ti〇2粒子的凝團，不易製備奈米級粉 體。溶膠凝膠法-般多用醇鹽為起始物，使用原料昂貴， 且反應程序，獨社業大量生產使用。 為了解決以上問題，發明人致力進行列研究實驗 之後’首先發簡定二氧化鈦鍾之合成方法，不但得到 具有超微峰健為結晶社二氧減缝，而完成本發 明0 X (請先閱讀背面之注意事項再填寫本頁} _裝 *訂 經 濟 部 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 SS3ZSM 本發明之目的在於提供一種合成超微細二氧化鈦 (叫）H棚之方法，及财法所合 几 ::方法係將含鈦離子之水溶液加入―含界面:： ，含有界面活_及共界面活㈣之麵娜 = 合或携拌，以使該水溶液分散於該有機溶射而 二 鈦離子之郷或顯微«溶液；再將另—含魏根離^ 本紙張尺度適用中國國家標準（CNS ) A4規格（2]〇χ297公釐 541285 A7 "~--- B7五、發明説明（斗） f溶液’依上財法，製備成含魏根離子之乳膠或顯微 礼谬液後’再將上述含麟子及氫氧根軒之乳谬或顯微 孔膠溶液混合錢拌，隨後、_摊（㈣她⑽⑴反應 处理以&成結aaa ,¾、之二氧化鈦粉體。本發明方法夢 膠或顯微«粒子之控制，並經由水熱反應，可製得次微 米級至奈米級之結晶態二氧化鈦粉體。其巾該水溶液與該 有機溶劑之體積比為讀〜2.()，該界面潍辦該有機溶 劑之體積比為_〜L2，該共界面雜顺财機溶劑之 體積比值為0〜1.2。 本發明之3 -目的在於提虹述合翁摘合成之二 氧化鈦陶瓷粉體。· 本發明之方法可製得具銳鈦礦型結晶態之二氧化欽粉 體’因乳縣液㈣，可成功製得奈雜an_ter^ 體’並改變其形態以增大比表面積，故增大為觸媒活性； 並因利用水熱反應，可於低溫製得結晶態粉體，以降低製 程成本。 (請先閱讀背面之注意事項再填寫本頁) >裝· 、訂 經濟部智慧財產局員工消費合作社印製 MSMSI 圖1係實例1所合成之二氧化鈦粉體之X射線繞射圖。 圖2係實例丨以合成之二氧化鈦粉體之穿透式電子顯微鏡 照片。 …、兄 本紙張尺度適用中國國家標準（CNS ) Μ規格（21〇Χ297公釐） 541285 A7 ______ B7 五、發明説明（ί ) 圖3係實例3所合成之二氧化鈦粉體之χ射線繞射圖。 圖4係實例3以合成之二氧化鈦粉體之穿透式電子顯微鏡 照片。 圖5係實例1所合成之二氧化鈦粉體之亞曱基藍分解狀態 與照光時間關係圖。 經濟部智慧財產局員工消費合作社印製 本务明係利用水相及有機相（油相）不互溶之觀余， 先製備將含有鈦離子之水溶液，製備得一均勻水溶液。再 將該水溶液置於有機溶劑中（例如笨、甲苯、二甲笨、己 、凡庚k、辛;|:兀、壬;J:兀、癸烧、礦油、環己烧、環庚烧、 環辛烧、環壬烧、及環癸院等，但不限於此），因水相與 油相互不相洛，故會形成一層溶液，為使水相溶液均勾分 散於有機溶劑，故加入界面活性劑或同時加入界面活性劑 與共界面活性劑於有機溶劑中，經混合或攪拌後，水相溶 液被分散為一顯微液滴或微胞，安定地分散於連續相（油 相）中，而形成第一種乳膠或顯微乳膠液。因每一液滴大 小在奈米（職〇她〇至次微米之間，且每一液滴為一獨 立反應器，故可使合成粉體之粒徑大為減小，且粒徑分布 狹窄，粉體形態均一。 再為促進二氧化鈦生成反應，再將含有氣氧根離子水 本紙張尺度適用中國國豕標準（CNS ) A4規格（210 χ 297公麓） 541285 Α7 Β7 五、發明説明（t) 洛液（例如氨水、氫氧化鈉水溶液、氫氧化鉀水溶液、氯 氧化鐘水溶液等，但不限於此）依上述方法置於有機溶劑 中混合後’加入含有界面活性劑或同時含有界面活性劑與 共界面活性劑之有機溶劑中予以混合或攪拌，形成第二種 乳膠或顯微乳膠液。 為促進粉體可於低溫結晶化，故不採傳統製程乾燥及 煆燒處理，本發明直接將上述含鈦離子及氫氧根離子之乳 膠或顯微乳膠溶液混合或攪拌後，置於水熱反應密閉容器 中，進行水熱（hydrothermal)反應，故於低溫反應下製得 具銳鈦礦型之超微細二氧化鈦粉體，粉體粒裎可控制於奈 米級，提高其比表面積，及增大光觸媒活性。 本發明之特色及在於結合乳膠法之概念及水熱反應之 優點，利用乳膠或顯微乳膠之形成，以控制微胞粒子大 小，可合成奈米粉體；再行利用水熱之低溫高溫反應，故 可於低溫合成100%純相之銳鈦礦型結構並具有奈米粒徑 之粉體，有效控制其粒徑，並增大光觸媒活性。 本發明之混合溶液之鈦離子及含有氫氧根族離子水溶 液濃度各自獨立為0·01 Μ〜10M，較佳濃度各自獨立為 0.05Μ〜8Μ，最佳濃度各自獨立為〇.1Μ〜5Μ。。所用 鈦金屬鹽或化合物只要是可溶解於水中者即可，並不特別 受限，例如可為硝酸鹽、醋酸鹽、硫酸鹽、草酸鹽、氯化 本紙張尺度適用中國國家標準（CNS ) Α4規格（210Χ297公釐） (請先閱讀背面之注意事項再填寫本頁) _裝_ 訂 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 541285 A7 —----- —_ B7 _ 五、發明説明（7) 物等。鈦離子及氫氧根離子水溶液與有機溶劑之體積比值 各自獨立為0.01〜2，較佳體積比值各自獨立為〇 〇5〜1;界 面活性劑與有機溶劑之體積比值為0.01〜I·2，較佳體積比 值為0.04〜〇.9;其中共界面活性劑與有機溶劑之體積比值為 〇 I·2，較佳體積比值為〇〜0.9。水熱反應溫度為1〇〇π〜 350°C，其中該水熱反應時間為3〇分鐘〜8小時。為控制 一種礼膠或顯微乳膠混合後之pH值，可另添加其他酸性 溶液（如硝酸）或鹼性溶液（如氨水）於混合溶液十，pH 值為1至12。 本發明之方法所使用之有機溶劑只要與水不互溶之有 機溶劑即可，其種類並不限定。常用之有機溶劑中，以 苯、甲苯、二甲苯、己烧、庚院、辛烧、壬烧、癸烧、礦 油、環己烷、環庚烷、環辛烷、環壬烷、環癸烷、及烷類 衍生物等較佳。其使用之有機溶劑可為上述之混合物。 本發明之方法中所使用之界面活性劑為只要能使水相 與所用之油相在混合攪拌之後形成顯微乳膠者即可，其種 類並不受限定。一般市售之界面活性劑中常用者有Span 20、Span 40、Span 60、Span 80、Span 85、ΟΡ-ΙΟ (聚氧化 乙烯辛基苯脂 polyoxyethylene (10) octylphenyl ether)(以上 為 Wako Pure Chemical Industries Ltd· Japan 之商品名，可由 市面上輕易購得且其成份一定）、Tween 20、Tween 40、 本紙張尺 用tii家標準（cns ) A4規格（ziox挪公釐） ----.--^------^9. (請先閲讀背面之注意事項再填寫本頁) 541285 A7 B7 五、發明説明（夕）Type, grain size, crystal phase, and specific surface area, etc., will have a great impact on the final photocatalyst activity. In the past, the Lithium Oxide flame thermal decomposition method was used to prepare% titanium dioxide. Due to the formation of powders in the high-temperature flame, the resulting product contains 3G% rutile phase and 7G% anatase TiO2. The pure phase anatase phase TiO2 is prepared, and the particle size is large and the agglomeration is serious, so the photocatalytic activity is not high. The money transfer method is used to prepare money, but because its hydrolysis rate is too fast ', it is easy to cause agglomeration of Ti02 particles, and it is not easy to prepare nano-grade powder. The sol-gel method usually uses alkoxide as a starting material, uses expensive raw materials, and has a reaction procedure, which is produced and used in large quantities by the company. In order to solve the above problems, the inventor committed to conduct a series of research experiments. 'First, the synthesis method of the titanium dioxide clock was first outlined, and not only the ultra-low peak strength was obtained, but the crystal oxygen reduction joint was completed. Please pay attention to this page before filling in this page} _ Binding * Order Printing of SS3ZSM by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The purpose of the present invention is to provide a method for synthesizing ultra-fine titanium dioxide (called) H shed, and a combination of financial law :: The method is to add an aqueous solution containing titanium ions to the interface containing ::, containing the surface activity and the co-interface activity, and to mix or carry together, so that the aqueous solution is dispersed in the organic solvent and the dititanium ion is Micro «solution; then another-containing Wei Genli ^ This paper size applies Chinese National Standard (CNS) A4 specifications (2) 0297 mm 541285 A7 " ~ --- B7 V. Description of the invention (bucket) f solution 'According to the law of wealth, prepare the latex or micro-liquor solution containing Weigen ions', and then mix the above-mentioned latex or microporous gum solution containing Linzi and hydroxide radicals, and then, (㈣She⑽ The reaction treatment is & forming aaa, ¾, titanium dioxide powder. The method of the present invention can be controlled by dream gel or microscopic «particles, and through hydrothermal reaction, crystalline titanium dioxide powder of submicron to nanometer grade can be prepared. The volume ratio of the aqueous solution to the organic solvent is read ~ 2. (), the interface Weiban the volume ratio of the organic solvent is _ ~ L2, and the volume ratio of the co-interface heterosequence solvent is 0 ~ 1.2. The third aspect of the present invention is to raise titanium dioxide ceramic powder synthesized by Hehong Heweng. · The method of the present invention can produce anatase-type crystalline dioxin powder 'Yinxian liquid tincture, The nano-anterite body can be successfully prepared and its morphology changed to increase the specific surface area, thus increasing the catalyst activity; and due to the use of hydrothermal reactions, crystalline powders can be produced at low temperatures to reduce process costs. (Please read the precautions on the back before filling out this page) > Packing, ordering, and printing MMSSI printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Figure 1 is an X-ray diffraction pattern of the titanium dioxide powder synthesized in Example 1. Figure 2 Examples 丨 Synthetic titanium dioxide powder Photograph of a transmission electron microscope.…, The size of this paper is applicable to the Chinese National Standard (CNS) M specification (21 × 297 mm) 541285 A7 ______ B7 V. Description of the invention (ί) Figure 3 is the titanium dioxide powder synthesized in Example 3 X-ray diffraction diagram. Fig. 4 is a transmission electron microscope photograph of the synthesized titanium dioxide powder in Example 3. Fig. 5 is a graph showing the relationship between the decomposition state of arylene blue and the irradiation time of the titanium dioxide powder synthesized in Example 1. Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the use of the water phase and the organic phase (oil phase) are not compatible, and first prepare an aqueous solution containing titanium ions to obtain a uniform aqueous solution. The aqueous solution is then placed in an organic solvent (e.g., benzyl, toluene, dimethylbenzyl, hexamethylene, pentylene k, xin; |: wu, ren; J: wu, sesame oil, mineral oil, cyclohexane, cycloheptane , Cycloxin, cyclic sesame, cyclohexan, etc., but is not limited to this), because the water phase and the oil are different from each other, a layer of solution will be formed. In order to disperse the aqueous phase solution in organic solvents, Add the surfactant or add the surfactant and co-surfactant in the organic solvent at the same time. After mixing or stirring, the aqueous solution is dispersed into a micro-droplet or micro-cell, and is stably dispersed in the continuous phase (oil phase ) To form the first latex or microemulsion. Because the size of each droplet is between nanometers and 0 microns, and each droplet is an independent reactor, the particle size of the synthetic powder can be greatly reduced, and the particle size distribution is narrow. In order to promote the titanium dioxide generation reaction, the paper size containing oxygen and oxygen ions is applied to the Chinese National Standard (CNS) A4 specification (210 χ 297 male feet) 541285 Α7 B7 V. Description of the invention (t ) Luo liquid (such as ammonia, sodium hydroxide, potassium hydroxide, chlorinated water, etc., but not limited to this) in the organic solvent mixed according to the method described above, 'adding surfactant or both surfactants It is mixed or stirred in an organic solvent with a co-surfactant to form a second latex or microemulsion. In order to promote the powder to crystallize at low temperature, the traditional process of drying and calcining is not used. After the above-mentioned latex or microemulsion solution containing titanium ions and hydroxide ions is mixed or stirred, it is placed in a hydrothermal reaction closed container to perform a hydrothermal reaction. An anatase-type ultra-fine titanium dioxide powder is prepared below, and the particle size of the powder can be controlled to the nanometer level to increase its specific surface area and increase the photocatalytic activity. The feature of the present invention is to combine the concept of latex method and water The advantages of thermal reaction, the use of latex or microemulsion formation to control the size of microcell particles, nano-powder can be synthesized; and the use of hydrothermal low temperature and high temperature reaction, so 100% pure phase anatase can be synthesized at low temperature The powder with a nanometer-sized structure and effective structure controls its particle size and increases the photocatalytic activity. The concentrations of the titanium ion and the hydroxide group ion-containing aqueous solution of the mixed solution of the present invention are each independently from 0. 01 M to 10 M. The preferred concentrations are each independently 0.05M to 8M, and the optimal concentrations are each independently 0.1M to 5M. The titanium metal salt or compound used is not particularly limited as long as it is soluble in water. For example, it may be Nitrate, acetate, sulfate, oxalate, chloride This paper is sized to the Chinese National Standard (CNS) A4 (210 × 297 mm) (Please read the precautions on the back before filling this page) _ 装 _ Order Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed 541285 A7 —----- —_ B7 _ V. Description of the Invention (7) etc. Titanium ion and hydroxide ion aqueous solution The volume ratios to the organic solvent are each independently 0.01 to 2, preferably the volume ratios are each independently to 0.05 to 1; the volume ratio of the surfactant to the organic solvent is 0.01 to 1.2, and the preferred volume ratio is 0.04 to 〇. .9; wherein the volume ratio of the co-surfactant to the organic solvent is 0I · 2, and the preferred volume ratio is 0 ~ 0.9. The hydrothermal reaction temperature is 100π ~ 350 ° C, where the hydrothermal reaction time is 30 minutes to 8 hours. In order to control the pH value of a kind of gift gel or microemulsion, other acidic solutions (such as nitric acid) or alkaline solutions (such as ammonia) can be added to the mixed solution. The pH value is 1 to 12. The organic solvent used in the method of the present invention is not limited as long as it is an organic solvent which is immiscible with water. Among the commonly used organic solvents, benzene, toluene, xylene, hexane, Gengyuan, octane, nonan, decane, mineral oil, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane Alkanes and alkane derivatives are preferred. The organic solvent used may be a mixture of the above. The surfactant used in the method of the present invention is not limited as long as it can cause the water phase and the oil phase used to form a microemulsion after being mixed and stirred. Commonly used commercially available surfactants are Span 20, Span 40, Span 60, Span 80, Span 85, ΟΡ-ΙΟ (polyoxyethylene (10) octylphenyl ether) (the above is Wako Pure Chemical The trade names of Industries Ltd. Japan can be easily purchased on the market with certain ingredients), Tween 20, Tween 40, and the paper ruler uses the TII standard (cns) A4 specification (ziox Norm) ----.- -^ ------ ^ 9. (Please read the notes on the back before filling out this page) 541285 A7 B7 V. Description of the invention (Xi)
Tween 60、Tween 65、Tween 80、Tween 85 (以上為 FlukaTween 60, Tween 65, Tween 80, Tween 85 (above Fluka
Chemie AG，Switzerland之商品名，可由市面上輕易購得且 其成份一定）、Brij 30、Brij 35、Brij52、Brij56、Brij 58、 Brij 72、Brij76、Brij 78、Brij92、Brij 97、Brij 98、Chemie AG, the trade name of Switzerland, can be easily purchased on the market with certain ingredients), Brij 30, Brij 35, Brij52, Brij56, Brij 58, Brij 72, Brij76, Brij 78, Brij92, Brij 97, Brij 98,
Span83、CTAB、Igepal CA-210、Igepal CA-520、Igepal CA-720、Igepal CO-210、Igepal CO-520、Igepal CO-720、 Igepal CO-890、Igepal CO-990、Igepal DM-970 (以上為 Aldrich Chemical Company.Inc·，U.S.A·之商品名，可由市面 上輕易購得且其成份一定）、犯>5、柯>9 (以上為Albright and WilsonAsiaPte. Ltd” Singapore 之商品名，可由市面上 輕易購得且其成份〇、Α〇τ (以上為恤❿⑽㈣ Company ’ U.S.A.之商品名’可由市面上輕易購得且其成 份-定）、NP4、DP6 (以上為 Phone_P〇ulencInc·之商品 名’可由市面上輕易購得且其成份一定）、TritonX·、 X] 14、Trit〇n χ·3〇5、刊她 (以上為心― 經濟部智慧財產局員工消費合作社印製 -裝-- (請先閱讀背面之注意事項再填寫本育) 訂 ^e’l'Japan之商品名，可由市面上輕易賭得且其成 刀一定）。其使用之界面活性劑可為上述之混合物。 該此ί增！7顯微乳膠之穩定度，可另外添加共界面溶劑， 限定二t劑只要可形成顯微乳膠者即可，其麵並不受 内醇Γ般常用之共界面活性劑有醇類及醇類衍生物，如 己醇、庚醇、異丙醇、異丁醇、異戊 541285 、發明説明（ 醇等。其使用之共界面活性劑可為上述之混合物。如顯微 乳膠穩定度已足夠時，可不須添加共界面溶劑。於本發明 所製知之—氧化鈦碰，可再進行高溫煆燒 ’以提南其結 晶性。假燒溫度範圍是3贼〜9()叱，較佳煆燒溫度範圍 是 400°C 〜800°C。 以下炫以貫施例例示本發明，但本發明並不受限於此 等實施例。實例1 (請先閱讀背面之注意事_ —^裝-- 項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 將四氯化鈦溶於水中後，製備得鈦離子濃度為α2Μ 之水溶液。另將氫氧化鈉溶於水中，得氫氧根離子濃度為 1 Μ之鹼性水溶液，分別製得含鈦離子之水相及含氫氧根 離子之水相。再於環己烷中加入界面活性劑〇ρ_1〇及共界 面活性劑己醇，製得油相溶液。界面活性劑與環己燒體積 比為0.3，共界面活性劑與環己烷體積比為0·2。取含鈦離 子之水相溶液與上述油相溶液於1 : 10體積比之情況下， 加以混合及攪拌後，製得含鈦離子之顯微乳膠溶液。再取 含氫氧根離子之水相溶液與上述油相溶液於1 : 1〇體積比 之情況下，加以混合及攪拌後，製得含氫氧根離子之顯微 乳膠溶液。再將含鈦離子之顯微乳膠溶液及含氫氧根離子 之顯微乳膠溶液混合與攪拌後，於150°C在密閉容器中進 -12- 一^^國國家標隼（CNS ) A4規格（210X297公釐） 訂 541285 A7 B7 五、發明説明（丨〇 ) 經濟部智慧財產局員工消費合作社印製 行水熱反應(hydr〇th_ireacti〇n)1小時，經過漁 之粉體進行X鱗齡分析，其縣圖秘圖錢仔 一 。如 |^| 所不’所彳f之粉體為二氧化鈦喊粉體，且由X 圖譜與標準®譜輯，可得知該化合物具有触礦相=、 構。所得粉體之穿透式電子顯微鏡照片如圖 : 2可知所合成二氧化鈦粉體粒徑為奈米級，粉體呈棒狀， 粉體形態均勻，分散良好。本實施顺日㈣用本發明 乳膠水熱合成法，可於15Gt低溫下料奈米級且具銳欽 礦相結構之二氧化鈦粉體。 ^MM2 將四氯化鈦溶於水中後，製備得鈦離子濃度為❶心之 水溶液。另調配濃麟i Μ之氨水驗性水溶液，分別製得 含鈦離子之水相及氨水之水相。再於環己院巾加入界面活 性劑ΟΡ-Η)及共界面活性劑己醇，製得油相溶液。界面活 性劑與環己㈣積比為0.3，共界面活性劑與環己院體積比 為0.2。取含鈦離子之水相溶液與上述油相溶液於丨：體 積比之情況下，加以混合及授拌後，製得含鈦離子之顯微 乳膠溶液。再取氨水之水相溶述油相溶液於】·· 1() 體積比之情況下，加以混合及授拌後，製得含氣氧根離子 之顯微乳膠溶液。再將含鈦離子之顯微乳膠溶液及含氫氧 (請先閲讀背面之注意事項再填寫本頁)Span83, CTAB, Igepal CA-210, Igepal CA-520, Igepal CA-720, Igepal CO-210, Igepal CO-520, Igepal CO-720, Igepal CO-890, Igepal CO-990, Igepal DM-970 (above Is the trade name of Aldrich Chemical Company. Inc., USA. It can be easily purchased on the market and its composition is certain), guilty > 5, Ke > 9 (The above are the trade names of Albright and WilsonAsiaPte. Ltd "Singapore. Easily available on the market and its ingredients 0, Α〇τ (the above is the product name of the company “USA” can be easily purchased on the market and its ingredients-fixed), NP4, DP6 (the above is the product of Phone_P〇ulencInc · The name 'can be easily purchased on the market and its ingredients are certain), TritonX, X] 14, Triton χ · 305, publication of her (the above is the heart-printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-installed- -(Please read the precautions on the back before filling in this education) Order ^ e'l'Japan's trade name, which can be easily betted on the market and it must be a knife.) The surfactant used in it can be the above mixture. This should increase! 7 The stability of the microemulsion can be Adding a co-interface solvent, limiting the two t agents as long as they can form a microemulsion, the surface is not affected by the internal alcohol Γ commonly used co-surfactants are alcohols and alcohol derivatives, such as hexanol, heptanol, Isopropanol, isobutanol, isoamyl 541285, description of the invention (alcohol, etc.). The co-surfactant used can be the above-mentioned mixture. If the stability of the microemulsion is sufficient, it is not necessary to add a co-interface solvent. Known by the invention-Titanium oxide can be subjected to high temperature sintering to improve its crystallinity. The temperature range of the false sintering is 3 ~ 9 () 煆, and the preferred sintering temperature range is 400 ° C to 800 ° C. The following examples are illustrative of the present invention, but the present invention is not limited to these examples. Example 1 (Please read the note on the back _ — ^ installed-before filling out this page) Intellectual Property of the Ministry of Economic Affairs The bureau ’s consumer cooperative printed the titanium tetrachloride dissolved in water to prepare an aqueous solution with a titanium ion concentration of α2M. In addition, sodium hydroxide was dissolved in water to obtain an alkaline aqueous solution with a hydroxide ion concentration of 1M, respectively. Preparation of aqueous phase containing titanium ions and aqueous phase containing hydroxide ions .The surfactant 〇ρ_1〇 and the co-surfactant hexanol were added to cyclohexane to prepare an oil phase solution. The volume ratio of the surfactant to cyclohexane was 0.3 and the volume ratio of the co-surfactant to cyclohexane. It is 0.2. A titanium emulsion-containing aqueous phase solution and the above oil-phase solution are mixed at a volume ratio of 1: 10, and after mixing and stirring, a titanium ion-containing microemulsion solution is prepared. Then, the aqueous phase solution containing hydroxide ions and the above-mentioned oil phase solution are mixed at a volume ratio of 1: 1, and after stirring and mixing, a microemulsion solution containing hydroxide ions is prepared. After mixing and stirring the microemulsion solution containing titanium ions and the microemulsion solution containing hydroxide ions, the mixture was stirred at 150 ° C in a closed container at -12- ^^ national national standard (CNS) A4 specifications (210X297 mm) Order 541285 A7 B7 V. Description of the invention (丨 〇) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the hydrothermal reaction (hydr〇th_ireacti〇n) was performed for 1 hour, and the fish powder was subjected to X-scale age. Analysis, the county map secret map Qian Zizi. For example, the powder of | ^ | 所 不 ’and 彳 f is a titanium dioxide powder, and from the X spectrum and the standard ® spectrum, it can be known that the compound has a catalyzed phase = and a structure. A transmission electron microscope photograph of the obtained powder is shown in Fig. 2: It can be seen that the particle size of the synthesized titanium dioxide powder is nanometer, the powder is rod-shaped, and the powder has a uniform shape and good dispersion. In this implementation, the latex hydrothermal synthesis method of the present invention can be used to feed nano-sized titanium dioxide powder with a sharp ore phase structure at a low temperature of 15 Gt. ^ MM2 After dissolving titanium tetrachloride in water, an aqueous solution with a concentration of titanium ions was prepared. In addition, a concentrated aqueous solution of ammonia water was prepared to prepare an aqueous phase containing titanium ions and an aqueous phase of ammonia. An interfacial active agent (OP-Η) and a co-surfactant hexanol were added to the cyclohexyl compound to prepare an oil phase solution. The volume ratio of surfactant to cyclohexane was 0.3, and the volume ratio of co-surfactant to cyclohexane was 0.2. Take the aqueous phase solution containing titanium ions and the above oil phase solution at a volume ratio, mix and mix them to prepare a microemulsion solution containing titanium ions. Then take the aqueous phase of the ammonia solution and the oil phase solution at the volume ratio of 1 (1), and after mixing and mixing, a microemulsion solution containing oxygen ions is prepared. Then add the microemulsion solution containing titanium ions and hydrogen and oxygen (please read the precautions on the back before filling this page)
-項再填I 裝. j---訂 -13- 本紙張尺度適用中國國家榡準（CNS )八4規格（2丨〇><297公釐） 541285 A7 _______ _B77、發明説明（丨丨） _子，微乳膠溶液混合與攪拌後，於15()t在密閉容 二件⑼體進行X射線繞射分析，其結果證實所得之粉 體為二氧化鈦陶莞粉體，且由X線繞射圖譜與標準圖触 ^，可得知合物具有銳鈦翻結構。依穿透式電子顯 =刀析可知所得粉體粒徑為奈米級，粉體形態均勾，粉 體分散良好。本實施例註明利用本發明方法，可於⑽艺 低溫下製得奈米級且魏鈦礦減構之二氧化鈦粉體。 實例g 將四氯化鈦溶於水中後，製備得鈦離子濃度為〇·2Μ之 水溶液。另將綠化鈉祕水巾，得氫氧根軒濃度為i Μ之驗性水絲，分膽得含鈦軒之水相及含氫氧根離 子之水相。再於環己燒中加入界面活性劑〇1>-1〇及共界面 活關己酉予’製得油相溶液。界面活性劑與環己烧體積比 為〇·3，共界面活性劑與環己烧體積比為〇.2。取含鈦離子 之水相溶液與上勒相驗於1 : 1G體積比讀況下，加 以混合及攪拌後，製得含鈦離子之顯微乳膠溶液。再取含 氫氧根離子之水相溶液與上述油相溶液於i : 5體積比之情 况下’加以混合及擾拌後，製得含氫氧根離子之顯微乳膠 溶液。再將含鈦離子之顯微乳膠雜及含氫氧根離子之顯 -14- 國國家標準(CNS )八4規^^7^!17-Items are refilled I. j --- Order-13- This paper size is applicable to China National Standard (CNS) 8-4 specifications (2 丨 〇 > < 297 mm) 541285 A7 _______ _B77, Description of the invention (丨丨) __, after the microemulsion solution was mixed and stirred, X-ray diffraction analysis was performed at 15 () t in the sealed two-piece carcass, and the result confirmed that the obtained powder was a titanium dioxide ceramic powder, and the X-ray Diffraction pattern and standard figure ^, we can know that the compound has anatase structure. According to the transmission electron display = knife analysis, it can be seen that the particle size of the obtained powder is nanometer, the powder shape is uniform, and the powder is well dispersed. This example indicates that by using the method of the present invention, nano-scale titanium dioxide powder with reduced titanite structure can be prepared at low temperature. Example g After titanium tetrachloride was dissolved in water, an aqueous solution having a titanium ion concentration of 0.2 M was prepared. In addition, the green mysterious water towel was obtained to obtain a test water silk having a hydroxide concentration of i Μ, and a water phase containing titanium oxide and a water phase containing hydroxide ion were obtained. Then, cyclohexylene was added with a surfactant 〇1> -10 and a co-interface activator to prepare an oil phase solution. The volume ratio of the surfactant to cyclohexane was 0.3, and the volume ratio of the co-surfactant to cyclohexane was 0.2. Take the titanium ion-containing aqueous phase solution and the Shangle phase to check the volume ratio of 1: 1 G, and after mixing and stirring, prepare a titanium ion-containing microemulsion solution. Then, the aqueous phase solution containing hydroxide ions and the above oil phase solution are mixed and stirred at a volume ratio of i: 5, and a microemulsion solution containing hydroxide ions is prepared. Then the micro-latex impurities containing titanium ions and hydroxide ions are displayed. -14- National National Standard (CNS) Regulation 8 ^^ 7 ^! 17
! (請先閲讀背面之注意事項再填寫表f) J— ί xy 、τ 經濟部智慧財產局員工消費合作社印製 541285 A7 B7 五 、發明说明（12〇 微乳膠溶液混合與娜後，於150t在密·器中進行水 熱反應(hydrothe聰lreacti〇n)1小時，經過濾乾额^ 體進行X射線繞射分析，其結果圖示於圖3中。如圖3所 不，所得之粉體為二氧化鈦陶錄體，且由χ線繞射圖譜 與標準圖譜比對，可得知該化合物具有銳鈦礦相結構。所曰 得粉體之穿透式電子顯微鏡照片如圖4所示，由圖*可知 所合成二氧化鈦龍粒縣奈純均勻，粉體 分散良好。本實施例言正明利用本發明方法，可於15〇。〇低 溫下製得奈米級且魏_減叙二氧化鈦粉體。 實例4 將四氯化鈦溶於水中後，製備得鈦離子濃度為〇.2“之 水溶液。另將氫氧仙溶於水巾，得氫氧根離子濃度為1 Μ之鹼性水溶液，分別製得含鈦離子之水相及含氫氧根離 子之水相。再於環己：)：完中加入界面活性劑〇Ρ_1〇及共界面 活性劑己醇，製得油相溶液。界面活性劑與環己炫體積比 為0.3，共界面活性劑與環己烷體積比為〇 2。取含鈦離子 之水相溶液與上述油相溶液於1 : 1〇體積比之情沉下，加 以混合及擾拌後，製得含鈦離子之顯微乳膠溶液。再取含 氫氧根離子之水相溶液與上述油相溶液於丨：1〇體積比之 情況下，加以混合及攪拌後，製得含氫氧根離子之顯微乳 -15- ------IT------Λ- (請先閲讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準（CNS ) A4規格（210X297公釐） 541285 五 、發明説明（丨3 ) 修合液。再將含鈦離子之罐«溶液及含氫氧根離子之 顯微乳膠溶液混合與攪拌後，於WC在密閉容器中進行 二”、、二(hydiotheimalreacti〇n)1小時，經過遽乾燥後得之 射線騎分析，證實所得之減為二氧化鈦陶 且由Χ線繞射圖譜與標準圖譜比對，可得知該化 合物具麵鈦礦相結構。依穿透式電子顯微鏡分析可知所 口成-氧化鈦粉體她為奈米級，粉體形態均勻，娜分 散良好。本實施例註明利用本發明方法，可於17(rc低^ 下製得奈米級且具銳鈦確相結構之二氧化鈦粉體。 實例5 訂 為分析所合成粉體之光觸媒特性，將實例】所合成之 二氧化鈦粉體_g分散於2.㈤亞甲基財（3_) =利用編波長之w燈照射，量測亞甲基藍受光觸 2分解情形。亞分練如w絲儀量測咖邮 特性峰大小評估，所得結果如圖5所示。由圖5可知所合 成之二氧化鈦’於6Gmin左右可將亞f顧全部分解 具有良好光觸媒活性。 本發明之方法及特徵，經上述實例說明將更為明顯， 瞭解的是，任何獨離本發㈣神下所為之修韩或改 、交’皆屬於本發明意圖保護者。 -16- 本紙張尺度適用中準（CNS ) A4規格（训“公襲）(Please read the precautions on the back before filling in form f) J— ί xy, τ Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 541285 A7 B7 V. Description of the invention (12o microemulsion solution mixed with Na, at 150t The hydrothermal reaction (hydrothe Conglactin) was performed in a dense container for 1 hour, and the X-ray diffraction analysis was performed on the filtered dry matter. The results are shown in Figure 3. As shown in Figure 3, the obtained powder The body is a titania ceramic body, and the χ-ray diffraction pattern is compared with the standard spectrum, which shows that the compound has an anatase phase structure. The transmission electron microscope photograph of the obtained powder is shown in Fig. 4, It can be seen from the figure * that the synthesized titanium dioxide dragon particles are homogeneous and the powder is well dispersed. This example is clear that using the method of the present invention, nano-grade and Wei_minimized titanium dioxide powder can be prepared at a low temperature of 15.0. Example 4 After dissolving titanium tetrachloride in water, an aqueous solution having a titanium ion concentration of 0.2 "was prepared. Another solution of hydroxide was dissolved in a water towel to obtain an alkaline aqueous solution having a hydroxide ion concentration of 1M. Aqueous phase containing titanium ions and hydroxide ion The aqueous phase. Then in cyclohexane :): After adding the surfactant OP_1〇 and co-surfactant hexanol, an oil phase solution is prepared. The volume ratio of surfactant to cyclohexyl is 0.3, co-surfactant The volume ratio with cyclohexane is 02. Take the titanium ion-containing aqueous phase solution and the above oil phase solution at a volume ratio of 1: 1, and mix and stir to obtain a titanium ion-containing microscope. Latex solution. Then take the aqueous phase solution containing hydroxide ions and the above oil phase solution at a volume ratio of 10:10, mix and stir to prepare a microemulsion containing hydroxide ions-15- ------ IT ------ Λ- (Please read the notes on the back before filling out this page) The paper printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs is compliant with Chinese National Standard (CNS) A4 (210X297 mm) 541285 V. Description of the invention (丨 3) Repair liquid. After mixing and stirring the solution containing titanium ion in the tank «solution and hydroxide ion containing microemulsion solution, it is carried out in a closed container at WC. Two ",, two (hydiotheimalreacti〇n) 1 hour, ray riding points obtained after drying Confirmed obtained from ceramic and titanium oxide is reduced by the diffraction pattern with the standard line Χ alignment pattern may be that this compound having the structure faces perovskite phase. According to the transmission electron microscope analysis, it was found that the titanium oxide powder was nano-grade, and the powder had a uniform shape and good nano-dispersion. This example indicates that by using the method of the present invention, a titanium dioxide powder having a nanometer grade and anatase phase structure can be prepared at a low temperature of 17 °. Example 5 is intended to analyze the photocatalyst characteristics of the synthesized powder. The synthesized titanium dioxide powder _g is dispersed in 2. ㈤ methylene chloride (3_) = measuring the decomposition of methylene blue by light touch 2 using a w lamp with a compiled wavelength. The subdivision is measured by a wire meter The peak size is evaluated, and the results are shown in Fig. 5. It can be seen from Fig. 5 that the synthesized titanium dioxide 'can decompose all the sub-Fu at about 6 Gmin and has good photocatalytic activity. The method and characteristics of the present invention will be further explained by the above examples. Obviously, it is understood that any repair or modification or resignation made by the God of this hair alone belongs to the intent of the present invention. -16- This paper standard is applicable to the standard (CNS) A4 specification (training "public attack" )