工23〇69〇 坎、發明說明： 【發明所屬之技術領域】 本發明係關於-種二氧化鈦光觸媒溶液及 &製造過程中藉由添加切成份之無機改^ 二/ 〉谷液與塗覆基材之間的密著性。 升一軋化鈦 【先前技術】 :米科技是指製作尺度約1〇-9米（1奈米等㈣'”的材 里測m應帛其特柄性隸 :萬象’涵蓋半導體、金屬、高分子、生醫材料及包 :才科的特性量測包括電、光、磁及化學特性等。湘= 新奇特性可應用在工業上的觸媒材 ： 利用生： 技術，增強器具的機械強度。此外， 材料奈米化’造成電子及電洞的高度量子侷限，增加 射:發光效率及崩潰溫度。將半導體材料奈米化使光電 整合與積體化。 +㈣將了〇“、光、磁及生化元件 -乳化鈦奈米粒子作為光觸媒，已廣泛應用於生活環境之提 ’且逐漸為消費大眾所接受。二氧化鈦光觸媒具有銳鈦礦 =USe)結構，粒徑大小在3〇⑽以下。經過波長小於38〇咖 1外先激發後’可在二氧化欽粒子表面產生活性物質並進行 =物的氧化或魏反應H由於表面氧料㈣離形成 南度親水性的特性，因而具有防霧、防塵等自我潔淨功能。二氧 化敛先觸媒應雜肢，具料祕去除H淨化、水質淨化、 除臭、抗菌、除塵、防霧等環境淨化之效能。 、，雖然光觸媒顆粒具有抗菌、去除污染物等功能，但在實用上 並不ux顆粒型怨直接使用，必須將奈米顆粒固定於某些基材表 面’如磁磚、玻璃、牆壁、金屬、塑膠等表面，這些表面必須具 1230690 1 不怕光觸氧化之特性，以免本身遭到氧化分解。因此光觸媒 基材之密著性，是決定光觸媒使用壽命的主要因 f。為.1使用上时便，通常配成光㈣溶液進㈣定化操作。 光觸媒〉谷液可以是酸性（pPj〈 6)或是 — 可依美材之#田&rn 中^(ΡΗ = 6〜8)，其應用範圍 : 的選擇。目前光觸媒溶液的製造可以從 : = 斗’或以鈦金屬之醇氧化物為起始原料 式化+法5成，以得卿粒A小在3Gn :方:有二:彳，粉體加水稀釋以製得* μ方法不谷易为散且容易造成沉澱， 液，將影響其附著性、耐久性盥魏 ^生之先觸媒溶 #SSMP 功此性之品質。只要附著性良好， ，媒P可持縯發揮功用，而成為具有長 菌、防霧、自潔等功能之產品。 于可除六抗 之制專利34"81 t ’提出製造非晶型過氧化鈦溶朦 至二二彳方法為以四氣化欽（ΤΑ)為起始物，以氨水滴定 2〜6後，在低溫（15t以下）加人雙氧纽錢，再於常溫下 3力工Γ二可製得非晶型過氧化欽溶膠’該種溶液可解決 彼復加工性之問題，作共兩你甘；* 二_ :才; :=:=在增進光_液 国專利弟侧21號中，提出以 膠：二：與經過軟加溫處理成晶型二氧化鈦溶 :::進:;基材被覆之方法’或將光觸媒溶液與二氧化鈦粉 二:，進行破覆之方法。另於中華民國專利第491883號中， 之==氧化欽溶液作為被覆劑’並以含有介電體或導電體 ^㈣作為中間層’再進行被覆基材之方法。又中華民國專 Γ」Γ219號中’提出以界面活性劑及溶劑，或另含膠態二氧 石乍為底層處理劑，再進行基材被覆之方法。而中華民國專利 1230690 第279Π5號中，提出以不會降解之枯合劑（氣化聚合物）盘二 氧化鈦顆粒混合’以形成光觸媒塗覆經成物，再進行被覆之方法 綜觀前案技術’為了提升光_溶液塗覆基材m 人使用有機添加劑直接添加於光㈣溶液巾，収善光觸媒 2基材之密著性。但該方法存在添加劑與細媒祕混合不均 =，化性、物性不相谷％問題’將影響光觸媒溶液之安定性愈功 此性。亦有人㈣在基材表面事先塗布枯著劑之方法再汾覆光 觸媒溶液，以增加與基材之㈣性。但财法駐過心複，且 y艮於基材材質’應用範圍受到限制。這些現行之二 媒溶液，經塗覆後與基材之㈣性f遍不佳， 成太= 剝落’影響其光觸媒功能的長效性。 成塗層 【發明内容】 2於習知技術的缺失，本發明係於二氧化鈦光觸媒溶液合 -LL太J人適ΐ的改質劑，以合成組成均句具光觸媒活性之 一乳化鈦〉谷液，以改進二氧化 — — 、’光觸媒〉谷液在塗覆過程中與基材 液:應用性且不須經過高溫锻燒處理，可增進二氧化鈦光觸媒溶 本發明之目的係提供_錄#拼 ^ 造方沬S尺 ’、種改貝之二氧化鈦光觸媒溶液之製 : ；(：) 解膠;：===物利-_定 m(c^ m , 丨^^性一乳化欽光觸媒溶液。當步 …二氧化_媒溶液二 觸媒溶液之pH值為知勝劑時’製得之酸性二氧化欽光 j述方法衣仔之改k氧化欽光觸媒溶液係為銳鈦礦結晶 1230690 之二氧化鈦光觸媒溶液。 前述鈇金屬鹽類係為四氣化鈦。 前述鹼性溶液係為氨水或氫氧化鈉。 前述沈澱物係為氫氧化鈦。其中方法係可進一步於前述步驟 (b)之後、步驟（c)之前增加一過濾水洗步驟移除沉澱物中之不純 物。 前述解膠劑係可選自中性或酸性物質。其中前述中性解膠劑 例如雙氧冰；酸性解膠劑例如頌酸、鹽酸或草酸。 前述解膠劑之滴定終點之pH值依使用之解膠劑不同而有所 差異。當步驟（c)使用之解膠劑為中性時，其滴定終點之pH值為 6〜9。當步驟（c)使用之解膠劑為酸性時，其滴定終點之pH值為 3〜7。 前述無機改質劑係為含矽成份之無機化合物。前述含矽成份 之無機化合物係為奈米尺寸（4-30 nm粒徑大小）之矽溶膠（Colloid Silica)、四乙基矽烷（TEOS)、四甲基矽烷（TMOS)、矽酸鹽溶液或 水玻璃溶液。 前述無機改質劑之添加量，以二氧化鈦光觸媒溶液之量為配 置基準，矽與鈦之莫耳比例介於1:5至1:30。 前述步驟（d)之加溫迴流之溫度係為40〜200°C、迴流時間為 2〜70小時。其中當前述步驟（c)使用中性解膠劑時，加溫迴流之溫 度較佳係為80〜200°C ;當前述步驟（c)使用酸性解膠劑時，加溫迴 流之溫度較佳係為40〜90°C。 前述步驟（d)之迴流時間為2〜8小時之範圍時，製得二氧化鈦 之粒徑小於20nm。前述步驟（d)之迴流時間為8〜70小時之範圍 時，製得二氧化鈦之粒徑為20〜60nm之範圍。 利用前述方法製得之二氧化鈦光觸媒溶液，其二氧化鈦含量 範圍為0_5〜20°/。、pH值範圍為1〜9、黏度範圍為1〜5cps。其中前 1230690 述二氧化ί太為具光觸媒活性之 物分解、抗菌、自我潔淨之功能。$ natase)結構，具有污染 液，係由前述之方法_彳曰二:種改貝之二氧化鈦光觸媒溶 β衣传，該改皙 — 二氧化鈦含量範圍4 05 、之-乳化欽光觸媒溶液，其中 1〜5cPS’其尹前述二氧：：：範圍為】〜9、點度範圍為 結構。 ㈣具7^觸媒活性之銳鈦礦unatase)Description of the invention: [Technical field to which the invention belongs] The present invention relates to a kind of titanium dioxide photocatalyst solution and & inorganic modification by adding cutting ingredients during the manufacturing process. Adhesion between substrates. Shengyi Rolled Titanium [Prior technology]: Rice technology refers to the production of materials with a scale of about 10-9 meters (1 nanometer, etc.), and the specific measurement should be based on its special characteristics: Vientiane 'covers semiconductors, metals, Polymers, biomedical materials, and packages: The characteristics of talents include electrical, optical, magnetic, and chemical characteristics. Xiang = novelty catalysts that can be used in industry: Use of biotechnology: technology to enhance the mechanical strength of appliances In addition, nanomaterialization of materials causes high quantum confinement of electrons and holes, increasing emission: luminous efficiency and breakdown temperature. Nanomaterialization of semiconductor materials enables integration and integration of optoelectronics. Magnetic and biochemical elements-emulsified titanium nano particles as photocatalysts have been widely used in the improvement of living environment and are gradually accepted by consumers. Titanium dioxide photocatalysts have anatase = USe) structure, and the particle size is below 303. After the wavelength is less than 38 ° C, it is first excited and can generate an active substance on the surface of the dioxin particles and oxidize or react with it.H Because the surface oxygen material is detached to form a southern hydrophilic property, it has anti-fog , Dust and other self-cleaning functions. Dioxin is the first catalyst to be mixed with limbs, which has the effects of environmental purification such as H purification, water purification, deodorization, antibacterial, dust removal, and anti-fog. Although the photocatalyst particles have antibacterial and pollutant removal functions, they are not directly used in practice. They must be fixed on the surface of certain substrates, such as tiles, glass, walls, metals, Plastic and other surfaces, these surfaces must have the characteristics of 1230690 1 not afraid of photo-contact oxidation, so as not to be oxidized and decomposed. Therefore, the adhesion of the photocatalyst substrate is the main factor determining the service life of the photocatalyst. For .1, it is usually ready to use, and it is usually formulated into a photocatalyst solution to perform the stabilization operation. Photocatalyst> Valley fluid can be acidic (pPj <6) or — according to # 田 & rn 中 ^ (ΡΗ = 6 ~ 8) in the United States, its application range: the choice. At present, the manufacture of photocatalyst solution can be from: = bucket or formula of titanium metal alcohol oxide as the starting material + method 50%, with Deqing particles A smaller than 3Gn: square: there are two: 彳, powder diluted with water The method of making * μ is not easy to disperse and easy to cause precipitation and liquid, which will affect its adhesion and durability. The quality of this catalyst is #SSMP. As long as the adhesion is good, the media P can perform its functions, and become a product with bacteria, anti-fog, self-cleaning and other functions. In the patent 34 " 81 t ', which can eliminate the sixth antibody, a method for manufacturing amorphous titanium dioxide to dissolve to dioxin was proposed by using tetrakis perylene (TA) as the starting material and titrating 2 ~ 6 with ammonia water. Adding dioxin at low temperature (below 15t), and then working at room temperature to produce amorphous peroxoacetin. This solution can solve the problem of processability. ; * 二 _: 才;: =: = In the promotion of light_Liquid Patent No. 21 side, it is proposed to use glue: 2: Dissolve with crystal titanium dioxide after soft heating treatment ::: jin :; substrate coating Method 'or a method of breaking the photocatalyst solution and titanium dioxide powder. In the Republic of China Patent No. 491883, the method of coating the substrate with == oxidized solution as a coating agent 'and containing a dielectric or electrical conductor as an intermediate layer'. Also in the Republic of China's No. Γ ″ Γ219 #, a method of using a surfactant and a solvent, or another colloidal dioxide as the underlying treatment agent, and then coating the substrate. In the Republic of China Patent No. 1230690 No. 279Π5, it is proposed to mix titanium dioxide particles with a non-degradable desiccant (gasified polymer) disk to form a photocatalyst coated warp, and then cover it. Looking at the previous case technology, in order to improve Photo-solution-coated substrate m The organic additive is directly added to the photocatalyst solution towel to improve the adhesion of the photocatalyst 2 substrate. However, this method has a problem of uneven mixing of additives and fine media, and the problems of chemical properties and physical properties will affect the stability of the photocatalyst solution. It is also known that the method of coating a substrate with a buffing agent in advance and then coating the photocatalyst solution to increase the resistance to the substrate. However, the financial law has been overwhelmed, and the scope of application of the substrate material is limited. These current secondary media solutions have poor compatibility with the substrate after coating, and fouling = peeling 'affects the long-term effect of their photocatalyst function. Coating [Content of the invention] 2 In the absence of conventional technology, the present invention is based on a titanium dioxide photocatalyst solution combined with -LL too suitable modifier for humans, to synthesize a composition with one of photocatalytic activity to emulsify titanium> valley liquid In order to improve the dioxide— “photocatalyst”, the valley liquid and the substrate liquid during the coating process: application and without the need for high temperature calcination treatment, can improve the photocatalytic dissolution of titanium dioxide. The purpose of the present invention is to provide _ 录 # 拼 ^沬 方尺 S 尺 ', the system of titanium dioxide photocatalyst solution modified by: ((:) degumming;: === 物 利 -_ 定 m (c ^ m, 丨 ^^ Emulsion photocatalyst solution. When Step… Oxidation_Medium solution The pH value of the catalyst solution is the acidic dioxin produced by the method described above. The method described in the article: The oxidation of the zircon oxide catalyst is anatase crystal 1230690 titanium dioxide photocatalyst. Solution. The rhenium metal salt is titanium tetragas. The alkaline solution is ammonia or sodium hydroxide. The precipitate is titanium hydroxide. The method may be further after step (b), step ( c) Add a filtration and washing step to remove the sink Impurities in the substance. The aforementioned degumming agent may be selected from neutral or acidic substances. Among them, the aforementioned neutral degumming agent such as hydrogen peroxide ice; the acidic degumming agent such as song acid, hydrochloric acid or oxalic acid. End point of titration of the aforementioned degumming agent The pH value varies depending on the degumming agent used. When the degumming agent used in step (c) is neutral, the pH value of the titration end point is 6 to 9. When the degumming used in step (c) When the agent is acidic, the pH at the end of the titration is 3 to 7. The aforementioned inorganic modifier is an inorganic compound containing a silicon component. The aforementioned inorganic compound containing a silicon component is a nanometer size (4-30 nm particle size) ) Colloid Silica, Tetraethyl Silane (TEOS), Tetramethyl Silane (TMOS), silicate solution or water glass solution. The amount of the inorganic modifier added is based on the amount of titanium dioxide photocatalyst solution. The configuration benchmark is that the molar ratio of silicon to titanium is between 1: 5 and 1:30. The temperature of the heating and reflowing in the step (d) is 40 ~ 200 ° C and the reflowing time is 2 ~ 70 hours. In the step (c), when a neutral degumming agent is used, the temperature of heating and refluxing is preferably 80. 200 ° C; when an acidic degumming agent is used in the step (c), the temperature for heating and refluxing is preferably 40 to 90 ° C. When the refluxing time in the step (d) is in the range of 2 to 8 hours, the system is prepared. The particle size of the titanium dioxide is less than 20 nm. When the reflow time of the step (d) is in the range of 8 to 70 hours, the particle size of the titanium dioxide is in the range of 20 to 60 nm. The titanium dioxide photocatalyst solution prepared by the above method has titanium dioxide The content range is 0_5 ~ 20 ° /., The pH value range is 1 ~ 9, and the viscosity range is 1 ~ 5cps. Among them, the first 1230690 said dioxide is a photocatalytic active matter decomposition, antibacterial, self-cleaning function. $ natase) structure, with contaminated liquid, is prepared by the aforementioned method _ 彳 二 two: a kind of modified titanium dioxide photocatalyst soluble β-coating pass, the modified-titanium dioxide content range 4 05, of which-emulsified photocatalyst solution, 1 ~ 5cPS '其 尹 The aforementioned two oxygen ::: The range is] ~ 9, the degree range is the structure. (Anatase unatase with 7 ^ catalyst activity)
可其之二—先觸二 :=== 基材之密著性，增進光觸媒溶液之射 v'、#二氧化鈦光觸媒溶液使用上之種種缺點。 【實施方式】 -本《明提供之一氧化欽光觸媒溶液之製造方法如第一圖 不’包含以下步驟：提供—含鈦金屬鹽類之反應物；加入驗性溶 液滴定中和獲得沈殿物；將沈殿物利用解膠劑滴定解膠；及加入 無機改質劑進行加溫迴流程序。But the second one is to touch two first: === The adhesiveness of the base material improves the radiation of the photocatalyst solution. V ', #titanium dioxide photocatalyst solution use various disadvantages. [Embodiment]-The method of manufacturing an oxide catalyst solution provided by Ming Dynasty as shown in the first figure does not include the following steps: providing-a reactant containing titanium metal salts; adding a test solution to titrate and obtain Shen Dianwu; Shen Dianwu was titrated with a degumming agent to degumming; and an inorganic modifier was added to perform a heating and refluxing procedure.
前述之改質劑係可選自雙氧水、硝1、鹽酸或草酸。前述無 機改質劑係為含矽成份之無機化合物。 … 本發明之方法可製得中性或酸性之改質之二氧化鈦光觸媒 溶液，其製造方法係分別敘述如下。 本發明之一種實施態樣係提供一種中性二氧化鈦光觸媒溶 液之‘造方法，如第二圖所示，其步驟詳述如下：首先提供一含 四氣化鈦反應物；接著加入氨水或氫氧化鈉進行滴定中和，以獲 得沈澱之氮氧化鈦，滴定終點之pH值約為6〜9 ;接著將沈殿之氮 氧化鈦過濾、清洗（持續攪拌約0.5〜4小時）後，利用雙氧水滴定 進行解膠，持續搜拌〇·5〜8小時，得到淡黃色透明之過氧化鈦溶 10 1230690 液；再於此淡黃色透明溶液中加入含矽成份如：奈米尺寸（4-30 nm 粒徑大小）之矽溶膠（Colloid Silica)、四乙基矽烷（TEOS)、四甲基 矽烷（TMOS)、矽酸鹽溶液或水玻璃溶液等無機化合物之改質劑， 最後於80〜200°C加溫迴流2〜70小時，即可製得黃色透明之改質 後的中性二氧化鈦光觸媒溶液。 製得之中性二氧化鈦光觸媒溶液，其pH值為6〜9、黏度為 1〜5cps、其所含有之二氧化鈦係為具有光觸媒活性之銳鈦礦 (Anatase)結構，濃度為0.5〜20%，而二氧化鈦之粒徑係取決於 加溫迴流時間：當迴流時間為2〜8小時，二氧化鈦粒徑小於 20nm ;當迴流時間為8〜70小時，二氧化鈦粒徑為20〜60nm。 本發明之另一種實施態樣係提供酸性二氧化鈦光觸媒溶液 之製造方法，如第三圖所示，其步驟詳述如下：提供一含四氧化 鈦之反應物；加入氨水或氫氧化納滴定中和獲得沈殿之氫氧化 鈦；滴定終點之pH值約為3〜7;接著將沈澱之氫氧化鈦過濾、清 洗（持續攪拌約0.5〜4小時）後；將沈澱之氫氧化鈦利用硝酸、鹽 酸或草酸進行滴定解膠，持續攪拌0.5〜8小時，得到淡黃色透明 之過氧化鈦澄清溶液；再於此淡黃色透明溶液中加入含矽成份 如··奈米尺寸（4-30 nm粒徑大小）之石夕溶膠（Colloid Silica)、四乙 基矽烷（TEOS)、四曱基矽烷（TMOS)、矽酸鹽溶液或水玻璃溶液 等無機化合物之改質劑，最後於40〜90°C加溫迴流2〜70小時即可 製得白色之改質後之酸性二氧化鈦光觸媒溶液。 製得之酸性二氧化鈦光觸媒溶液，其pH值為1〜4、黏度 1〜5cps、其所含有之二氧化鈦係為具有光觸媒活性之銳鈦礦 (Anatase)結構，濃度為0.5〜20%，而二氧化鈦之粒徑係取決於 加溫迴流時間：當迴流時間為2〜8小時，二氧化鈦粒徑小於 20nm ;當迴流時間為8〜70小時，二氧化鈦粒徑為20〜60nm。 以下實施例係用於進一步了解本發明之優點，並非用於限制 1230690 本發明之申請專利範圍。 實施例1·改質之中性二氧化鈦光觸媒溶液之製備 .取20g的四氣化鈦為反應物，加入250g的純水於4°C下稀 釋，攪拌至澄清透明後，滴加400〜500mL 20%的氨水，使其形成 氫氧化鈦沈澱，滴定終點之pH值為8.0± 0.5,再持續攪拌2小時。 沈澱物經過濾、數次水洗以去除氯離子，使氣離子濃度低於 0.001M後，添加35% 125mL過氧化氫水溶液與1.5L純水，均勻 混合2小時，可得到淡黃色透明之過氧化鈦溶液，接著加入適量 之矽溶膠或四乙基矽烷，二氧化矽與二氧化鈦之重量比為1:20， 加入改質劑之液體，再經90°C加熱回流8小時，可得到黃色透明 的溶液，此溶液在常溫常壓下靜置6個月以上，不會沈澱，經高 速離心機試驗，亦無沈殿發生，pH值為6〜9，為中性之二氧化鈦 光觸媒溶液，結晶為銳鈦礦，二氧化鈦含量1〜3 wt%，粒徑：長 軸：10〜60 nm，短軸：5〜20 nm，枯度為1〜5 cps。利用此法製備 之中性二氧化鈦光觸媒溶液，被覆於基材後，較未改質之中性二 氧化鈦光觸媒溶液之被覆膜具有較佳的密著性。 實施例2.改質之中性二氧化鈦光觸媒溶液之密著性比較 取出1%中性二氧化鈦光觸媒溶液（與實施例1相同程序但未 添加無機矽鹽改質劑）與實施例1製備之改質之中性二氧化鈦光 觸媒溶液之溶液各250 mL，分別標記為A液與B液，另配置1°/〇 事後改質之中性二氧化鈦光觸媒溶液（C液），C液的配置方法為： 取適量A液添加四乙基矽烷（TEOS)並在80°C下攪拌5小時即 完成，其中Ti02/Si = 20，並亦取出C液250 mL。分別將三種溶 液置入浸鍍用燒杯中，再分別放入約50cm2的不織布含浸於三種 溶液，其材質為PE/coPET 50g/m2,浸置30分鐘後，取出晾乾後， 放入烘箱以90±5QC恆溫2小時，秤重計算其光觸媒之塗佈量。 12 1230690 之後，再將三份樣品分別置入250mL的純水中，25 °C下以超音 . 波（120W 47kHz)震盪30分鐘，再放入烘箱以90士5°C恆溫2小時， 秤重計算其光觸媒之塗佈量與脫落量。其結果如表一所示。可知 “ 在以B液為鍍液時，其附著量最高（0.0469g)，而經物理性的超音 波破壞測試下，B液樣品光觸媒損失率最低（2.56%)，而事後改質 · 中性光觸媒溶液（C液）的損失率最高（12.30%)。可知本方法所提出 的改質光觸媒溶液方法可使無機黏著劑有效地與光觸媒粒子結 合，而事後添加則會導致分散不均的情況，使其對不織布基材的 附著性更差。 ❿ 表一：中性二氧化鈦光觸媒溶液密著性之比較 A液 B液 C液 黏著劑比例(Ti02/Si) —— 20 20 不織布淨重量 0.1098 g 0.1059 g 0.1097 g 塗佈烘乾後重量 0.1417 g 0.1528 g 0.1471 g 光觸媒附著量 0.0319 g 0.0469 g 0.0374 g 超音波測試後烘乾重量 0.1395 g 0.1516g 0.1425 g 光觸媒附著量 0.0297 g 0.0457 g 0.0328 g 光觸媒損失量 0.0022 g 0.0012 g 0.0046 g 光觸媒損失率 6.90% 2.56 % 12.30% 註：A液：無改質中性二氧化鈦光觸媒溶液 B液：本發明之改質之中性二氧化鈦光觸媒溶液 C液：合成後改質之中性二氧化鈦光觸媒溶液 實施例3·改質之中性二氧化鈦光觸媒溶液之自我潔淨功能比較 自我潔淨的功能檢驗在本發明中以叙水性來表示，親水性則 以光觸媒玻璃試片表面與水之接觸角來代表，接觸角示意如第四 圖所示，當接觸角小時顯示基材表面與水的親和力良好，為親水 性材質，反之，接觸角越大時，表示基材表面為疏水性。使用溶 液如同實施例2之A、B、C三溶液。分別將三種溶液置入浸鍍用 燒杯中，再分別放入約5 X 10 cm2的玻璃片含浸於三種溶液，浸 13 1230690 置2分鐘後，以2.4cm/min拉伸速度上升，將玻璃片放入烘箱以 200土5°(：恆溫2小時後，完成浸鍍程序。再將三份樣品分別置入 200mL的純水中浸泡30分鐘，以去除表面雜質，再放入烘箱以 100±5QC恆溫1小時，再照射0.65 μλν/cm2的紫外光2小時後， 將試片取出測定其與水之接觸角。使用First Ten Angstrom FTA-125型接觸角測量儀進行接觸角測試，以4μί去離子水滴上 光觸媒玻璃試片進行測試，結果其結果如表二所示。可知在以Β 液為鍍液時，其接觸角最小，其次為C液樣品，未添加四乙基矽 烷（TEOS)的Α液，其親水性更差，另外，未塗佈光觸媒的空 白玻璃試片，其接觸角為48度左右，無自我潔淨之效果。由結 果可知本方法所提出的改質光觸媒溶液方法可使無機黏著劑有 效地與光觸媒粒子結合，進而可與玻璃基材有良好附著性，使基 材表面基材具良好之親水性效果。 表二：中性二氧化鈦光觸媒溶液親水性之比較 ^式片 接觸^\ A液試片 Β液試片 C液試片 空白試片 第一點 29.4° <5° 14.2° 46.9° 第二點 29.3° <5° 13.5° 50.Γ 第三點 29.5° <5° 15.5° 47.3° 平均值 29.4° <5° 1· 48.1^ 註· A液 :無改質中β L二氧化鈦光觸媒溶液 0B液：本發明之改質之中性二氧化鈦光觸媒溶液 C液：合成後改質之中性二氧化鈦光觸媒溶液 實施例4·改質之酸性二氧化鈦光觸媒溶液之製備 取20g的四氣化鈦為反應物，加入250g的純水於4°C下稀 釋，攪拌至澄清透明後，滴加1〇〇〜200mL 20%的氨水，使其形成 氫氧化鈦沈澱，滴定終點之pH值為4.0± 0.5,在持續攪拌2小時。 沈澱物經過濾、數次水洗以去除氣離子，使氣離子濃度低於 0.001M後，添加0.25M、400mL的硝酸水溶液，均勻混合2小時， 14 1230690 可得到淡黃色透明之過氧化鈦溶液，加入適量之矽溶膠或四乙基 矽烷，二氧化矽與二氧化鈦之重量比為1:20,加入改質劑之液體， 再經90°C加熱迴流8小時，可得到白色透明的溶液，此溶液在常 溫常壓下靜置6個月以上不會沈澱，經高速離心機試驗亦無沈澱 發生，pH值為1〜4，為酸性之二氧化鈦光觸媒溶液，結晶為銳鈦 礦，二氧化鈦含量1〜6 wt%，粒徑：長軸：10〜60 nm，短軸：5〜20 nm，钻度為1〜5 cps。改質之酸性二氧化鈦溶液，被覆於基材後， 較未改質之酸性二氧化鈦光觸媒溶液之被覆膜具有較佳的密著 性。本實施例中的硝酸溶液，可以用鹽酸溶液或草酸溶液代替， 同樣可得到酸性之二氧化鈦光觸媒溶液。 實施例5·改質之酸性二氧化鈦光觸媒溶液之密著性比較 取出1%酸性二氧化鈦光觸媒溶液（與實施例4相同程序但未 添加無機矽鹽改質劑）與實施例4製備之1%改質之酸性二氧化鈦 光觸媒溶液）之溶液250 mL，分別標記為D與E液，並配置1% 事後改質之酸性二氧化鈦光觸媒溶液（F液），F液的配置方法為： 取適量D液添加四乙基矽烷（TEOS)並在80°C下攪拌5小時即 完成，其中Ti02/Si = 20，並亦取出F液250 mL。分別將三種溶 液置入浸鍍用燒杯中，再分別放入約50cm2的不織布含浸於三種 溶液，其材質為PE/coPET 50g/m2，浸置30分鐘後，取出晾乾後， 放入烘箱以90土5°C恆溫2小時，秤重計算其光觸媒之塗佈量。之 後，再將三份樣品分別置入250mL的純水中，25°C下以超音波 (225 W 35kHz)震盪30分鐘，再放入烘箱以90 土 5°C恆溫2小時， 秤重計算其光觸媒之塗佈量與脫落量。其結果如表三所示。可知 在以E液為鍍液時，其附著量最高（0.0444g)，而經物理性的超音 波破壞測試下，E液樣品光觸媒損失率最低（4.05 %)，而D與F 液的損失率較高。可知本方法所提出的改質光觸媒溶液方法可使 無機黏著劑有效地與光觸媒粒子結合，而事後添加則會導致分散 15 1230690The aforementioned modifier may be selected from hydrogen peroxide, nitrate 1, hydrochloric acid, or oxalic acid. The aforementioned inorganic modifiers are inorganic compounds containing silicon. … The method of the present invention can produce a modified titanium dioxide photocatalyst solution that is neutral or acidic, and the manufacturing methods thereof are described separately below. An embodiment of the present invention provides a method for manufacturing a neutral titanium dioxide photocatalyst solution. As shown in the second figure, the steps are detailed as follows: firstly, a reactant containing titanium tetraoxide is provided; then ammonia or hydroxide is added. Sodium was titrated and neutralized to obtain precipitated titanium oxynitride. The pH at the end of the titration was about 6 ~ 9. Then, Shen Dianzhi's titanium oxynitride was filtered, washed (continuously stirred for about 0.5 ~ 4 hours), and then carried out with hydrogen peroxide titration. Degumming, continue to search for 0.5 to 8 hours to obtain a pale yellow transparent titanium oxide solution of 10 1230690; then add silicon-containing ingredients such as nanometer size (4-30 nm particle size) to this pale yellow transparent solution Size) modifiers of inorganic compounds such as Colloid Silica, Tetraethyl Silane (TEOS), Tetramethyl Silane (TMOS), silicate solution or water glass solution. Finally add at 80 ~ 200 ° C. After refluxing at a temperature of 2 to 70 hours, a yellow transparent modified titanium dioxide photocatalyst solution can be prepared. A neutral titanium dioxide photocatalyst solution was prepared with a pH value of 6 to 9 and a viscosity of 1 to 5 cps. The titanium dioxide contained therein was an anatase structure with photocatalytic activity, with a concentration of 0.5 to 20%, and The particle size of titanium dioxide depends on the heating reflow time: when the reflow time is 2 to 8 hours, the titanium dioxide particle size is less than 20nm; when the reflow time is 8 to 70 hours, the titanium dioxide particle size is 20 to 60nm. Another embodiment of the present invention provides a method for manufacturing an acidic titanium dioxide photocatalyst solution. As shown in the third figure, the steps are detailed as follows: provide a reactant containing titanium tetraoxide; add ammonia or sodium hydroxide to titrate and neutralize Obtain Shendian's titanium hydroxide; the pH at the end of the titration is about 3 ~ 7; after filtering and washing the precipitated titanium hydroxide (continuous stirring for about 0.5 ~ 4 hours); use the precipitated titanium hydroxide with nitric acid, hydrochloric acid or Oxalic acid is titrated for degumming, and stirring is continued for 0.5 to 8 hours to obtain a light yellow transparent transparent titanium oxide clarified solution; and then a silicon-containing component such as nanometer size (4-30 nm particle size is added to the light yellow transparent solution). Modifiers for inorganic compounds such as Colloid Silica, Tetraethyl Silane (TEOS), Tetramethylsilyl Silane (TMOS), silicate solution or water glass solution. Finally add at 40 ~ 90 ° C. After refluxing for 2 to 70 hours, a white modified acidic titanium dioxide photocatalyst solution can be obtained. The prepared acidic titanium dioxide photocatalyst solution has a pH value of 1 to 4 and a viscosity of 1 to 5 cps. The titanium dioxide contained therein is an anatase structure with photocatalytic activity, and the concentration is 0.5 to 20%. The particle size depends on the heating reflow time: when the reflow time is 2 to 8 hours, the titanium dioxide particle size is less than 20nm; when the reflow time is 8 to 70 hours, the titanium dioxide particle size is 20 to 60nm. The following examples are for further understanding of the advantages of the present invention, and are not intended to limit the scope of patent application of the present invention. Example 1 Preparation of modified neutral titanium dioxide photocatalyst solution. Take 20 g of titanium tetrachloride as a reactant, add 250 g of pure water and dilute it at 4 ° C, stir until clear and transparent, and add 400 ~ 500 mL 20 dropwise. % Ammonia water to form a titanium hydroxide precipitate. The pH value at the end of the titration is 8.0 ± 0.5, and stirring is continued for 2 hours. The precipitate was filtered and washed several times to remove chloride ions. After the gas ion concentration was lower than 0.001M, 35% 125mL aqueous hydrogen peroxide solution and 1.5L of pure water were added and mixed uniformly for 2 hours to obtain a pale yellow transparent peroxide. Titanium solution, followed by adding an appropriate amount of silica sol or tetraethylsilane, the weight ratio of silicon dioxide to titanium dioxide is 1:20, adding a modifier liquid, and heating and refluxing at 90 ° C for 8 hours to obtain a yellow transparent Solution, this solution is left to stand at room temperature and pressure for more than 6 months without precipitation. After high-speed centrifuge test, no Shen Dian occurs. The pH value is 6 ~ 9. It is a neutral titanium dioxide photocatalyst solution and crystallizes into anatase. Ore, titanium dioxide content 1 ~ 3 wt%, particle size: long axis: 10 ~ 60 nm, short axis: 5 ~ 20 nm, and buff is 1 ~ 5 cps. The neutral titanium dioxide photocatalyst solution prepared by this method has better adhesion than the coating film of the unmodified neutral titanium dioxide photocatalyst solution after being coated on the substrate. Example 2. Comparison of Adhesion of Modified Neutral Titanium Dioxide Photocatalyst Solution Take out 1% neutral titanium dioxide photocatalyst solution (same procedure as in Example 1 but without adding inorganic silicon salt modifier) and the modification prepared in Example 1. 250 mL of each solution of neutral titanium dioxide photocatalyst solution, marked as liquid A and liquid B, respectively, and equipped with 1 ° / 0 modified neutral titanium dioxide photocatalyst solution (C liquid) afterwards, the configuration method of C liquid is: take an appropriate amount Add TEOS in solution A and stir at 80 ° C for 5 hours to complete, where Ti02 / Si = 20, and take out 250 mL of solution C. Put the three solutions into the beaker for dip plating, and then put about 50cm2 of non-woven cloth impregnated with the three solutions. The material is PE / coPET 50g / m2. After immersing for 30 minutes, take out to dry, put them into the oven to 90 ± 5QC constant temperature for 2 hours, the weight of the photocatalyst is calculated by weighing. 12 After 1230690, place the three samples into 250mL of pure water and shake them with ultrasonic waves (120W 47kHz) for 30 minutes at 25 ° C, then put them in an oven and keep them at 90 ± 5 ° C for 2 hours. Recalculate the amount of coating and shedding of the photocatalyst. The results are shown in Table 1. It can be known that “When the B liquid is used as the plating solution, the adhesion amount is the highest (0.0469g), and the physical catalyst ultrasonic test shows that the B liquid sample has the lowest photocatalyst loss rate (2.56%), and afterwards it is modified and neutral. The loss rate of the photocatalyst solution (C solution) is the highest (12.30%). It can be known that the modified photocatalyst solution method proposed in this method can effectively bind the inorganic adhesive with the photocatalyst particles, and the subsequent addition will cause uneven dispersion. It makes the adhesion to the non-woven substrate worse. ❿ Table 1: Comparison of the adhesion of the neutral titanium dioxide photocatalyst solution A liquid B liquid C liquid adhesive ratio (Ti02 / Si) —— 20 20 Non-woven fabric net weight 0.1098 g 0.1059 g. g 0.0012 g 0.0046 g Photocatalyst loss rate 6.90% 2.56% 12.30% Note: Liquid A: No modified neutral titanium dioxide photocatalyst solution Liquid B: Modified neutral II of the present invention Titanium oxide photocatalyst solution C: Modified neutral titanium dioxide photocatalyst solution after synthesis Example 3 · Self-cleaning function of modified neutral titanium dioxide photocatalyst solution Comparison of self-cleaning function test In the present invention, it is represented by water-repellent, hydrophilic The property is represented by the contact angle between the surface of the photocatalyst glass test piece and water. The contact angle is shown in the fourth figure. When the contact angle is small, it shows that the surface of the substrate has good affinity with water. It is a hydrophilic material. When it is large, it means that the surface of the substrate is hydrophobic. The solution used is the same as the three solutions A, B, and C in Example 2. The three solutions are placed in beakers for dip plating, and then placed into glass pieces of about 5 X 10 cm2. Immerse in three kinds of solutions. After immersing in 13 1230690 for 2 minutes, raise it at a stretching speed of 2.4cm / min. Place the glass piece in an oven at 200 ° C and 5 ° (: After 2 hours of constant temperature, complete the dipping process. Three more The samples were immersed in 200mL of pure water for 30 minutes to remove surface impurities, and then placed in an oven at 100 ± 5QC for 1 hour, and then irradiated with 0.65 μλν / cm2 UV light for 2 hours. Determine its contact angle with water. Use a First Ten Angstrom FTA-125 contact angle tester to perform a contact angle test, and test the photocatalyst glass test piece with 4μί deionized water droplets. The results are shown in Table 2. When the B solution is a plating solution, the contact angle is the smallest, followed by the C solution sample, and the A solution without the addition of tetraethylsilane (TEOS) is less hydrophilic. In addition, a blank glass test piece that is not coated with photocatalyst. The contact angle is about 48 degrees, and there is no self-cleaning effect. From the results, it can be known that the modified photocatalyst solution method proposed in this method can effectively combine the inorganic adhesive with the photocatalyst particles, and further can have good adhesion to the glass substrate, so that the substrate on the surface of the substrate has a good hydrophilic effect. Table 2: Comparison of hydrophilicity of neutral titanium dioxide photocatalyst solution ^ contact with the film ^ A liquid test piece B liquid test piece C liquid test blank blank first point 29.4 ° < 5 ° 14.2 ° 46.9 ° second point 29.3 ° < 5 ° 13.5 ° 50.Γ Third point 29.5 ° < 5 ° 15.5 ° 47.3 ° Average 29.4 ° < 5 ° 1 · 48.1 ^ Note · A solution: β L titanium dioxide photocatalyst solution without modification 0B Liquid: The modified neutral titanium dioxide photocatalyst solution C of the present invention. Liquid C: the modified neutral titanium dioxide photocatalyst solution after synthesis. Example 4: Preparation of modified acidic titanium dioxide photocatalyst solution. 20 g of titanium tetraoxide is used as a reactant. Add 250g of pure water and dilute it at 4 ° C. After stirring until it is clear and transparent, add 100 ~ 200mL 20% ammonia water dropwise to form a titanium hydroxide precipitate. The pH at the end of the titration is 4.0 ± 0.5. Stir for 2 hours. The precipitate was filtered and washed several times to remove gas ions. After the gas ion concentration was lower than 0.001M, 0.25M, 400mL nitric acid aqueous solution was added and mixed uniformly for 2 hours. 14 1230690 A pale yellow transparent titanium peroxide solution was obtained. Add an appropriate amount of silica sol or tetraethylsilane, the weight ratio of silicon dioxide to titanium dioxide is 1:20, add the modifier liquid, and heat and reflux at 90 ° C for 8 hours to obtain a white transparent solution. This solution It will not precipitate after standing for more than 6 months at normal temperature and pressure. No precipitation occurs after high-speed centrifuge test. The pH value is 1 ~ 4. It is an acidic titanium dioxide photocatalyst solution. The crystal is anatase. The titanium dioxide content is 1 ~ 6. wt%, particle size: long axis: 10 ~ 60 nm, short axis: 5 ~ 20 nm, drill degree is 1 ~ 5 cps. After the modified acidic titanium dioxide solution is coated on the substrate, it has better adhesion than the coating film of the unmodified acidic titanium dioxide photocatalyst solution. The nitric acid solution in this embodiment can be replaced by a hydrochloric acid solution or an oxalic acid solution, and an acidic titanium dioxide photocatalyst solution can also be obtained. Example 5: Comparison of Adhesiveness of Modified Acidic Titanium Dioxide Photocatalyst Solution Take out 1% acidic titanium dioxide photocatalyst solution (same procedure as in Example 4 but without adding inorganic silicon salt modifier) and 1% modification prepared in Example 4 250 mL of acidic titanium dioxide photocatalyst solution), labeled as D and E liquids, and configured with 1% acid titanium dioxide photocatalyst solution (F liquid) modified afterwards. The configuration method of F liquid is: Take an appropriate amount of D liquid and add tetraethyl Silane (TEOS) was stirred at 80 ° C for 5 hours to complete, where Ti02 / Si = 20, and 250 mL of F liquid was also taken out. Put the three solutions into the beaker for dip plating, and then put about 50cm2 of non-woven cloth impregnated with the three solutions. The material is PE / coPET 50g / m2. After immersing for 30 minutes, take it out to dry, put it into the oven to The temperature is 90 ° C and 5 ° C for 2 hours, and the coating amount of the photocatalyst is calculated by weighing. After that, the three samples were placed in 250mL of pure water, shaken with ultrasound (225 W 35kHz) for 30 minutes at 25 ° C, and then placed in an oven at 90 ° C and 5 ° C for 2 hours. Photocatalyst coating amount and peeling amount. The results are shown in Table III. It can be seen that when the E liquid is used as the plating solution, the adhesion amount is the highest (0.0444g), and the physical catalyst ultrasonic test shows that the E liquid sample has the lowest photocatalyst loss rate (4.05%), and the D and F liquid loss rates Higher. It can be known that the modified photocatalyst solution method proposed in this method can effectively bind the inorganic adhesive with the photocatalyst particles, and the subsequent addition will cause dispersion 15 1230690
B液·本發明之改質之酸性二藍 + C液：合成後改質之酸性二氧化鈦光觸媒心及 實施例6·改質之酸性二氧化鈦光觸媒溶液之自我潔淨功能比較 自我潔淨的功能的檢驗方法與實施例3.檢驗中性溶液相同， =其結果如表四所示。可知在以E液為錢液時，其接觸角最小， ”次為F液樣品’未添加四乙基純（TE〇s) % d液其親水 性更差’另外’未塗佈光觸媒的空白玻璃試片，其接觸角為485 度左右’無自我潔淨之效果。由結果可知本方法所提出的改 觸媒溶液方法可使無機黏著劑有效地與光觸媒粒子結合，進而 與玻璃基材有良㈣純，使基材表面純具良好^親水性^Solution B · The modified acidic two blue + C of the present invention: The modified acidic titanium dioxide photocatalyst core after synthesis and Example 6 · The self-cleaning function of the modified acidic titanium dioxide photocatalyst solution is compared with the test method of self-cleaning function and Example 3. The neutral solution is the same, and the results are shown in Table 4. It can be seen that when the E liquid is used as the liquid, the contact angle is the smallest, and the "F liquid sample" is not added with tetraethyl pure (TE0s)% d liquid, which has a lower hydrophilicity. In addition, there is a blank that is not coated with a photocatalyst. The glass test piece has a contact angle of about 485 degrees. 'There is no self-cleaning effect. From the results, it can be seen that the modified catalyst solution method proposed by this method can effectively combine the inorganic adhesive with the photocatalyst particles, and then has a good relationship with the glass substrate. ㈣Pure, so that the surface of the substrate is pure ^ hydrophilic ^
16 1230690 實施例7·利用改質之二氧化鈦光觸媒溶液去除一氧化氮 以不織布（PE/coPET)作為基材進行浸鍍二氧化鈦作業，使用 ， 如實施例1製成之改質後之中性二氧化鈦光觸媒溶液。浸鍍後之 4 樣品，置於烘箱乾燥，於13(TC下，維持1小時，即完成塗層材 . 料之製備，試片面積200cm2,二氧化鈦含量0.6g。一氧化氮（NO) 標準氣體經與空氣混合稀釋成lppm，以質量流量控制器精確控制 其流量（1〜3L/min )後，開始進行測試。設定流速為3L/min，當 一氧化氮氣體（NO)‘進入反應箱時，先不開啟紫外線燈管，待進 料濃度穩定（約20分鐘）後，此時始開啟紫外線燈管進行二氧 籲 化鈦之光觸媒反應測試。實驗結果如第五圖所示，當紫外線燈管 開啟後約3分鐘後，一氧化氮濃度由lppm降低至0.7ppm ;再調 降流速為1 L/min，降低至0.3ppm，且可穩定維持。測試結果顯示 本發明之改質後之二氧化鈦塗層材料具有極佳的光觸媒活性，去 除一氧化氮之效果顯著。 本實施例中的改質之中性二氧化鈦光觸媒溶液，可用改質之 酸性二氧化鈦光觸媒溶液替代，同樣具有良好的去除一氧化氮之 效果。 比較例1利用未添加無機矽鹽之中性光觸媒溶液去除一氧化氮 鲁 同前述實施例7之方法，使用未添加無機矽鹽之中性光觸媒 溶液（A液）去除一氧化氮之實驗結果如第六圖所示，結果顯示在 相同流量的條件下，使用無機矽鹽改質劑之中性二氧化鈦光觸媒 _ 溶液相較於未改質之中性二氧化鈦光觸媒溶液，其一氧化氮之去 1 除能力並無差異，代表本發明之二氧化鈦光觸媒溶液的改質，能 增加二氧化鈦光觸媒溶液在塗覆過程中與基材之密著性，且並不 ’ 影響其一氧化氮之去除效能。 · 實施例8·利用改質之二氧化鈦光觸媒溶液去除乙醛 17 1230690 以玻璃片作為基材進行浸鍍二氧化鈦作業，使用如實施例1 製成之改質後之二氧化鈦光觸媒溶液。浸鍍後之樣品，置於烘箱 乾燥，於105t下，維持1小時，即完成塗層材料之製備，試片 面積100cm2，二氧化鈦含量O.Olg。乙醛標準氣體經與空氣混合 稀釋且以質量流量控制器精確控制其流量及濃度（0.5L/min， 400ppm)後，開始進行測試。當乙醛氣體進入反應箱時，先不開 啟紫外線燈管，俟乙醛進料濃度穩定（約20分鐘）後，此時始 開啟紫外線燈管進行二氧化鈦之光觸媒反應測試。實驗結果如第 七圖所示可看出紫外線燈管開啟後約10分鐘内，乙醛濃度無明 顯變化；10〜20分鐘，乙酸濃度由400ppm降低至200ppm ; 20〜40 分鐘，乙酸濃度由200ppm降低至50ppm，然後一直維持於50ppm 左右，直至實驗結束。測試結果顯示本二氧化鈦塗層材料具有極 佳的光觸媒活性，分解乙醛氣體之效果顯著。本實施例中的中性 二氧化鈦溶液，可用酸性二氧化鈦溶液取代，同樣具有良好的分 解乙醛之效果。 比較例2.利用未添加無機矽鹽之中性光觸媒溶液分解乙醛 同前述實施例8之方法，使用未添加無機矽鹽之中性二氧化 鈦光觸媒溶液（A液）分解乙醛之實驗結果如第八圖所示，結果顯 示使用無機矽鹽改質劑之中性二氧化鈦光觸媒溶液相較於未改 質之中性二氧化鈦光觸媒溶液，其乙酸之分解能力並無差異，代 表本發明之二氧化鈦光觸媒溶液的改質，能增加二氧化鈦光觸媒 溶液在塗覆過程中與基材之密著性，且並不影響其乙醛之分解效 能。 綜上所述，本發明提供一種二氧化鈦奈米光觸媒溶液改質之 製造的方法，以四氣化鈦為起始物，經過鹼液滴定中和沉澱，沉 澱物經水洗去除氣離子，以解膠劑解膠後，再加入適當比例之無 機改質劑，經過加溫迴流，製成具光觸媒活性之銳鈦礦結晶結構 18 1230690 二氧化鈦光觸媒溶液，具 — 佳之基材密著性，且不須期貯存，同時具有更 觸媒溶液之應用性。 阿，皿鈑燒處理，可增進二氧化鈦光 …x月已以較佳實施例揭露如上，麸1並非用 發明，任何熟悉此技蓺者， 、八^用乂限疋本 可作夂#、衣者在不脱離本务明之精神和範圍内，當 ϋ乍σ種之更動與潤飾，因此，本發 由技直田 个知月之保4靶圍，當視後附之 申明專利祀圍所界定者為準。16 1230690 Example 7: Removal of Nitric Oxide by Using Modified Titanium Dioxide Photocatalyst Solution Using a non-woven fabric (PE / coPET) as a substrate for dip-dip TiO2 operation, use the modified neutral TiO2 photocatalyst prepared in Example 1 Solution. The 4 samples after immersion plating were dried in an oven and maintained at 13 ° C for 1 hour to complete the coating material. The preparation of the material, the test piece area was 200 cm2, and the titanium dioxide content was 0.6 g. Nitric oxide (NO) standard gas After mixing and diluting with air to lppm, the mass flow controller precisely controls its flow rate (1 ~ 3L / min), and then starts the test. Set the flow rate to 3L / min, when the nitric oxide gas (NO) 'enters the reaction box Without turning on the UV lamp, wait until the feed concentration is stable (about 20 minutes), and then turn on the UV lamp for the photocatalytic reaction test of titanium dioxide. The experimental results are shown in the fifth figure. Approximately 3 minutes after the tube was opened, the nitric oxide concentration was reduced from 1 ppm to 0.7 ppm; the flow rate was further reduced to 1 L / min to 0.3 ppm, and it can be stably maintained. The test results show that the modified titanium dioxide of the present invention The coating material has excellent photocatalytic activity, and the effect of removing nitric oxide is remarkable. The modified neutral titanium dioxide photocatalyst solution in this embodiment can be replaced by the modified acidic titanium dioxide photocatalyst solution, which also has good properties. Good removal effect of nitric oxide. Comparative Example 1 uses the neutral photocatalyst solution without added inorganic silicon salt to remove nitric oxide in the same manner as in Example 7 above, using a neutral photocatalyst solution without added inorganic silicon salt (A liquid ) The experimental results of removing nitric oxide are shown in the sixth figure. The results show that under the same flow conditions, the inorganic silicon salt modifier is used to modify the neutral titanium dioxide photocatalyst solution. Compared with the unmodified neutral titanium dioxide photocatalyst solution, There is no difference in the removal ability of nitric oxide, which represents the modification of the titanium dioxide photocatalyst solution of the present invention, which can increase the adhesion of the titanium dioxide photocatalyst solution to the substrate during the coating process, and does not affect one of them. Removal efficiency of nitrogen oxides. Example 8: Removal of acetaldehyde using modified titanium dioxide photocatalyst solution 17 1230690 Using glass flakes as substrate for dip titanium dioxide operation, using the modified titanium dioxide photocatalyst solution prepared as in Example 1. The samples after dip plating are dried in an oven and maintained at 105t for 1 hour to complete the preparation of the coating material and the area of the test piece. 100cm2, titanium dioxide content O.Olg. The acetaldehyde standard gas is diluted with air and its flow rate and concentration (0.5L / min, 400ppm) are precisely controlled by a mass flow controller. The test is started. When the acetaldehyde gas enters the reaction box At this time, the ultraviolet lamp is not turned on first. After the concentration of acetaldehyde feed is stable (about 20 minutes), the ultraviolet lamp is turned on for the photocatalytic reaction test of titanium dioxide. The experimental results can be seen in the seventh figure. The acetaldehyde concentration did not change significantly within about 10 minutes after the tube was opened; 10 to 20 minutes, the acetic acid concentration was reduced from 400 ppm to 200 ppm; 20 to 40 minutes, the acetic acid concentration was reduced from 200 ppm to 50 ppm, and then maintained at about 50 ppm until the experiment End. The test results show that the titanium dioxide coating material has excellent photocatalytic activity, and the effect of decomposing acetaldehyde gas is remarkable. The neutral titanium dioxide solution in this example can be replaced by an acidic titanium dioxide solution, which also has a good effect of decomposing acetaldehyde. Comparative Example 2. Decomposition of acetaldehyde by neutral photocatalyst solution without added inorganic silicon salt The method of Example 8 described above, the experimental results of decomposition of acetaldehyde by neutral titanium dioxide photocatalyst solution (liquid A) without added inorganic silicon salt are shown in the first section. As shown in Figure 8, the results show that the neutral titanium dioxide photocatalyst solution using the inorganic silicon salt modifier has no difference in the decomposition ability of acetic acid compared with the unmodified neutral titanium dioxide photocatalyst solution, which represents the performance of the titanium dioxide photocatalyst solution of the present invention. The modification can increase the adhesion between the titanium dioxide photocatalyst solution and the substrate during the coating process, and does not affect its acetaldehyde decomposition efficiency. In summary, the present invention provides a method for the modification of a nanometer titanium dioxide photocatalyst solution. The titanium tetraoxide is used as a starting material, and the precipitate is neutralized by alkali titration. The precipitate is washed with water to remove gas ions to degelatinize. After degumming the agent, an appropriate proportion of inorganic modifier is added, and after heating and refluxing, an anatase crystal structure with photocatalytic activity is made. 18 1230690 Titanium dioxide photocatalyst solution, with excellent substrate adhesion and no need Storage, while having more applicable catalyst solution. Ah, the sintering of the plate can enhance the titanium dioxide light ... The above has been disclosed in the preferred embodiment. The bran 1 is not an invention. Anyone who is familiar with this technology can use it as the #, clothing. Those who do not deviate from the spirit and scope of this matter, when the change and retouching of the σ σ species, therefore, the present invention is defined by the technical Naoki Gezhiyuebao 4 target range, as defined in the attached patent sacrifice. Whichever comes first.
19 1230690 【圖式簡單說明】 程圖 圖。第-圖係為本發明之改質之二氧化鈦光觸媒溶液製備流程 程圖第二圖係為本發明之改質之中性二氧化鈦光觸媒溶液製備流 第三圖係為本發明之改質之酸性二氧化鈦光觸媒溶液製備流 第五圖係為利用本發明之改質之 第四圖係為塗層親水性/疏水性示意圖。 氧化氮之結果圖。 第六圖係為利用未改質之二 之結果圖。 氧化鈦光觸媒溶液去除 氧化鈦光觸媒溶液去除一氧化氮 第七圖係為湘本發明之改質之二氧化鈇光觸媒溶液分解乙 之結果圖。 第八圖係為利用未改質之二 果圖。 氧化鈦光觸媒溶液分解 乙醛之結19 1230690 [Brief description of the diagram] Process diagram. The first picture is the process flow for preparing modified titanium dioxide photocatalyst solution of the present invention. The second picture is the preparation flow of modified neutral titanium dioxide photocatalyst solution of the present invention. The third picture is the modified acid titanium dioxide photocatalyst of the present invention. The fifth diagram of the solution preparation flow is a modification of the present invention. The fourth diagram is a schematic diagram of the hydrophilicity / hydrophobicity of the coating. Graph of the results of nitrogen oxides. The sixth picture is the result of using the unmodified second. Removal of Titanium Dioxide Photocatalyst Solution Removal of Nitric Oxide by Titanium Dioxide Photocatalyst Solution The seventh picture is the result of decomposition of B by the modified hafnium dioxide photocatalyst solution of the present invention. The eighth picture is the result map using the second unmodified. Decomposition of titanium oxide photocatalyst solution
2020