TWI458685B - Titanium dioxide nanopowder and manufacturing method thereof - Google Patents
Titanium dioxide nanopowder and manufacturing method thereof Download PDFInfo
- Publication number
- TWI458685B TWI458685B TW100122829A TW100122829A TWI458685B TW I458685 B TWI458685 B TW I458685B TW 100122829 A TW100122829 A TW 100122829A TW 100122829 A TW100122829 A TW 100122829A TW I458685 B TWI458685 B TW I458685B
- Authority
- TW
- Taiwan
- Prior art keywords
- titanium dioxide
- titanium
- producing
- dioxide nanopowder
- nano
- Prior art date
Links
Description
本發明係關於一種奈米粉體之製造方式，特別是關於一種正八面體形二氧化鈦奈米粉體之製造方式。The present invention relates to a method for producing a nano-powder, and more particularly to a method for producing a regular octahedral titanium dioxide nano-powder.
近年來全球奈米科技之發展方興未艾，不少奈米材料之成功開發著實改善了人們的生活，也開創了無限商機。由於二氧化鈦(TiO2 )的半導體能階具有寬能帶，因此被廣泛地用來做為多功能光觸媒。雖然氧化鋅的半導體能階也具有寬能帶，也可能做為多功能觸媒材料，但其化學穩定性較差(例如，不耐酸性溶液)。因此，大部分奈米光觸媒材料還是以二氧化鈦為主，其為目前最廣泛使用的奈米材料。In recent years, the development of global nanotechnology has been in the ascendant. The successful development of many nano materials has improved people's lives and created unlimited business opportunities. Since the semiconductor energy level of titanium dioxide (TiO 2 ) has a wide energy band, it is widely used as a multifunctional photocatalyst. Although the semiconductor level of zinc oxide also has a broad band, it may also be used as a multifunctional catalyst material, but its chemical stability is poor (for example, it is not resistant to acidic solutions). Therefore, most of the nano photocatalyst materials are mainly titanium dioxide, which is currently the most widely used nano material.
二氧化鈦奈米粉體的製造方法甚多，主要可分為物理法及化學法。物理法是最早的製造方法，其利用如氣相冷凝法、及高能球磨法等物理方式來獲得奈米粉體。氣相冷凝法的原理是利用各種方式使物質蒸發或揮發成氣相，並利用特殊技術冷凝(如液氮)成核，以得到奈米粉體。以這種方法製造的粉體純度高、顆粒大小分布均勻、尺寸可控制，適合生產高熔點奈米金屬粒子或奈米顆粒薄膜。高能球磨法是利用球磨機轉動和振動時的巨大能量，將原料粉碎為奈米級顆粒。其優點為操作簡單、易實現連續生產，缺點則是顆粒大小不均勻，並且容易引入雜質。化學法是另一種製造奈米粉體的方法，在其過程中牽涉到一些化學反應。用於製造奈米粉體的化學法主要有沉澱法、水解法、溶膠凝膠法、水熱法、噴霧法、氧化還原法、激光合成法、及電化學製造法等。以上只是大致的分類，在二氧化鈦奈米粉體的製造過程中，也可能將上述方法搭配使用。例如，沈澱法和噴霧法常牽涉到水解反應及氧化還原反應；水熱法也常結合溶膠凝膠法以製造不同形貌的奈米粉體，例如奈米線、奈米棒、奈米管、奈米微球等。There are many manufacturing methods for titanium dioxide nano-powder, which can be mainly divided into physical methods and chemical methods. The physical method is the earliest manufacturing method, and uses a physical method such as a vapor phase condensation method and a high energy ball milling method to obtain a nano powder. The principle of the gas phase condensation method is to evaporate or volatilize the substance into a gas phase by various means, and nucleate by special technique condensation (such as liquid nitrogen) to obtain a nanometer powder. The powder produced by this method has high purity, uniform particle size distribution and controllable size, and is suitable for producing high melting point nano metal particles or nano particle films. The high-energy ball milling method uses the enormous energy of the ball mill to rotate and vibrate, and pulverizes the raw material into nano-sized particles. The advantages are simple operation and easy continuous production, and the disadvantage is that the particle size is not uniform and impurities are easily introduced. Chemical methods are another method of making nano-powders, and some chemical reactions are involved in the process. The chemical methods used to produce the nano-powder are mainly a precipitation method, a hydrolysis method, a sol-gel method, a hydrothermal method, a spray method, a redox method, a laser synthesis method, and an electrochemical manufacturing method. The above is only a rough classification. In the manufacturing process of titanium dioxide nanopowder, the above method may also be used in combination. For example, precipitation and spray methods often involve hydrolysis reactions and redox reactions; hydrothermal methods are often combined with sol-gel methods to produce nano-sized powders of different morphologies, such as nanowires, nanorods, nanotubes, Nano microspheres, etc.
在上述的各種製造二氧化鈦奈米粉體的方法中，噴霧裂解法是目前將二氧化鈦奈米粉體商品化的主要製程之一，利用此製程可得到粒徑均一且品質穩定的奈米粉體。此外，利用溶膠凝膠法及水熱法，可以製造出各種形貌的二氧化鈦奈米粉體；並且可藉由控制反應溶液的pH值、水熱溫度、反應時間及溶液濃度，調整其奈米尺寸。此為目前取得多樣化奈米結構最常見的方法。Among the various methods for producing titanium dioxide nanopowder described above, the spray cracking method is one of the main processes for commercializing titanium dioxide nanopowder, and a nanometer powder having uniform particle size and stable quality can be obtained by this process. In addition, by using the sol-gel method and the hydrothermal method, various shapes of titanium dioxide nano-powder can be produced; and the nanometer size can be adjusted by controlling the pH value, hydrothermal temperature, reaction time and solution concentration of the reaction solution. . This is the most common method for obtaining diverse nanostructures.
隨著科技產業的快速發展，各種形貌的二氧化鈦奈米粉體在各領域中的應用也日益增加。通常，在製造正八面體形二氧化鈦奈米粉體時，使用的是水熱法、微乳液法、及模板法等等。然而，上述方法需要較昂貴的生產設備，且不利於大量及連續生產；此外，藉由該等方法所製造之粉體，其均勻性仍有待改善。因此，需要開發出一種正八面體形二氧化鈦奈米粉體的製造方法，其適合大量生產、製造成本低廉、且製得的二氧化鈦奈米粉體具有均勻的粒徑大小。With the rapid development of the technology industry, the application of various shapes of titanium dioxide nano-powder in various fields is also increasing. Usually, in the production of the regular octahedral titanium dioxide nanopowder, hydrothermal method, microemulsion method, template method and the like are used. However, the above methods require relatively expensive production equipment and are disadvantageous for large-scale and continuous production; in addition, the uniformity of the powder produced by these methods still needs to be improved. Therefore, there is a need to develop a method for producing a regular octahedral titanium dioxide nanopowder which is suitable for mass production, inexpensive to manufacture, and has a uniform particle size of the prepared titanium dioxide nanopowder.
有鑑於此，本發明之目的即是在於提供一種可滿足上述需求的二氧化鈦奈米粉體之製造方法。In view of the above, an object of the present invention is to provide a method for producing a titanium dioxide nanopowder which can satisfy the above needs.
本發明之第一態樣為一種二氧化鈦奈米粉體之製造方法，包括下列步驟：(a)將鈦前驅物及鹼性螯合劑加入水中；(b)將有機膠溶劑加入由步驟(a)所得之混合物中；(c)令由步驟(b)所得之混合物進行水熱反應；以及(d)分離由步驟(c)所得之產物以得到二氧化鈦奈米粉體。A first aspect of the present invention is a method for producing a titanium dioxide nanopowder comprising the steps of: (a) adding a titanium precursor and an alkaline chelating agent to water; and (b) adding an organic peptizing agent to the step (a). And (c) separating the product obtained in the step (c) to obtain a titanium dioxide nanopowder.
本發明之第二態樣為一種二氧化鈦奈米粉體，具有正八面體之晶型及介於30至500nm之間的粒徑大小。A second aspect of the present invention is a titanium dioxide nanopowder having a crystal form of a regular octahedron and a particle size of between 30 and 500 nm.
藉著本發明之方法，可以低廉的成本製造出粒徑均勻之正八面體形二氧化鈦奈米粉體，且其粒徑尺寸分布可輕易加以調整。By the method of the present invention, a regular octahedral titanium dioxide nano-powder having a uniform particle size can be produced at a low cost, and the particle size distribution can be easily adjusted.
本發明之其它目的及優點由隨後之詳細說明及隨附之申請專利範圍當可更加明白。Other objects and advantages of the present invention will become apparent from the following detailed description and appended claims.
本發明主要係利用溶膠凝膠法及水熱法以製造正八面體形二氧化鈦奈米粉體。圖1展示本發明之二氧化鈦奈米粉體的製造方法。在步驟S1中，將鈦前驅物及鹼性螯合劑加入水中。鈦前驅物可為四氯化鈦(Titanium tetrachloride)、四丙氧基鈦(titanium isopropoxide)、四正丁醇鈦(titanium butoxide)、或者是鈦醇鹽。而鈦醇鹽之烷基可具有1至6個碳原子。鹼性螯合劑可為醇胺，例如三乙醇胺(Triethanolamine)。步驟S1可於惰性氣體下進行，例如氮氣或氬氣。再者，步驟S1之反應條件可為於4至15℃的溫度下持續攪拌約24至72小時。The present invention mainly utilizes a sol-gel method and a hydrothermal method to produce a regular octahedral titanium dioxide nano-powder. Fig. 1 shows a method of producing the titanium dioxide nanopowder of the present invention. In step S1, a titanium precursor and an alkaline chelating agent are added to the water. The titanium precursor may be Titanium tetrachloride, titanium isopropoxide, titanium butoxide, or titanium alkoxide. The alkyl group of the titanium alkoxide may have 1 to 6 carbon atoms. The alkaline chelating agent can be an alcohol amine such as Triethanolamine. Step S1 can be carried out under an inert gas such as nitrogen or argon. Further, the reaction condition of the step S1 may be continued stirring at a temperature of 4 to 15 ° C for about 24 to 72 hours.
在步驟S2中，將有機膠溶劑加入由步驟S1所得之混合物中。有機膠溶劑可為胺鹼，例如二乙胺(Diethylamine)。步驟S2可於惰性氣體下進行，例如氮氣或氬氣。步驟S2之反應條件可為於3至100℃的溫度下持續攪拌約24至72小時。In step S2, an organic gum solvent is added to the mixture obtained in step S1. The organic peptizer may be an amine base such as diethylamine. Step S2 can be carried out under an inert gas such as nitrogen or argon. The reaction condition of the step S2 may be continued stirring at a temperature of from 3 to 100 ° C for about 24 to 72 hours.
在步驟S3中，令由步驟S2所得之混合物進行水熱反應。水熱反應可為於50至300℃的溫度下持續攪拌約2至200小時。水熱法是指在一密封的壓力容器中，以水作為溶劑，製備奈米材料的一種方法。一般而言，在常溫-常壓環境中不易氧化的物質，會因水熱法中高溫-高壓的環境而進行快速的氧化反應。水熱反應是高溫高壓下在水溶液或水蒸氣等流體中，進行有關化學反應的總稱。此水熱法於本發明中所提供的功效在於，所製備的粉體具有粒徑分佈均勻、顆粒團聚輕及可連續生產、易得到適合化學計量比的奈米氧化物粉體之優點。在水熱過程中，成核長晶的過程會持續而成長出更大的晶體結構，因此會使得奈米氧化物具有特定晶相，而無須再藉由相轉移的方式來得到特定晶相。也就是說，無須進行高溫煆燒處理，即可得到高結晶性的物質，因此可避免引入雜質而造成缺陷等困擾，使所製得的粉體具有高的燒結活性。在步驟S4中，分離由步驟S3所得之產物以得到二氧化鈦奈米粉體。此方法更可包含將二氧化鈦奈米粉體加以乾燥。In step S3, the mixture obtained in the step S2 is subjected to a hydrothermal reaction. The hydrothermal reaction can be continued for about 2 to 200 hours at a temperature of 50 to 300 °C. Hydrothermal method refers to a method of preparing a nanomaterial by using water as a solvent in a sealed pressure vessel. In general, substances that are not easily oxidized in a normal temperature-normal pressure environment undergo rapid oxidation reactions due to a high-temperature environment in a hydrothermal process. The hydrothermal reaction is a general term for performing chemical reactions in a fluid such as an aqueous solution or water vapor under high temperature and high pressure. The hydrothermal method provides the effect of the present invention in that the prepared powder has the advantages of uniform particle size distribution, light particle agglomeration and continuous production, and easy availability of a suitable stoichiometric ratio of nano-oxide powder. In the hydrothermal process, the process of nucleating crystal growth continues to grow into a larger crystal structure, thus allowing the nano oxide to have a specific crystal phase without the need for phase transfer to obtain a specific crystal phase. That is to say, a material having high crystallinity can be obtained without performing a high-temperature calcination treatment, so that it is possible to avoid the introduction of impurities and cause defects and the like, and the obtained powder has high sintering activity. In step S4, the product obtained in the step S3 is separated to obtain a titanium dioxide nanopowder. The method may further comprise drying the titanium dioxide nanopowder.
由實驗結果已發現到，當未加入三乙醇胺(鹼性螯合劑)而只加入二乙胺(有機膠溶劑)時，奈米粒子較無特定形貌上的規則性以及其大小較不均一。相反的，同時加入三乙醇胺及二乙胺，則奈米粒子會具有規則的正八面體形貌及其大小較均一。It has been found from the experimental results that when triethanolamine (alkaline chelating agent) is not added and only diethylamine (organic gel solvent) is added, the nanoparticles are less uniform in terms of specific morphology and their size is less uniform. Conversely, when triethanolamine and diethylamine are added at the same time, the nanoparticles will have a regular regular octahedral morphology and a uniform size.
在步驟S3的水熱法中，二氧化鈦奈米粉體之粒徑大小會隨著水熱反應的時間及溫度而改變。如下述實施例之結果所顯示，當水熱反應之溫度越高、時間越長時，二氧化鈦奈米粉體之粒徑會越大。In the hydrothermal method of step S3, the particle size of the titanium dioxide nanopowder varies with the time and temperature of the hydrothermal reaction. As shown by the results of the following examples, the higher the temperature of the hydrothermal reaction and the longer the time, the larger the particle size of the titanium dioxide nanopowder.
將100mL的去離子水以高速攪拌的同時以每秒1至數滴的速率逐滴將四丙氧基鈦(titanium isopropoxide)及三乙醇胺(Triethanolamine)加入去離子水中(兩者的莫耳數比約為1比1)，可得到鈦前驅物溶液，並且可以選擇性地通入氮氣或氬氣。繼續攪拌約24至72小時；然後再加入形貌控制之二乙胺(Diethylamine)，並將溫度提高至100℃且持續攪拌約24至72小時；然後再將溫度提高至230~270℃且持續攪拌約2至72小時。Add 100 mL of deionized water to the deionized water at a rate of 1 to several drops per second while stirring at a high speed (the molar ratio of the two is added to deionized water) Approximately 1 to 1), a titanium precursor solution can be obtained, and nitrogen or argon can be selectively introduced. Stirring is continued for about 24 to 72 hours; then the morphology controlled diethylamine is added and the temperature is raised to 100 ° C and stirring is continued for about 24 to 72 hours; then the temperature is increased to 230 to 270 ° C and continued Stir for about 2 to 72 hours.
以進行水熱反應。將獲得的混合液接著利用過濾或離心之類的方式收集粉體。將上述粉體以去離子水清洗至少三次，以去除殘留的溶劑、三乙醇胺或二乙胺；再以溫度介於60至500℃之間的烘箱加以乾燥，因而獲得本發明之正八面體形二氧化鈦奈米粉體。本實施例藉著控制水熱反應之溫度與時間，可得到不同尺寸之奈米粉體，其結果如表1所示。依據不同的水熱反應條件，所得奈米粉體之粒徑大小範圍介於30~50nm、50~100nm、50~200nm、100~300nm、200~400nm、或300~500nm。又，由表1之結果可推知：當水熱反應之溫度越高、時間越長時，二氧化鈦奈米粉體之粒徑會越大。因此，本發明可藉著改變水熱反應之時間及溫度來調整正八面體形二氧化鈦奈米粉體的粒徑大小分佈。For hydrothermal reaction. The obtained mixture is then collected by means of filtration or centrifugation or the like. The above powder is washed with deionized water at least three times to remove residual solvent, triethanolamine or diethylamine; and dried in an oven at a temperature between 60 and 500 ° C, thereby obtaining the regular octahedral titanium dioxide of the present invention. Nano powder. In this embodiment, by controlling the temperature and time of the hydrothermal reaction, nano-sized powders of different sizes can be obtained, and the results are shown in Table 1. According to different hydrothermal reaction conditions, the obtained nanometer powder has a particle size ranging from 30 to 50 nm, 50 to 100 nm, 50 to 200 nm, 100 to 300 nm, 200 to 400 nm, or 300 to 500 nm. Further, from the results of Table 1, it can be inferred that the larger the temperature of the hydrothermal reaction and the longer the time, the larger the particle size of the titanium dioxide nanopowder. Therefore, the present invention can adjust the particle size distribution of the regular octahedral titanium dioxide nanopowder by changing the time and temperature of the hydrothermal reaction.
此外，圖2(a)至圖2(f)顯示上述實施例所得到之正八面體形二氧化鈦奈米粉體之掃描式電子顯微鏡(SEM)影像，圖3顯示其X光繞射圖，各圖或曲線所對應的水熱反應條件係顯示於表1中。由圖2及圖3可明顯看出，上述實施例所得之二氧化鈦奈米粉體具有規則的正八面體形貌以及均勻之粒徑大小。由圖3的結果可看出此正八面體形二氧化鈦奈米粉體為銳鈦礦(Anatase)晶相，也證實藉由水熱法所成長出的奈米氧化物是具有特定晶相的物質。圖4利用掃描式電子顯微鏡(SEM)來拍攝奈米材料微結構，可看出正八面體形二氧化鈦奈米粉體排列成薄膜的形貌。根據本發明之製造方法，可以在同一種合成架構之下生成正八面體形結構的二氧化鈦奈米粉體，其奈米粒子尺寸可控制在30nm~500nm間之各範圍中，並且在各範圍中均呈現良好的尺寸均勻度。於先前技術中，瑞士洛桑理工學院(EPFL)的M.Grätzel實驗室所研發的二氧化鈦奈米粉體僅具有小尺寸的粒徑大小範圍(15~30nm)，相對而言，本發明以不同的合成方式可得到大於30nm之粒徑範圍。2(a) to 2(f) show scanning electron microscope (SEM) images of the regular octahedral titanium dioxide nano-powder obtained in the above embodiment, and FIG. 3 shows X-ray diffraction patterns thereof, or The hydrothermal reaction conditions corresponding to the curves are shown in Table 1. As is apparent from Fig. 2 and Fig. 3, the titanium dioxide nanopowder obtained in the above embodiment has a regular regular octahedron morphology and a uniform particle size. It can be seen from the results of Fig. 3 that the regular octahedral titanium dioxide nanopowder is an anatase crystal phase, and it has also been confirmed that the nano oxide grown by hydrothermal method is a substance having a specific crystal phase. Figure 4 uses a scanning electron microscope (SEM) to capture the microstructure of nanomaterials. It can be seen that the regular octahedral titanium dioxide nanopowders are arranged in a thin film. According to the manufacturing method of the present invention, a titanium dioxide nano-powder having a regular octahedral structure can be produced under the same synthetic framework, and the nanoparticle size can be controlled in various ranges between 30 nm and 500 nm, and is exhibited in each range. Good size uniformity. In the prior art, the titanium dioxide nano-powder developed by the M. Grätzel laboratory of the EPFL in Switzerland has only a small size range (15-30 nm), and the present invention is relatively different in synthesis. In a manner, a particle size range of more than 30 nm can be obtained.
利用本發明所製備不同尺寸大小的正八面體形二氧化鈦奈米粉體，可進一步用來製備不同尺寸大小的二氧化鈦奈米薄膜。其方法如下：將利用上述方法製得的正八面體形二氧化鈦奈米粉體加入水、水性溶劑、或油性溶劑之中，再加入例如有機小分子、 寡聚體、高分子的分散劑，以形成漿料或溶液。其中，亦可選擇性地加入陰離子型及陽離子型界面活性劑。接著，再利用網印、旋轉塗佈、噴塗等方式，在基板上形成正八面體形二氧化鈦奈米薄膜。The regular octahedral titanium dioxide nano-powders of different sizes prepared by the invention can be further used to prepare titanium dioxide nano-films of different sizes. The method is as follows: the normal octahedral titanium dioxide nano-powder prepared by the above method is added to water, an aqueous solvent or an oily solvent, and then added, for example, an organic small molecule, A dispersant of an oligomer or a polymer to form a slurry or a solution. Among them, anionic and cationic surfactants may be optionally added. Next, a regular octahedral titanium dioxide nano film is formed on the substrate by screen printing, spin coating, spray coating or the like.
將前述之正八面體形二氧化鈦奈米粉體6g與1mL的醋酸混合，攪拌三分鐘；加入5mL的去離子水，攪拌3分鐘使之均勻混合；接著加入15mL乙醇、20g松油醇、及30g乙基纖維素後，攪拌12小時使之均勻分散，即完成正八面體形二氧化鈦奈米漿料之製造。Mixing 6g of the above-mentioned regular octahedral titanium dioxide nanopowder with 1mL of acetic acid, stirring for three minutes; adding 5mL of deionized water, stirring for 3 minutes to make it evenly mixed; then adding 15mL of ethanol, 20g of terpineol, and 30g of ethyl After the cellulose was stirred for 12 hours to be uniformly dispersed, the production of the regular octahedral titanium dioxide nano slurry was completed.
藉由網版印刷，將前述之正八面體形二氧化鈦奈米漿料塗佈在透明導電玻璃基材上，並利用高溫燒結以去除有機物質，燒結溫度介於300至600℃之間，燒結時間則介於1至5小時；接著冷卻至室溫，可在基材上形成正八面體形二氧化鈦奈米薄膜，厚度為1至10微米，其可使用於例如太陽能電池之透明電極。該薄膜的硬度係介於3B至6H的鉛筆硬度之間。圖4為依據上述實施例配置於基材上之正八面體形二氧化鈦奈米薄膜之掃描式電子顯微鏡影像。利用本發明之二氧化鈦奈米粉體所製成的薄膜應用於染料敏化太陽能電池上，與習知技術相比有較高的光電轉換效率。表2展示本發明之二氧化鈦奈米薄膜(HD30，其水熱反應條件顯示於表1中)與習知瑞士洛桑理工學院(EPFL)的M.Grätzel實驗室所發展的二氧化鈦奈米薄膜(NP)相比較的結果。在相同厚度下的兩種薄膜所量測出的結果可看出由於HD30的奈米尺寸較NP來的大，因此比表面積較NP來的小，而造成在染敏系統中的染料吸附在HD30上較NP來的少，而使得所提供出的短路電流密度較小。但因為HD30的材料本質較佳而有較高的開路電壓及填滿因子，因此導致轉換效率較NP來的高。The above-mentioned regular octahedral titanium dioxide nano slurry is coated on a transparent conductive glass substrate by screen printing, and is sintered at a high temperature to remove organic substances, and the sintering temperature is between 300 and 600 ° C, and the sintering time is Between 1 and 5 hours; followed by cooling to room temperature, a regular octahedral titanium dioxide nanofilm can be formed on the substrate to a thickness of 1 to 10 microns, which can be used for transparent electrodes such as solar cells. The hardness of the film is between 3 and 6H pencil hardness. 4 is a scanning electron microscope image of a regular octahedral titanium dioxide nano film disposed on a substrate according to the above embodiment. The film made of the titanium dioxide nanopowder of the present invention is applied to a dye-sensitized solar cell, and has higher photoelectric conversion efficiency than the prior art. Table 2 shows the titanium dioxide nano film (HD30 of the present invention, whose hydrothermal reaction conditions are shown in Table 1) and the titanium dioxide nano film (NP) developed by the M. Grätzel laboratory of the Swiss Institute of Technology in Lausanne (EPFL). The result of the comparison. The results measured by the two films at the same thickness can be seen that since the nano-size of HD30 is larger than that of NP, the specific surface area is smaller than that of NP, and the dye in the dye-sensitive system is adsorbed on HD30. It is less than the NP, so that the short-circuit current density is small. However, because the HD30 has a better material quality and a higher open circuit voltage and fill factor, the conversion efficiency is higher than that of NP.
依據本發明之方法，可突破習知以單一合成方式製備二氧化鈦奈米粉體所遭遇的尺寸限制。使得利用本發明所製備的二氧化鈦奈米粉體能更加廣泛地應用於染料敏化太陽能電池中之薄膜的製備，可用以提高光電轉化效率及薄膜製備上的實用性。According to the method of the present invention, the size limitation encountered in the preparation of titanium dioxide nanopowder by a single synthesis can be broken. The titanium dioxide nanopowder prepared by the invention can be more widely used in the preparation of a film in a dye-sensitized solar cell, and can be used to improve photoelectric conversion efficiency and practicality in film preparation.
本發明可在不離開本發明之精神及基本特徵下做各種特定之例示。因此上述實施例應被視為舉例性而非限制性者，且本發明之範圍為由隨附之申請專利範圍所限定，而非由上述說明所限制，所有與申請專利範圍意義相等之變化均應包含於本發明之範疇中。The invention may be embodied in various specific forms without departing from the spirit and scope of the invention. The above-described embodiments are to be considered as illustrative and not restrictive, and the scope of the invention is defined by the scope of the appended claims It should be included in the scope of the present invention.
S1‧‧‧將鈦前驅物及鹼性螯合劑加入水中S1‧‧‧Adding titanium precursor and alkaline chelating agent to the water
S2‧‧‧將有機膠溶劑加入由步驟S1所得之混合物中S2‧‧‧Adding the organic gum solvent to the mixture obtained in step S1
S3‧‧‧令由步驟S2所得之混合物進行水熱反應S3‧‧‧ The hydrothermal reaction of the mixture obtained in step S2
S4‧‧‧分離由步驟S3所得之產物以得到二氧化鈦奈米粉體S4‧‧‧ separating the product obtained in step S3 to obtain titanium dioxide nanopowder
圖1展示本發明之二氧化鈦奈米粉體的製造方法。Fig. 1 shows a method of producing the titanium dioxide nanopowder of the present invention.
圖2顯示依據本發明所製備之正八面體形二氧化鈦奈米粉體之掃瞄式電子顯微鏡影像。(a)粒徑為30至50nm；(b)粒徑為50至100nm；(c)粒徑為50至200nm；(d)粒徑為100至300nm；(e)粒徑為200至400nm；(f)粒徑為300至500nm。Figure 2 shows a scanning electron microscope image of a regular octahedral titanium dioxide nanopowder prepared in accordance with the present invention. (a) a particle diameter of 30 to 50 nm; (b) a particle diameter of 50 to 100 nm; (c) a particle diameter of 50 to 200 nm; (d) a particle diameter of 100 to 300 nm; (e) a particle diameter of 200 to 400 nm; (f) The particle size is from 300 to 500 nm.
圖3顯示依據本發明所製備之正八面體形二氧化鈦奈米粉體之X光繞射圖。Figure 3 shows an X-ray diffraction pattern of a regular octahedral titanium dioxide nanopowder prepared in accordance with the present invention.
圖4為配置於基材上之正八面體形二氧化鈦奈米薄膜之掃描式電子顯微鏡影像，此二氧化鈦奈米薄膜係由本發明之正八面體形二氧化鈦奈米粉體所製成。4 is a scanning electron microscope image of a regular octahedral titanium dioxide nano film disposed on a substrate, which is made of the regular octahedral titanium dioxide nano powder of the present invention.
S1‧‧‧將鈦前驅物及鹼性螯合劑加入水中S1‧‧‧Adding titanium precursor and alkaline chelating agent to the water
S2‧‧‧將有機膠溶劑加入由步驟S1所得之混合物中S2‧‧‧Adding the organic gum solvent to the mixture obtained in step S1
S3‧‧‧令由步驟S2所得之混合物進行水熱反應S3‧‧‧ The hydrothermal reaction of the mixture obtained in step S2
S4‧‧‧分離由步驟S3所得之產物以得到二氧化鈦奈米粉體S4‧‧‧ separating the product obtained in step S3 to obtain titanium dioxide nanopowder
Claims (11)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100122829A TWI458685B (en) | 2011-06-29 | 2011-06-29 | Titanium dioxide nanopowder and manufacturing method thereof |
| CN201110191437.4A CN102849793B (en) | 2011-06-29 | 2011-07-08 | Titanium dioxide nanopowder and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| TW100122829A TWI458685B (en) | 2011-06-29 | 2011-06-29 | Titanium dioxide nanopowder and manufacturing method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201300324A TW201300324A (en) | 2013-01-01 |
| TWI458685B true TWI458685B (en) | 2014-11-01 |
Family
ID=47396843
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW100122829A TWI458685B (en) | 2011-06-29 | 2011-06-29 | Titanium dioxide nanopowder and manufacturing method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN102849793B (en) |
| TW (1) | TWI458685B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106698503B (en) * | 2015-11-13 | 2018-03-16 | 中国石油化工股份有限公司 | A kind of synthetic method of titanic oxide nano |
| WO2018003851A1 (en) * | 2016-06-29 | 2018-01-04 | 住友大阪セメント株式会社 | Titanium oxide particles, and titanium oxide particle dispersion and cosmetics using same |
| JP6984407B2 (en) * | 2017-12-28 | 2021-12-22 | 住友大阪セメント株式会社 | Titanium oxide powder, and dispersions and cosmetics using it |
| JP6988471B2 (en) * | 2017-12-28 | 2022-01-05 | 住友大阪セメント株式会社 | Titanium oxide powder, and dispersions and cosmetics using it |
| WO2019131871A1 (en) * | 2017-12-28 | 2019-07-04 | 住友大阪セメント株式会社 | Titanium oxide powder, and dispersion liquid and cosmetic using said powder |
| EP3884085A4 (en) * | 2018-11-20 | 2022-09-07 | Pixelligent Technologies, LLC | Synthesis, capping, and dispersion of tio2 nanocrystals |
| CN109970100B (en) * | 2019-05-13 | 2021-07-06 | 沈阳工业大学 | Titanium dioxide powder with nanocrystalline lap joint loose structure and preparation method thereof |
| JP2021011395A (en) * | 2019-07-03 | 2021-02-04 | 住友大阪セメント株式会社 | Titanium oxide powder, and dispersion liquid and cosmetic using the same |
| WO2021002459A1 (en) * | 2019-07-03 | 2021-01-07 | 住友大阪セメント株式会社 | Titanium oxide powder and method for producing same, and dispersion and cosmetics using same |
| CN111573720B (en) * | 2020-04-24 | 2022-06-21 | 浙江理工大学 | Preparation method, product and application of titanium dioxide oligomer material |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW539650B (en) * | 2000-09-14 | 2003-07-01 | Sumitomo Chemical Co | Process for producing titanium oxide |
| CN1686821A (en) * | 2005-05-23 | 2005-10-26 | 北京工业大学 | Method for preparing medium pore molecular sieve of titanium dioxide |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4517080B2 (en) * | 2005-10-14 | 2010-08-04 | 独立行政法人産業技術総合研究所 | Single crystal anatase TiO2 and method for producing the same |
-
2011
- 2011-06-29 TW TW100122829A patent/TWI458685B/en not_active IP Right Cessation
- 2011-07-08 CN CN201110191437.4A patent/CN102849793B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW539650B (en) * | 2000-09-14 | 2003-07-01 | Sumitomo Chemical Co | Process for producing titanium oxide |
| CN1686821A (en) * | 2005-05-23 | 2005-10-26 | 北京工业大学 | Method for preparing medium pore molecular sieve of titanium dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 超音波法製備銳鈦型二氧化鈦之研究，陳阿煌，2010/6/14 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102849793A (en) | 2013-01-02 |
| CN102849793B (en) | 2014-12-10 |
| TW201300324A (en) | 2013-01-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI458685B (en) | Titanium dioxide nanopowder and manufacturing method thereof | |
| Chen et al. | Self-assembly synthesis of CuO/ZnO hollow microspheres and their photocatalytic performance under natural sunlight | |
| Pan et al. | Nanophotocatalysts via microwave-assisted solution-phase synthesis for efficient photocatalysis | |
| Xiaobo | Titanium dioxide nanomaterials and their energy applications | |
| Pál et al. | Hydrothermal synthesis of prism-like and flower-like ZnO and indium-doped ZnO structures | |
| Karthick et al. | Formation of anatase TiO2 nanoparticles by simple polymer gel technique and their properties | |
| Cheng et al. | Same titanium glycolate precursor but different products: successful synthesis of twinned anatase TiO 2 nanocrystals with excellent solar photocatalytic hydrogen evolution capability | |
| Biswas et al. | Morphologically different WO 3 nanocrystals in photoelectrochemical water oxidation | |
| Salek et al. | Room temperature inorganic polycondensation of oxide (Cu2O and ZnO) nanoparticles and thin films preparation by the dip-coating technique | |
| Qiu et al. | Fabrication of TiO2 nanotube film by well-aligned ZnO nanorod array film and sol–gel process | |
| Kobayashi et al. | Hydrothermal synthesis of brookite-type titanium dioxide with snowflake-like nanostructures using a water-soluble citratoperoxotitanate complex | |
| Li et al. | A novel route to ZnO/TiO2 heterojunction composite fibers | |
| Rui et al. | Template-free synthesis of hierarchical TiO2 hollow microspheres as scattering layer for dye-sensitized solar cells | |
| Ma et al. | Controllable synthesis and self-template phase transition of hydrous TiO2 colloidal spheres for photo/electrochemical applications | |
| Ramasamy et al. | A general approach for synthesis of functional metal oxide nanotubes and their application in dye-sensitized solar cells | |
| Zhu et al. | Crack-free hematite inverse opal photo-anodes for enhancing photo-electrochemical water splitting | |
| CN103833074A (en) | Method for preparing titanium dioxide nanoparticles | |
| Zhu et al. | Room-temperature synthesis of cuprous oxide and its heterogeneous nanostructures for photocatalytic applications | |
| Pawade et al. | Multifunctional Nanostructured Metal Oxides for Energy Harvesting and Storage Devices | |
| Zhang et al. | A single-step direct hydrothermal synthesis of SrTiO 3 nanoparticles from crystalline P25 TiO 2 powders | |
| Lekphet et al. | Effect of surfactants on the morphologies of TiO2 particles with high-performance scattering layer in dye-sensitized solar cells | |
| Gholami et al. | Investigating the role of a Schiff-base ligand in the characteristics of TiO2 nano-particles: particle size, optical properties, and photo-voltaic performance of dye-sensitised solar cells | |
| Jia et al. | Selective growth of TiO 2 beads on Ag nanowires and their photocatalytic performance | |
| KR101227087B1 (en) | Morphology control method of nano-structured material | |
| Javed et al. | Morphological effects of reflux condensation on nanocrystalline anatase gel and thin films |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |