TWI428183B - Preparation of Modified Titanium Dioxide with Better Degradation Efficiency - Google Patents
Preparation of Modified Titanium Dioxide with Better Degradation Efficiency Download PDFInfo
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- TWI428183B TWI428183B TW99143254A TW99143254A TWI428183B TW I428183 B TWI428183 B TW I428183B TW 99143254 A TW99143254 A TW 99143254A TW 99143254 A TW99143254 A TW 99143254A TW I428183 B TWI428183 B TW I428183B
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本發明是有關於一種改質二氧化鈦的製法,特別是指一種摻雜特定比例的金屬,而具有較佳降解效率之改質二氧化鈦的製法。The invention relates to a method for preparing modified titanium dioxide, in particular to a method for preparing modified titanium dioxide with a specific proportion of metal and having better degradation efficiency.
近年來工商業蓬勃發展,伴隨所帶來環境污染問題也日益嚴重,其中有機物更是一主要污染源,雖然目前已有可降解有機物的環保處理程序,然而現有處理程序主要以吸附與沉降方式進行,所以易產生大量廢棄物,而造成處理上的負擔。In recent years, the industry and commerce have flourished, and the environmental pollution problems have become more and more serious. Among them, organic matter is a major source of pollution. Although there are environmentally friendly treatment procedures for degradable organic matter, the existing treatment procedures are mainly carried out by adsorption and sedimentation. It is easy to produce a lot of waste, which causes a burden on the treatment.
光觸媒是能利用光能驅動反應進行的物質,若能製造出可直接利用太陽光能等可見光的光觸媒,將能更貼近「綠色地球」的目標。由於二氧化鈦具有高光活性、穩定的化學性質及熱性質及耐腐蝕無毒等優點,因此開啟了利用半導體作為光觸媒,並可以有效分解有機污染物的研究。n-type半導體二氧化鈦在受到能量大於能帶間隙(energy band gap)的入射光照射後,價帶電子即可躍遷至傳導帶產生電子/電洞分離。由於空間電荷層的作用,使得電洞往介面方向移動,此電洞可與吸附水分子或氫氧根離子進行作用,產生氧化力極強的氫氧自由基(OH‧),這些氧化力極強的氫氧自由基(OH‧)可將水中有機物質氧化分解。由於位在傳導帶的電子無法越過空間電荷層的位能差,故無法發生還原反應,因此被電洞所氧化的有機物不會因為電子進行逆反應,而能達到有效分解水中有害有機物的目的。Photocatalyst is a substance that can be driven by light energy. If a photocatalyst that can directly use visible light such as solar energy can be produced, it will be closer to the "green earth" target. Due to its high photoactivity, stable chemical properties, thermal properties, corrosion resistance and non-toxicity, titanium dioxide has opened up the study of using semiconductors as photocatalysts and effectively decomposing organic pollutants. After the n-type semiconductor titania is irradiated with incident light having an energy greater than the energy band gap, the valence band electrons can transition to the conduction band to generate electron/hole separation. Due to the action of the space charge layer, the hole moves toward the interface, and the hole can interact with the adsorbed water molecules or hydroxide ions to generate a highly oxidizing hydroxyl radical (OH‧), which is extremely oxidizing. Strong hydroxyl radicals (OH‧) oxidatively decompose organic matter in water. Since the electrons located in the conduction band cannot cross the space energy difference of the space charge layer, the reduction reaction cannot occur, and therefore the organic matter oxidized by the hole does not reversely react with electrons, thereby achieving the purpose of effectively decomposing harmful organic substances in the water.
但是二氧化鈦光觸媒的主要吸收波長較集中在紫外光區,而紫外光在太陽光中所佔的比例僅約5%,且對人體有害,因而不是一個理想的光能來源。為了提升二氧化鈦作為光觸媒的實用性與經濟價值,已有許多研究開發出具有可見光吸收能力的二氧化鈦。如中華民國第096144718號發明專利申請案所揭露之「金屬植入二氧化鈦奈米管之製造方法」、第97140988號所公開之「金屬/二氧化鈦漿料以及光觸媒物質之製造方法」及第951158135號發明專利申請案所揭露之「二氧化鈦可見光光觸媒及其製造方法」分別藉由不同的製造方法在二氧化鈦中植入或添加金屬,使其具有可吸光可見光的功能。另外,現有文獻,如,”Zhu J.,Chen F.,Zhang J.,Chenb H.,Anpo M.(2006)“Fe3+ -TiO2 photocatalysts prepared by combining sol-gel method with hydrothermal treatment and their characterization”,Journal of Photochemistry and Photobiology A: Chemistry Vol. 180,196-204.”及”Karthik,K.,Kesava Pandian,S.,Victor Jaya N.,(2010) Effect of nickel doping on structural,optical and electrical properties of TiO2 nanoparticles by sol-gel method. Applied Surface Science 256,6829-6833”亦分別揭示以溶膠-凝膠法製出含有鐵或鎳的二氧化鈦光觸媒,及其具有能夠吸收可見光進行降解的內容。如上所述,雖然目前已能順利製出能夠吸收可見光的二氧化鈦光觸媒,但鑑於大量有機污染物的處理需求,目前仍有持續開發具有更佳的可見光降解效率之改質二氧化鈦光觸媒的需求,才能符合快速處理大量有機污染物的實用需求與經濟效益。However, the main absorption wavelength of titanium dioxide photocatalyst is concentrated in the ultraviolet region, and the proportion of ultraviolet light in sunlight is only about 5%, which is harmful to the human body, and thus is not an ideal source of light energy. In order to enhance the practicality and economic value of titanium dioxide as a photocatalyst, many studies have developed titanium dioxide having visible light absorbing ability. The "Method for Producing Metal Implanted Titanium Dioxide Nanotubes" disclosed in the Patent Application No. 096144718 of the Republic of China, the "Metal/TiO2 Slurry and Photocatalyst Material Manufacturing Method" disclosed in No. 97140988, and the Invention No. 951158135 The "TiO2 visible light photocatalyst and its manufacturing method" disclosed in the patent application respectively have a function of absorbing visible light by implanting or adding metal in titanium dioxide by different manufacturing methods. In addition, the existing literature, for example, "Zhu J., Chen F., Zhang J., Chenb H., Anpo M. (2006) "Fe 3+ -TiO 2 photocatalysts prepared by combining sol-gel method with hydrothermal treatment and their Characterization", Journal of Photochemistry and Photobiology A: Chemistry Vol. 180,196-204." and "Karthik, K., Kesava Pandian, S., Victor Jaya N., (2010) Effect of nickel doping on structural, optical and electrical properties Applied TiO 2 nanoparticles by sol-gel method. Applied Surface Science 256, 6829-6833" also discloses the preparation of a titanium dioxide photocatalyst containing iron or nickel by a sol-gel method, and having a content capable of absorbing visible light for degradation. As described above, although titanium dioxide photocatalyst capable of absorbing visible light has been successfully produced, in view of the demand for processing a large amount of organic pollutants, there is still a need to continuously develop a modified titanium dioxide photocatalyst having better visible light degradation efficiency. Practical needs and economic benefits of rapidly processing large amounts of organic pollutants.
因此,本發明的目的,是在提供一種能夠提高可見光吸收值且品質穩定,而能符合實用需求與經濟效益的具有較佳降解效率之改質二氧化鈦的製法。Accordingly, it is an object of the present invention to provide a process for producing modified titanium dioxide having improved degradation efficiency which is capable of improving the visible light absorption value and having stable quality while meeting practical needs and economical benefits.
於是,本發明具有較佳降解效率之改質二氧化鈦的製法,包含下列步驟:Thus, the method for preparing modified titanium dioxide having better degradation efficiency of the present invention comprises the following steps:
(A)混合無水乙醇與去離子水,並加入聚乙烯醇化合物混合以形成一預混物;(A) mixing anhydrous ethanol with deionized water and adding a polyvinyl alcohol compound to form a premix;
(B)於該預混物中添加單質子酸水溶液、含有一摻雜金屬的金屬鹽化合物及二氧化鈦前驅物,使其相混合並攪拌均勻而獲得一預成膠混合液,其中,該摻雜金屬為鐵或鎳,且當該摻雜金屬為鐵時,以二氧化鈦前驅物中的鈦的用量為100重量份計,該摻雜金屬的用量為0.05~0.5重量份,當該摻雜金屬為鎳時,以二氧化鈦前驅物中的鈦的用量為100重量份計,該摻雜金屬的用量為5~15重量份;(B) adding a monoprotic acid aqueous solution, a metal salt compound containing a doping metal, and a titanium dioxide precursor to the premix, mixing and stirring uniformly to obtain a pre-gelling mixture, wherein the doping The metal is iron or nickel, and when the doping metal is iron, the doping metal is used in an amount of 0.05 to 0.5 parts by weight based on 100 parts by weight of titanium in the titanium dioxide precursor, when the doping metal is In the case of nickel, the doping metal is used in an amount of 5 to 15 parts by weight based on 100 parts by weight of titanium in the titanium dioxide precursor;
(C)使該預成膠混合液進行一加熱步驟,以獲得一膠狀物;及(C) subjecting the pre-molecule mixture to a heating step to obtain a jelly;
(D)使該膠狀物進行一高溫燒結步驟,以獲得一摻雜金屬的改質二氧化鈦結晶物。(D) subjecting the gum to a high temperature sintering step to obtain a metal-doped modified titanium dioxide crystal.
本發明的有益效果在於:本發明利用溶膠-凝膠法製造具有可見光吸收能力的改質二氧化鈦,並藉由在製造過程中限制摻雜金屬種類及該摻雜金屬與鈦的用量比例範圍,使所製出的改質二氧化鈦在不同光源的可見光下都能產生極佳的降解效率,藉此,當實際應用於有機污染物的處理時,能夠發揮更有效且快速的處理效率,因此,本發明的製法有助於獲得高效能之改質二氧化鈦產物,不但能符合市場需求與經濟效益,且極適合發展為工業上大量製造生產改質二氧化鈦的方法,因而深具實用價值。The invention has the beneficial effects that the present invention utilizes a sol-gel method to produce modified titanium dioxide having visible light absorbing ability, and by limiting the type of doping metal and the ratio of the amount of the doping metal to titanium in the manufacturing process, The modified titanium dioxide produced can produce excellent degradation efficiency under the visible light of different light sources, thereby enabling more efficient and rapid processing efficiency when actually applied to the treatment of organic pollutants, and thus the present invention The method of preparation helps to obtain high-performance modified titanium dioxide products, which not only meets market demand and economic benefits, but also is very suitable for the development of industrially mass-produced and modified titanium dioxide, and thus has practical value.
有關本發明之前述及其他技術內容、特點與功效,在以下配合參考圖式之一個較佳實施例的詳細說明中,將可清楚的呈現。The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.
參閱圖1,本發明具有較佳降解效率之改質二氧化鈦的製法的一較佳實施例包含下列步驟:步驟101是混合無水乙醇與去離子水,並加入聚乙烯醇化合物混合以形成一預混物。Referring to Figure 1, a preferred embodiment of the process for producing modified titanium dioxide having preferred degradation efficiency of the present invention comprises the steps of: step 101 is mixing anhydrous ethanol with deionized water, and adding a polyvinyl alcohol compound to form a premix. Things.
步驟102是於該預混物中添加單質子酸水溶液、含有一摻雜金屬的金屬鹽化合物及二氧化鈦前驅物,使其相混合並攪拌均勻而獲得一預成膠混合液,其中,該摻雜金屬為鐵或鎳,且當該摻雜金屬為鐵時,以二氧化鈦前驅物中的鈦的用量為100重量份計,該摻雜金屬的用量較佳為0.05~0.5重量份,最佳則為0.1重量份,當該摻雜金屬為鎳時,以二氧化鈦前驅物中的鈦的用量為100重量份計,該摻雜金屬的用量較佳為5~15重量份,最佳則為10重量份。在本實施例中所用的金屬鹽化合物分別為硝酸鐵與硝酸鎳。Step 102 is: adding a monoprotic acid aqueous solution, a metal salt compound containing a doping metal, and a titanium dioxide precursor to the premix, mixing and stirring uniformly to obtain a pre-molten mixture, wherein the doping The metal is iron or nickel, and when the doping metal is iron, the amount of the doping metal is preferably 0.05 to 0.5 parts by weight based on 100 parts by weight of titanium in the titanium dioxide precursor, and most preferably 0.1 parts by weight, when the doping metal is nickel, the amount of the doping metal is preferably 5 to 15 parts by weight, and most preferably 10 parts by weight, based on 100 parts by weight of titanium in the titanium dioxide precursor. . The metal salt compounds used in this example were respectively iron nitrate and nickel nitrate.
其中,該一元酸水溶液較佳是選自於鹽酸水溶液、醋酸水溶液或硝酸水溶液。且在本實施例中是選用鹽酸水溶液。該二氧化鈦前驅物較佳是選自於異丙醇鈦(titanium(IV)isopropoxide)、四氯化鈦(TiCl4 ,titanium tetrachloride)或四丙基醇氧鈦(titanium tetraisopropoxide,簡稱為TTIP),在本實施例中則是選用異丙醇鈦作為二氧化鈦前驅物。Among them, the monobasic acid aqueous solution is preferably selected from an aqueous hydrochloric acid solution, an aqueous acetic acid solution or an aqueous solution of nitric acid. In the present embodiment, an aqueous hydrochloric acid solution is selected. The titania precursor is preferably selected from titanium isopropoxide (titanium (IV) isopropoxide), Titanium tetrachloride (TiCl 4, titanium tetrachloride) titanium or tetra-propyl alcohol oxygen (titanium tetraisopropoxide, simply referred to as TTIP), in In this embodiment, titanium isopropoxide is used as the titanium dioxide precursor.
步驟103是使該預成膠混合液進行一加熱步驟,以獲得一膠狀物。在本實施例中,以利用矽油進行油浴加熱,且該預成膠混合物是以60℃/小時的速率升溫加熱,並於升溫至溫度110℃時繼續於該溫度下進行加熱,直到該預成膠混合物呈凝膠狀而獲得該膠狀物為止,就能停止加熱。In step 103, the pre-gelatinized mixture is subjected to a heating step to obtain a gel. In this embodiment, the oil bath is heated by using eucalyptus oil, and the pre-gel mixture is heated at a temperature of 60 ° C / hour, and heating is continued at the temperature when the temperature is raised to 110 ° C until the pre-heating The gelation mixture is gelled to obtain the gel, and heating can be stopped.
步驟104是使該膠狀物進行一高溫燒結步驟,以獲得一摻雜金屬的改質二氧化鈦結晶物。其中,為了獲得具有較佳光觸媒活性的二氧化鈦結晶物,較佳是於溫度400℃~600℃的條件下進行該膠狀物的高溫燒結,在本實施例中,則是於溫度400℃的條件上進行高溫燒結,且高溫燒結的時間較佳為4小時。In step 104, the gel is subjected to a high temperature sintering step to obtain a metal-doped modified titanium dioxide crystal. Wherein, in order to obtain a titanium dioxide crystal having a preferred photocatalytic activity, high temperature sintering of the jelly is preferably carried out at a temperature of 400 ° C to 600 ° C, and in this embodiment, at a temperature of 400 ° C. The high temperature sintering is performed thereon, and the time for high temperature sintering is preferably 4 hours.
步驟105是使該改質二氧化鈦結晶物進行一研磨步驟,以獲得一摻雜金屬的改質二氧化鈦粉末。In step 105, the modified titanium dioxide crystal is subjected to a grinding step to obtain a doped metal modified titanium dioxide powder.
以下以數個具體例說明本發明的製法所製出的改質二氧化鈦,並分別與未經改質的純二氧化鈦及市售之商用二氧化鈦(P-25,Degussa Co.)進行比較,並進一步說明本發明製法所獲得的改質二氧化鈦在外觀形態、對有機污染物的吸附能力與光催化能力,以及其在可見光源下對有機物的降解情形與純二氧化鈦的差別。Hereinafter, the modified titanium dioxide produced by the process of the present invention will be described in a number of specific examples, and compared with unmodified pure titanium dioxide and commercially available commercial titanium dioxide (P-25, Degussa Co.), respectively, and further illustrated. The modified titanium dioxide obtained by the method of the present invention differs in appearance morphology, adsorption capacity and photocatalytic ability to organic pollutants, and degradation of organic matter under visible light source with pure titanium dioxide.
在以下的具體例中,是選用水楊酸作為污染標的物,水楊酸是造紙業、化妝品業、焚化灰渣滲出水等工業廢水中當出現的有機污染物,因其化學結構上帶有芳香環,故不易被分解,且在光催化降解的過程中會產生鄰苯二酚與多羥基衛生物等中間產物,因此,在進行降解實驗時,是同時針對水楊酸去除率與水楊酸礦化率進行評估。其中,礦化率(mineralization rate)是指水楊酸中,有機態化合物轉化為無機態化合物的比率,在此是藉由量測待測試液中殘留的溶解性有機碳濃度決定水楊酸的礦化率。其中,水楊酸濃度是使用紫外/可見光分光光度計(λ=298nm)並配合製作水楊酸檢量線而測得,溶解性有機碳濃度則是以環署檢方法編號NIEA W531.51C的方法進行檢測。下列各具體例中與水楊酸降解效率有關的計算皆依式(21)~(24)進行計算:In the following specific examples, salicylic acid is selected as the target of pollution. Salicylic acid is an organic pollutant that appears in industrial wastewater such as papermaking, cosmetics, incineration ash and effluent, because of its chemical structure. The aromatic ring is not easy to be decomposed, and intermediate products such as catechol and polyhydroxy sanitizer are produced in the process of photocatalytic degradation. Therefore, when the degradation experiment is carried out, the salicylic acid removal rate and salicylate are simultaneously applied. The acid mineralization rate is evaluated. Wherein, the mineralization rate refers to the ratio of the organic compound to the inorganic compound in the salicylic acid, and the salicylic acid is determined by measuring the concentration of the dissolved organic carbon remaining in the test solution. Mineralization rate. Among them, the salicylic acid concentration is measured by using an ultraviolet/visible spectrophotometer (λ=298 nm) and the salicylic acid calibration line is prepared, and the dissolved organic carbon concentration is determined by the method of the inspection method number NIEA W531.51C. The method is tested. The calculations related to the degradation efficiency of salicylic acid in the following specific examples are calculated according to the formulas (21) to (24):
SA降解效率: SA degradation efficiency:
SA殘餘百分比: SA residual percentage:
中間產物生成百分比: Percentage of intermediate product generation:
礦化百分比: Mineralization percentage:
其中,C0 :水楊酸之初始濃度(mgL-1 );Wherein C 0 : initial concentration of salicylic acid (mgL -1 );
Ct :於時間t時的水楊酸殘餘濃度(mgL-1 );C t : residual concentration of salicylic acid at time t (mgL -1 );
C0(as C) :水楊酸之初始濃度,以有機碳之濃度表示(mgL-1 );C 0 (as C) : initial concentration of salicylic acid expressed as the concentration of organic carbon (mgL -1 );
Ct(as C) :於時間t時的SA殘餘濃度,以有機碳之濃度表示(mgL-1 );及C t(as C) : the residual concentration of SA at time t, expressed as the concentration of organic carbon (mgL -1 );
DOCt :於時間t的溶解性有機碳殘餘濃度(mgL-1 )。DOC t : residual organic carbon concentration (mgL -1 ) at time t.
此外,參閱圖2,為以下各具體例進行光源照射所用的一恆溫光照箱裝置3的示意圖,所有測試皆於溫度25 ℃下進行,該恆溫光照箱裝置3具有一用於容置所配置之預定濃度水楊酸溶液的石英反應槽31中,及八支等間隔圍繞該石英反應槽31設置的燈管32,每支燈管32與該石英反應槽31皆維持等間距,且該等燈管32的燈源可依實驗目的分別替換為可見光燈管或日光燈管。In addition, referring to FIG. 2, a schematic diagram of a constant temperature light box device 3 used for illuminating a light source in the following specific examples, all tests are performed at a temperature of 25 ° C. The constant temperature light box device 3 has a configuration for accommodating. a quartz reaction tank 31 of a predetermined concentration of salicylic acid solution, and eight tubes 32 disposed at equal intervals around the quartz reaction tank 31, each of the tubes 32 and the quartz reaction tank 31 are maintained at equal intervals, and the lamps are The light source of the tube 32 can be replaced with a visible light tube or a fluorescent tube, respectively, depending on the purpose of the experiment.
(1-1)單獨以光源氧化水楊酸之背景實驗: 配製水楊酸濃度10 mgL-1 及pH=4的溶液,且其溫度為25 ℃,以UV-A(365 nm)之燈源照射,反應時間為0~180 min,無添加二氧化鈦,實驗結果顯示溶液中水楊酸濃度並無降低的現象,故去除率為0,由此可知,單獨以紫外光照射水楊酸並無降解情況發生,顯示水楊酸經紫外光照射後極為穩定,因此,後續相同實驗時可忽略光降解水楊酸之情況。 (1-1) Background experiment of oxidizing salicylic acid by light source alone: preparing a solution with salicylic acid concentration of 10 mgL -1 and pH=4, and its temperature is 25 °C, with UV-A (365 nm) light source Irradiation, the reaction time is 0-180 min, no added titanium dioxide, the experimental results show that the salicylic acid concentration in the solution does not decrease, so the removal rate is 0, it can be seen that the salicylic acid alone is not degraded by ultraviolet light irradiation. Occurred, it showed that salicylic acid was extremely stable after being irradiated by ultraviolet light. Therefore, the photodegradation of salicylic acid was neglected in the subsequent experiments.
(1-2)純二氧化鈦的製備: 取無水乙醇14ml與1 ml的去離子水混和,再加入聚乙烯醇化合物1g混合為一預混物,利用矽油對該預混物進行油浴(30℃),再加入HCl 2.5ml混合,接著,加入異丙醇鈦5ml,並攪拌30分鐘後取出磁石,再以油浴方式逐漸升溫至110℃,並繼續加熱至獲得乾燥的白色膠狀物,後將該膠狀物置於高溫爐以400℃加熱4小時使其形成二氧化鈦結晶物,最後經由研磨可得純二氧化鈦粉末p。 (1-2) Preparation of pure titanium dioxide: 14 ml of absolute ethanol is mixed with 1 ml of deionized water, and 1 g of polyvinyl alcohol compound is added to be mixed as a premix, and the premix is subjected to oil bath with eucalyptus oil (30 ° C Then, add 2.5 ml of HCl to mix, then add 5 ml of titanium isopropoxide, and stir for 30 minutes, then take out the magnet, then gradually raise the temperature to 110 ° C in an oil bath, and continue heating until a dry white gum is obtained. The gum was placed in a high temperature furnace and heated at 400 ° C for 4 hours to form titanium dioxide crystals, and finally pure titanium dioxide powder p was obtained by grinding.
(1-3)吸附能力比較 :配製水楊酸濃度10 mgL-1 及pH=4的溶液2份,且其溫度皆為25 ℃,分別將(1-2)所製備的二氧化鈦粉末p與商用二氧化鈦P-25分別添加至上述溶液中,添加量皆為0.5 gL-1 ,吸附反應時間為0~180分鐘,且皆不照射紫外光,結果顯示隨著時間的增加,溶液中的水楊酸皆有減少情形,且經量測顯示,本發明製法所製得二氧化鈦p與商用二氧化鈦P-25的水楊酸去除率分別為30.1%與18.2%,即二種二氧化鈦皆有吸附情形產生,以本發明製法所製出的純二氧化鈦p的吸附能力優於商用二氧化鈦P-25。 (1-3) Comparison of adsorption capacity : Prepare 2 parts of salicylic acid concentration 10 mgL -1 and pH=4, and the temperature is 25 °C, respectively (1-2) prepared titanium dioxide powder p and commercial Titanium dioxide P-25 was added to the above solution, the addition amount was 0.5 gL -1 , the adsorption reaction time was 0-180 minutes, and neither of them was irradiated with ultraviolet light. The results showed that salicylic acid in the solution increased with time. There are cases of reduction, and the measurement shows that the salicylic acid removal rates of titanium dioxide p and commercial titanium dioxide P-25 prepared by the method of the present invention are 30.1% and 18.2%, respectively, that is, both kinds of titanium dioxide have adsorption conditions, The adsorption capacity of the pure titanium dioxide p produced by the process of the invention is superior to that of the commercial titanium dioxide P-25.
(1-4)光催化能力比較 :同(1-3)的內容,只是在反應時間內還提供紫外光光源照射水楊酸溶液,結果顯示,以本發明製法所製出的純二氧化鈦p與商用二氧化鈦P-25皆在120min內將水楊酸完全破壞。由(1-3)與(1-4)的比較結果可知,以本發明製法所製出的二氧化鈦具有不亞於市售商用二氧化鈦的吸附能力與光催化能力,據此說明本發明製法已可製出符合商用規格的二氧化鈦,而具有應用於工業製造生產的實用價值。 (1-4) Comparison of photocatalytic ability : the same as (1-3), only the ultraviolet light source is irradiated with the salicylic acid solution during the reaction time, and the result shows that the pure titanium oxide p produced by the method of the present invention Commercial titanium dioxide P-25 completely destroyed salicylic acid within 120 min. From the comparison results of (1-3) and (1-4), it is known that the titanium dioxide produced by the process of the present invention has the adsorption capacity and photocatalytic ability comparable to commercially available commercial titanium dioxide, and accordingly, the process of the present invention is Titanium dioxide conforming to commercial specifications is produced, and has practical value for industrial manufacturing.
(2-1)純二氧化鈦的製備: 與(1-2)所述內容完全相同,在此不再贅述,最後可獲得純二氧化鈦粉末p。 (2-1) Preparation of pure titanium dioxide: It is exactly the same as that described in (1-2), and will not be described again here, and finally pure titanium oxide powder p can be obtained.
(2-2)摻雜鐵之改質二氧化鈦的製備: 取無水乙醇14ml與1 ml去離子水混和,再加入聚乙烯醇化合物1g混合為一預混物,利用矽油對該預混物進行油浴(30℃),再加入HCl2.5ml混合,並加入摻雜之金屬,在此是加入硝酸鐵(Fe(NO3 )3 ‧9H2 O,純度為99%,Merck)混和,接著,加入異丙醇鈦5ml,於攪拌30分鐘後取出磁石,再以油浴方式逐漸升溫至110℃,並繼續加熱至獲得乾燥的白色膠狀物,後將該膠狀物置於高溫爐以400℃加熱4小時使其型成二氧化鈦結晶物,最後經由研磨可得摻雜鐵之改質二氧化鈦粉末。以異丙醇鈦中的鈦的用量為100重量份計,所添加的硝酸鐵的量分別使其中的鐵的量相當於0.01、0.05、0.1、0.5重量份,並分別製得a1、a2、a3及a4四種改質二氧鈦粉末。在本例中所用的5ml異丙醇鈦其重量相當於5g,據此再配合該異丙醇鈦的純度就能算出其中鈦的用量,再由鈦的用量可推算出應添加的鐵的用量,再由鐵的用量,配合硝酸鐵的純度及鐵在硝酸鐵中的含量比例,就能分別獲得應添加的硝酸鐵的用量,此計算過程為相關領域技術人員所熟知,在此不再詳述。 (2-2) Preparation of modified titanium dioxide doped with iron: 14 ml of absolute ethanol is mixed with 1 ml of deionized water, and 1 g of polyvinyl alcohol compound is added to be mixed as a premix, and the premix is oiled with eucalyptus oil. Bath (30 ° C), add HCl 2.5ml mixed, and add doped metal, here is the addition of ferric nitrate (Fe (NO 3 ) 3 ‧9H 2 O, purity 99%, Merck) mixed, then, add 5 ml of titanium isopropoxide, after stirring for 30 minutes, the magnet was taken out, and then gradually heated to 110 ° C in an oil bath, and heating was continued until a dry white gum was obtained, and then the gel was placed in a high temperature furnace and heated at 400 ° C. It was shaped into titanium dioxide crystals in 4 hours, and finally, iron-doped modified titanium dioxide powder was obtained by grinding. The amount of iron nitrate added is equivalent to 0.01, 0.05, 0.1, 0.5 parts by weight, respectively, based on the amount of titanium in titanium isopropoxide, and a1, a2, respectively. A3 and a4 four modified titanium oxynitride powders. In the present example, 5 ml of titanium isopropoxide has a weight equivalent to 5 g, and accordingly, the amount of titanium can be calculated by matching the purity of the titanium isopropoxide, and the amount of iron to be added can be calculated from the amount of titanium. Then, the amount of iron, the purity of iron nitrate and the proportion of iron in iron nitrate can be used to obtain the amount of ferric nitrate to be added separately. This calculation process is well known to those skilled in the relevant art, and is not detailed here. Said.
(2-3)摻雜鎳之改質二氧化鈦的製備: 同(2-2)的製法,只是將硝酸鐵改為硝酸鎳(Ni(NO3 )2 ‧6H2 O,98%,Alfa Aesar)。其中以異丙醇鈦中的鈦的用量為100重量份計,所添加的硝酸鎳的量分別使其中的鎳的量相當於1、5、10、15重量份,並分別製得b1、b2、b3及b4四種改質二氧鈦粉末。其計算過程同樣為本領域技術人員所熟知且易於推算者,在此不再詳述。 (2-3) Preparation of modified titanium dioxide doped with nickel: the same method as (2-2) except that the ferric nitrate was changed to nickel nitrate (Ni(NO 3 ) 2 ‧6H 2 O, 98%, Alfa Aesar) . Wherein the amount of nickel added is 100 parts by weight of titanium in titanium isopropoxide, and the amount of nickel added is equivalent to 1, 5, 10, and 15 parts by weight, respectively, and b1 and b2 are respectively prepared. , b3 and b4 four modified titanium oxide powder. The calculation process is also well known to those skilled in the art and is easy to be extrapolated, and will not be described in detail herein.
結果分析:Result analysis:
(2-4)將(2-1)、(2-2)、(2-3)所製得的純二氧化鈦及摻雜鐵之改質二氧化鈦a1、a2、a3及a4以摻雜鎳之改質二氧化鈦b1、b2、b3及b4以SEM顯微鏡觀察(在此是使用兼具有EDS功能的場發射電子掃描顯微鏡,FE-SEM/EDS,型號為JSM-7401F,廠牌為JEOL),並分別以比表面積分析儀(BET surface analyzer,型號為ASAP2020,廠牌為micromeritic)算出其比表面積。(2-4) The pure titanium dioxide prepared by (2-1), (2-2), and (2-3) and the modified titanium dioxide a1, a2, a3, and a4 doped with iron are modified by doping nickel. Titanium dioxide b1, b2, b3 and b4 were observed by SEM microscopy (here, using field emission electron scanning microscopy with EDS function, FE-SEM/EDS, model JSM-7401F, brand JEOL), and respectively The specific surface area was calculated using a BET surface analyzer (model ASAP2020, branded micromeritic).
如圖3所示,從SEM影像可觀察出鐵改質之二氧化鈦a1、a2、a3及a4,其粒徑大小與未改質的純二氧化鈦p相同,皆為15-20nm左右,且顆粒近似圓球狀。而摻雜鎳之改質二氧化鈦b1、b2、b3及b4,其粒徑大小亦與未改質的純二氧化鈦大致相同,且與鐵改質之二氧化鈦光觸媒也沒有明顯差異,粒徑亦為15-20nm左右,顆粒近似圓球狀。雖然由SEM影像顯示未改質與摻雜金屬改質之二氧化鈦光觸媒的粒徑大小無明顯改變,但比較圖3的影像可看出,摻雜金屬的改質二氧化鈦其顆粒聚集現象較未改質之二氧化鈦明顯。為了進一步確定前述製法所製出的改質二氧化鈦中確實含有摻雜金屬,進一步以能量分散光譜儀(EDS)分析摻雜鐵、鎳之改質二氧化鈦a4、b4,結果如圖4之(I)、(II)所示,該二EDS圖譜上分別出現所添加之金屬的波峰訊號,由此可知改質後之二氧化鈦a4、b4觸媒上確實有鑲嵌有鐵、鎳。據此可證實本發明的製法所製出的改質二氧化鈦分別摻雜有所添加的金屬。As shown in Fig. 3, the iron-modified titanium dioxide a1, a2, a3 and a4 can be observed from the SEM image, and the particle size is the same as that of the unmodified pure titanium dioxide p, which is about 15-20 nm, and the particles are approximately round. Spherical. The nickel-doped modified titanium dioxides b1, b2, b3 and b4 have the same particle size as the unmodified pure titanium dioxide, and there is no significant difference from the iron-modified titanium dioxide photocatalyst, and the particle size is also 15- Around 20 nm, the particles are approximately spherical. Although the SEM image shows that the particle size of the unmodified and doped metal modified titanium dioxide photocatalyst does not change significantly, comparing the image of FIG. 3, it can be seen that the metal-doped modified titanium dioxide has a particle aggregation phenomenon that is not modified. The titanium dioxide is obvious. In order to further confirm that the modified titanium dioxide produced by the above method does contain a doping metal, the modified titanium dioxide a4 and b4 doped with iron and nickel are further analyzed by an energy dispersive spectrometer (EDS), and the result is shown in FIG. 4(I). As shown in (II), the peak signal of the added metal appears on the two EDS maps, and it can be seen that the modified titanium dioxide a4 and b4 catalysts are indeed embedded with iron and nickel. From this, it was confirmed that the modified titanium oxide produced by the process of the present invention was doped with an added metal, respectively.
如下表-1所示,可看出添加鐵之改質二氧化鈦光觸媒其比表面積約在90~95 m2 /g,而添加鎳之改質二氧化鈦光觸媒,其比表面積約在98~103 m2 /g,據此顯示相較於未添加金屬的二氧化鈦p,添加鐵、鎳之改質二氧化鈦光觸媒a1~a4及b1~b4對比表面積皆略有提高的趨勢,此外,商用二氧化鈦P-25的比表面積僅為50 m2 /g,顯然本發明所製出的添加鐵或鎳之改質二氧化鈦光觸媒的比表面積均遠高於商用P-25。As shown in Table-1 below, it can be seen that the modified titanium dioxide photocatalyst with iron has a specific surface area of about 90-95 m 2 /g, and the modified titanium dioxide photocatalyst with nickel has a specific surface area of about 98-103 m 2 / g, according to this, compared with the titanium dioxide p without added metal, the modified titanium dioxide photocatalysts a1~a4 and b1~b4 added with iron and nickel have a slight increase in the comparative surface area, and in addition, the specific surface area of commercial titanium dioxide P-25 It is only 50 m 2 /g. It is obvious that the specific surface area of the modified titanium dioxide photocatalyst added with iron or nickel prepared by the present invention is much higher than that of the commercial P-25.
(2-5)以X光粉末繞射儀(X-ray powder diffractometer,型號為Rigaku-TTR AXⅢ,製造商為Japan)分析(2-1)、(2-2)、(2-3)所製得的純二氧化鈦及摻雜鐵之改質二氧化鈦a1、a2、a3及a4以摻雜鎳之改質二氧化鈦b1、b2、b3及b4。(2-5) Analysis by X-ray powder diffractometer (model Rigaku-TTR AXIII, manufacturer: Japan) (2-1), (2-2), (2-3) The obtained pure titanium dioxide and iron-doped modified titanium oxides a1, a2, a3 and a4 are doped with nickel-modified titanium dioxides b1, b2, b3 and b4.
在參閱分析結果前,需要補充說明的是,二氧化鈦具有三種常見之晶體結構,分別為銳鈦礦(anatase)、金紅石(rutile)及板鈦礦(brookite)。板鈦礦因結構不穩定,屬亞穩相,極少被應用,而金紅石和銳鈦礦用途則較廣泛,兩者雖屬同一晶系,但前者結構排列較致密,相對密度、折射率較高,因此金紅石對紫外光具有良好的遮蔽性,常被應用於防紫外光的材料上,此三種晶體結構中,以銳鈦礦的光觸媒活性較佳,因此,若XRD分析結果顯示銳鈦礦的晶相越明顯,表示該二氧化鈦產物的光觸媒活性越佳應能提供較佳的降解效率。Before referring to the results of the analysis, it should be added that titanium dioxide has three common crystal structures, namely anatase, rutile and brookite. Because of its unstable structure, brookite is a metastable phase and is rarely used. Rutile and anatase are widely used. Although the two are of the same crystal system, the former has a denser structure, relative density and refractive index. High, so rutile has good shielding properties against ultraviolet light, and is often used in anti-ultraviolet light materials. Among the three crystal structures, the photocatalytic activity of anatase is better. Therefore, if the XRD analysis results show anatase The more pronounced the crystal phase of the ore, the better the photocatalytic activity of the titanium dioxide product should provide better degradation efficiency.
其結果如圖5與圖6之XRD圖譜所示,XRD圖譜中以A標示處,即為銳鈦礦晶相的主峰出現的位置,據此可看出400℃燒結溫度下所製備之未改質或改質二氧化鈦光觸媒,在2 deg/min的掃描速率下,進行晶相皆分析,接著再與XRD儀器中的JCPDS資料庫(此資料庫為收集二氧化鈦各種不同晶相的資料庫,可作為判定待測物是屬於何種晶相結構的標準)進行比對後,更可明確證實本製法所製出的二氧化鈦粉末皆只呈現銳鈦礦(Anatase)的單一晶相,未發現有金紅石(rutile)晶相,據此說明在400℃的燒結溫度條件下所製出的改質二氧化鈦其晶相仍以銳鈦礦為主。此外,由EDS光譜的結果可說明本發明所添加之過渡金屬離子已摻雜在改質二氧化鈦中,而由XRD圖譜中未發現任何過渡金屬氧化物的繞射峰出現的結果,更進一步說明,鐵、鎳等過渡金屬氧化物沒有在所製得的改質二氧化鈦光觸媒表面聚集造成金屬氧化物的晶粒,據此說明該等過渡金屬應是高度嵌入二氧化鈦結晶物的內部結構中,甚至取代部分鈦金屬位置。The results are shown in the XRD patterns of Fig. 5 and Fig. 6. The XRD pattern is indicated by A, which is the position where the main peak of the anatase crystal phase appears. It can be seen that the preparation at the sintering temperature of 400 °C has not been changed. The quality or modification of titanium dioxide photocatalyst, the crystal phase analysis at 2 deg / min scanning rate, and then with the JCPDS database in the XRD instrument (this database is a database for collecting various crystal phases of titanium dioxide, can be used as It is confirmed that the titanium dioxide powder produced by the method only exhibits a single crystal phase of anatase, and no rutile is found. (rutile) crystal phase, according to which the modified titanium dioxide produced at a sintering temperature of 400 ° C has a crystal phase which is mainly anatase. In addition, the results of the EDS spectrum indicate that the transition metal ions added in the present invention have been doped in the modified titanium dioxide, and the diffraction peaks of any transition metal oxides are not found in the XRD pattern, further illustrating that The transition metal oxides such as iron and nickel do not aggregate on the surface of the modified titanium dioxide photocatalyst to form crystal grains of the metal oxide, and it is explained that the transition metal should be highly embedded in the internal structure of the titanium dioxide crystal, or even replace the part. Titanium position.
(3-1)單獨以不同光源氧化水楊酸之背景實驗: 配製水楊酸濃度10 mgL-1 及pH=4的溶液,且其溫度為25 ℃,在不添加二氧化鈦的情形下,分別以可見光、日光燈及太陽光為光源照射,反應時間為0~180 min。實驗結果顯示不管使用何種光源,溶液中水楊酸濃度皆無降低的現象,故去除率為0,由此可知,單獨以不同光源照射水楊酸並無降解情況發生,顯示水楊酸經不同光源照射後極為穩定,因此,後續相同實驗時可忽略光降解水楊酸之情況。 (3-1) Background experiment of oxidizing salicylic acid by different light sources separately: preparing a solution with salicylic acid concentration of 10 mgL -1 and pH=4, and the temperature is 25 °C, without adding titanium dioxide, respectively The visible light, fluorescent lamp and sunlight are used as the light source, and the reaction time is 0-180 min. The experimental results show that the salicylic acid concentration in the solution does not decrease regardless of the light source used, so the removal rate is 0. It can be seen that the salicylic acid alone is not degraded by different light sources, indicating that the salicylic acid is different. The light source is extremely stable after irradiation, so the photodegradation of salicylic acid can be ignored in the subsequent experiments.
(3-2)單獨以摻雜鐵之改質二氧化鈦吸附水楊酸的背景實驗: 配製水楊酸濃度10 mgL-1 及pH=4的溶液5份,且其溫度皆為25 ℃,分別將<具體例-1> 之(1-2)所製備的二氧化鈦粉末p與<具體例-2> 之(2-2)所製備的四種摻雜不同比例鐵之改質二氧化鈦粉末a1、a2、a3及a4分別添加至上述溶液中,添加量皆為0.5 gL-1 ,吸附反應時間為0~180分鐘,且皆不提供光源照射。 (3-2) Background experiment of adsorbing salicylic acid with iron-doped modified titanium dioxide alone: preparing 5 parts of salicylic acid concentration 10 mgL -1 and pH=4, and the temperature is 25 °C, respectively <Specific Example-1> The titanium dioxide powder p prepared in (1-2) and the four modified titanium dioxide powders a1 and a2 doped with different ratios of iron prepared in (2-2) of <Specific Example-2> A3 and a4 were respectively added to the above solution, and the addition amount was 0.5 gL -1 , and the adsorption reaction time was 0 to 180 minutes, and no light source irradiation was provided.
結果顯示隨著時間的增加,溶液中的水楊酸皆有減少情形,且純二氧化鈦與摻雜不同比例鐵之改質二氧化鈦粉末的水楊酸去除率並無明顯差異,皆為32%,據此說明,摻雜鐵之改質二氧化鈦相較於無摻雜金屬之純二氧化鈦,其吸附能力並無明顯提升The results showed that the salicylic acid in the solution decreased with the increase of time, and there was no significant difference in the salicylic acid removal rate between the pure titanium dioxide and the modified titanium dioxide powder doped with different proportions of iron, all of which were 32%. This shows that the modified titanium dioxide doped with iron has no significant improvement in its adsorption capacity compared to pure titanium dioxide without undoped metal.
(3-3)摻雜鐵之改質二氧化鈦於可見光下降解水楊酸之實驗: 配製水楊酸濃度10 mgL-1 及pH=4的溶液5份,且其溫度皆為25 ℃,分別將(1-2)所製備的二氧化鈦粉末p與(2-2)所製備的四種摻雜不同比例鐵之改質二氧化鈦粉末a1、a2、a3及a4分別添加至上述溶液中,其添加量皆為0.5 gL-1 ,反應時間為9小時,利用如圖2所示的恆溫光照箱裝置3,在反應期間持續提供可見光照射。其中,所用之可見光燈管廠牌為DiDai,型號為PL-S,規格為13W/BLUE,波長範圍400 nm~500 nm,單支燈管光照強度為5.2 W/m2 ,本實施例所用之恆溫光照箱裝置3配有8支燈管,每支燈管32與該石英反應槽31的間距皆為5公分,平均光照強度為30 W/m2 。 (3-3) Experiment of degrading salicylic acid under the visible light of modified titanium dioxide doped with iron: Prepare 5 parts of salicylic acid with a concentration of 10 mgL -1 and pH=4, and the temperature is 25 °C, respectively (1-2) The prepared titanium dioxide powder p and the four kinds of modified titanium dioxide powders a1, a2, a3 and a4 doped with different proportions of iron prepared by (2-2) are respectively added to the above solution, and the addition amount thereof is For 0.5 gL -1 , the reaction time was 9 hours, and the constant temperature illumination device 3 as shown in Fig. 2 was used to continuously provide visible light irradiation during the reaction. Among them, the visible light lamp label used is DiDai, the model is PL-S, the specification is 13W/BLUE, the wavelength range is 400 nm~500 nm, and the illumination intensity of a single tube is 5.2 W/m 2 , which is used in this embodiment. The constant temperature light box device 3 is provided with 8 lamps, each of which has a distance of 5 cm from the quartz reaction tank 31 and an average light intensity of 30 W/m 2 .
結果如圖7之(I)所示,純二氧化鈦p與不同鐵比例之改質二氧化鈦a1、a2、a3與a4於可見光下降解水楊酸9小時後,水楊酸的殘留率隨著反應時間逐漸降低,以100%分別扣除殘留率後,即能獲得水楊酸的去除率,分別為58.8%、63%、75.9%、100%、78.8%。其中,以a3(即鐵與鈦之用量的重量比例為0.1:100時所製得之改質二氧化鈦)的去除率最佳,高達100%,顯見當鈦前驅物中的鈦的用量為100重量份時,則所添加的鐵鹽化合物中的鐵的用量控制在0.1重量份時可獲得具有最佳降解效率的改質二氧化鈦,此外,a1、a2與a4對水楊酸的去除率皆優於p,顯示摻雜鐵之改質二氧化鈦對水楊酸的降解效率皆比未改質的二氧化鈦較佳。其中,當鐵與鈦之用量的重量比例增加為0.5:100時,水楊酸去除率反而降低,顯示雖然適量添加之改質金屬會捕捉二氧化鈦照光激發所生成之電子,降低電子和電洞再結合的機率,使其有效分離,進而提升二氧化鈦光觸媒之催化活性,但是過量的金屬添加,可能會使金屬沈積在觸媒表面而成為電子電洞再結合中心,反而造成二氧化鈦光觸媒之催化活性降低。The results are shown in Fig. 7 (I). After the pure titanium dioxide p and the modified iron oxides a1, a2, a3 and a4 of different iron ratios degrade the salicylic acid under visible light for 9 hours, the residual ratio of salicylic acid with the reaction time Gradually, after removing the residual rate by 100%, the removal rate of salicylic acid was obtained, which were 58.8%, 63%, 75.9%, 100%, and 78.8%, respectively. Among them, the removal rate of a3 (that is, the modified titanium dioxide prepared by the weight ratio of iron to titanium is 0.1:100) is the best, up to 100%, and it is obvious that the amount of titanium in the titanium precursor is 100 weight. In the case where the amount of iron in the iron salt compound to be added is controlled to 0.1 part by weight, the modified titanium oxide having the best degradation efficiency can be obtained, and in addition, the removal rates of salicylic acid are superior to a1, a2 and a4. p, the modified titanium dioxide exhibiting iron-doped degradation of salicylic acid is better than unmodified titanium dioxide. Among them, when the weight ratio of iron to titanium is increased to 0.5:100, the salicylic acid removal rate is decreased, indicating that although the appropriate amount of modified metal will capture the electrons generated by the excitation of titanium dioxide, reduce electrons and holes. The probability of combination makes it effectively separate, thereby enhancing the catalytic activity of the titanium dioxide photocatalyst, but the excessive metal addition may cause the metal to deposit on the surface of the catalyst and become the center of recombination of the electron hole, which in turn causes the catalytic activity of the titanium dioxide photocatalyst to decrease.
再進一步分析添加不同二氧化鈦的水楊酸溶液於0~9小時礦化率,結果如圖7之(II)所示,可得知在水楊酸溶液內所偵測到的溶解性有機碳殘留濃度(DOC)隨時間遞減,且純二氧化鈦p與不同鐵比例之改質二氧化鈦a1、a2、a3與a4於可見光下降解水楊酸9小時後的礦化率分別為48.43%、53.76%、66.61%、92.98%、71.94%。其中,亦以a3(即鐵與鈦之用量的重量比例為0.1:100時所製得之改質二氧化鈦)的礦化率最佳。Further analysis of the mineralization rate of the salicylic acid solution with different titanium dioxide added in 0-9 hours, the results show that the dissolved organic carbon residues detected in the salicylic acid solution are shown in Fig. 7 (II). The concentration (DOC) decreased with time, and the mineralization rates of pure titanium dioxide p and different iron ratios of modified titanium dioxide a1, a2, a3 and a4 after degrading salicylic acid under visible light for 9 hours were 48.43%, 53.76% and 66.61, respectively. %, 92.98%, 71.94%. Among them, the mineralization rate of a3 (the modified titanium dioxide prepared at a weight ratio of iron to titanium of 0.1:100) is also the best.
(3-4)摻雜鐵之改質二氧化鈦於日光燈下降解水楊酸之實驗: 實驗方式與(3-3)完全相同,亦使用如圖2所示的恆溫光照箱裝置3進行測試,只是將該等燈管32換為日光燈管,並將照光與反應時間延長為24小時。其中,所用之日光燈管廠牌為PHILIPS,型號為PL-S,13W/865,波長範圍400 nm~700 nm,單支燈管光照強度為12 W/m2 ,該石英反應槽31受該等燈管32的平均光照強度為46.5 W/m2 。 (3-4) Experiment of degrading salicylic acid with fluorescent modified titanium dioxide under fluorescent lamp: The experimental method is exactly the same as (3-3), and the test is also carried out using the constant temperature light box device 3 shown in Fig. 2, The lamps 32 were replaced with fluorescent tubes, and the illumination and reaction time were extended to 24 hours. Among them, the fluorescent tube label used is PHILIPS, the model is PL-S, 13W/865, the wavelength range is 400 nm~700 nm, and the illumination intensity of a single tube is 12 W/m 2 , and the quartz reaction tank 31 is subject to such The average light intensity of the tube 32 was 46.5 W/m 2 .
結果如圖8之(I)所示,純二氧化鈦p與不同鐵比例之改質二氧化鈦a1、a2、a3與a4於日光燈下降解水楊酸24小時後,水楊酸的去除率分別為67.83%、73.77%、90.79%、100%、86.89%。其中,仍以a3(即鐵與鈦之用量的重量比例為0.1:100時所製得之改質二氧化鈦)的去除率最佳,高達100%,而a1、a2與a4對水楊酸的去除率亦皆優於p,顯示摻雜鐵之改質二氧化鈦對水楊酸的降解效率皆比未改質的二氧化鈦較佳。As a result, as shown in (I) of FIG. 8, the removal rate of salicylic acid was 67.83% after pure titanium dioxide p and modified iron oxides a1, a2, a3 and a4 of different iron ratios were degraded by salicylic acid for 24 hours under fluorescent lamps, respectively. , 73.77%, 90.79%, 100%, 86.89%. Among them, the removal rate of a3 (the modified titanium dioxide prepared by the weight ratio of iron and titanium is 0.1:100) is the best, up to 100%, and the removal of salicylic acid by a1, a2 and a4 The rate is also better than p, indicating that the modified titanium dioxide-doped titanium dioxide has better degradation efficiency for salicylic acid than unmodified titanium dioxide.
再進一步分析添加不同二氧化鈦的水楊酸溶液於0~24小時之礦化率,結果如圖8之(II)所示,可得知在水楊酸溶液內所偵測到的溶解性有機碳殘留濃度(DOC)隨時間遞減,且純二氧化鈦p與不同鐵比例之改質二氧化鈦a1、a2、a3與a4於日光燈下降解水楊酸24小時後的礦化率分別為44.86%、55.60%、78.79%、89.64%、70.07%。其中,仍以a3的礦化率最佳,與去除率的結果相似。Further analysis of the mineralization rate of salicylic acid solution with different titanium dioxide added in 0-24 hours, the results show that the dissolved organic carbon detected in the salicylic acid solution is shown in Fig. 8 (II). The residual concentration (DOC) decreased with time, and the mineralization rates of pure titanium dioxide p and different iron ratios of modified titanium dioxide a1, a2, a3 and a4 after degrading salicylic acid under fluorescent lamp for 24 hours were 44.86% and 55.60%, respectively. 78.79%, 89.64%, 70.07%. Among them, the mineralization rate of a3 is still the best, similar to the removal rate.
(3-5)摻雜鐵之改質二氧化鈦於太陽光下降解水楊酸之實驗: 配製水楊酸濃度10 mgL-1 及pH=4的溶液5份,且其溫度皆為25 ℃,分別將(1-2)所製備的二氧化鈦粉末p與(2-2)所製備的四種摻雜不同比例鐵之改質二氧化鈦粉末a1、a2、a3及a4分別添加至上述溶液中,再將其分別倒入石英反應槽內,並直接置放於戶外以陽光照射,在實驗過程中,同步以太陽光照強度器記錄光照強度變化趨勢,量測結果顯示實驗過程的光照強度平均值約為880~950 W/m2 。 (3-5) Experiment of degrading salicylic acid by modified titanium dioxide in sunlight: preparing 5 parts of salicylic acid concentration 10 mgL -1 and pH=4, and the temperature is 25 °C, respectively The titanium dioxide powder p prepared in (1-2) and the four modified titanium dioxide powders a1, a2, a3 and a4 doped with different ratios of iron prepared in (2-2) are respectively added to the above solution, and then They were respectively poured into a quartz reaction tank and placed directly outdoors for sunlight. During the experiment, the sunlight intensity was recorded by the solar light intensity meter. The measurement results showed that the average light intensity during the experiment was about 880~. 950 W/m 2 .
結果如圖9之(I)所示,純二氧化鈦p與不同鐵比例之改質二氧化鈦a1、a2、a3與a4於太陽光下降解水楊酸3小時後,水楊酸的去除率分別為59%、78.6%、96.80%、100%、97.8%。其中,仍以a3(即鐵與鈦之用量的重量比例為0.1:100時所製得之改質二氧化鈦)的去除率最佳,高達100%,而a1、a2與a4對水楊酸的去除率亦皆優於p,據此說明摻雜鐵之改質二氧化鈦對水楊酸的降解效率皆比未改質的二氧化鈦較佳。As a result, as shown in (I) of Fig. 9, the removal rate of salicylic acid was 59 after pure titanium dioxide p and modified iron oxides a1, a2, a3 and a4 of different iron ratios were degraded by salicylic acid for 3 hours under sunlight. %, 78.6%, 96.80%, 100%, 97.8%. Among them, the removal rate of a3 (the modified titanium dioxide prepared by the weight ratio of iron and titanium is 0.1:100) is the best, up to 100%, and the removal of salicylic acid by a1, a2 and a4 The rate is also better than p, according to which it is better to modify the salicylic acid than the unmodified titanium dioxide.
再進一步分析添加不同二氧化鈦的水楊酸溶液於0~24小時之礦化率,結果如圖9之(II)所示,可得知在水楊酸溶液內所偵測到的溶解性有機碳殘留濃度(DOC)隨時間遞減,且純二氧化鈦p與不同鐵比例之改質二氧化鈦a1、a2、a3與a4於太陽光下降解水楊酸3小時後的礦化率分別為45.51%、66.95%、90.03%、94.07%、93.26%。其中,仍以a3的礦化率最佳。Further analyzing the mineralization rate of salicylic acid solution with different titanium dioxide added in 0-24 hours, the results show that the dissolved organic carbon detected in the salicylic acid solution is shown in Fig. 9 (II). The residual concentration (DOC) decreased with time, and the mineralization rates of pure titanium dioxide p and different iron ratios of modified titanium dioxide a1, a2, a3 and a4 after degrading salicylic acid under sunlight for 3 hours were 45.51% and 66.95%, respectively. , 90.03%, 94.07%, 93.26%. Among them, the mineralization rate of a3 is still the best.
(3-6)綜合比較不同光源下摻雜鐵之改質二氧化鈦之水楊酸降解效率: 將(3-3)~(3-5)所量測到的未改質的二氧化鈦粉末p四種摻雜不同比例鐵之改質二氧化鈦粉末a1、a2、a3及a4,於不同光源下降解水楊酸反應3小時的水楊酸去除率與礦化率分別整理成圖10(I)、(II),以了解不同光源下光催化降解水楊酸的情形。由圖10(I)可看出改質二氧化鈦a3在太陽光為光源下,光催化水楊酸在3小時的去除率內就可達到100%的去除率,日光燈與可見光去除率皆低於太陽光。其中,以改質二氧化鈦a3在不同光源下的去除率最佳,顯見a3之鐵與鈦的用量比例為具有最佳降解效率的比例,而添加鐵之其他改質二氧化鈦a1、a2與a4對水楊酸的降解效率皆比未改質的二氧化鈦p為佳。由圖10之(II)可得知,改質二氧化鈦a3在太陽光下光催化水楊酸3小時的礦化率為94.1%,不同光源下降解水楊酸的去除率與礦化率皆以a3最佳。此外,由上述結果亦可說明製作改質二氧化鈦時,當金屬鹽化合物中的金屬為鐵,且其用量與鈦前驅物中的鈦的用量比為0.1:100時可製得具有最佳降解效率的改質二氧化鈦 (3-6) Comprehensive comparison of salicylic acid degradation efficiency of modified titanium dioxide doped with different light sources: four kinds of unmodified titanium dioxide powders measured by (3-3)~(3-5) The salicylic acid removal rate and mineralization rate of the modified titanium dioxide powders a1, a2, a3 and a4 doped with different proportions of iron under different light sources for 3 hours were arranged into Fig. 10(I), (II). ) to understand the photocatalytic degradation of salicylic acid under different light sources. It can be seen from Fig. 10(I) that under the sunlight as the light source, the photocatalytic salicylic acid can achieve 100% removal rate within 3 hours of removal rate, and the fluorescent lamp and visible light removal rate are lower than the sun. Light. Among them, the removal rate of modified titanium dioxide a3 under different light sources is the best, it is obvious that the ratio of iron to titanium in a3 is the ratio with the best degradation efficiency, while the other modified titanium dioxide a1, a2 and a4 are added to the water. The degradation efficiency of salicylic acid is better than that of unmodified titanium dioxide p. It can be seen from (II) of Fig. 10 that the mineralization rate of the modified titanium dioxide a3 under photocatalytic salicylic acid for 3 hours under sunlight is 94.1%, and the removal rate and mineralization rate of degraded salicylic acid under different light sources are A3 is the best. In addition, the above results also indicate that when the modified titanium dioxide is produced, when the metal in the metal salt compound is iron, and the amount of titanium in the titanium precursor is 0.1:100, the optimum degradation efficiency can be obtained. Modified titanium dioxide
(4-1)單獨以摻雜鎳之改質二氧化鈦吸附水楊酸的背景實驗: 配製水楊酸濃度10 mgL-1 及pH=4的溶液5份,且其溫度皆為25 ℃,分別將(1-2)所製備的二氧化鈦粉末p與(2-3)所製備的四種摻雜不同比例鎳之改質二氧化鈦粉末b1、b2、b3及b4分別添加至上述溶液中,添加量皆為0.5 gL-1 ,吸附反應時間為0~180分鐘,且皆不提供光源照射。 (4-1) Background experiment of adsorbing salicylic acid with nickel-doped modified titanium dioxide alone: Prepare 5 parts of salicylic acid concentration 10 mgL -1 and pH=4, and the temperature is 25 °C, respectively (1-2) The prepared titanium dioxide powder p and the four kinds of modified titanium dioxide powders b1, b2, b3 and b4 doped with different ratios of nickel (2-3) are respectively added to the above solution, and the addition amount is 0.5 gL -1 , adsorption reaction time is 0-180 minutes, and no light source is provided.
結果顯示隨著時間的增加,溶液中的水楊酸皆有減少情形,且純二氧化鈦與摻雜不同比例鎳之改質二氧化鈦粉末的水楊酸去除率並無明顯差異,皆為32%,據此說明,摻雜鎳之改質二氧化鈦相較於無摻雜金屬之純二氧化鈦,其吸附能力並無明顯提升The results showed that the salicylic acid in the solution decreased with time, and the salicylic acid removal rate of pure titanium dioxide and modified titanium dioxide powder doped with different proportions of nickel did not differ significantly, both were 32%. This shows that the modified titanium dioxide doped with nickel has no significant improvement in adsorption capacity compared to pure titanium dioxide without undoped metal.
(4-2)摻雜鎳之改質二氧化鈦於可見光下降解水楊酸之實驗: 配實驗條件與方式皆與<具體例-3> 之(3-3) 所述者相同,只是將添加於水楊酸溶液中的改質二氧化鈦光觸媒分別改為<具體例-1> 之(1-2) 所製備的二氧化鈦粉末p及<具體例-2> 之(2-3) 所製備的四種摻雜不同比例鎳之改質二氧化鈦粉末b1、b2、b3及b4。 (4-2) Experiment of degrading salicylic acid under visible light with modified titanium dioxide: The experimental conditions and methods are the same as those described in (3-3) of <Specific Example-3> , but will be added a modified titanium dioxide photocatalyst acid solution were changed to <specific Example-1> of the (1-2) prepared and four kinds of titanium dioxide powder doped p <specific Example-2> of (2-3) prepared in Modified titanium dioxide powders b1, b2, b3 and b4 of different proportions of nickel.
結果如圖11之(I)所示,純二氧化鈦與不同鎳比例之改質二氧化鈦b1、b2、b3與b4於可見光下降解水楊酸9小時後,水楊酸的去除率分別為58.8%、66.70%、73.29%、91.1%、81.3%。其中,以b3(即鎳與鈦之用量的重量比例為10:100時所製得之改質二氧化鈦)的去除率最佳,高達100%,顯見當鈦前驅物中的鈦的用量為100重量份時,則所添加的鎳鹽化合物中的鎳的用量若控制在10重量份時可獲得具有最佳降解效率的改質二氧化鈦,此外,b1、b2與b4對水楊酸的去除率皆優於p,顯示摻雜鎳之改質二氧化鈦對水楊酸的降解效率皆比未改質的二氧化鈦較佳。其中,當鎳與鈦之用量的重量比例增加為15:100時,水楊酸去除率反而降低,說明添加適量之改質金屬會捕捉二氧化鈦照光激發所生成之電子,因而可降低電子和電洞再結合的機率,並使其有效分離,進而提升二氧化鈦光觸媒之催化活性,但是過量的金屬添加,可能會使金屬沈積在觸媒表面而成為電子電洞再結合中心,反而造成二氧化鈦光觸媒之催化活性降低。The results are shown in Fig. 11 (I). After the modified titanium dioxide b1, b2, b3 and b4 of different titanium ratios degraded salicylic acid under visible light for 9 hours, the salicylic acid removal rate was 58.8%. 66.70%, 73.29%, 91.1%, 81.3%. Among them, the removal rate of b3 (that is, the modified titanium dioxide prepared when the weight ratio of nickel to titanium is 10:100) is the best, up to 100%, and it is obvious that the amount of titanium in the titanium precursor is 100 weight. When the amount of nickel in the nickel salt compound to be added is controlled to 10 parts by weight, the modified titanium oxide having the best degradation efficiency can be obtained, and in addition, the removal rates of salicylic acid are excellent for b1, b2 and b4. At p, it is shown that the modified titanium dioxide-doped titanium dioxide has better degradation efficiency for salicylic acid than unmodified titanium dioxide. Among them, when the weight ratio of nickel to titanium is increased to 15:100, the salicylic acid removal rate is decreased, indicating that adding an appropriate amount of modified metal can capture the electrons generated by the excitation of titanium dioxide, thereby reducing electrons and holes. Recombining the probability and effectively separating it, thereby enhancing the catalytic activity of the titanium dioxide photocatalyst, but excessive metal addition may cause the metal to deposit on the surface of the catalyst and become the center of recombination of the electron hole, which may cause the catalytic activity of the titanium dioxide photocatalyst. reduce.
再進一步分析添加不同二氧化鈦的水楊酸溶液於0~9小時礦化率,結果如圖11之(II)所示,可得知在水楊酸溶液內所偵測到的溶解性有機碳殘留濃度(DOC)隨時間遞減,且純二氧化鈦p與不同鎳比例之改質二氧化鈦b1、b2、b3與b4於可見光下降解水楊酸9小時後的礦化率分別為48.43%、53.92%、57.81%、78.09%、68.05%。其中,亦以b3的礦化率最佳。將前述結果再與圖11之(I)的結果相比較,則可看出反應9小時後,雖然b3已將大部分水楊酸(水楊酸去除率達91.1%)破壞。Further analysis of the mineralization rate of the salicylic acid solution with different titanium dioxide added in 0-9 hours, the results show that the dissolved organic carbon residues detected in the salicylic acid solution are shown in Fig. 11 (II). The concentration (DOC) decreased with time, and the mineralization rates of pure titanium dioxide p and different nickel ratios of modified titanium dioxide b1, b2, b3 and b4 after degrading salicylic acid under visible light for 9 hours were 48.43%, 53.92%, 57.81, respectively. %, 78.09%, 68.05%. Among them, the mineralization rate of b3 is also the best. Comparing the foregoing results with the results of (I) of Fig. 11, it can be seen that after 9 hours of the reaction, although b3 has destroyed most of the salicylic acid (salitar acid removal rate of 91.1%).
(4-3)摻雜鎳之改質二氧化鈦於日光燈下降解水楊酸之實驗: 實驗方式與<具體例-3> 之(3-4) 完全相同,只是改變添加於水楊酸溶液中的改質二氧化鈦光觸媒種類為摻雜鎳之b1、b2、b3與b4,故不再贅述。結果如圖12之(I)所示,純二氧化鈦p與不同鎳比例之改質二氧化鈦b1、b2、b3與b4於日光燈下降解水楊酸24小時後,水楊酸的去除率分別為67.83%、82.02%、75.82%、98.50%、93.81%。其中,仍以b3的去除率最佳,高達98.50%,而b1、b2與b4對水楊酸的去除率亦皆優於p,顯示摻雜鐵之改質二氧化鈦對水楊酸的降解效率皆比未改質的二氧化鈦較佳。 (4-3) Experiment of degrading salicylic acid under fluorescent lamp with modified nickel-doped titanium dioxide: The experimental method is exactly the same as (3-4) of <Specific Example-3> except that the addition is added to the salicylic acid solution. The modified titanium dioxide photocatalyst type is b1, b2, b3 and b4 doped with nickel, so it will not be described again. The results are shown in Fig. 12 (I). After the modified titanium dioxide p and the different nickel ratios of the modified titanium oxides b1, b2, b3 and b4 degraded salicylic acid under fluorescent lamps for 24 hours, the salicylic acid removal rates were 67.83%. , 82.02%, 75.82%, 98.50%, 93.81%. Among them, the removal rate of b3 is still the best, up to 98.50%, and the removal rate of salicylic acid by b1, b2 and b4 is also better than p, indicating that the degradation efficiency of salicylic acid is improved by the modified titanium dioxide. It is preferred over unmodified titanium dioxide.
再進一步分析添加不同二氧化鈦的水楊酸溶液於0~24小時之礦化率,結果如圖12之(II)所示,可得知在水楊酸溶液內所偵測到的溶解性有機碳殘留濃度(DOC)隨時間遞減,且純二氧化鈦p與不同鐵比例之改質二氧化鈦b1、b2、b3與b4於日光燈下降解水楊酸24小時後的礦化率分別為44.86%、53.63%、59.05%、84.86%、76.65%。其中,仍以b3的礦化率最佳,與去除率的結果相似。Further analyze the mineralization rate of salicylic acid solution with different titanium dioxide added for 0-24 hours. As shown in Fig. 12(II), the dissolved organic carbon detected in salicylic acid solution can be known. The residual concentration (DOC) decreased with time, and the mineralization rates of pure titanium dioxide p and different iron ratios of modified titanium dioxide b1, b2, b3 and b4 after degradation of salicylic acid under fluorescent lamp for 24 hours were 44.86% and 53.63%, respectively. 59.05%, 84.86%, 76.65%. Among them, the mineralization rate of b3 is still the best, similar to the removal rate.
(4-4)摻雜鎳之改質二氧化鈦於太陽光下降解水楊酸之實驗: 實驗方式與<具體例-3> 之(3-5) 完全相同,只是改變添加於水楊酸溶液中的改質二氧化鈦光觸媒種類為摻雜鎳之b1、b2、b3與b4,故不再贅述。 (4-4) Experiment of degrading salicylic acid by modified titanium dioxide doped with sunlight in sunlight: The experimental method is exactly the same as (3-5) of <Specific Example-3> except that the change is added to the salicylic acid solution. The modified titanium dioxide photocatalyst type is b1, b2, b3 and b4 doped with nickel, so it will not be described again.
結果如圖13之(I)所示,純二氧化鈦p與不同鎳比例之改質二氧化鈦b1、b2、b3與b4於太陽光下降解水楊酸3小時後,水楊酸的去除率分別為65%、88.5%、92.10%、100%、95.70%。其中,仍以b3的去除率最佳,高達100%,而b1、b2與b4對水楊酸的去除率亦皆優於p,據此說明摻雜鎳之改質二氧化鈦對水楊酸的降解效率皆比未改質的二氧化鈦較佳。As a result, as shown in (I) of FIG. 13, after the purified titanium dioxide p and the different nickel ratios of the modified titanium oxides b1, b2, b3 and b4 degraded salicylic acid under sunlight for 3 hours, the salicylic acid removal rates were 65, respectively. %, 88.5%, 92.10%, 100%, 95.70%. Among them, the removal rate of b3 is still the best, up to 100%, and the removal rate of salicylic acid by b1, b2 and b4 is also better than p, according to the degradation of salicylic acid by the modified titanium dioxide doped with nickel. The efficiency is better than the unmodified titanium dioxide.
再進一步分析添加不同二氧化鈦的水楊酸溶液於0~24小時之礦化率,結果如圖13之(II)所示,可得知在水楊酸溶液內所偵測到的溶解性有機碳殘留濃度(DOC)隨時間遞減,且純二氧化鈦p與不同鎳比例之改質二氧化鈦b1、b2、b3與b4於太陽光下降解水楊酸3小時後的礦化率分別為45.51%、71.88%、74.67%、86.17%、81.75%。其中,仍以b3的礦化率最佳。Further analysis of the mineralization rate of salicylic acid solution with different titanium dioxide added in 0-24 hours, the results show that the dissolved organic carbon detected in the salicylic acid solution is shown in Fig. 13 (II). The residual concentration (DOC) decreased with time, and the mineralization rates of pure titanium dioxide p and different nickel ratios of modified titanium dioxide b1, b2, b3 and b4 after degrading salicylic acid under sunlight for 3 hours were 45.51% and 71.88%, respectively. 7,4.67%, 86.17%, 81.75%. Among them, the mineralization rate of b3 is still the best.
(4-5)綜合比較不同光源下摻雜鎳之改質二氧化鈦之水楊酸降解效率: 將(4-2)~(4-4)所量測到的未改質的二氧化鈦粉末p四種摻雜不同比例鎳之改質二氧化鈦粉末b1、b2、b3與b4,於不同光源下降解水楊酸反應3小時的水楊酸去除率與礦化率分別整理成圖14(I)、(II),以了解不同光源下光催化降解水楊酸的情形。由圖14(I)可看出改質二氧化鈦b3在太陽光為光源下,光催化水楊酸在3小時的去除率內就可達到100%的去除率,日光燈與可見光去除率皆低於太陽光。其中,以改質二氧化鈦b3在不同光源下的去除率最佳,顯見b3之鎳與鈦的用量比例為具有最佳降解效率的比例,而添加鎳之其他改質二氧化鈦b1、b2與b4對水楊酸的降解效率皆比未改質的二氧化鈦p為佳。由圖14之(II)可得知,改質二氧化鈦b3在太陽光下光催化水楊酸3小時的礦化率為86.2%,不同光源下降解水楊酸的去除率與礦化率皆以b3最佳,據此說明,製作改質二氧化鈦時,當金屬鹽化合物中的金屬為鎳,且其用量與鈦前驅物中的鈦的用量比為10:100時可製得具有最佳降解效率的改質二氧化鈦。 (4-5) Comprehensive comparison of salicylic acid degradation efficiency of modified titanium dioxide doped with nickel under different light sources: four kinds of unmodified titanium dioxide powders measured by (4-2)~(4-4) The salicylic acid removal rate and mineralization rate of the modified titanium dioxide powders b1, b2, b3 and b4 doped with different proportions of nickel under different light sources for 3 hours were arranged into Fig. 14(I), (II). ) to understand the photocatalytic degradation of salicylic acid under different light sources. It can be seen from Fig. 14(I) that under the sunlight as the light source, the photocatalytic salicylic acid can achieve 100% removal rate within 3 hours, and the fluorescent lamp and visible light removal rate are lower than the sun. Light. Among them, the removal rate of modified titanium dioxide b3 under different light sources is the best, it is obvious that the ratio of nickel to titanium in b3 is the ratio with the best degradation efficiency, while the other modified titanium dioxide added b1, b2 and b4 to water The degradation efficiency of salicylic acid is better than that of unmodified titanium dioxide p. It can be seen from (II) of Fig. 14 that the mineralization rate of the modified titanium dioxide b3 under photocatalytic salicylic acid for 3 hours under sunlight is 86.2%, and the removal rate and mineralization rate of degraded salicylic acid under different light sources are B3 is the best, according to the description, when the modified titanium dioxide is produced, when the metal in the metal salt compound is nickel, and the ratio of the amount of titanium to the titanium precursor is 10:100, the best degradation efficiency can be obtained. The modified titanium dioxide.
(5-1)摻雜鐵之改質二氧化鈦的製備: 參考<具體例-2> 之(2-2)所述的方法製備摻雜鐵之改質二氧化鈦,且以異丙醇鈦中的鈦的用量為100重量份計,所添加的硝酸鐵的量皆使其中的鐵的量等於0.1重量份,依前述摻雜比例先製備出四份白色膠狀物,再將該等膠狀物置於高溫爐並分別以400℃、500℃、600℃、700℃加熱4小時使其型成二氧化鈦結晶物,最後經由研磨就能獲得不同燒結溫度之摻雜鐵的改質二氧化鈦粉末c1、c2、c3、c4。 (5-1) Preparation of modified iron-doped titanium dioxide: Preparation of iron-doped modified titanium dioxide by the method described in ( Example 2-2) (2-2), and titanium in titanium isopropoxide The amount of iron nitrate added is 100 parts by weight, and the amount of iron is equal to 0.1 parts by weight. Four white gums are prepared according to the above doping ratio, and then the gel is placed. The high-temperature furnace is heated at 400 ° C, 500 ° C, 600 ° C, and 700 ° C for 4 hours to form titanium dioxide crystals. Finally, the iron-doped modified titanium dioxide powders c1, c2, and c3 having different sintering temperatures can be obtained by grinding. , c4.
依<具體例-3> 與<具體例-4> 所述的測試方式,分別量測c1、c2、c3、c4在可見光、日光燈與太陽光等不同光源下對降解水楊酸的去除率與礦化率,各種光源的條件皆與前述具體例所述者相同,結果如下表-2所示:According to the test methods described in <Specific Example-3> and <Specific Example-4> , the removal rates of degraded salicylic acid under different light sources such as visible light, fluorescent lamp and sunlight are measured respectively. The mineralization rate and the conditions of various light sources are the same as those described in the above specific examples. The results are shown in Table 2 below:
由表-2的結果可看出,當燒結溫度400℃~600℃所製得的摻雜鐵之改質二氧化鈦在不同光源下降解水楊酸的去除率與礦化率都能達50%以上,其中又以燒結溫度400℃所製得的改質二氧化鈦具有最佳的去除率與礦化率,而能表現最佳的降解效率,據此說明燒結溫度亦會影響到該改質二氧化鈦的降解效率,因此,為了獲得較佳光催化能力的光催化產品,除了控制摻雜金屬與鈦前驅物中的鈦的用量比例外,仍需限制其燒結溫度。It can be seen from the results in Table-2 that the modified iron-doped titanium dioxide prepared at a sintering temperature of 400 ° C to 600 ° C can degrade the salicylic acid at different light sources and the mineralization rate can reach 50% or more. Among them, the modified titanium dioxide prepared at a sintering temperature of 400 ° C has the best removal rate and mineralization rate, and can exhibit the best degradation efficiency, according to which the sintering temperature also affects the degradation of the modified titanium dioxide. Efficiency, therefore, in order to obtain a photocatalytic product with better photocatalytic ability, in addition to controlling the ratio of the amount of titanium in the doping metal to the titanium precursor, it is still necessary to limit the sintering temperature.
(5-2)綜合比較不同光源下不同燒結溫度之改質二氧化鈦的水楊酸降解效率: 進一步地,將不同燒結溫度之摻雜鐵的改質二氧化鈦粉末c1、c2、c3與c4,於不同光源下降解水楊酸反應3小時的水楊酸去除率與礦化率分別整理成圖15(I)、(II),以了解不同光源下光催化降解水楊酸的情形。由圖15之(I)可得知,燒結溫度400℃所製備之改質二氧化鈦在太陽光下光催化水楊酸3小時的去除率可達到100%,以日光燈與可見光為光源去除率皆低於太陽光。其中,燒結溫度400℃之二氧化鈦在不同光源下的去除率皆為最佳,顯示燒結溫度400℃為最佳製備條件。圖15之(II)所顯示的結果與(I)類似,顯示燒結溫度400℃所製備之二氧化鈦具有最佳的礦化率。 (5-2) Comprehensively compare the salicylic acid degradation efficiency of the modified titanium dioxide at different sintering temperatures under different light sources: further, the modified titanium dioxide powders c1, c2, c3 and c4 of different sintering temperatures are different The salicylic acid removal rate and mineralization rate under degradation of salicylic acid for 3 hours under light source were compiled into Fig. 15(I) and (II), respectively, to understand the photocatalytic degradation of salicylic acid under different light sources. It can be seen from (I) of Fig. 15 that the modified titanium dioxide prepared at a sintering temperature of 400 ° C can remove 100% of photocatalytic salicylic acid in sunlight for 3 hours, and has a low removal rate by using fluorescent lamps and visible light as a light source. In the sun. Among them, the removal rate of titanium dioxide with sintering temperature of 400 °C under different light sources is the best, showing that the sintering temperature of 400 °C is the best preparation condition. The result shown in (II) of Fig. 15 is similar to (I), and it is shown that the titanium oxide prepared at a sintering temperature of 400 ° C has an optimum mineralization ratio.
(6-1)摻雜鎳之改質二氧化鈦的製備: 參考<具體例-2> 之(2-3)所述的方法製備摻雜鎳之改質二氧化鈦,且以異丙醇鈦中的鈦的用量為100重量份計,所添加的硝酸鎳的量皆使其中的鎳的量等於10重量份,依前述摻雜比例先製備出四份白色膠狀物,再將該等膠狀物置於高溫爐並分別以400℃、500℃、600℃、700℃加熱4小時使其型成二氧化鈦結晶物,最後經由研磨就能獲得不同燒結溫度之摻雜鐵的改質二氧化鈦粉末d1、d2、d3、d4。 (6-1) Preparation of modified titanium dioxide doped with nickel: Preparation of nickel-doped modified titanium dioxide by the method described in < 2-3 of the specific example-2> , and titanium in titanium isopropoxide The amount of nickel nitrate added is 100 parts by weight, and the amount of nickel is equal to 10 parts by weight. Four white gums are prepared according to the above doping ratio, and then the gel is placed. The high-temperature furnace is heated at 400 ° C, 500 ° C, 600 ° C, and 700 ° C for 4 hours to form titanium dioxide crystals. Finally, the iron-doped modified titanium dioxide powders d1, d2, and d3 at different sintering temperatures can be obtained by grinding. , d4.
依<具體例-3>
與<具體例-4>
所述的測試方式,分別量測d1、d2、d3、d4在可見光、日光燈與太陽光等不同光源下對降解水楊酸的去除率與礦化率,各種光源的條件皆與前述具體例所述者相同,結果如下表-3所示:
由表-3的結果可看出,當燒結溫度400℃~600℃所製得的摻雜鎳之改質二氧化鈦在不同光源下降解水楊酸的去除率與礦化率都能達50%以上,其中又以燒結溫度400℃所製得的改質二氧化鈦具有最佳的去除率與礦化率,而能表現最佳的降解效率,據此同樣證實燒結溫度會影響到該改質二氧化鈦的降解效率,且為了獲得較佳光催化能力的光催化產品,除了控制摻雜金屬與鈦前驅物中的鈦的用量比例外,仍需限制其燒結溫度。It can be seen from the results in Table-3 that the removal rate and mineralization rate of salicylic acid degraded by different nickel-doped modified titanium dioxide prepared at a sintering temperature of 400 ° C to 600 ° C can reach 50% or more. The modified titanium dioxide prepared at a sintering temperature of 400 ° C has the best removal rate and mineralization rate, and can exhibit the best degradation efficiency, and accordingly confirms that the sintering temperature affects the degradation of the modified titanium dioxide. In terms of efficiency, and in order to obtain a photocatalytic product with better photocatalytic ability, in addition to controlling the ratio of the amount of titanium in the doped metal to the titanium precursor, it is still necessary to limit the sintering temperature.
(6-2)綜合比較不同光源下不同燒結溫度之改質二氧化鈦的水楊酸降解效率 :進一步地,將不同燒結溫度之摻雜鎳的改質二氧化鈦粉末d1、d2、d3與d4,於不同光源下降解水楊酸反應3小時的水楊酸去除率與礦化率分別整理成圖16(I)、(II),以了解不同光源下光催化降解水楊酸的情形。由圖16之(I)可得知,燒結溫度400℃所製備之改質二氧化鈦在太陽光下光催化水楊酸3小時的去除率可達到100%,以日光燈與可見光為光源去除率皆低於太陽光。其中,燒結溫度400℃之二氧化鈦在不同光源下的去除率皆為最佳,顯示燒結溫度400℃為最佳製備條件。圖16之(II)所顯示的結果亦與(I)類似,顯示燒結溫度400℃所製備之二氧化鈦具有最佳的礦化率。 (6-2) Comprehensive comparison of salicylic acid degradation efficiency of modified titanium dioxide at different sintering temperatures under different light sources : Further, the modified titanium dioxide powders d1, d2, d3 and d4 of different sintering temperatures are different The salicylic acid removal rate and mineralization rate under degradation of salicylic acid for 3 hours under light source were compiled into Fig. 16(I) and (II), respectively, to understand the photocatalytic degradation of salicylic acid under different light sources. It can be seen from (I) of Fig. 16 that the modified titanium dioxide prepared at a sintering temperature of 400 ° C can remove 100% of photocatalytic salicylic acid in sunlight for 3 hours, and has a low removal rate by using fluorescent lamps and visible light as a light source. In the sun. Among them, the removal rate of titanium dioxide with sintering temperature of 400 °C under different light sources is the best, showing that the sintering temperature of 400 °C is the best preparation condition. The result shown in (II) of Fig. 16 is also similar to (I), and it is shown that the titanium oxide prepared at a sintering temperature of 400 ° C has an optimum mineralization ratio.
歸納上述,本發明具有較佳降解效率之改質二氧化鈦的製法,可獲致下述的功效及優點,故能達到本發明的目的:In summary, the method for preparing modified titanium dioxide having better degradation efficiency of the present invention can attain the following effects and advantages, so that the object of the present invention can be achieved:
一、由<具體例-1> 的結果可以看出,以本發明製法所製出的二氧化鈦具有不亞於市售商用二氧化鈦的吸附能力與光催化能力,據此說明本發明製法確實能製出符合商用規格的二氧化鈦,故具有可應用於工業製造生產的實用價值。1. It can be seen from the results of <Specific Example-1> that the titanium dioxide produced by the method of the present invention has an adsorption capacity and a photocatalytic ability comparable to those of commercially available commercial titanium dioxide, and accordingly, the method of the present invention can be produced. It meets the commercial specifications of titanium dioxide, so it has practical value for industrial production.
二、由<具體例-2> 的結果可以看出,燒結溫度400℃下所製備之未改質或改質二氧化鈦光觸媒,由EDS光譜則可說明透過本發明製法確實能將過渡金屬離子摻雜在改質二氧化鈦中,再由其XRD圖譜顯示所製出的二氧化鈦粉末皆只呈現銳鈦礦(Anatase)的單一晶相,未發現有金紅石(rutile)晶相,據此說明在400℃的燒結溫度條件下所製出的改質二氧化鈦其晶相仍以銳鈦礦為主,且摻雜金屬並不會影響到純二氧化鈦的晶相,在XRD圖譜中未出現任何過渡金屬氧化物的繞射峰,則說明鐵、鎳等過渡金屬應是高度嵌人二氧化鈦結晶物的內部結構中,甚至取代部分鈦金屬的位置,因此,本發明的製法能製得品質穩定的改質二氧化鈦產品。2. It can be seen from the results of <Specific Example-2> that the unmodified or modified titanium dioxide photocatalyst prepared at a sintering temperature of 400 ° C can be used to indicate that the transition metal ions can be doped by the method of the present invention by the EDS spectrum. In the modified titanium dioxide, the XRD pattern showed that the prepared titanium dioxide powder showed only a single crystal phase of anatase, and no rutile crystal phase was found, which was explained at 400 ° C. The modified titanium dioxide produced at the sintering temperature still has an anatase phase, and the doping metal does not affect the crystal phase of pure titanium dioxide. No transition metal oxide is formed in the XRD pattern. The peak of the shot indicates that the transition metal such as iron or nickel should be highly embedded in the internal structure of the titanium dioxide crystal, or even replace the position of a part of the titanium metal. Therefore, the method of the present invention can produce a modified titanium dioxide product with stable quality.
三、由<具體例-3> 與<具體例-4> 的結果可以看出,本發明藉由限制摻雜金屬與鈦前驅物中鈦的用量比例範圍,確實有助於製出能於不同可見光光源下進行光催化作用且具有較佳降解效率的改質二氧化鈦產品,使本發明所製出的產品確實能改善光觸媒的效能而具實用價值與經濟效益。3. It can be seen from the results of <Specific Example-3> and <Specific Example-4> that the present invention can contribute to different production by limiting the range of the ratio of the doping metal to the amount of titanium in the titanium precursor. The modified titanium dioxide product which performs photocatalysis under visible light source and has better degradation efficiency makes the product prepared by the invention can improve the performance of the photocatalyst and has practical value and economic benefit.
四、由<具體例-5> 與<具體例-6> 的結果可以看出,除了限制摻雜金屬與鈦前驅物中鈦的用量比例範圍外,進一步限制製造過程中的燒結溫度,同樣有助於製出高降解效率的改質二氧化鈦,故本發明的製法藉由限制主要原料的用量比例與燒結溫度能製得具有最佳降解效率的光觸媒產品,且以該改質二氧化鈦光觸產品應用於有機污染物處理時,還能將有機物降解後的中間產物進一步分解為無毒的無機態化合物,而有較佳的環保效能,據此說明本發明製法本身不但有開發為工業製程的實用價值與經濟效益,據此所製出的產品亦能有效降理有機污染物,而能符合環保需求。4. From the results of <Specific Example-5> and <Specific Example-6> , it can be seen that, in addition to limiting the range of the ratio of the doping metal to the amount of titanium in the titanium precursor, the sintering temperature in the manufacturing process is further limited, and there are also Helping to produce modified titanium dioxide with high degradation efficiency, the method of the present invention can produce a photocatalytic product having the best degradation efficiency by limiting the proportion of the main raw materials and the sintering temperature, and applying the modified titanium dioxide light touch product. In the treatment of organic pollutants, the intermediate products degraded by organic matter can be further decomposed into non-toxic inorganic compounds, and the environmental protection performance is better, thereby indicating that the method of the present invention not only has the practical value of being developed into an industrial process. The economic benefits, according to the products produced can also effectively reduce organic pollutants, and can meet environmental protection needs.
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.
3‧‧‧恆溫光照箱裝置3‧‧‧ thermostat light box device
31‧‧‧石英反應槽31‧‧‧Quartz reaction tank
32‧‧‧燈管32‧‧‧Light tube
圖1是本發明具有較佳降解效率之改質二氧化鈦的製法一較佳實施例的一流程圖;圖2是以該較佳實施例所製出的改質二氧化鈦進行水楊酸降解實驗所用的一恆溫光照箱裝置的一示意圖;圖3是SEM影像圖,說明該較佳實施例所製出的不同金屬摻雜比例的改質二氧化鈦的外觀型態;圖4之(I)、(II)是EDS光譜圖,說明該較佳實施例所製出的摻雜鐵、鎳之改質二氧化鈦含有摻雜金屬的情形;圖5是XRD圖譜,說明該較佳實施例所製出的摻雜鐵之改質二氧化鈦與純二氧化鈦的晶相;圖6是XRD圖譜,說明該較佳實施例所製出的摻雜鎳之改質二氧化鈦與純二氧化鈦的晶相;圖7之(I)、(II)為曲線圖,分別說明不同比例鐵改質二氧化鈦於可見光下降解水楊酸的殘留率與礦化率; 圖8之(I)、(II)為曲線圖,分別說明不同比例鐵改質二氧化鈦於日光燈下降解水楊酸的殘留率與礦化率;圖9之(I)、(II)為曲線圖,分別說明不同比例鐵改質二氧化鈦於太陽光下降解水楊酸的殘留率與礦化率;圖10之(I)、(II)為柱狀圖,分別說明不同比例鐵改質二氧化鈦於不同光源下降解水楊酸的去除率與礦化率;圖11之(I)、(II)為曲線圖,分別說明不同比例鎳改質二氧化鈦於可見光下降解水楊酸的殘留率與礦化率;。圖12之(I)、(II)為曲線圖,分別說明不同比例鎳改質二氧化鈦於日光燈下降解水楊酸的殘留率與礦化率;圖13之(I)、(II)為曲線圖,分別說明不同比例鎳改質二氧化鈦於太陽光下降解水楊酸的殘留率與礦化率;圖14之(I)、(II)為柱狀圖,分別說明不同比例鎳改質二氧化鈦於不同光源下降解水楊酸的去除率與礦化率;圖15之(I)、(II)為柱狀圖,分別說明不同燒結溫度之鐵改質二氧化鈦於不同光源下降解水楊酸的去除率與礦化率;及圖16之(I)、(II)為柱狀圖,分別說明不同燒結溫度之鎳改質二氧化鈦於不同光源下降解水楊酸的去除率與礦化率。1 is a flow chart of a preferred embodiment of the process for producing modified titanium dioxide having better degradation efficiency of the present invention; and FIG. 2 is a schematic diagram of salicylic acid degradation experiments using the modified titanium dioxide produced by the preferred embodiment. A schematic view of a thermostatic light box device; FIG. 3 is an SEM image showing the appearance of modified titanium dioxide of different metal doping ratios produced by the preferred embodiment; (I) and (II) of FIG. It is an EDS spectrum, which illustrates the case where the modified iron and nickel modified titanium dioxide produced by the preferred embodiment contains a doped metal; and FIG. 5 is an XRD pattern illustrating the doped iron produced by the preferred embodiment. The crystal phase of the modified titanium dioxide and the pure titanium dioxide; FIG. 6 is an XRD pattern illustrating the crystal phase of the nickel-doped modified titanium dioxide and the pure titanium dioxide produced in the preferred embodiment; (I), (II) of FIG. ) is a graph showing the residual rate and mineralization rate of salicylic acid degraded by visible iron in different proportions of iron modified titanium dioxide; (I) and (II) of Fig. 8 are graphs respectively showing the residual rate and mineralization rate of salicylic acid degraded by different proportions of iron-modified titanium dioxide under fluorescent lamps; (I) and (II) of Fig. 9 are graphs. , respectively, indicating the residual rate and mineralization rate of salicylic acid degraded by different proportions of iron-modified titanium dioxide in sunlight; (I) and (II) in Figure 10 are bar graphs, respectively indicating different ratios of iron-modified titanium dioxide in different Degradation rate and mineralization rate of salicylic acid under light source; (I) and (II) of Fig. 11 are graphs showing the residual rate and mineralization rate of salicylic acid degraded by visible light in different proportions of nickel modified titanium dioxide. ; Fig. 12 (I) and (II) are graphs showing the residual rate and mineralization rate of salicylic acid degraded by different proportions of nickel-modified titanium dioxide under fluorescent lamps; (I) and (II) of Fig. 13 are graphs. , respectively, indicate the residual rate and mineralization rate of salicylic acid degraded by different proportions of nickel-modified titanium dioxide under sunlight; (I) and (II) of Fig. 14 are bar graphs, respectively indicating different ratios of nickel-modified titanium dioxide in different Degradation rate and mineralization rate of salicylic acid under light source; (I) and (II) of Fig. 15 are bar graphs showing the removal rate of salicylic acid degraded by iron-modified titanium dioxide with different sintering temperatures under different light sources. And the mineralization rate; and (I) and (II) of Fig. 16 are bar graphs, respectively illustrating the removal rate and mineralization rate of salicylic acid degraded by nickel modified titanium dioxide at different sintering temperatures under different light sources.
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