Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/28217
標題: 探討碳含量及鍛燒溫度對於碳摻雜二氧化鈦之特性影響及其光催化反應動力模式
The effect of C content and calcination temperature on the characteristic and photocatalytic activity of nano-sized C-doped TiO2
作者: 陳芳吟
Chen, Fang-Yin
關鍵字: C-doped TiO2;碳摻雜二氧化鈦;Visible-light photocatalyst;glucose;Carbon dopan;Langmuir-Hinshelwood rate;ethylene;visible light illumination;photocatalytic oxidation;葡萄糖;可見光光觸媒;乙烯;光催化反應;Langmuir-Hinshelwood反應動力模式
出版社: 土壤環境科學系所
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摘要: 
二氧化鈦材料因具有理想能帶結構,且不受光腐蝕的特性,常應用於光催化反應處理有機污染物。但是純二氧化鈦的能隙為3.0 eV,僅能吸收紫外光波段,太陽光中僅佔入射光5 % ~ 8 %,其餘為可見光波段,且若能將材料的光吸收波長範圍移到可見光波段 (波長為400 nm ~ 700 nm),其應用性將大為提昇,因此本研究致力於改質二氧化鈦的特性,並以乙烯作為目標污染物,探討其動力模式,以期未來應用於蔬果的儲藏運輸環境,控制水果熟化速度保存新鮮度,以提高生產力及獲利。
本研究使用溶膠凝膠法製備碳摻雜二氧化鈦光觸媒,製備過程控制碳源與鈦源添加比例及鍛燒溫度,實驗所製備的碳摻雜二氧化鈦材料能隙降低至2.9 eV,可有效地吸收可見光波段,碳原子以interstitial carbon型態存在於二氧化鈦結構中。鍛燒溫度對特性影響的實驗結果顯示,溫度提高有助於rutile晶相生成,導致粒徑成長及比表面積減少;碳源與鈦源添加比例結果顯示,添加比例增加將可降低粒徑成長,並些微地提高比表面積。粒徑、比表面積、晶相組成和能隙能量皆影響著光催化效能,批次實驗結果顯示,碳源與鈦源添加比例為1,鍛燒溫度為400 oC時具有最大降解效率 (8 %)。
動力實驗改變氣體流速、乙烯初始濃度、水氣濃度、氧氣濃度、光強度及反應溫度,實驗結果顯示,光催化反應為Langmuir-Hinshelwood反應動力模式。水氣分子與乙烯分子吸附於相同的活性位置,由於水氣分子與乙烯分子的競爭吸附作用,過量的水氣分子將抑制反應速率。然而氧氣分子與乙烯分子吸附於不同的活性位置,加上氧氣分子於光催化反應中可產生自由基,將有助於反應速率進行。綜合以上動力實驗結果,推導其反應動力方程式及作用機制,以預測光催化反應速率。

C-doped TiO2 have been prepared by sol-gel process. Glucose is applied as C source. The molar ratio of glucose to TBT is 0.02 to 3.00. Calcination temperatures ranged from 400 oC to 600 oC. Thus, the effect of molar ratio and calcination temperature on the characteristic of C-doped TiO2 is investigated by XRD, UV-Vis, FTIR, TGA, BET, DLS, and FESEM. Eventually, soft X-ray spectroscopy, X-ray absorption (XAS) and XPS are used to assess the relationship between the structure of nanocrystalline C-doped TiO2 and associated electronic properties as a function of calcination temperature and molar ratio of glucose to TBT. It has been observed that C dopants promote the phase transformation from anatase to rutile, as well as the optical band gap reduces to 2.9 eV. Spectrum of carbon indicates that the formation of C-O binding is assigned to the doped carbon to the interstitial one. The formation of a midgap level mixing with O2p and C2p levels locates 0.3 eV above the top of O2p valence band of TiO2 while the Ti3d conduction band is unchanged. Therefore, the optimum C content is 0.5% at 400 oC, namely, G10T4 which is the one with higher specific surface area (51.69 m2/g) and small particle size (10 nm). In the batch experiment, the removal of C2H4 about 8 % is highest for G10T4 in the period of 2 h.
Ethylene is chosen as the target. It illustrates that C-doped TiO2 is capable of oxidizing the C2H4 under the illumination of visible light. The photodegradation follows the Langmuir-Hinshelwood rate. All experiments were performed at 1 L/min flow rate so that the reaction rate was controlled by surface reaction. Three components, C2H4, O2, and H2O, were the key factors in the reaction. The reaction rate increased with increase in the concentration of C2H4, reaction temperature, O2 content, flow rate, and light intensity. The concentration of C2H4 had influence on reaction rate which increased with increase in C2H4 concentration result from the active sites enough on the surface of C-doped TiO2. The adsorption of O2 molecules was available to involve in the reaction with radicals. Thus, the reaction rate increased with increasing in the O2 content. The rate kept constant above 1 % due to the saturation of adsorption on the surface. The different adsorption sites between O2 and C2H4 was indicated. The increase of water vapor inhibited the reaction rate oppositely due to the competition between water vapor and C2H4. In a term of light intensity, the e--h+ recombination was dominant. In the future, the utilization of e--h+ pairs was the major subject to promote the efficiency for the degradation of organic compounds. Thus, the conceptual diagram in the photodegradation is populated.
URI: http://hdl.handle.net/11455/28217
其他識別: U0005-0702201123061200
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