光能利用率的提升一直是目前光觸媒研究最重要的課題，減少被光激發產生的電子電洞對再結合，是一種讓吸收的光能充分利用的方法。外加電壓可以非常有效地抑制電子和電洞再結合，為充分發揮外加電壓的效益，本研究首先探討光觸媒在外加電壓與沒有外加電壓的條件下，材料特性與光催化、光電催化活性的關係。為了進一步獲得更高光催化或光電催化活性的光觸媒，我們嘗試合成具有奈米纖維陣列結構的二氧化鈦薄膜，探討二氧化鈦奈米纖維陣列的合成條件與特性分析，並檢測其光催化與光電催化活性。
　　在第一部份的研究，以磁控反應性濺鍍法在ITO導電玻璃基材上製備二氧化鈦薄膜。改變濺鍍條件包括濺鍍功率、腔體總壓、氧氣分壓得到不同材料特性的二氧化鈦薄膜，並評估其光電流活性。
結果顯示薄膜厚度1.2 μm與顆粒尺寸50 nm得到最佳的光電流。當晶粒尺寸小於22 nm時，可觀察到量子尺寸效應造成的光學能隙藍位移。以濺鍍功率和腔體總壓建構的晶型結構相圖可顯示，其中除了描述銳鈦礦和金紅石的轉換，同時界定銳鈦礦（101）和（112）長晶優勢位向的轉換。（112）長晶優勢位向的銳鈦礦因為具有柱狀的結構，有利於電子的傳遞，因此其光電流大於（101）長晶優勢位向的銳鈦礦。
　　在第二部分的研究，以濺鍍法製備二氧化鈦薄膜，利用改變濺鍍條件，使不同特性的二氧化鈦薄膜沈積在鈦片上。選擇測定甲基橙的脫色速率，作為鑑定光催化與光電催化活性的標的。同時也量測光電流，以此和脫色速率比較，並且計算系統的光電流效率。
　　結果顯示濺鍍在鈦片上的二氧化鈦薄膜具有良好的晶體結構產生光催化活性，不需再經由鍛燒熱處理。其平均晶粒尺寸介於22到49 nm之間。銳鈦礦和金紅石晶型都存在製備的薄膜中。光學能隙介於3.1至3.3 eV。平帶電位主要介於-0.14到-0.29 V vs. Ag/AgCl。
甲基橙脫色反應僅發生在光電極槽（陽極）。光電流效率介於1.42到4.46%之間。二氧化鈦薄膜在沒有外加電壓的光催化甲基橙脫色速率較高的，在外加電壓的催化反應中，產生的光電流有較多作用於甲基橙脫色。連接至Pt電極，使脫色速率平均增加67%。外加電壓使脫色速率再增加127%。
　　對於光催化反應，材料特性包括高結晶度、高銳鈦礦含量、負的平帶電位可得到較高的脫色速率。但對於光電催化反應，銳鈦礦含量和平帶電位的影響不重要。薄膜電阻成為最主要影響脫色速率的因素。
　　第三部分研究嘗試開發一種二氧化鈦奈米纖維陣列的合成法。利用NaOH溶液與二氧化鈦粉末與鈦片反應，可在鈦片表面生成二氧化鈦奈米纖維陣列。此方法不需使用模版、在常壓下進行，為一簡單、快速、溫和的合成方法。使用2.5 M NaOH在常溫下即可進行合成反應。使用95℃的溶液，NaOH濃度僅需0.1 M。在10 M NaOH溶液與95℃的條件下，2 min的時間即可觀察到纖維的生成。鈦片表面生成的纖維直徑約15 nm，組成為二氧化鈦，包含銳鈦礦和金紅石晶型。
纖維的形成包括二氧化鈦的分解再重構的過程，因此原始二氧化鈦粉末的顆粒大小不影響纖維的型態。鹼液的濃度是使二氧化鈦分解的主要驅動力，對生成的纖維型態有明顯的影響。纖維結構在水熱反應後形成，後續的水洗與酸洗程序是為除去殘留的鈉離子，以提升光催化活性。
　　鍛燒前的奈米纖維陣列因為結晶度不佳，不具良好的光催化活性。鍛燒至550℃可增加其結晶度，並仍保留其纖維結構。和鍛燒至750℃擁有最佳結晶度但不具纖維結構的電極比較，纖維結構電極的光電流是非纖維結構電極光電流的四倍。對於光電催化活性，奈米纖維的沈積量有一最佳值，過長的反應時間因為纖維的交錯反而影響電子傳輸並使電阻上升，造成光電催化活性下降。對於光催化活性，沈積量增加使光催化活性增加並趨近一穩定值。

　How to increase the efficiency of the photocatalytic process is an issue currently attracting attention. Reducing the recombination of electrons and holes, e.g. by applying a potential, is an effective way to increase the efficiency of photo-energy utilization. In order to maximize the function of the applied potential, we first investigated correlations between the material properties and the photocatalytic and photoelectrocatalytic activities of photcatalysts in the absence and presence of an applied potential. To obtain the best photocatalysts, i.e. those with the highest photocatalytic or photoelectrocatalytic activities, we attempted to synthesize a TiO2 thin film with a nanofiber array structure. The synthesis, characterization, and the photocatalytic and photoelectrocatalytic activities of the TiO2 nanofiber array were also explored.
　In the first part, a systematic study of the photocurrent activity and the nanostructure of a TiO2 indium tin oxide (ITO) electrode prepared using reactive sputtering was carried out. Various TiO2 films were synthesized by controlling deposition times, sputtering powers, total pressures, and the mole percentage of oxygen used in reactive sputtering.
　The results indicated that the optimal photocurrent was obtained at a thickness of approximately 1.2 μm with a mean particle size of approximately 50 nm. The quantum size effect (blue shift in the bandgap energy) was observed when the grain size was smaller than 22 nm. The preferred orientation of the anatase region for (101) and (112) was determined in the phase diagram defined by the total pressure and sputtering power. The (112)-preferred orientation anatase had a higher photocurrent than (101)-orientation anatase due to the (112)-orientation anatase having a more regular columnar structure that was beneficial to electron transfer.
　In the second part, correlations between the photocatalytic and photoelectrocatalytic decolorization of methyl orange, using TiO2 thin films sputtered under various conditions, were made. TiO2 thin films with various characteristics were deposited onto a Ti plate using reactive sputtering. The rate of decolorization of methyl orange was monitored and used to evaluate the activity of photocatalytic and photoelectrocatalytic reactions in this work. In addition, the photocurrent was measured to compare the different methods used to evaluate the photoelectrocatalytic activity including the rate of decolorization and photocurrent density. The photocurrent efficiency of the photoelectrocatalytic decolorization of methyl orange was also evaluated.
　The results indicated that the sputtered TiO2 thin films had good crystallinity even without calcination and their average grain sizes were in the range from 22 to 49 nm. Both anatase and rutile phases were found in the prepared films. The values of the bandgap energy were in the range from 3.1 to 3.3 eV. The flatband potential of the sputtered TiO2 film was in the range from -0.14 to -0.29 V vs. Ag/AgCl.
　It was found that the decolorization of methyl orange only occurred on the anode of the TiO2/Ti electrode. The photocurrent efficiency was between 1.42 and 4.46%. TiO2 films had higher activities in photocatalytic reactions in the absence of an applied potential, and also had a higher selectivity for the decolorization of methyl orange in the presence of an applied potential. With the photocatalyst connected to a Pt plate, the average photocatalytic decolorization rate of methyl orange increased by 67%. The decolorization rate was further increased by 127% in the presence of an applied potential of 1 V vs. Ag/AgCl.
For the photocatalytic reaction, the materials with high crystallinity, high quantity of anatase, and more negative flatband potential gave a higher decolorization rate. For the photoelectrocatalytic reaction, the crystal phase was not important and the flatband potential effect was not affected when connected to Pt. However, the resistance of the film was the most important factor for determining the photoelectrocatalytic activity.
　The third part details the development of a novel synthesis method for the preparation of a TiO2 nanofiber array. The TiO2 nanofiber array was formed on Ti foil by the reaction between Ti foil, TiO2 powder, and NaOH solution. This is an extremely easy and fast way to synthesize the nanofiber array under moderate conditions. No mode is required and it can be produced at normal pressures with only one step. The synthesis can be carried out in aqueous NaOH (2.5 M) at room temperature. If we use a higher temperature e.g. 95℃, the concentration of NaOH solution can be reduced to 0.1 M in a procedure lasting approximately 20 min. However, the nanofiber can be obtained after 2 min in a 10 M NaOH solution at 95℃. The fiber was 15 nm in diameter and composed of anatase and rutile TiO2.
　The formation of the nanofiber was achieved by the decomposition and subsequent restructuring of TiO2 powder. The original particle size distribution of the TiO2 powder does not affect the morphology of the final nanofiber. The driving force causing the decomposition of the TiO2 is the concentration of the alkaline. The morphology of the nanofiber is strongly influenced by the concentration of the alkali. The nanofiber was formed immediately after the hydrothermal reaction. The follow-up procedures (e.g. rinsing with DI water and acid) serve to wash out the remaining Na+ ions. These remnants do not affect the morphology of the nanofiber but do decrease the photocatalytic activity of TiO2 nanofiber array.
The nanofiber has good crystallinity with high photocatalytic activity. The nanofiber structure was still maintained while the calcination temperature increased to 550℃. When the temperature further increased to 750℃, the nanofiber structure of the TiO2 disappeared although the crystallinity further improved. The nanofiber TiO2 with the calcination temperature at 550℃ has excellent photoelectrocatalytic activity, by a factor of 4, compared to that with the calcination temperature at 750℃. The amount of deposition of nanofiber array has an optimal value for photoelectrocatalytic activity. If this optimal value is surpassed, the photoelectrocatalytic activity of the nanofiber decreases due to the increased resistance of the transmission of the electrons. However, the accumulation of the nanofibers would increase the photocatalytic activity and reach a saturation point.

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