本研究旨在製備二氧化鈦光電極，並以光電化學法(PEC)分解水之反應探討其光電化學反應活性及產氫速率。文中首先以正丁醇氧化鈦為前驅物，利用溶膠凝膠法製備TiO2/ITO光電極。文中探討TiO2氧化層塗覆厚度及鍛燒溫度對光電極表面形態、晶態及PEC反應活性之影響。實驗結果顯示，以溶凝膠法所製備之二氧化鈦薄膜，經400-650oC鍛燒後，所得晶態以銳鈦礦(anatase)結構為主。在照光(低壓汞燈，主要波長253.7 nm，極板平均照度1.59mW/cm2)下，以塗覆四層之TiO2膜(膜厚約250 nm)經600oC鍛燒所得電極之飽和光電流(0.1958 mA/cm2)為最大，其光電轉換效率為1.9%，顯示光催化活性並不顯著。
為了提昇光電極之光電活性，另以陽極氧化法製備奈米管狀結構之TiO2/Ti光電極。實驗中，改變陽極氧化法之操作變因，如施加電壓、電解液種類及濃度、反應溫度及時間、電解液攪拌速率等因素來製備TiO2 / Ti光電極，探討各條件下所得光電極特性，包括：表面形態、管徑大小及長度、氧化層厚度及晶態等影響，並推測TiO2奈米管生成機制。另外，對光電極之光催化活性進行測試，以探討電極在光電化學反應之活性。
實驗結果顯示，陽極氧化法所得TiO2 / Ti光電極之活性頗佳。其中，以H3PO4 (0.5 M)-HF (0.15 M)為電解液，在定電壓20 V下反應90 min後，經500oC鍛燒所得之奈米管狀二氧化鈦光陽極為最佳，其PEC反應之飽和光電流(0.4777 mA/cm2)為最大，且光電轉換效率高達15.1%，產氫速率為4.297 μmol/cm2hr。
進一步，嘗試含浸鉑於TiO2奈米管電極上以製備Pt-TiO2/Ti光電極，實驗發現含浸0.06 wt%鉑於二氧化鈦表面可減少電子-電洞再結合率，進而提高光電轉換效率(19.5%)及產氫速率(4.870 μmol/cm2hr)；但鉑添加過量時，反而因遮蔽效應造成光電極活性之降低。
由本研究可知，陽極氧化法所得TiO2 / Ti光電極之光催化活性較溶膠凝膠法所得TiO2 / Ti光電極為佳；另外，含浸適量鉑於TiO2電極上對光催化轉化效率具有促進作用，顯示此法所得之光電極在水分解產氫上具備應用開發之潛力。

In this work, TiO2 photoanodes were prepared for hydrogen generation via photoelectrochemical (PEC) splitting of water. Experimentally, TiO2/ITO photoanodes were firstly prepared by the sol-gel method starting from tetrabutyl orthotitanate (Ti(OBun)4) as the precursor. The effects of preparation conditions including number of coating and calcination temperature on the properties of TiO2/ITO electrodes such as surface morphology, crystalline structure, and the PEC activities were investigated. The experimental results showed that the sol-gel derived TiO2 layers calcined at 400-650oC were mainly anatase structure. From results of PEC reactions under UV illumination (low pressure mercury lamp, λmax＝253.7 nm, I0 = 1.59 mW/cm2), it found that the TiO2/ITO photoelectrode (calcined at 600oC, TiO2 layer thickness about 250 nm) demonstrated a maximum saturation current density (0.1958 mA/cm2) with the PEC conversion efficiency of 1.9%. It revealed the sol-gel derived TiO2/ITO electrode exhibited low photocatalytic activity.
In order to further promote the photocatalytic activity, alternatively, the nanotubular TiO2/Ti electrodes were prepared by the anodization method. Experimentally, the preparation conditions including applied voltage, nature, concentration of electrolyte, anodizing temperature and time, and stirring rate were varied. The properties of TiO2/Ti electrodes such as surface morphology, tube diameter and length, TiO2 layer thickness and crystalline structure were investigated. Based on the results, the formation mechanism of TiO2 nanotubues could be deduced. In addition, the usability of the nanotubular TiO2/Ti photoanodes was evaluated from the PEC tests.
The experimental results showed that the nanotubular TiO2/Ti photoanode prepared by anodization method exhibited great photoactivity. Among various electrodes, the nanotubular TiO2/Ti photoanode which was anodized in H3PO4(0.5 M)-HF(0.15 M) solution at 20 V for 90 min and followed by calcining at 500oC demonstrated the maximum saturation current density (0.4777 mA/cm2) with a high PEC conversion efficiency of 15.1%, and hydrogen generation rate of 4.297 μmol/cm2hr.
Furthermore, Pt-TiO2/Ti photoanodes were attempted to be prepared by impregnating Pt on the TiO2 nanotubes. The experimental results found that the Pt (0.06 wt%)-TiO2/Ti photoanodes exhibited the maximum enhancement on the photoconversion efficiency (19.5%) and hydrogen generation rate 4.870 μmol/cm2hr), due to diminishing the recombination rate of electron-hole pairs. However, overloading of Pt would lead to the decrease of photocatalytic activity owing to the shading effect.
From this study, it could be concluded that the photoelectrochemical activities of the nanotubular TiO2/Ti photoanodes by anodization method were greatly higher than those of sol-gel derived TiO2/ITO photoanodes. In addition, appropriately loading of Pt on the TiO2/Ti electrode would promote the photoconversion efficiency. As a result, the nanotubular TiO2/Ti photoanodes demonstrate great promising potentials for the application on hydrogen generation from water splitting.

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