表面特性在光催化還原CO2過程中扮演重要角色，以磷酸修飾形成的表面酸性位址及其對光催化還原CO2的特性並不完全了解清楚。本實驗利用不同濃度的磷酸修飾鈦酸鹽奈米管(titanate nanotubes, TNTs)並在不同溫度下鍛燒以形成磷酸化TiO2觸媒，並探討其在氣相光催化還原CO2的活性及選擇性。TNT衍生的TiO2主要將CO2催化還原成CO與CH4，磷酸修飾可提高TiO2催化還原活性，最佳合成P/Ti莫爾比為0.06-0.13，儘管高溫燒結大幅降低比表面積，然而觸媒活性隨鍛燒溫度提高卻增加，於900℃鍛燒下，CO比表面積產率可高達12.13 mol/m2，13-PT900 (P/Ti=0.13)有高AQE(0.052 %)。XRD及TEM觀察到磷酸抑制TiO2型態與晶相轉變，並使TiO2維持較高比表面積，同時也增加觸媒吸附CO2的量以提高觸媒克重還原活性。Pyridine-FTIR、NH3-TPD與CO2-TPD結果顯示磷酸修飾於觸媒表面導入布朗斯特酸，同時提高觸媒表面弱酸位址比例，因此利於CO2吸附，進而提高反應活性。

Surface properties play an important role in the photocatalytic CO2 reduction process, and the surface acid sites formed by phosphoric acid modification and their properties for photocatalytic CO2 reduction are not fully understood. In this experiment, titanate nanotubes (TNTs) were modified with different concentrations of phosphoric acid and calcined at different temperatures to form phosphated titania, and the activity and selectivity of photocatalytic CO2 reduction in gas phase were investigated. TNT-derived titania converted CO2 into CO and CH4. Phosphation effectively enhanced the reduction activity. The optimal P/Ti molar ratio was 0.06-0.13. Although calcination greatly decreased the specific surface area, the activity of the catalysts increased due to formation of reduced Ti3+ species. After 900℃ calcination, the specific surface CO2 production yield reached 12.13 mol/m2. The 13-PT900 sample exhibited the highest apparent quantum efficiency (AQE) of 0.052%. TEM and XRD results revelated that the phosphate species retarded structural transformation and crystallization of titania to maintain high surface areas. Moreover, phosphation increased CO2 adsorption of the catalysts. Pyridine-FTIR, NH3-TPD, and CO2-TPD analysis indicated that the phosphate species introduced Bronsted acid sites onto the surface and increased the fractions of weak acids. The increased amounts of the weak acid sites facilitated CO2 adsorption and favored CO2-to-CO converstion.

摘要 i
ABSTRACT ii
目錄 iii
表目錄 vi
圖目錄 vii
第一章 前言 1
1.1 研究動機與背景 1
1.2 研究目的 2
第二章 文獻回顧 3
2.1 TiO2光催化還原CO2 3
2.2 TiO2奈米管 (TNT) 6
2.3 磷酸化修飾 13
2.4 磷酸鹽修飾TiO2光催化反應機制 18
第三章 研究方法 21
3.1 實驗架構 21
3.2 實驗藥品 22
3.3 觸媒製備方法 23
3.3.1 質子化鈦酸鹽奈米管 23
3.3.2 磷酸化TiO2奈米管 23
3.4 光催化 CO2 還原氣相系統 24
3.5 材料鑑定分析 25
3.5.1 穿透式電子顯微鏡(Transmission Electron Microscopy-Energy Dispersive spectrum,TEM) 25
3.5.2 紫外光可見光分光光譜儀(UV-Vis Spectrophotometer) 25
3.5.3 等溫氮氣吸脫附分析儀(Nitrogen adsorption-desorption Isothermal analyzer) 26
3.5.4 X光粉末繞射儀(X-ray Powder Diffraction Spectrum, XRD) 26
3.5.5 化學分析電子儀(Electron Spectroscopy for Chemical Analysis , ESCA) 27
3.5.6 轉換紅外線光譜儀(Fourier Transform Infrared Spectrometer, FTIR) 27
3.5.7 溫度程控脫附儀(Temperature programmed desorption, TPD) 29
3.5.8 氣相層析儀(Gas Chromatography, GC) 30
3.5.9 電子順磁共振儀(Electron paramagnetic resonance, EPR) 31
第四章 結果與討論 32
4.1 光催化還原活性 32
4.2 基本特性 36
4.2.1 TEM微結構特性 36
4.2.1 XRD與BET結果 40
4.2.2 光學特性 42
4.3 表面特性 44
4.3.1 XPS 44
4.3.2 FTIR 48
4.4 酸性位址 50
4.4.1 pyridine-FTIR 50
4.4.2 NH3-TPD 52
4.5 CO2 吸附能力 54
第五章 結論 56
參考文獻 57
附錄 64

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