銦摻雜氧化鈰應用於二氧化碳脫氧反應的特性分析｜國立臺灣科技大學博碩士論文系統

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研究生：	江南蒨 Nan-Chian Chiang
論文名稱：	銦摻雜氧化鈰應用於二氧化碳脫氧反應的特性分析 Analysis of indium doped CeO2 for the oxygen stripping of CO2
指導教授：	林昇佃 Shawn D. Lin
口試委員:	游文岳 Wen-Yueh Yu 胡哲嘉 Chechia Hu 鍾博文 Po-Wen Chung
學位類別：	碩士 Master
系所名稱：	工程學院 - 化學工程系 Department of Chemical Engineering
論文出版年：	2023
畢業學年度：	111
語文別：	中文
論文頁數：	128
中文關鍵詞：	二氧化碳脫氧反應、氧化鈰、氧空缺
外文關鍵詞：	oxygen stripping of CO2, CeO2, oxygen vacancy
相關次數：	點閱：357 下載：1
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上一筆

本研究以共沉澱法合成具有氧空缺之不同摻雜量的 In、Sm 修飾 CeO2 進行 CO2 脫氧反應。首先鑑定觸媒對於 H2-TPR 和 CO2-TPO 的反應活性，CO2-TPO 結果顯示 SmyCe1-yOx 在測試溫度下無活性，In 摻雜 CeO2 樣品，In0.2Ce0.8Ox 與 In0.5Ce0.5Ox 在 400 °C 至 600 °C 有 CO2 脫氧反應活性，尤以 In0.5Ce0.5Ox 之 CO 產率最高。在重複反應條件與降低 H2 還原溫度之實驗均顯示 In0.2Ce0.8Ox 與 In0.5Ce0.5Ox 在相同溫度仍有相同的反應活性，其中 In0.5Ce0.5Ox 在重複兩次測試中仍舊維持近九成的 CO 產率且無積碳現象。XRD 結果顯示 SmyCe1-yOx 在反應前後維持相同的晶相，InyCe1-yOx 反應後由單晶相轉變為雙晶相，是為 H2- TPR 後出現之金屬 In0 提高觸媒之脫氧反應活性。由臨場紅外光譜儀分析經 700 °C H2 還原之 CeO2、In2O3、In0.5Ce0.5Ox、Sm0.5Ce0.5Ox 上的 CO2 程溫吸附，結果顯示在 CeO2、Sm0.5Ce0.5Ox 上的吸附強，但吸附 CO2 時表面穩定而無法遷移氧離子，而在 In2O3、In0.5Ce0.5Ox 上的吸附弱，且 In0.5Ce0.5Ox 有著和 In2O3 相似的吸附訊號，推論 CO2 脫氧反應的主要關鍵為結構中的 In，且 CO2 脫氧反應主要是由表面活性點的活性所決定。

In this study, we synthesized different ratio of Indium or Samarium doped CeO2 with oxygen vacancies by coprecipitation method. CO2-TPO results shows SmyCe1-yOx has no activity while In0.2Ce0.8Ox and In0.5Ce0.5Ox have CO2 deoxygenation from 400 °C to 600 °C. From 2 cycle test and reducing temperature of H2-TPR, In0.2Ce0.8Ox and In0.5Ce0.5Ox still have similar activity. There is no significant carbon deposition and almost 90% CO yield of In0.5Ce0.5Ox. XRD results shows that after CO2-TPO, SmyCe1-yOx has same crystal phase, while InyCe1-yOx has two separated phases. In-situ FTIR is used to analyze CO2 temperature-programmed adsorption on H2 reduced CeO2, In2O3, In0.5Ce0.5Ox, and Sm0.5Ce0.5Ox. CO2 adsorption on CeO2 and Sm0.5Ce0.5Ox are strong, however, catalysts surface are stable and has low oxygen mobility. CO2 adsorption on In2O3 and In0.5Ce0.5Ox are strong while there are similar peaks. It is suggested that metallic Indium appearing after H2-TPR enhanced deoxygenation activity.

摘要 ............................................................................................................I Abstract..................................................................................................... II
誌謝 ......................................................................................................... III
目錄 .........................................................................................................IV
圖目錄 .................................................................................................. VIII
表目錄 ................................................................................................... XII
第 1 章、 緒論 ....................................................................................... 1
1 前言.................................................................................................1
2 文獻回顧.........................................................................................2
2.1 CO2 轉化技術 ............................................................................ 2
2.2 CeO2 材料及摻雜物對氧空缺性質之影響 .............................. 4
2.3 CeO2 材料用於 CO2 轉化反應 .................................................. 6
3 研究目的.........................................................................................7
第 2 章、 實驗設備與方法 ................................................................... 8
1 實驗架構.........................................................................................8
2 藥品與儀器設備.............................................................................8
2.1 藥品...........................................................................................8
2.2 氣體...........................................................................................9
2.3 使用儀器.................................................................................... 9
3 觸媒製備.......................................................................................11
3.1 共沉澱法(Co-Precipitation)製備InyCe1-yOx觸媒.................11
3.2 共沉澱法(Co-Precipitation)製備SmyCe1-yOx觸媒...............11
4 觸媒特性分析方法.......................................................................13
4.1 X 光繞射儀 (XRD)................................................................. 13
4.2 表面積與孔隙度測定儀.........................................................13
4.3 程溫還原反應 Temperature Programmed Reduction (TPR) 14
4.4 質譜儀 (Mass Spectrometer, MS) ......................................... 15
4.5 熱重分析儀 (ThermogravimetricAnalyzer,TGA)...............16
4.6 臨 場 紅 外 線 光 譜 儀 (In-situ Fourier Transform Infrared
Spectroscopy).................................................................................... 16
4.7 X 射線光電子能譜儀 (X-ray Photoelectron Spectroscopy, XPS) ........................................................................................................... 17
5 CO2 脫氧反應測試實驗流程 ....................................................... 18
第 3 章、 結果與討論 ......................................................................... 19
1 摻雜成分對CeO2之CO2脫氧活性影響....................................19
1.1 結構特性分析.........................................................................19
1.2 H2-TPR 與 CO2-TPO 反應測試 .............................................. 31
2 觸媒氧氣空缺生成與活性的重複測試.......................................37
2.1 H2-TPR 900 °C/ CO2-TPO 700 °C 2 次循環測試 .................. 37
2.2 以 H2-TPR 700 °C/ CO2-TPO 700 °C 條件進行 2 次循環測試 ........................................................................................................... 42
3 CO2 脫氧反應測試前後觸媒結構特性變化 ................................ 48
4 觸媒於 CO2 脫氧反應活性之特性分析 ....................................... 68
4.1 臨場紅外線光譜應用於CO2脫氧反應分析........................69
4.1.1 CO2 於 CeO2 表面的吸附分析 ......................................... 69
4.1.2 CO2 於 In2O3 表面的吸附分析 ......................................... 74
4.1.3 CO2 於 In0.5Ce0.5Ox 吸附分析............................................ 78
4.1.4 CO2 於 Sm0.5Ce0.5Ox 吸附分析.......................................... 80
4.2 氧離子傳導性文獻分析.........................................................85
4.3 In2O3 導電性文獻分析 ............................................................ 93
第 4 章、 結論 ..................................................................................... 95
參考文獻 ................................................................................................. 97
第 5 章、 附錄 ................................................................................... 105
                                

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