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研究生：	郭晏瑱 Kuo, Yen-Tien
論文名稱：	La1-xSrxMnO3粉末之鑑定及催化CO+NO反應之研究 Characterization of La1-xSrxMnO3 Powders and Their Catalytic Properties for the CO+NO Reaction
指導教授：	黃啟祥 Hwang, Chii-Shyang
學位類別：	碩士 Master
系所名稱：	工學院 - 材料科學及工程學系 Department of Materials Science and Engineering
論文出版年：	2003
畢業學年度：	91
語文別：	中文
論文頁數：	118
外文關鍵詞：	CO＋NO, La1-xSrxMnO3
相關次數：	點閱：59 下載：34
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廢氣中之氮氧化物及一氧化碳已成為目前空氣污染最主要的來源。為減少此等氣體，貴金屬以及鈣鈦礦結構之陶瓷粉末被研發作為其催化反應的觸媒。其中貴金屬粉末價格較昂貴且於高溫反應中易發生燒結現象；而鈣鈦礦型氧化物則有較佳之熱穩定性，且價格比較便宜，因而深受注目。本研究旨在合成鈣鈦礦結構之La1-xSrxMnO3觸媒粉末，並檢討Sr取代分率對觸媒特性及CO＋NO活性反應之影響。
La1-xSrxMnO3觸媒是以檸檬酸鹽法製備。Sr的添加可降低結晶性La1-xSrxMnO3的合成溫度。La1-xSrxMnO3觸媒之晶格常數與表面積是隨Sr含量的增加而增加；粒徑大小與結晶子大小則是隨Sr含量的增加而減小。Sr添加量少時（x≦0.15）合成的粉末僅含鈣鈦礦結構的晶相，Sr添加量增多時( x ≧0.2)，則除鈣鈦礦晶相外，亦含有SrCO3之晶相。
LaMnO3觸媒的活性可藉Sr的添加而提高，本研究中具有最佳活性的觸媒是La0.85Sr0.15MnO3，其可將CO + NO氣體轉化T90之溫度降至約400℃。氣體進料體積濃度比為CO：NO＝1：2時，La0.85Sr0.15MnO3觸媒在400℃下有較佳的轉化率。TPD、TPR及TPO之實驗結果顯示：La1-xSrxMnO3 ( x = 0 ~ 0.2 )觸媒催化CO及NO之反應是屬於氧化還原機制，且於反應中仍保持為鈣鈦礦結晶相。

NOx and CO removal from the combustion exhaust gases has become a serious environmental problem. In order to reduce these pollutants both noble metals and perovskite-type catalysts have been used. Compared to noble metals being expensive and having the sintered problem, perovskite oxides have better thermal stability and are cheaper, therefore it is noticeable in the last years. The aim of this study was to synthesize the perovskite catalyst of La1-xSrxMnO3, and to investigate the influence of Sr content on the characteristics and the activity for CO+NO reaction.

La1-xSrxMnO3 catalysts were prepared by the amorphous citrate method. Dopping Sr can reduce the temperature for synthesizing La1-xSrxMnO3 . The powder synthesized at 700℃ showed only one phase of La1-xSrxMnO3 perovskite for x≦0.15, and the other phases of SrCO3 for x≧0.2. The lattice parameters and specific surface area of La1-xSrxMnO3 increased and the particle sizes, crystalline sizes of La1-xSrxMnO3 decreased with an increase in the fraction of Sr.

The activity of LaMnO3 catalysts can be enhanced by dopping Sr. In this study, the La0.85Sr0.15MnO3 catalyst had the highest activity and with this catalyst, the temperature for complete conversion of CO＋NO could be down to 400℃. The catalyst also gave a higher conversion of CO into CO2 and NO into N2 at 400℃in the condition of CO：NO＝1：2 (volume ratio). The results of temperature programmed test showed that the La1-xSrxMnO3 (x = 0 ~ 0.2) catalysts for the CO+NO reaction was an oxidation-reduction mechanism and the catalysts after catalytic reaction preserved perovskite phase.

中文摘要...............................................Ⅰ
英文摘要...............................................Ⅱ
誌謝...................................................Ⅲ
目錄...................................................Ⅳ
表目錄.................................................Ⅶ
圖目錄.................................................Ⅷ
第一章 緒論.............................................1
1-1 前言................................................1
1-2 空氣污染之來源及其影響..............................2
1-3 一氧化碳的形成與特性及其影響........................3
1-3-1 一氧化碳的形成與特性..............................3
1-3-2 一氧化碳之影響....................................4
1-4 氮氧化物的形成與特性及其影響........................5
1-4-1 氮氧化物的形成與特性..............................5
1-4-2 氮氧化物之處理技術................................7
1-4-2-1 燃燒控制技術....................................7
1-4-2-2 後燃燒控制技術..................................9
1-5 觸媒的種類與特性比較...............................11
1-6 奈米材料之應用.....................................12
1-7 研究目的...........................................13
第二章 理論基礎與前人研究..............................19
2-1 微粒觸媒近代之研究.................................19
2-2 鈣鈦礦結構.........................................20
2-3 檸檬酸凝膠法.......................................22
2-3-1檸檬酸凝膠法之概述................................22
2-3-2檸檬酸錯化合物法反應機構..........................23
2-3-3檸檬酸凝膠法......................................24
2-3-4檸檬酸鹽法........................................24
2-3-5檸檬酸官能基......................................25
2-4 吸附理論...........................................26
2-4-1 物理吸附.........................................27
2-4-2 化學吸附.........................................27
2-5 催化...............................................28
2-5-1催化概述..........................................28
2-5-2 催化反應之特性...................................29
第三章 實驗方法與步驟..................................42
3-1 粉末製備流程.......................................42
3-2 觸媒粉末之製備.....................................43
3-2-1 起始原料.........................................43
3-2-2 混合.............................................43
3-2-3 乾燥與研磨.......................................43
3-2-4 煆燒處理.........................................43
3-3 觸媒活性測試.......................................44
3-3-1 設備說明.........................................44
3-3-2 實驗步驟.........................................45
3-4 觸媒物性與化性之鑑定...............................46
3-4-1 設備說明.........................................46
3-4-2 一氧化氮之程溫脫附...............................46
3-4-3 一氧化碳之程溫還原...............................47
3-4-4 一氧化氮之程溫氧化...............................48
3-5 性質分析及實驗設備.................................49
3-5-1 X射線繞射儀......................................49
3-5-2 自動氣相物理吸附儀...............................50
3-5-3 穿透式電子顯微鏡.................................50
3-5-4 掃瞄式電子顯微鏡.................................50
3-5-5 熱機械分析儀.....................................50
3-6 合成粉末之名稱.....................................51
第四章 結果與討論......................................64
4-1 相分析.............................................64
4-2 結晶粒徑大小.......................................64
4-3 粒子形態分析.......................................65
4-4 反應時間對觸媒粉體之影響...........................66
4-5 觸媒活性測試.......................................66
4-5-1 Sr部份取代La之含量對觸媒反應之影響...............66
4-5-2 不同進料濃度對觸媒反應之影響.....................69
4-6 一氧化氮程溫脫附實驗...............................70
4-7 一氧化碳程溫還原實驗...............................70
4-8 一氧化氮之程溫氧化實驗.............................71
4-9 程溫實驗前後觸媒之XRD分析..........................73
第五章 結  論.........................................108
未來研究方向..........................................110
參考文獻..............................................111
                                    

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