臺灣博碩士論文加值系統

本實驗的目的在於研究鉀添加或物理混合對含鉻、錳、釔或鈰之無電鍍銅觸媒在一氧化碳氧化反應之影響。觸媒是以Al2O3為擔體，而銅含量固定在15wt%，添加劑則從1%到5%不等。在觸媒表面特性的研究上，本實驗以程式升溫的方法來測試一系列無電鍍銅觸媒之活性，並以TPR、N2O化學吸附、XRD、SEM等來作分析。
程溫反應結果顯示，鉀的添加對於含鉻、錳之無電鍍銅觸媒在一氧化碳氧化反應上均有負面作用，且對銅錳觸媒影響較大。TPR結果顯示鉀的添加會使無電鍍銅觸媒的還原波峰，變的低矮而且有拖尾(tailing)的情況，且鉀添加量越多，還原溫度會拖的越長，且還原波峰往有高溫移動的現象，顯示鉀添加後，銅觸媒需要更高的溫度才能完全還原。N2O化學吸附及XRD結果證實鉀的添加會降低銅金屬的分散性、使銅晶粒變大、銅表面積減少，尤其當鉀添加量增加到3%時，分散性降低的情形最為明顯。
在添加鉻、錳、鈰、釔之無電鍍銅觸媒與鉀物理混合後之反應結果顯示，物理混合鉀有促進一氧化碳氧化反應之效果，這是因為鉀可增加觸媒供給電子的能力，使得具
有很強之拉電子能力之氧氣吸附。不管其添加劑含量寡，物理混合鉀量越多，促進效果越大;但其中對含鈰之無電鍍
銅觸媒的促進效果最大，此因鈰具氧空洞為導氧離子的緣故。

The purpose of this study is to investigate the effect of potassium
addition or potassium physical mixing on the additive(Cr, Mn, Y or Ce) added electroless copper catalyst for CO oxidation. γ-Al2O3 was used as support and 15wt% copper loading was chosen as a base for the catalysts. The content of the additives varied from 1% to 5%. All the catalysts with potassium addition were characterized by TPR, N2O Chemisorption, XRD and SEM.
When potassium was coimpregnated with the additive on the electroless copper catalyst, it was found from CO oxidation results that the potassium addition presented negative effect on the catalyst activity , especially for the Cu-Mn catalyst. The TPR profiles indicate
that the addition of potassium would reduce the hight of TPR curve and caused the TPR peak shifting to higher temperature, suggesting that the addition of potassium makes the copper oxide reduction more difficulty. It is also evidence from chemisorption data and XRD spectrum that the addition of potassium would cause copper sintering
, especially when 3% potassium was added into the catalyst .
When potassium was physically mixed with the additive added electroless copper catalyst, CO oxidation data showed that physical
mixing of potassium has provided quite good promoting effect on the copper catalyst for CO oxidation , The more potassium was mixed, the better promoting effect would be obtain. Among the four additive added electroless copper catalysts , Cu-Ce catalyst obtained the most effective promotion in activity from potassium due to their oxygen-conduction nature.

目 錄
摘要…………………………………………………………….I
英文摘要………………………………………………..……III
目錄……………………………………………………………V
圖表索引…………………………………………………..VIII
符號說明………………………………………..……….… X
第一章 緒論………………………………………………….1
第二章 文獻回顧……………………………………………..5
2.1一氧化碳氧化反應觸媒之演進………..….………….5
2.2無電鍍銅觸媒的發展過程……………………………8
2.3金屬添加劑對銅觸媒之影響…………………..……11
2.3.1第一列過渡元素金屬……………………….…11
2.3.2其他金屬添加劑………………………………..14
2.4鉀對觸媒之影響………………………………..…….16
2.5程式升溫還原(TPR)………………………..….…….18
2.6銅表面積之測量…………………………….…..……20
第三章 實驗方法與步驟………………………….…..……23
3.1實驗藥品、氣體與儀器設備…………….…………..23
3.1.1藥品………………………………..……….…..23
3.1.2氣體……………………………………………..24
3.1.3儀器設備…………………………………….…24
3.2觸媒的製備…………………………………………..25
3.2.1無電鍍銅觸媒的製備…………..………..…25
3.2.2修飾性無電鍍銅觸媒的製備……….….……26
3.3觸媒特性的鑑定…………………..………….………27
3.3.1 X光繞射分析(XRD)……………….…………27
3.3.2掃瞄式電子顯微鏡(SEM)……………...……29
3.3.3程式升溫還原(TPR)…………………….……30
3.3.4化學吸附測定銅表面積………………...……31
3.4觸媒反應裝置與反應步驟…………………..….…..32
3.4.1反應裝置…………………………….…………32
3.4.2反應條件…………………………….…………33
3.4.3反應步驟…………………………….…………33
3.4.4轉化率的計算………………………..……..…33
第四章 實驗結果與討論………………….…….………….35
4.1共含浸鉀之無電鍍銅系列觸媒……….…..………..35
4.1.1一氧化碳氧化反應……………………….……36
4.1.2程溫還原(TPR)………………………………....45
4.1.3金屬銅表面積測量（化學吸附分析）………..51
4.1.4 X-Ray繞射分析(XRD)………………………..59
4.1.5掃瞄式電子顯微鏡(SEM)…………………….63
4.2無電鍍銅觸媒與鉀物理混合之結果……………….69
4.2.1程溫還原(TPR)…………………………………69
4.2.2一氧化碳氧化反應…………………………….72
第五章 結論……………………………………………….85
參考文獻…………………………………………………….88

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