駱尚廉臺灣大學:環境工程學研究所洪健豪Hong, Jian-HaoJian-HaoHong2010-05-102018-06-282010-05-102018-06-282008U0001-1407200813503700http://ntur.lib.ntu.edu.tw//handle/246246/181536利用光觸媒對氨氮進行光催化降解實驗，已被證實是一具可行性之處理方式，效率高且極具經濟性。因此本研究嘗試利用具ㄧ維結構與離子交換能力之氧化鈦奈米管作為光觸媒載體，選定Ni、Pd、Pt對其進行改質，評估金屬的不同屬性與負載比例改變對水中氨氮光催化降解效率之影響，以及產物之分布影響，後續並探討其反應機制。 當以Pd/TNTs與Pt/TNTs為光觸媒時，負載比例的提升，可有效增加光催化降解效率，且未見遮蔽效應之產生；除了顯示Pd與Pt適合作為氧化鈦奈米管之負載金屬外，無遮蔽效應的產生可歸因於氧化鈦奈米管獨特之離子交換特性。而當以Ni/TNTs為光觸媒時，負載比例的提升僅會使氨氮降解速率下降；推測Ni並無法有效抑制電子電洞對的再結合，反而因其本身佔據氧化鈦奈米管之活性位置，導致離子交換與吸附能力的下降與遮蔽效應的主導。 在產物分佈方面，Pd/TNTs傾向於生成亞硝酸鹽與硝酸鹽，當負載比例提升至某一程度，則會產生部分氮氣，但此時亞硝酸鹽與硝酸鹽仍為主要生成產物。Pt/TNTs相對於其它金屬負載型氧化鈦奈米管而言，在高負載比例情況下對氨氮有非常好的離子交換與吸附能力，此可能為Pt/TNTs高度選擇性光催化水中氨氮為氮氣之原因，以30% Pt/TNTs為例，有高達87.8%的氮氣產率，但確實之反應機制仍需藉由分析修飾觸媒之表面特性來加以確認。The photocatalytic oxidation technology applied on the removal of ammonia in water has been proved to be an effective and economical treatment process. Therefore in this research we chose titania nanotubes (TNTs) which have one-dimensional structure and ion exchangeability as photocatalyst. Meanwhile nickel, palladium and platinum were chose for modifying its surface. The effects of kind of metal, loading amount on degradation efficiency of ammonia and distribution of products were examined. Finally, we discussed the reaction mechanism. When Pd/TNTs and Pt/TNTs were used as photocatalysts, the degradation efficiency of ammonia increased with the increase of loaded amount, indicating palladium and platinum are applicable to modify titania nanotubes surface. Also, there were no shielding effect occurred in this two case. It can be ascribed to the ion exchangeability of titania nanotubes. When Ni/TNTs were used as photocatalyst, the degradation efficiency of ammonia decreased with the increase of loaded amount. We supposed nickel loaded on titania nanotubes could not suppress the recombination of photo-holes and photo-electrons, but occupied active sites of titania nanotubes instead to result in the decrease of ion exchangeability and adsorption capacity. So inhibiting effect dominated the overall reaction in the case of Ni/TNTs. Pd/TNTs prefer the formation of nitrite and nitrate regarding the distribution of products. Moreover, the loaded amount increased to a certain extent would lead to a few yield of nitrogen gas, yet nitrite and nitrate were still their primary products. Pt/TNTs with high loaded amount have good ion exchangeability and adsorption capacity for ammonia in comparison with the other two metal-loaded titania nanotubes. It may be the reason that Pt/TNTs are highly selective to produce nitrogen gas in the photocatalytic oxidation of ammonia. Take 30% Pt/TNTs for example, its yield of nitrogen gas was up to 87.8%. However, the actual reaction mechanism should be confirmed by analyzing surface property of metal-loaded titania nanotubes.摘要 ibstract ii錄 iv目錄 vii目錄 ix一章 緒論 1-1 研究緣起 1-2 研究目的 2-3 研究內容 2二章 文獻回顧 3-1 氨氮簡介 3-1-1 氨的物化性質 3-1-2 氨氮的來源 6-1-3 氨氮的危害 7-2 光反應 10-2-1 光反應種類 10-2-2 氨氮的光催化技術 12-3 氧化鈦奈米管 14-3-1 氧化鈦奈米管之製備 14-3-2 氧化鈦奈米管酸洗影響 15-3-3氧化鈦奈米管之離子交換與吸附 16-3-4 氧化鈦奈米管之光催化特性 16三章 實驗方法與材料 18-1 實驗設計 18-2 實驗藥品與設備 18-2-1 藥品 18-2-2 設備 20-3 實驗方法與內容 22-3-1 反應材料之製備 22-3-2 背景實驗 23-3-3 液相氨氮光催化反應實驗 24-3-4 偵測氮氣實驗 25-3-5 亞硝酸鹽光催化反應實驗 25-4 分析系統與設備 26-4-1 觸媒物性化性分析 26-4-2 污染物與產物定量分析 28四章 結果與討論 31-1背景實驗 31-1-1 微波型TNTs之合成功率選擇 31-1-2 氨氮揮發實驗 33-1-3 直接光解實驗 34-1-4 金屬修飾氧化鈦奈米管之TPR實驗 35-2 金屬修飾之氧化鈦奈米管對氨氮降解之光催化反應實驗 38-2-1 Pd/TNTs對氨氮降解之光催化反應實驗 38-2-2 Pt/TNTs對氨氮降解之光催化反應實驗 46-2-3 Ni/TNTs對氨氮降解之光催化反應實驗 52-2-4 不同光催化劑對氨氮降解實驗之比較 57-3 氮氣偵測實驗 60-4 金屬修飾之氧化鈦奈米管對亞硝酸鹽之光催化反應實驗 63-5 氨氮之光催化氧化反應機制探討 66五章 結論與建議 70-1 實驗結論 70-2 建議研究方向 72六章 參考文獻 73錄 實驗數據 79application/pdf2611525 bytesapplication/pdfen-US氨氮金屬負載光催化氧化鈦奈米管二氧化鈦ammoniametal-loadedphotolysistitania nanotubestitanium dioxidethesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/181536/1/ntu-97-R95541119-1.pdf