臺灣博碩士論文加值系統

氮氧化物的來源主要分為自然界及人為因素。自然界形成氮氧化物主要是來自於雷電、火災及微生物的固氮作用；人為活動主要係以燃燒行為所排放，而燃燒過程則來自於固定污染源(如發電廠、焚化爐等)及移動污染源(如汽機車)。氮氧化物不僅會造成人體的危害，可能會引起支氣管炎、肺氣腫，還會造成光化學煙霧、酸雨之形成及臭氧層破壞等環境危害。為了解決氮氧化物污染問題，本研究利用光催化技術，進行氮氧化物之降解，然而大多數半導體光催化劑存在著只能被紫外光激發，且易產生光生載流子容易複合等問題。
本研究利用簡單、低成本之水熱法製備出氮摻雜碳量子點(N-CQDs)，以檸檬酸及尿素作為碳源，再使用溶劑熱法，以SnCl4∙5H2O及C4H10O6Zn作為金屬源，成功合成出N-CQDs/ZnSn(OH)6/SnO2複合光催化劑，利用簡單且無二次污染之光催化反應，來降解氮氧化物，並進一步利用XRD、DRS、FTIR、ESR等儀器來進行特徵分析。實驗以不同pH值之前驅液及N-CQDs添加量之不同，於NO 400ppb之濃度下進行光催化降解實驗測試，以找尋最佳合成材料及實驗參數，並嘗試推論N-CQDs/ZnSn(OH)6/SnO2光催化劑對降解NO之反應機制。
實驗結果顯示，ZnSn(OH)6前驅液之pH會影響產物是否含有SnO2，且於400ppb之NO光催化降解實驗中，在可見光下，ZnSn(OH)6有無存在SnO2及引入N-CQDs之條件下，N-CQDs/ZnSn(OH)6/SnO2有36.6%之活性大於N-CQDs/ZnSn(OH)6之16.8%之活性；且在調整N-CQDs之添加量，以N-CQDs/ZnSn(OH)6/SnO2-600在可見光下具有最佳降解效果，達到35.5%之降解率及149.13ppb之去除量，且二氧化氮生成量幾乎為0ppb，這可以說明此催化劑不會產生二次污染物—二氧化氮是一個對環境友善之材料。N-CQDs之引入使其光觸媒可以利用可見光直接降解污染物，並在分解污染物過程中不易失活，且因為SnO2與ZnSn(OH)6之協同作用，使N-CQDs/ZnSn(OH)6/SnO2複合材料之催化活性為四種條件下最佳。

Source of Nitrogin Oxide mainly divided into nature and hunam factors. The formation of nitrogan oxides in nature is mainly caused by lighting, fire and microbial nitrogen fixation. Human activities are mainly emitted by combusion behavior, while the combustion process comes from stationary pollution sources (such as power plants, incinerators ,etc.) and mobile pollution sources (such as steam locomotive). Nitrogen oxides not only cause harm to the human body, but also may cause bronchitis, emphysema, and environmental hazards such as photochemical smog, acid rain, and ozone layer damage. In order to solve the problem of nitrogen oxide pollution, this study uses photocatalytic technology to degrade nitrogen oxides. However, most semiconductor photocatalysts can only be excited by ultraviolet light, and it is easy to produce photo-generated carriers that are easy to recombine.
In this study, N-CQDs were prepared by simple and low-cost hydrothermal method with citric acid and urea as carbon sources, and then N-CQDs/ZnSn(OH)6/SnO2 was successfully synthesized by using solvothermal method with SnCl4∙5H2O and C4H10O6Zn as metal sources. The composite photocatalyst utilizes a simple and non-primary photocatalytic reaction to degrade nitrogan oxides, and further utilizes XRD, DRS, FTIR, ESR and other instruments for feature analysis. Using different pH of precursor solution and different additions of N-CQDs to find the best synthetic materials and experimental parameters in experiment of removal NO at 400 ppb. Then discussed the reaction principle of N-CQDs/ ZnSn(OH)6/SnO2 photocatalyst on NO degrade.
The experimental results show that the pH of the ZnSn(OH)6 precursor affects whether the product contains SnO2, and in the 400 ppb NO photocatalytic degradation experiment, the presence or absence of SnO2 is observed in the visible light of ZnSn(OH)6. Under the conditions of introducing N-CQDs, 36.6% of the activity of N-CQDs/ZnSn(OH)6/SnO2 is greater than 16.8% of the activity of N-CQDs/ZnSn(OH)6; and the amount of N-CQDs added is adjusted. N-CQDs/ZnSn(OH)6/SnO2-600 has the best degradation effect under visible light, achieving a degradation rate of 35.5% and a removal of 149.13 ppb, and the production of nitrogen dioxide was almost 0 ppb.This suggests that the catalyst does not produce secondary contaminants - nitrogen dioxide. It is an environmentally friendly material. The introduction of N-CQDs enables its photocatalyst to directly degrade pollutants by visible light and is not easily deactivated during the decomposition of pollutants. Because of the synergistic action of SnO2 and ZnSn(OH)6, the catalytic activity of N-CQDs/ZnSn(OH)6/SnO2 composite is optimal under four conditions.

目錄
摘要 I
ABSTRACT II
目錄 IV
圖目錄 VI
表目錄 VIII
第一章、 緒論 1
1.1、 研究動機 1
1.2、 研究目的 3
1.3、 研究架構 4
第二章、 文獻回顧 5
2.1、 氮氧化物 5
2.1.1、 氮氧化物之危害 7
2.1.2、 氮氧化物處理技術 9
2.2、 光催化技術 12
2.3、 半導體光催化劑的反應機制 12
2.4、 提高光催化效率的方法 15
2.4.1、 貴金屬沉積 15
2.4.2、 離子摻雜 16
2.4.3、 表面光敏化 17
2.4.4、 半導體複合 17
2.5、 氫氧化錫酸鋅研究進展 18
2.5.1、 氫氧化錫酸鋅的結構特徵 19
2.5.2、 氫氧化錫酸鋅的光催化性質及應用性質 20
2.5.3、 氫氧化錫酸鋅的阻燃抑煙性質及應用 21
2.5.4、 氫氧化錫酸鋅材料製備方法 21
2.6、 碳量子點的研究進展 24
2.6.1、 碳量子點的結構特徵 24
2.6.2、 碳量子點的螢光性能 25
2.6.3、 光電荷轉移特性 26
2.7、 光催化應用 28
第三章、 實驗設備與方法 30
3.1、 研究架構 30
3.2、 材料製備與合成 32
3.2.1、 N-CQDs製備 32
3.2.2、 ZHS前驅液製備 32
3.2.3、 N-CQDs/ZHS複合光催化劑之合成 32
3.3、 實驗儀器之方法介紹 33
3.3.1、 紫外可見漫射光(UV-Vis reflective spectrum，DRS) 33
3.3.2、 X-射線繞射分析(X-ray diffraction，XRD) 34
3.3.3、 拉曼光譜(Raman spectra) 35
3.3.4、 傅立葉紅外光譜儀(FT-IR) 36
3.3.5、 X射線光電子能譜分析(XPS) 36
3.3.6、 光致發光光譜(PL) 37
3.3.7、 透射電子顯微鏡(TEM) 37
3.3.8、 比表面積和孔徑分析測試(BET) 38
3.3.9、 電化學阻抗譜(EIS) 38
3.3.10、 電子順磁共震波譜(ESR)測試 39
3.4、 光催化活性系統及性能測試 40
3.5、 光電化學性能測試 42
3.5.1、 光電極製備 42
3.5.2、 光電流 42
3.6、 實驗藥品及試劑 43
3.7、 實驗儀器 44
第四章、 結果與討論 46
4.1、 光催化劑特性分析 48
4.1.1、 紫外-可見漫反射吸收(UV-Vis reflective spectrum，DRS) 48
4.1.2、 X-射線繞射分析(X-ray diffraction，XRD) 50
4.1.3、 拉曼(Raman spectra) 53
4.1.4、 光催化效能測試結果 54
4.2、 N-CQDs添加量之特性分析 57
4.2.1、 紫外-可見漫反射吸收(UV-Vis reflective spectrum，DRS) 57
4.2.2、 X-射線繞射分析(X-ray diffraction，XRD) 59
4.2.3、 光催化效能測試結果 60
4.2.4、 穩定性測試 62
4.2.5、 FT-IR紅外光 65
4.2.6、 X射線光電子能譜分析(XPS) 67
4.2.7、 透射電子顯微鏡(TEM)分析 72
4.2.8、 比表面積和孔徑分析測試(BET) 75
4.2.9、 光致發光光譜(PL) 78
4.2.10、 光電流測試 79
4.2.11、 電化學阻抗譜(EIS) 80
4.2.12、 電子順磁共震波譜(ESR)測試 81
4.3、 N-CQDs/ZHS/SnO2光催化劑反應機制 84
第五章、 結果與討論 87
5.1、 結果 87
5.2、 建議 89
參考文獻 90

圖目錄
圖1.1、研究流程圖 4
圖2.1、半導體光催化劑反應機制 13
圖2.2、光催化分解水示意圖 14
圖2.3、ZnSn(OH)6的結構示意圖 19
圖2.4、激發依賴上轉換螢光發射光譜 26
圖2.5、CQDs及N-CQDs的紫外-可見光吸收光譜。插圖為在紫外光下（365 nm）CQDs和N-CQDs溶液的照片 27
圖3.1、實驗步驟 31
圖3.2、XRD塗片法示意圖 35
圖3.3、(a)蒸發皿、(b)反應艙規格 40
圖3.4、光催化降解NOX系統流程圖 41
圖4.1、不同pH值的前驅液所製備的ZHS之吸收光譜，插圖為樣品S吸收光譜 49
圖4.2、樣品S之XRD繞射譜圖 51
圖4.3、四種不同體系下之XRD繞射譜圖 51
圖4.4、N-CQDs之XRD繞射譜圖 52
圖4.5、ZHS之拉曼譜圖 53
圖4.6、不同體系下，可見光下光催化劑降解NO之效能測試 56
圖4.7、不同體系下，模擬太陽光下光催化劑降解NO之效能測試 56
圖4.8、Z-S及Z-S-C(200-800)奈米複合材料的紫外漫反射吸收光譜 58
圖4.9、Z-S及Z-S-C複合物之XRD繞射譜圖 59
圖4.10、Z-S及Z-S-C複合物之可見光下光催化劑降解NO之效能測試 61
圖4.11、可見光下樣品Z-S-C-600降解NO之循環壽命圖 63
圖4.12、可見光下樣品Z-S-C-600降解NO之穩定性測試 64
圖4.13、Z-S及Z-S-C-600奈米複合材料紅外譜圖 66
圖4.14、Z-S-C-600穩定性測試使用前後之FTIR分析 66
圖4.15、Z-S、Z-S-C-600及N-CQDs之XPS-Survey 69
圖4.16、Z-S及Z-S-C-600之Zn2p之高分辨電子光譜 69
圖4.17、Z-S及Z-S-C-600之Sn3d之高分辨電子光譜 70
圖4.18、Z-S、Z-S-C-600及N-CQDs之O1s之高分辨電子光譜 70
圖4.19、Z-S、Z-S-C-600及N-CQDs之C1s之高分辨電子光譜 71
圖4.20、Z-S、Z-S-C-600及N-CQDs之N1s之高分辨電子光譜 71
圖4.21、a)為Z-S，b)為Z-S-C-600，c)為Z-S-C-600，插圖為Z-S-C-600複合材料繞射棒之TEM分析；d)為Z-S，e)為Z-S-C-600複合材料表面N-CQDs，f)為Z-S-C-600表面SnO2之高分辨透射電鏡分析 73
圖4.22、Z-S-C-600之元素分析 74
圖4.23、(a)Z-S (b)Z-S-C-600之粒徑分佈圖 76
圖4.24、Z-S及Z-S-C-600之等溫吸附線 77
圖4.25、Z-S-C複合之光致發光譜 78
圖4.26、Z-S及Z-S-C-600之光電流實驗結果 79
圖4.27、Z-S及Z-S-C-600之交流阻抗圖 80
圖4.28、Z-S在可見光照射所形成之DMPO-OH之ESR光譜 82
圖4.29、Z-S-C-600在可見光照射所形成之DMPO-OH之ESR光譜 82
圖4.30、Z-S在可見光照射所形成之DMPO- ∙O2-之ESR光譜 83
圖4.31、Z-S-C-600在可見光照射所形成之DMPO- ∙O2-之ESR光譜 83
圖4.32、N-CQDs/ZHS/SnO2之反應機制圖 85


表目錄
表2.1、氮氧化物中英文、分子式及其性質對照表 5
表2.2、人體吸入不同濃度NO2之影響 8
表2.3、人體暴露於高濃度NO2之三階段反應 8
表2.4、氮氧化物之處理技術 9
表2.5、氫氧化錫酸鋅基本性質 18
表4.1、各樣品代號及前驅液pH值 47
表4.2、特性分析之儀器設備 47
表4.3、Z-S-C-600十次循環實驗分別對NO之降解效率及NO2之生成量 63
表4.4、Z-S及Z-S-C-600之XPS-Survey組成成分分析 68
表4.5、Z-S及Z-S-C-600之比表面積及孔體積 75

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