臺灣博碩士論文加值系統

本研究開發石墨型碳氮化物(Graphitic carbon nitride, g-C3N4)複合α-硫 (cyclooctasulfur, α-Sulfur)及還原氧化石墨烯(reduced graphene oxide, RGO)之奈米光觸媒複合材料(CNRGOS8)，利用批次式反應器光催化處理染料羅丹明B(Rhodamine, RhB)與四環素(Tetracyclines, TC)，做為觸媒之光活性測試。研究中探討pH值、複合相觸媒混合比例、光觸媒加藥量等操作參數對於RhB與TC分解之影響，且進一步求得RhB與TC分解之反應動力模式及反應速率常數。
結果顯示，複合材料中以CNRGOS8(70:5:25)具最佳催化效果，光催化處理RhB的實驗結果在pH 3具最佳的降解效果；而TC則以pH 7有最佳的降解效果。此外，循環光降解去除污染物的效率在5個循環後，降解速率幾乎沒有任何影響，顯示CNRGOS8(70:5:25)複合材料的結構穩定性佳。為檢測光催化反應途徑及機制，通過加入2-Propanol (·OH的捕捉劑)、benzoquinone (O2•－的捕捉劑)和sodium oxalate (h+ 的捕捉劑)，發現主要降解污染物之活性物種為超氧自由基，其次為羟基自由基。
環境中天然有機物質(如腐植酸(humic acid, HA))於環境水體之存在廣泛，故可能與污染物共存，進而影響光觸媒處理污染物之效率與反應途徑，於本研究測試中，發現腐植酸之存在可加速傳遞導帶電子生成活性氧化物種，唯其同時與污染物競爭觸媒材料的反應位點，故使污染物整體去除效率遭到抑制。

A visible-light-driven graphitic carbon nitride/reduced graphene oxide/α-Sulfur composite (CNRGOS8) was synthesized as efficient photocatalysts for environmental applications. The photocatalytic reactivity of the fabricated CNRGOS8 was determined by the degradation of Rhodamine B (RhB) and tetracycline (TC). The effects of pH, mixed ratio of catalysts, dosage of photocatalyst were optimized, and the reaction kinetics and reaction pathway were studied.
The results indicated the optimized pH values for RhB and TC degradation was 3 and 7, respectively. In addition, no deterioration of the efficiency was found for CNRGOS8 (70:5:25) after 5 cycles of operation. Such a result was indicative of a prolonged lifetime of the CNRGOS8 (70:5:25). With probing by the scavengers, 2-Propanol (·OH capture reagent), benzoquinone (O2•－ capture reagent) and sodium oxalate (h+ capture reagent), the major reactive species were identified as superoxide radicals and hydroxyl radicals.
The abundant natural organic matter such as humic acid (HA) oftentimes coexists with the pollutants in the aquatic environment, which may affect the efficiency and alter reaction pathways of photodegradation of the pollutants. An enhanced electron transfer and reactive oxide species production were found for CNRGOS8 (70:5:25) in the presence of humic acid. However, the overall removal efficiency of the pollutants was suppressed due to the competition between CNRGOS8 (70:5:25) and the coexisting HA for the active sites.

摘要 i
Abstract ii
目錄 iii
圖目錄 vii
表目錄 xiv
第一章 緒論 1
1-1 研究緣起 1
1-2 研究內容與目標 2
第二章 文獻回顧 3
2-1 石墨型碳氮化合物之特性 3
2-1-1 石墨型碳氮化合物之結構 3
2-1-2 石墨型碳氮化合物之製備與改質 5
2-2 光催化反應 6
2-2-1 光催化之基本原理 6
2-2-2 石墨型碳氮化合物之光催效果 6
2-3 染整廢水 8
2-3-1 染整廢水之危害 8
2-3-2 染料廢水之處理技術 9
2-4 新興污染物之影響 10
2-4-1 四環素 10
2-4-2 四環素之光催化處理效果 11
第三章 實驗方法與設備 12
3-1 實驗架構 12
3-2 實驗藥品與材料 13
3-3 實驗設備與分析儀器 14
3-4 實驗內容與方法 16
3-4-1 g-C3N4 /RGO/α-Sulfur (CNRGOS8)複合光觸媒製備 16
3-4-2 光催化實驗 20
3-5 分析項目及方法 24
3-5-1 觸媒特性分析 24
3-5-2 水樣品分析 30
第四章 結果與討論 31
4-1 光觸媒特性分析 31
4-1-1 材料表面形貌分析-SEM 31
4-1-2 材料表面形貌分析-TEM 40
4-1-3 比表面積分析儀(BET) 45
4-1-4 高解析X光繞射分析(XRD) 47
4-1-5 傅立葉紅外線光譜儀(FTIR) 49
4-1-6 電子能譜分析(XPS) 51
4-1-7 紫外光可見光光譜分析 57
4-1-8 螢光光譜分析(FL) 62
4-1-9 界面電位分析(Zeta) 64
4-2 可見光光催降解實驗 66
4-2-1 直接光解實驗 66
4-2-2 不同製備法之光觸媒光催化實驗 71
4-2-3 不同組成光觸媒之光催化實驗 72
4-2-4 不同比例之光觸媒實驗 74
4-2-5 不同初始pH之光觸媒實驗 76
4-2-6 最佳加藥量實驗 78
4-2-7 四環素降解 79
4-2-8 重複性實驗 80
4-2-9 可見光催化下活性物種測試實驗 82
4-2-10 環境中存在有機陰離子之實驗 84
4-3 電化學實驗 86
4-3-1 不同組成/不同比例之光觸媒EIS 86
4-3-2 不同組成/不同比例之光觸媒CV 87
4-3-3 Mott−Schottky plots 實驗 89
4-3-4 不同比例光觸媒之光電流實驗 91
4-4 環境中的天然有機物(HA)之存在 92
4-4-1 單獨HA對RhB之不同初始pH值之UV光下光催降解 92
4-4-2 紫外/可見光與可見光下光催降解比較 94
4-4-3 不同pH值之有無存在HA之光催降解 96
4-4-4 探討添加HA之RhB降解途徑 97
4-4-5 光觸媒降解RhB與TC之機制途徑 105
第五章 結論 107
第六章 參考文獻 109

 
圖目錄
圖2-1石墨型碳氮化物之製備 4
圖2-2石墨型碳氮化物之多功能表面性質 4
圖2-3異質光催化 7
圖2-4四環素之結構圖 11
圖3-1實驗架構圖 12
圖3-2 層疊包覆法合成之CNRGOS8複合光觸媒製備流程圖 18
圖3-3 水熱法合成之CNRGOS8複合光觸媒製備流程圖 19
圖3-4光催化實驗流程 21
圖4-1 CN之10,000倍SEM圖 32
圖4-2 CN之50,000倍SEM圖 32
圖4-3 S8之5,000倍SEM圖 33
圖4-4 S8之10,000倍SEM圖 33
圖4-5 RGO之10,000倍SEM圖 34
圖4-6 RGO之50,000倍SEM圖 34
圖4-7 CNRGOS8(25:5:70)光觸媒之5,000倍SEM圖 35
圖4-8 CNRGOS8(47.5:5:47.5)光觸媒之5,000倍SEM圖 35
圖4-9 CNRGOS8(70:5:25)光觸媒之5,000倍SEM圖 36
圖4-10 CNRGOS8(90:5:5)光觸媒之5,000倍SEM圖 36
圖4-11 CNRGOS8(25:5:70)光觸媒之50,000倍SEM圖 37
圖4-12 CNRGOS8(47.5:5:47.5)光觸媒之50,000倍SEM圖 37
圖4-13 CNRGOS8(70:5:25)光觸媒之50,000倍SEM圖 38
圖4-14 CNRGOS8(90:5:5)光觸媒之50,000倍SEM圖 38
圖4-15 CNRGOS8(70:5:25)光觸媒之Mapping圖 39
圖4-16 CN材料之TEM圖 40
圖4-17 RGO之TEM圖 41
圖4-18 CNRGO複合材料之TEM圖 41
圖4-19 CNS8複合材料之TEM圖 42
圖4-20 RGOS8複合材料之TEM圖 42
圖4-21 CNRGOS8(25:5:70)複合材料之TEM圖 43
圖4-22 CNRGOS8(47.5:5:47.5)複合材料之TEM圖 43
圖4-23 CNRGOS8(70:5:25)複合材料之TEM圖 44
圖4-24 CNRGOS8(90:5:5)複合材料之TEM圖 44
圖4-25不同比例之氮吸附等溫線圖比較 45
圖4-26 (a)CNRGOS8 (25:5:70) (b)CNRGOS8 (47.5:5:47.5) (c)CNRGOS8 (70:5:25) (d)CNRGOS8 (90:5:5)之氮吸附等溫線圖 46
圖4-27 半導體材料之XRD圖譜 48
圖4-28 複合材料之XRD圖譜 48
圖4-29半導體材料之FTIR圖譜 50
圖4-30複合材料之FTIR圖譜 50
圖4-31(a)CN(b)CNRGOS8 (25:5:70) (c)CNRGOS8 (47.5:5:47.5) (d)CNRGOS8 (70:5:25) (e)CNRGOS8 (90:5:5)之XPS全譜圖 52
圖4-32 (a)CN(b)CNRGOS8 (25:5:70) (c)CNRGOS8 (47.5:5:47.5) (d)CNRGOS8 (70:5:25) (e)CNRGOS8 (90:5:5)之C1s XPS圖譜 53
圖4-33 (a)CN(b)CNRGOS8 (25:5:70) (c)CNRGOS8 (47.5:5:47.5) (d)CNRGOS8 (70:5:25) (e)CNRGOS8 (90:5:5)之N1s XPS圖譜 54
圖4-34 (a)CNRGOS8 (25:5:70) (b)CNRGOS8 (47.5:5:47.5) (c)CNRGOS8 (70:5:25) (d)CNRGOS8 (90:5:5)之S2p XPS圖譜 55
圖4-35不同製備方法之光觸媒紫外光/可見光光譜圖 59
圖4-36不同製備方法之光觸媒能能隙圖 59
圖4-37不同組成之光觸媒紫外光/可見光光譜圖 60
圖4-38不同組成之光觸媒能隙圖 60
圖4-39不同比例之光觸媒紫外光/可見光光譜圖 61
圖4-40不同比例之光觸媒能隙圖 61
圖4-41不同製備方法之光觸媒螢光光譜圖 62
圖4-42不同組成之光觸媒螢光光譜圖 63
圖4-43 不同比例之光觸媒螢光光譜圖 63
圖4-44 (a)CNRGOS8 (25:5:70) (b)CNRGOS8 (47.5:5:47.5) (c)CNRGOS8 (70:5:25) (d)CNRGOS8 (90:5:5)之界面電位分析 65
圖4-45 RhB之界面電位分析 [1] 65
圖4-46 RhB之檢量線(吸光值 = 554 nm) 67
圖4-47 TC之檢量線(吸光值 = 358 nm) 67
圖4-48在可見光下之RhB直接光解(RhB = 10 ppm, pH = 3) 68
圖4-49 在紫外/可見光下之RhB直接光解(RhB = 10 ppm, pH = 3) 68
圖4-50在可見光下之TC直接光解(TC = 10 ppm, pH = 7) 69
圖4-51在pH值(3, 7, 9)之RhB紫外光/可見光光譜圖 69
圖4-52在可見光下之RhB紫外光/可見光光譜圖 70
圖4-53不同製備方法之光催化比較(Catalysts = 0.4 g/L, RhB = 10 ppm) 71
圖4-54不同組成光觸媒之光催化比較(Catalysts = 0.4 g/L, RhB = 10 ppm, pH = 7.0) 73
圖4-55不同組成光觸媒之光催化比較k值 73
圖4-56不同比例之光觸媒光催比較(Catalysts = 0.4 g/L, RhB = 10 ppm, pH = 7.0) 75
圖4-57不同比例之光觸媒光催比較k值 75
圖4-58不同初始pH之光觸媒光催比較(Catalysts = 0.4 g/L, RhB = 10 ppm, pH = 2, 3, 5, 7, 9, 11) 77
圖4-59不同初始pH之光觸媒光催比較k值 77
圖4-60 最佳加藥量實驗(RhB = 10 ppm, pH = 3.0) 78
圖4-61不同初始pH之光觸媒光催比較(Catalysts = 0.4 g/L, 四環素 = 10 ppm, pH = 3, 7, 9) 79
圖4-62 CNRGOS8(70:5:25)之重複性實驗(Catalysts = 0.4 g/L, RhB = 10 ppm, pH = 3.0) 80
圖4-63 CNRGOS8(70:5:25)之重複性實驗(Catalysts = 0.4 g/L, 四環素 = 10 ppm, pH = 7.0) 81
圖4-64 CNRGOS8(70:5:25)光催化降解反應前後之FTIR圖譜 81
圖4-65光催降解之活性物種試驗(Catalysts = 0.4 g/L, RhB = 10 ppm, SO = 1 mM, BQ = 1 mM, IPA = 1 mM, K2Cr2O7= 1 mM, pH = 3.0) 83
圖4-66光催降解之活性物種試驗(Catalysts = 0.4 g/L, 四環素 = 10 ppm, SO = 1 mM, N2, IPA = 1 mM, K2Cr2O7= 1 mM, pH = 7.0) 83
圖4-67光催降解之活性物種試驗(a) RhB (b) TC(Catalysts = 0.4 g/L, RhB&TC = 10 ppm, SO = 1 mM, N2, BQ = 1 mM, IPA = 1 mM, K2Cr2O7= 1 mM) 83
圖4-68在可見光下存在不同有機陰離子(NaHCO3, NaCl, Na2SO4, NaNO3, KH2PO4 = 5 mM)之光催實驗(Catalysts = 0.4 g/L, RhB = 10 ppm, pH = 7.0) 85
圖4-69在可見光下存在不同有機陰離子之k值 85
圖4-70 不同組成之光觸媒EIS比較(Electrolyte = 10 mM赤血鹽含0.1 M KCl, Frequency = 0.1Hz~100kHz) 86
圖4-71不同比例之光觸媒EIS比較(Electrolyte = 10 mM赤血鹽含0.1 M KCl, Frequency = 0.1Hz~100kHz) 87
圖4-72不同組成之光觸媒CV比較(Electrolyte = 10 mM赤血鹽含0.1 M KCl, Scan rate = 0.01 V/s) 88
圖4-73不同比例之光觸媒CV比較(Electrolyte = 10 mM赤血鹽含0.1 M KCl, Scan rate = 0.01 V/s) 88
圖4-74 Mott−Schottky plots CN(Electrolyte = 0.5 M Na2SO4, Init = -0.64 V, Frequency = 2 kHz) 89
圖4-75 Mott−Schottky plots S8(Electrolyte = 0.5 M Na2SO4, Init = -0.73 V, Frequency = 2 kHz) 90
圖4-76 Mott−Schottky plots CNRGOS8(70:5:25) (Electrolyte = 0.5 M Na2SO4, Init = -0.64 V, Frequency = 2 kHz) 90
圖4-77不同比例光觸媒之光電流比較(-0.5 V vs. Ag/AgCl) 91
圖4-78不同比例光觸媒之光電流比較(-0.5 V vs. Ag/AgCl) 91
圖4-79 HA對RhB之光催降解(RhB = 10 ppm, HA = 10 ppm, pH = 3, 7, 9) 93
圖4-80 HA對RhB之光催降解k值 93
圖4-81在紫外/可見光與可見光下之RhB降解比較(Catalysts = 0.4 g/L, RhB = 10 ppm, HA = 10 ppm, pH = 3) 94
圖4-82在紫外/可見光與可見光下之RhB降解比較(Catalysts = 0.4 g/L, RhB = 10 ppm, HA = 10 ppm, pH = 7) 95
圖4-83在紫外/可見光與可見光下之RhB降解比較(Catalysts =0.4 g/L, RhB = 10 ppm, HA = 10 ppm, pH = 9) 95
圖4-84在可見光下有無HA之RhB降解比較；插圖:暗反應下有無HA之RhB降解比較(Catalysts = 0.4 g/L, RhB = 10 ppm, HA = 10 ppm, pH = 3, 7, 9) 96
圖4-85 CNRGOS8(70:5:25)之·OH產量(Catalysts = 0.4 g/L, pH = 3, 7, 9) 97
圖4-86有無添加HA之·OH產量(Catalysts = 0.4 g/L, pH = 3) 98
圖4-87有無添加HA之·OH產量(Catalysts = 0.4 g/L, pH = 7) 98
圖4-88有無添加HA之·OH產量(Catalysts =0.4 g/L, pH = 9) 99
圖4-89 CNRGOS8(70:5:25)之O2•－產量(Catalysts = 0.4 g/L, pH = 3, 7, 9) 100
圖4-90有無添加HA之O2•－產量(Catalysts = 0.4 g/L, pH = 3) 100
圖4-91有無添加HA之O2•－產量(Catalysts = 0.4 g/L, pH = 7) 101
圖4-92有無添加HA之O2•－產量(Catalysts = 0.4 g/L, pH = 9) 101
圖4-93照光前後之CB e-產量(Catalysts = 20mg/mL, pH = 3) 102
圖4-94照光前後之CB e-產量(Catalysts = 20m g/mL, pH = 7) 103
圖4-95照光前後之CB e-產量(Catalysts = 20m g/mL, pH = 9) 103
圖4-96有無添加HA之CB e-產量(Catalysts = 20m g/mL, HA = 10 ppm, pH = 3) 104
圖4-97有無添加HA之CB e-產量(Catalysts = 20m g/mL, HA = 10 ppm, pH = 7) 104
圖4-98有無添加HA之CB e-產量(Catalysts = 20m g/mL, HA = 10 ppm, pH = 9) 105
圖4-99光觸媒降解RhB與TC之機制途徑 106
 
表目錄
表2-1染料廢水之放流水標準 8
表3-1光觸媒製備之藥品與材料 13
表3-2電化學分析之藥品與材料 13
表3-3光催化降解實驗之藥品與材料 14
表3-4樣品命名列表 22
表3-5實驗參數 23
表4-1不同光觸媒之比表面積 45
表4-2各比例複合材料之C1s官能基比例 56
表4-3各比例複合材料之N1s官能基比例 56
表4-4各比例複合材料之S2p官能基比例 56
表4-5複合材料之能隙表 58
表4-6不同組成光觸媒之光催化k值/ R2 72
表4-7不同比例之光觸媒k值/ R2 74
表4-8不同初始pH之光觸媒k值/ R2 76
表4-9在可見光下存在不同有機陰離子之光觸媒k值/ R2 84
表4-10能帶隙/導帶(E vs Ag/AgCl/E vs NHE)/價帶 89
表4-11 HA對RhB之光觸媒k值/ R2 92
 

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