結論與建議

5-1 結論

本研究第一部份係以均相催化系統(Co

²⁺

/PMS)處理 AB1 染料，並鑑定各 反應之中間產物及探討其可能的反應機構與路徑；第二部份為以不同水熱方 法合成奈米級Bi

2

WO

6

觸媒，於UV/Bi

2

WO

6

非均相催化系統下處理CV 染 料，並探討各Bi

2

WO

6

觸媒之材料特性與降解CV 染料效率之差異，並鑑定 其反應之中間產物及探討其可能的反應機構與路徑。

1. 在 Co

²⁺

/PMS 系統催化下反應速率隨著[Co

²⁺

]與[PMS]之濃度增加而增加。

2. 本研究亦成功鑑別以 Co

²⁺

/PMS 系統催化降解 AB1 染料在 50 分鐘的層析 時間內成功找到9 個中間產物。 並顯示在 35-50 分鐘時之 HPLC 層析圖 無任何紫外光吸收，表示其無雙鍵、極性又小，由質譜圖並判別出質量

較大，由此可判斷此可能為長鏈結構的巨大有機分子。而在滯留時間5

分鐘以內之的化合物，表示其極性大；其質譜圖亦顯示斷裂碎片均為高 分子量，且並無UV 吸收，判斷可能為磺酸化烷烴類的中間產物。

3. 本研究成功以 Autoclave 水熱法、微波水熱法及傳統水熱法，製成 Bi

2

WO

6

觸媒。實驗結果以Autoclave 水熱法合成之 Bi

2

WO

6

觸媒光催化降解CV 染料之效率最佳，在48 小時即可達到 98%的降解效果。

4. 經 FE-SEM 圖發現，以不同水熱合成方法合成之 Bi

2

WO

6

之形貌包括粉狀 顆粒、片狀、薄片層狀堆疊類似花瓣狀之結構。

5. HRXPS 圖譜中並在 Bi

2

WO

6

皆可發現在BE (Bi 4f

7/2

)=156.4 eV 處出現另 一自旋軌域的雙吸收峯。推測此可能部分的氧產生空缺而導致部份的Bi 存在(+3-x)的價態，並導致往層狀結構發展。

6. 三種不同水熱合成方法其 XPS 之 Bi 4f 圖譜中，顯示 CH 系列之樣品均 Bi

³⁺

之特性吸收峰的強度較Bi

^(+3-x)

高，表示層狀結構並不明顯；MH 系列 之樣品則以Bi

^(+3-x)

為主，顯示此時 Bi 存在的化學環境多為 Bi

2

O

2

layer 的層狀結構；而AH 系列之樣品則隨反應時間增加，Bi

³⁺

與Bi

^(+3-x)

之特徵 峰呈現此消彼長，終至72 小時，兩者接近相等。其結構分佈可與 FE-SEM 圖相互呼應。

7. BET 比表面積由大至小依序為 AH 系列(34.9436~50.1481 m

²

/g) > MH 系 列(14.1823~ 23.2437m

²

/g) > CH 系列(平均 1.3999~4.0970 m

²

/g)，結果可證 明利用Autoclave 水熱合成方法可製備出顆粒細小並具有比表面積較大 的Bi

2

WO

6

奈米晶體。

8. 傳統水熱法反應時間在 48 小時和 72 小時之 Bi

2

WO

6

樣品具有類似的 特徵峰，強度並隨反應時間增長而增加，顯示結晶度趨於成熟；CH 24 樣品，推測其可能為Bi

2

O

3

與Bi

14

WO

24

之混和晶相，而並與以EDS 測得 之W/Bi 原子比例 0.04-0.021，即與化學劑量比(W : Bi = 1:14) 相符。

9. MH 0.5 和 MH 1 之 Bi

2

WO

6

具有類似的特徵峰及強度，但反應時間增長 至1.5 小時，繞射峰的強度即減弱，但仍保持一定的結晶性，而 MH 0.25 之XRD 圖譜僅於 2θ 等於 25.3 處出現單一繞射峰，明顯異於 Bi

2

WO

6

之 特徵峰，目前仍為未知之晶相。

10. AH 24 樣品之 Bi/W 原子比例為 6.90，在 XRD 圖譜上顯示出不同之繞射 峰，經比對後推論AH 24 樣品可能由 Bi

14

W

2

O

27

及Bi

2

WO

6

所組成。

11. Bi

2

WO

6

/UV 去除 CV 程序之反應中間產物，共 19 種(A-J、a-f 與 α-γ)。

12. 推測主要可能之反應機構為發色基團之(1)去甲基化(N-de-methylated)與 (2)分裂發色基團之共振結構(Cleavage of conjugated chromophore

structure)

13. 晶體的表面形態會影響反應機構。

14. CV 染料之 pH 值對反應機構之影響無顯著差異。

5-2 未來方向與建議

1. 發展層析方法，進一步鑑定出 Co

²⁺

/PMS 系統降解 AB1 染料之未知中間 產物。

2. 以 Co

²⁺

/PMS 系統降解其他有機污染物。

3. 以 Phosphate buffer 調控 pH 值，尋找最適化條件。

4. 以 Bi

2

WO

6

觸媒照射可見光降解CV 染料，探討其效率與反應機構。

5. 研究不同高級氧化程序處裡 CV 染料，其可能的反應機構與路徑。

6. 探討不同染料與染料混合廢水，其可能的反應機構。

建議未來可設計連續流之UV/ Bi

2

WO

6

光催化反應系統。

 

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在文檔中 合成奈米級鎢酸鉍觸媒暨過硫酸鹽高級氧化程序降解三苯甲烷類染料的效率和機構探討 (頁 157-166)