臺灣博碩士論文加值系統

現在雖TiO2被廣泛的應用，但因為快速的重組及有限的可見光吸收造成低量子效率，並且含量逐漸減少，現今嘗試找尋新的光催化劑能克服這些問題。本研究製備g-C3N4與Bi2O2CO3合成g-C3N4/Bi2O2CO3複合光催化劑，來提升光吸收的效果及減少電子-電洞的重組，進而提升光催化的效率。
本研究以尿素在不同煅燒溫度、方式、時間下製備成g-C3N4，Bi(NO3)．5H2O及Na2CO3以複分解方式製備成Bi2O2CO3， 並依重量比例用兩種不同方法合成g-C3N4/Bi2O2CO3光催化劑，在25ppm濃度下之活性黑染料 (RB5)進行吸附及降解測試，找尋最佳的合成材料及比例，並觀察此光催化劑與反應溫度及光強度對光催化之效果，探討不同製備條件及環境條件對光催化劑的影響。
在25ppm RB5的去除測試中，Bi2O2CO3有很好的吸附效果可達64.48%， g-C3N4的吸附效果較低但降解效果優於Bi2O2CO3，總去除率皆可達59.77%。一段式或二段式煅燒兩種方式所製備的g-C3N4晶體差異並不明顯，而二段式煅燒的吸附效果皆優於一段式的煅燒，以總去除量來看，在二段式煅燒的兩小時是有最好的去除效果，可以達到55.33%之去除率、27.66mg/g之去除量。直接複合光催化劑中，二段式煅燒的吸附效果皆優於一段式的煅燒，不論是一段式或二段式煅燒，直接複合的吸附效果皆優於混合合成。C/B-2/2合成比例在1:3時可以達到最好的吸附及降解效果，總去除率為60%。在高溫的環境下，水中溶氧會下降，而會抑制光催化反應中電子-電洞還原氧的能力，而使超氧自由基減少，影響光催化效果。光子越多，單位時間和面積所激發出來的電子也多，電子－電洞也就多，氧化能力也就增強，因此光強度對光催化非常關鍵，強度大於140Lux時，催化反應的效果會有明顯的增加。本研究之複合光催化劑，可有效使用可見光進行染料的脫色而是TiO2無法達到的效果。

Nowadays, although TiO2 is widely used, because of rapid recombination and limited visible light absorption, resulting in low quantum efficiency and decreasing content, it is possible to overcome these problems by trying to find new photocatalysts.
In this study, g-C3N4 / Bi2O2CO3 composite photocatalyst was synthesized by using self-made g-C3N4 and Bi2O2CO3 to enhance the effect of light absorption and reduce the recombination of electron-electric hole. g-C3N4 was prepared by urea at different calcination temperatures, method and time. Bi(NO3) 3．5H2O and Na2CO3 were used to prepare Bi2O2CO3, and the g-C3N4 / Bi2O2CO3 composite photocatalyst was synthesized by two different methods. The adsorption and degradation test of Reactive black dye (RB5) at 25ppm concentration was carried out to find the best synthetic material and ratio, and to investigate the influence of reaction temperature and light intensity.
In the 25ppm RB5 removal test, Bi2O2CO3 has a good adsorption effect of 60%, while the adsorption of g-C3N4 is low but the degradation is better than Bi2O2CO3, the total removal is 60%. The differences is not significant in the g-C3N4 crystals prepared by the one-stage or two-stage calcination, the adsorption effect of the two-stage calcination is better than that of the one-stage calcination. In terms of total removal, the best removal effect was achieved in the two-stage calcination for two hours, and the removal rate of 55.33% and the removal of 27.66 mg / g. In the direct composite (C+B), the adsorption of the two-stage calcination is better than that of the one-stage calcination. The adsorption of the direct composite is better than that of the mixed synthesis(C/B). C/B-2/2 ratio of 1: 3 can achieve the best adsorption and degradation effect, the total removal rate of 60%. In the high temperature, the dissolved oxygen in the water will decline, it will inhibit the photocatalytic reaction of the electron - hole reduction of oxygen capacity, affecting the photocatalytic effect. The more the photon, unit time and area of electrons - holes also increase, and the oxidation capacity will be enhanced, so the light intensity is very critical to photocatalysis, with greater than 140 Lux the intensity, the catalytic reaction will have significant increase. In this study, the composite photocatalyst can effectively use the visible light for the decolorization of the dye, but not for TiO2.

目錄
摘要 I
Abstract II
目錄 III
圖目錄 V
表目錄 VI
第一章 前言 7
1.1 研究緣起 7
1.2 研究目的與內容 8
1.3 研究架構 9
第二章 文獻回顧 10
2.1 光催化反應 10
2.1.1 光催化機制 12
2.1.2 新型光催化劑 14
2.1.3 半導體特性 16
2.2 類石墨稀結構氮化碳 18
2.2.1 基本特性 18
2.2.2 製備方法 20
2.3 鹼式碳酸鉍 21
2.3.1 基本特性 21
2.3.2 製備方法 22
2.4 染料廢水之特性 23
2.4.1 活性黑染料 24
2.4.2 染料處理 25
第三章 實驗設備與方法 26
3.1 研究架構 26
3.2 材料製備與合成 28
3.2.1 類石墨烯結構氮化碳製備 28
3.2.2 鹼式碳酸鉍製備 29
3.3 染料去除試驗 30
3.4 實驗藥品與設備 31
3.4.1 實驗藥品 31
3.4.2 實驗器材 32
第四章 結果與討論 33
4.1 材料特性分析 33
4.1.1 FTIR分析 34
4.1.2 XRD分析 36
4.1.3 BET分析 37
4.1.4 SEM分析 39
4.1.5 EDS分析 41
4.2 Bi2O2CO3、g-C3N4對RB5之去除 45
4.3 不同合成方式對RB5之去除 48
4.3.1 混合合成C/B 48
4.3.2 直接複合C+B 51
4.4 不同煅燒方式對RB5之去除 54
4.4.1 一段式煅燒 54
4.4.2 二段式煅燒 57
4.5 實驗條件最佳化 60
4.5.1 不同合成比例對RB5去除之影響 60
4.5.2 不同溫度條件下對RB5去除之影響 63
4.5.3 不同光強度條件下對RB5去除之影響 65
4.6 製備成本 68
第五章、結論與建議 69
5.1 結論 69
5.2 建議 70
第六章、參考文獻 71

 
圖目錄
圖 1 1研究架構流程圖 9
圖 2 1光催化反應和光合作用示意圖 10
圖 2 2光觸媒反應機制 13
圖 2 3不同材料之能帶結構 16
圖 2 4五種氮化碳之結構 18
圖 2 5氮化碳結構式 19
圖 2 6前驅物縮聚成氮化碳之結構變化 20
圖 2 7鹼式碳酸鉍之結構式 21
圖 2 8活性黑之結構式 24
圖 3 1研究架構流程圖 27
圖 4 1 FTIR分析圖譜 35
圖 4 2 XRD 分析圖譜 36
圖 4 3粒徑分布圖 38
圖 4 4 SEM分析圖 40
圖 4 5 BOC之EDS分析 42
圖 4 6 CN2/2之EDS分析 43
圖 4 7 1:3C/B-2/2之EDS分析 44
圖 4 8 BI2O2CO3及G-C3N4對時間與C/C0關係圖 47
圖 4 9 BI2O2CO3及G-C3N4吸附與降解圖 47
圖 4 10混合合成光催化劑對時間與C/C0關係圖 50
圖 4 11混合合成光催化劑吸附與降解圖 50
圖 4 12直接複合光催化劑對時間與C/C0關係圖 53
圖 4 13直接複合光催化劑吸附與降解圖 53
圖 4 14一段式煅燒複合光催化劑對時間與C/C0關係圖 56
圖 4 15一段式煅燒混合合成光催化劑吸附與降解圖 56
圖 4 16二段式煅燒複合光催化劑對時間與C/C0關係圖 59
圖 4 17二段式煅燒混合合成光催化劑吸附與降解圖 59
圖 4 18不同比例C/B-2/2複合光催化劑對時間與C/C0關係圖 62
圖 4 19不同比例C/B-2/2光催化劑吸附與降解圖 62
圖 4 20不同溫度條件下對RB5染料的去除率 64
圖 4 21不同溫度條件下對RB5染料的去除量 64
圖 4 22不同光強度條件下對RB5染料的去除率 66
圖 4 23不同光強度條件下對RB5染料的去除量 67

 
表目錄
表 2 1鹼式碳酸鉍的基本性質 22
表 4 1特性分析之儀器設備 33
表 4 2各催化劑之BET分析 37
表 4 3 BOC之EDS分析 42
表 4 4 CN2/2之EDS分析 43
表 4 5 1:3C/B-2/2之EDS分析 44
表 4 6碳酸鉍及氮化碳對RB5之去除效率及去除量 46
表 4 7混合合成之複合光催化劑對RB5之去除效率及去除量 49
表 4 8直接複合之複合光催化劑對RB5之去除效率及去除量 52
表 4 9一段式煅燒之複合光催化劑對RB5之去除效率及去除量 55
表 4 10二段式煅燒之複合光催化劑對RB5之去除效率及去除量 58
表 4 11不同合成比之C/B-2/2之光催化劑對RB5之去除效率及去除量 61
表 4 12在不同溫度下對RB5之去除效率及去除量 63
表 4 13在不同光強度下對RB5之去除效率及去除量 66
表 4 14合成10克之1:3 C/B-2/2光催化劑所需成本 68

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