臺灣博碩士論文加值系統

本研究主要在類石墨氮化碳二維材料表面附載不同氧化態之氧化鉬材料，來提升應用於可見光下光催化二氧化碳之活性，並探討所製得之觸媒材料性質對二氧化碳光催化還原反應效率之影響。

第一部分：三氧化鉬/類石墨氮化碳光觸媒之製備與性質研究
本研究第一部分以鍛燒法與水熱法製備三氧化鉬/類石墨氮化碳複合(MoO3-gC3N4)。以鉬酸銨四水化合物(Ammonium molybdate tetrahydrate)為鉬前驅物，使用水熱法(210oC)製備三氧化鉬。以含氮之碳氫化合物三聚氰胺(Melamine)為前驅物，以馬費爐於靜態空氣環境下，溫度450oC進行鍛燒製備出含氮之片狀類石墨氮化碳。水熱後之氧化鉬與類石墨氮化碳混合後鍛燒(450oC)。以X光繞射光譜儀鑑定MoO3之晶相和g-C3N4之特徵峰，並使用掃描式電子顯微鏡觀察MoO3及g-C3N4之形貌，且藉由穿透式電子顯微鏡觀察其分布情形，也利用紫外-可見光光譜儀、螢光光譜儀進行光觸媒光學特性之分析；UV-VIS光譜得知類石墨氮化碳的添加有助於吸收邊緣紅位移(相較於MoO3)；由ESCA分析結果顯示，氬氣環境下鍛燒的觸媒MoO3-gCN-Ar，其三氧化鉬因缺氧環境下鍛燒，部分還原成二氧化鉬，因而提高其光催化活性。以光催化二氧化碳還原反應評估不同合成路徑之光觸媒之光催化活性，觸媒MoO3-gCN-Ar於8W, 254nm之光源照射8小時下，一氧化碳為唯一還原產物，其產率為0.067 mol/gcat。

第二部分：氧化鉬量子點/類石墨氮化碳光觸媒之製備與性質研究
本研究以鍛燒法與水熱法製備氧化鉬量子點/類石墨氮化碳複合材料( MoOx-QDs-gC3N4 )。以鉬粉為氧化鉬量子點前驅物，使用水熱法(80 °C)製備氧化鉬量子點。以含氮之碳氫化合物三聚氰胺(melamine)為前驅物，以馬費爐於靜態空氣環境下，於溫度500 °C及550 °C進行鍛燒製備出含氮之片狀類石墨氮化碳(g-C3N4)。經水熱後之氧化鉬量子點與類石墨氮化碳混合後鍛燒(300 °C)，即得本研究之觸媒；以XRD、XPS、EDX分析皆證實觸媒中含有微量的氧化鉬量子點，鍛燒後類石墨氮化碳仍保有其特徵結構；TEM影像證實類石墨氮化碳上確實含有氧化鉬量子點；UV-VIS光譜得知氧化鉬量子點的添加有助於觸媒吸收邊緣紅位移。本研究以UVA(8 W, 365 nm)光源探討觸媒之光催化還原二氧化碳活性，研究顯示觸媒 MoOx-0.3gCN有最佳之光活性，12小時光源照射下，能將二氧化碳轉為一氧化碳，產率達 0.418 mol/gcat。
 
第三部分：原位合成氧化鉬/類石墨氮化碳光觸媒之製備與性質研究
本研究以原位合成的方法置備光觸媒，首先我們以熱縮合的方法置得此研究所需的類石墨氮化碳，並將其加入含有二硫化鉬的雙氧水水溶液，經雙氧水強氧化的能力，把二硫化鉬的硫取代成為氧化鉬，含鉬的離子態與類石墨氮化碳表面的氮活性位點可以分散的生長於其表面上，隨後經過酸鹼中和，除掉取代後的硫，經過離心洗滌，即可得到本研究所需的光觸媒XMS-0.1CN。藉由ESCA分析觀察到觸媒30MS-0.1CN相對於其他比例合成的觸媒，擁有最高的Mo4+價態的含量比例，而Mo4+價態的出現，由過去的文獻指出，確實可以提高電荷的傳輸能力並促進其光催化活性。從UV-Vis及Tauc Plot的分析圖譜中可以發現原位合成的觸媒與純類石墨氮化碳相比，吸收邊緣有發生紅位移的現象且能隙也變窄約0.1~0.2eV。由PL圖譜顯示，一系列觸媒發光強度並無隨著趨勢降低，但與純類石墨氮化碳相比螢光強度確實有明顯的降低，表示原位生長後的氧化鉬能有效降低光生電子-電洞的再結合效率。二氧化碳光催化還原反應中，一氧化碳為唯一的成功轉換的產品，30MS-0.1CN是擁有最高轉換產率的觸媒，其轉換率為3.937 ( mol/gcat )，呼應先前ESCA所發現的Mo4+價態比例。此研究顯示原位生長的觸媒與純類石墨氮化碳相比確實能有效提高光催化活性。

In this study, molybdenum oxides with various oxidation states were decorated on two-dimensional graphitic carbon nitride (gCN) to enhance the photocatlytic activity of CO2 reduction under visible light irradiation and to correlate the characteristics of photocatalysts to the efficiency of CO2 conversion.

Part 1: Preparation and Properties of Molybdenum Trioxide / Graphitic Carbon Nitride Composite for Photocatalysis
Molybdemum trioxide/graphitic carbon nitride was prepared by calcination and hydrothermal method. Ammonium molybdate tetrahydrate was the precursor of molybdenum and melamine was for gCN. Molybdenum trioxide (MoO3) was obtained by hydrothermal method (210 °C) and graphitic carbon nitride was by calcination method (450 °C) at Air or Ar. XRD result confirmed the crystal phase of MoO3 and characteristic peaks of gCN. SEM images confirmed the morphology of MoO3 and gCN. TEM images presented the distribution of MoO3. A significant red shift, compared to pure MoO3, revealed from UV-VIS spectra of samples with the presence of gCN. After calcination under Ar, some MoO3 reduced to MoO2 as evidenced from ESCA results of MoO3-gCN-Ar and thus increased photocatalytic activity. Photocatalytic reduction of CO2 showed MoO3-gCN-Ar (8 W, 254 nm) could successfully convert CO2 into CO, and the yield of CO was 0.067 mol/gcat.

Part 2: Preparation and Properties of Molybdenum Oxide Quantum Dots / Graphitic Carbon Nitride Composite for Photocatalysis
In order to further improve the photocatalytic activity of CO2, molybdenum oxide quantum dots/graphitic carbon nitride composites (MoOx-QDs-gCN) were prepared in the second part of this study. Molybdenum oxide quantum dots were prepared by hydrothermal method (80 °C) using molybdenum powder as the precursor. The melamine was used as a precursor to prepare graphitic carbon nitride (gCN) by calcining at 500 °C and 550 °C under air atmosphere. The obtained molybdenum oxide quantum dots were mixed with gCN and then calcined at 300 °C. XRD, ESCA and EDX results confirmed that the catalyst contained molybdenum oxide with various oxidation states on gCN. TEM images showed after calcination graphitic carbon nitride still mentain their characteristic structure. A significant red shift of the absorption edge of MoOx-QDs-gCN, compared to gCN, was observed from UV-VIS spectra. Carbon dioxide photocatalytic reduction results showed MoOx-0.3gCN (8 W, 254 nm) had the best conversion yield of CO and the yield of CO was 0.418 mol/gcat.

Part 3：In-Situ Preparation and Properties of Molybdenum Oxide / Graphitic Carbon Nitride Composite for Photocatalysis
In the third part of this study, in-situ preparation of molybdenum oxide (MoOx) on gCN was attemped to improve the interaction of gCN and MoOx. Thermal condensation method was applied to fabricate graphitic carbon nitride(gCN). Different amounts of molybdenum disulfide (MoS2) were dissolved with hydrogen peroxide solution, followed by the addition of gCN. Strong oxidation of hydrogen peroxide with molybdenum disulfide was ulilized to replace the sulfur atoms of molybdenum disulfide to oxygen atoms. The presence of nitrogen active sites on gCN surface has electronic affinity with molybdenum ions. After the deposition of molybdenum oxide particals on gCN, the remained sulfur ions were removed by neutralization by alkali. After centrifugated and washed, we could obtain the composite photocatalysts and named XMS-0.1CN, where X indicates the volume of MoS2. The results of XPS-Mo3d confirmed that the photocatalyst 30MS-0.1CN had the highest ratio of Mo4+ (compared with the other photocatalyst). The appearance of Mo4+ could improve the charge transport capacity and promote photocatalytic activity. The UV-Vis and Tauc Plot analysis results were shown that the in-situ synthesized photocatalyst had a red shift of the absorption edge compared with pure gCN and the band-gap was narrowed by 0.1 to 0.2 eV. The results of PL spactrum analysis showed that the photoluminescence intensity of in-situ prepared photocatalyst was lower than that from that emitted from pure gCN. This result indicated that molybdenum oxide after in-situ growth could effectively reduce the recombination efficiency of photogenerated electron-holes. In the photocatalytic reduction of carbon dioxide, carbon monoxide was the only successful conversion product. 30MS-0.1CN had the highest conversion yield, 3.937 mol/gcat, as the highest Mo4+ ratio was estimated by ESCA. This study showed that the in-situ growth of the photocatalyst was indeed effective at improving photocatalytic activity compared to pure gCN.

摘 要 II
Abstract V
致 謝 VIII
目 錄 IX
圖目錄 XII
表目錄 XIX
第一章　緒論 1
1-1 前言 1
1-2 研究動機與目的 3
第二章　文獻回顧 5
2-1 二氧化碳之減量反應 5
2-1-1 二氧化碳簡介 5
2-1-2 二氧化碳之處理技術 7
2-1-3 二氧化碳光催化反應原理 9
2-1-4 提升光催化還原二氧化碳反應 12
2-2 光觸媒簡介 21
2-2-1 光觸媒原理 22
2-2-2 光觸媒-光催化還原二氧化碳反應機制 25
2-2-3 提高光觸媒之反應活性 28
2-3 類石墨氮化碳簡介 31
2-3-1 類石墨氮化碳之性質 32
2-3-2 類石墨氮化碳之製備方法 38
2-3-3 類石墨氮化碳之應用 41
2-4 鉬氧化物光觸媒簡介 45
2-4-1 鉬氧化物之性質 46
2-5 類石墨氮化碳複合材料於光催化二氧化碳之文獻 47
第三章　實驗方法 58
3-1 實驗觸媒之製備 58
3-1-1 實驗藥品 58
3-1-2 實驗儀器型號與規格 60
3-1-3 類石墨氮化碳之製備 62
3-1-4 三氧化鉬之製備 64
3-1-5 氧化鉬量子點之製備 65
3-1-6 三氧化鉬/類石墨氮化碳光觸媒之製備 66
3-1-7 氧化鉬量子點/類石墨氮化碳光觸媒之製備 67
3-1-8 原位合成氧化鉬/類石墨氮化碳光觸媒之製備 68
3-1-9 觸媒代號說明 70
3-2 觸媒之特性分析 72
3-2-1 分析儀器型號與規格 72
3-2-2 分析儀器之原理及方法 73
3-3 光催化活性評估 85
3-3-1 亞甲基藍光催化脫色 85
3-3-2 羅丹明B光催化脫色 86
3-4 二氧化碳光催化反應 87
3-4-1 光催化反應器 87
3-4-2 反應產量檢測 90
3-4-3 光觸媒於光催化二氧化碳還原之效率評估 91
第四章　結果與討論 92
4-1 觸媒特性鑑定與分析 92
4-1-1 X射線繞射圖譜分析( XRD ) 92
4-1-2 穿透式電子顯微鏡分析 ( TEM ) 98
4-1-3 掃描式電子顯微鏡分析 ( SEM ) 104
4-1-4 化學分析電子能譜儀鑑定 ( ESCA-XPS ) 109
4-1-5 紫外光-可見光(UV-Vis)吸收光譜分析 132
4-1-6 螢光(PL)光譜分析 138
4-2 二氧化碳光催化還原反應 141
4-2-1 三氧化鉬/類石墨氮化碳 141
4-2-2 氧化鉬量子點/類石墨氮化碳 142
4-2-3 原位合成氧化鉬/類石墨氮化碳 147
4-3 光能量轉換效率比較 149
第五章 結論 150
第六章 參考文獻 153
第七章 附錄 165

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