製備奈米鈀金屬於氮摻雜中孔洞碳複合材料在有機催化反應之應用

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題名:	製備奈米鈀金屬於氮摻雜中孔洞碳複合材料在有機催化反應之應用
作者:	陳柏宏;Chen, Po-Hung
貢獻者:	化學學系
關鍵詞:	中孔洞碳材;催化;鈀金屬
日期:	2020-07-28
上傳時間:	2020-09-02 15:12:20 (UTC+8)
出版者:	國立中央大學
摘要:	本論文主要分為兩大部分，在第一部分研究中，利用奈米鈀金屬還原在中孔洞碳氮材料之三維結構N-CMK9以及未摻雜氮之三維結構CMK-9中，利用化學還原劑使金屬還原速率上升，並藉由N-CMK9具有高比表面積以及缺陷的CN位點，使離子鈀金屬能快速平均分散並負載在N-CMK9孔洞之中並還原奈米鈀金屬顆粒。實驗過程中利用高分子界面活性劑P123作為模板，和矽源TEOS(Tetraethyl orthosilicate)在酸性下進行合成，得到對稱性為Ia3d cubic構型的中孔洞矽材KIT-6，再利用糠醇做為碳源將矽材碳化後，可得到有序中孔洞管狀碳材CMK-9，由於CMK-9具有高比表面積以及良好的孔洞體積，此外加上摻雜氮於此中孔洞材材料，合成出的N-CMK9作為載體可以提高奈米鈀金屬分散率進而提高催化活性。本實驗將製成的Pd(x)@N-CMK9以及Pd(x)@CMK9應用在鈴木偶聯催化反應當中，分別探討三維結構碳材及氮摻雜碳材結構、不同含浸量、鹼以及不同溶劑對催化活性之影響。經過一系列的研究，使用Pd(10)@N-CMK9作為催化劑去進行鈴木偶聯催化反應，其轉換頻率(TOF)高達1965.4 h-1 。在這項研究中，Pd(10)@N-CMK9展示了其用於鈴木偶聯催化反應為高活性催化劑。第二部分研究中，同樣透過奈米模鑄法(Nanocasting)合成出中孔洞碳氮材料(N-CMK9)，並將奈米鈀金屬顆粒負載在N-CMK9上作為催化觸媒。藉由N-CMK9上不僅可以利用有缺陷的CN位點和氮間隙可以很均勻分散鈀金屬顆粒，從而提高催化活性。將CMK-9以及N-CMK9含浸於鈀金屬離子前驅液，利用化學還原法將金屬離子還原成金屬奈米顆粒(Pd@CMK-9, Pd@N-CMK9)，本實驗將材料應用於4-Nitrophenol還原催化反應，分別探討不同載體以及不同含浸金屬量對催化活性之影響。在催化4-Nitrophenol還原反應的研究中，Pd(5)@N-CMK9表現出很高的催化活性，其k值高達77336.4 s-1g-1。在這項研究中，Pd(5)@N-CMK9展示了其用於4-Nitrophenol還原催化反應中為高活性催化劑。 ;This thesis consists of two parts. In the first part of this study, the palladium nanoparticles (Pd NPs) are successfully confined within the 3D structure of the mesoporous nitrogen-doped carbon material N-CMK9 and the carbon material CMK-9. The mixture chemically reduced by reagent containing NaBH4 and NH3BH3 to obtain Pd(x)@CMK-9 and Pd(x)@N-CMK-9. It was found that N-CMK9 has a high specific surface area and defective CN sites, so that the palladium metal can be quickly and evenly dispersed in the pores of the N-CMK9. The polymer surfactant P123 was used as a template to synthesize with TEOS (Tetraethyl orthosilicate) under acidic conditions to obtain the mesoporous silicon KIT-6, which has a cubic structure with Ia3 ̅d symmetry. Using furfuryl alcohol as the carbon source and after carbonization, a 3D hollow-type ordered mesoporous carbon CMK-9 can be obtained. Since CMK-9 has a high specific surface area and a good pore volume, in addition of the nitrogen doped in the mesoporous material (N-CMK9) which can be used as a carrier. It can enhance the dispersion and improve the catalytic activity. In this experiment, the Pd(x)@N-CMK9 and Pd(x)@CMK9 were used in the Suzuki coupling catalytic reaction, furthermore compare 3D carbon material and nitrogen-doped carbon material, different base and different solvent respectively. Among all the as-prepared catalysts, Pd(10)@N-CMK9 exhibited the highest turnover frequency (TOF) of 1965.4 h-1. In this study, Pd(10)@N-CMK9 is an excellent high active catalyst for Suzuki coupling reaction. In the second part of the study, a mesoporous N-doped carbon material (N-CMK9) was synthesized by nanocasting, and palladium nanoparticles were supported to N-CMK9 as a catalytic catalyst. N-doped carbon material N-CMK9 not only has defective CN sites and nitrogen gaps can be used to uniformly disperse palladium metal particles, but also improve catalytic activity. CMK-9 and N-CMK9 were impregnated with palladium metal ion precursor solution, and the metal ions were reduced to metal nanoparticles by chemical reduction method (Pd@CMK-9, Pd@N-CMK9). It was used as the catalyst for the reduction of 4-nitrophenol besides explored the effects of different carriers and different amounts of impregnated metal on the catalytic activity. In the study of the catalytic reduction of 4-Nitrophenol, Pd(5)@N-CMK9 exhibited the highest turnover frequency of 80467.3 s-1g-1.
顯示於類別:	[化學研究所] 博碩士論文

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