具多重孔洞MFI沸石材料之合成與催化應用研究

Synthesis and Catalytic Studies of Hierarchical MFI Zeolite Materials

陳銘毅(Ming-Yi Chen)

指導教授 ： 楊家銘

國立清華大學/理學院/化學系/碩士(2015年)

https://doi.org/10.6843/NTHU.2015.00105

摘要

本論文旨在利用自行設計合成之新型結構導向試劑及不同類型前驅物的選擇下，合成具多層次孔洞含鋁MFI沸石ZSM-5，並以表面官能化的方式負載鈀金屬作為觸媒，應用於苯酚選擇性氫化反應。在結構導向試劑的設計上，結合了兩側具結構導引能力的四級銨親水端，以及丙氧基鏈疏水部分；並研究水熱條件合成系統中，前驅物的選擇對沸石形貌、結構及孔洞性質的影響。在選用TEOS為矽源、Al(OsBu)3為鋁源的合成條件下，可得到具有花瓣狀的silicalite-1或層板堆疊的ZSM-5；而以水玻璃為矽源，硫酸鋁為鋁源的之合成條件，所得的沸石材料顆粒大小均一性提升，並具自我支撐垂直交錯之結構，且可將鋁充分的引入沸石結構中形成四配位鋁。我們便利用這些ZSM-5材料作為載體，將其表面修飾烯基以和Pd(II)錯合，再經還原後得到高分散性的鈀奈米顆粒。最後我們發現由較佳質傳效能、表面疏水化的多層次孔洞ZSM-5負載鈀奈米顆粒的複合材料，相較傳統的商用Pd/C觸媒，在常壓水相的苯酚選擇性氫化反應具有較佳的催化活性，以及環己酮的選擇性。

關鍵字

沸石材料 ； 催化應用

並列摘要

In this study, hierarchical zeolite ZSM-5 materials were hydrothermally synthe-sized by using a novel tri-block structure directing agent (SDA) and different silicon sources and were further functionalized then loaded with palladium for the catalytic selective phenol hydrogenation. The tri-block SDA contains repeated propylene oxide units with both ends connented to three quaternary ammonium groups. The effects of the kinetic parameter of the synthesis on the morphology and lamellar structure of the resulting ZSM-5 and MFI zeolites were investigated by tuning the precursors with different silicon and aluminum sources. In the TEOS-Al(OsBu)3 synthesis system, lamellar stacking and flower-like morphology was formed. On the other hand, highly uniform self-pillared structure containing almost exclusively tetrahedrally coordinated framework aluminum was obtained in the water glass-aluminum sulfate synthesis system. For the deposition of Pd nanoparticles, the Pd(II) ions were coordinated with vinyl groups on zeolite surface and highly dispersed Pd nanoparticles were form after reduction. The Pd@ZSM-5 catalyst exhibited higher phenol conversion and cyclo-hexanone selectivity under room temperature and atmospheric pressure than reference catalysts including commercial Pd/C and conventional ZSM-5-supported catalyst did. The superior catalytic activity in mainly attributed to shorter diffusion path length, hydrophobic surface and small and highly dispersed Pd nanoparticles.

並列關鍵字

Zeolite Materials ； Catalytic Studies

參考文獻

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