階層性沸石與介孔鈦矽酸鹽的合成與催化研究

Synthesis and Catalytic Studies of Hierarchical Zeolites and Nanoporous Titanosilicates

張鈞彥(Chang, Albert)

指導教授 ： 楊家銘

國立清華大學/理學院/化學系所/博士(2019年)

摘要

本研究旨在設計與製備以應用為目的之新型態孔洞材料。於本論文中所研究及討論之材料，可依種類及合成策略將其分為兩類。其一為利用雙功能結構導向試劑合成由沸石奈米層板組成之階層性沸石材料。本實驗室設計與開發出新型三節式結構導向試劑，其由中央疏水之聚丙氧基鏈串連兩端親水之結構導向官能基所組成。實驗結果顯示此三節式結構導向試劑能有效地調控沸石奈米層板的堆疊以及交錯成長，進而得到具有不同形貌的階層性沸石材料。此外，我們發現具有高比例交錯成長形貌之 silicalite-1 奈米層板擁有高比例之網狀矽醇基，其最有可能位在奈米層板之交錯處。此類型之silicalite-1 奈米層板於氣相 Beckmann rearrangement 上展現相當高以及穩定的活性與選擇性。我們更進一步地利用三節式結構導向試劑之聚丙氧基鏈與石墨烯表面間的疏水作用力，以石墨烯作為載體引導沸石奈米層板於其表面進行成長。同時我們也設計另一雙節式結構導向試劑，其一端由芘構築而成，利用芘與石墨烯間之

關鍵字

貝克曼重排反應 ； 生質柴油 ； 階層性沸石 ； 介孔鈦矽酸鹽 ； 沸石奈米層板

並列摘要

The thesis aims to design and prepare novel porous materials toward catalytic and other applications. Two synthetic strategies were developed to prepare distinct types of materials. Inspired by the synthesis of hierarchical zeolites comprising nanosheets using bifunctional structure-directing agents (SDAs), we developed a series of triblock SDAs featuring a polypropylene oxide (PO) linker between two heads of structure directing groups. Experimental results suggested that branching and stacking of zeolite nanosheets could be rationally controlled by using the designed triblock SDAs. Moreover, the highly-branched silicalite-1 nanosheets catalysts possessing significant amount of nest-like silanols which were generated most likely at the junctions of well-organized nanosheets/nanoplates exhibited excellent and stable activity for the vapor-phase Beckmann rearrangement and high lactam selectivity. We further employed the hydrophobic interaction between the PO linker of triblock SDA and the surface of graphene flakes to direct the restricted growth of zeolite nanosheets on graphene flakes. For the same purpose, a diblock SDA composed of a moiety of pyrene was synthesized to utilize the strong

並列關鍵字

Beckmann rearrangement ； Biodiesel fuel ； Hierarchical zeolites ； Nanoporous titanosilicates ； Zeolite nanosheets

參考文獻

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