多孔性材料於生物質催化之應用

Applications of Hierarchical Porous Materials in Biomass Catalysis

劉力豪(Li-Hao Liu)

指導教授 ： 林嘉和 ； 劉婉舲

中原大學/理學院/化學研究所/博士(2019年)

https://doi.org/10.6840/cycu201900091

摘要

本論文主要以開發新穎的多孔性材料並將其應用於生物質催化領域，研究可分為兩部份分別陳述研究內容與成果。
第一部分將金屬有機骨架材料 (metal-organic frameworks, MOFs)作為模板，製備多孔性碳材並作為脂解酶固定化之載體，進行生物性催化反應合成生質柴油。研究結果指出，透過控制碳化溫度可調整材料之羧酸根含量與孔洞尺寸，由於此碳材摻雜金屬氧化物，故更利於酵素固定化之成效。最佳化條件下，以MIL-100(Al)經600 oC煅燒所得之碳材，作為脂解酶固定化微反應器，可展現最佳的酵素負載量以及生質柴油催化能力。此外，本研究所開發之新穎性多孔性碳材，不需經任何修飾便可將酵素進行固定化並穩定進行九次催化反應，其產率仍可維持在66%，足以顯示此材料在生物性催化和生質能源製備應用相當具有潛力。
第二部分則利用金屬有機凝膠 (metal-organic gels, MOGs)作為固態酸催化劑，催化果糖進行轉化合成5-羥甲基糠醛 (5-hydroxymethyl-2-furaldehyde, HMF)。研究結果顯示，MOGs製備簡單且快速，因結構造成的缺陷可締造中孔利於質傳，以及材料金屬中心具有催化活性，以金屬中心為鋯之MOG (Zr-BDC)催化可生成HMF，展現最佳催化效果，至少可連續五次催化反應，產率仍可達6成以上。最後，本實驗為首次以MOGs作為固態酸催化劑，並成功應用於果糖轉化HMF之反應，其催化效能可與傳統固態酸催化劑相互媲美外，此材料具重複使用之優勢。

關鍵字

多孔性材料 ； 生質精煉

並列摘要

In this two-part study, the applications of novel hierarchical porous materials as catalysts for biomass conversion were explored.
For the first part, metal-organic frameworks (MOFs) were used as templates to prepare hierarchical porous carbon materials (PCMs) for lipase immobilization and applied as biocatalyst in biodiesel synthesis. The PCM derived from direct carbonization of MOFs presented tunable carboxylate functionalities, porosities, and metallic properties at different calcination temperature, which is more beneficial for enzyme immobilization. Under the optimized conditions, the PCM was obtained via pyrolysis of MIL-100(Al) at 600 oC and applied as the support for lipase immobilization, which performed the highest enzyme loading and catalytic efficiencies for biodiesel synthesis. In addition, the developed novel hierarchical PCMs as support for enzyme immobilization do not require any post-synthetic modification with maintained catalytic efficiency of 66% even after 9th catalytic cycles. These results indicate that PCM derived from MOFs has potential for biocatalysis and bioenergy application.
The second part of the study is focused on metal-organic gels (MOGs) as solid acid catalysts towards the conversion of fructose to 5-hydroxymethyl-2-furaldehyde (HMF). The simple and rapid preparation of MOGs showed its mesoporous structure is due to structural defects leading to rapid mass transfer and good catalytic activity bestowed by open metal site. Under the optimized conditions, the zirconium based MOGs (Zr-BDC) afforded the highest catalytic activity in the conversion of fructose to HMF with more than 60% yield even after 5th catalytic cycles. This study demonstrates for the first time the application of MOGs as solid acid catalyst for fructose to HMF conversion. The catalytic performance was found comparable with literatures so far.

並列關鍵字

Hierarchical porous materials ； biorefinery

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