合成具有酸及離子液體官能基之中孔洞氧化矽奈米催化劑並應用於纖維素至羥甲基糠醛的生質轉化

Synthesis of Mesoporous Silica Nanoparticles Exhibiting Sulfonic Groups and Ionic Liquids toward Cellulose-to-5-Hydroxymethylfurfural (HMF) Biomass Conversion

李盈瑩(Yin-Ying Lee)

指導教授 ： 吳嘉文

國立臺灣大學/工學院/化學工程學研究所/碩士(2012年)

https://doi.org/10.6342/NTU.2012.02343

摘要

本研究主要致力於合成一系列具有磺酸基(HSO3)及離子液體(ILs)的中孔徑矽奈米粒子(MSN)，並應用於木質纖維性生質物至精緻化學品的一步轉化反應。我們利用具有高表面積和多官能基修飾的MSN做為有效的固體催化劑，以達到纖維素在二甲基亞碸(DMSO)中直接轉化為5-羥甲基糠醛(HMF)的目的。

首先，我們合成了孔徑大小約40奈米的MSN，命名為大孔徑的中孔徑矽奈米粒子(LPMSN)，接著利用共縮合的方式將酸HSO3-)及離子液體的官能基同時修飾上去，形成雙官能化的LPMSN ([HSO3+(ILs/CrCl2)]-LPMSN)。此外，我們也分別合成了只單獨具有酸或是離子液體的LPMSN (亦即HSO3-LPMSN, ILs/CrCl2-LPMSN)。我們利用固態核磁共振儀和元素分析儀作MSN材料表面官能基的定量分析。此外，我們也研究了果糖轉化在有/無含材料系統中的動力學表現，並發現反應級數、活化能以及反應速率常數會隨著催化劑的存在與否而有所改變。值得一提的是，果糖至HMF的反應活化能由80.05 kJ/mol降至67.5 kJ/mol。

最後，四種材料(亦即LPMSN、HSO3-LPMSN、ILs/CrCl2-LPMSN和 [HSO3+(ILs/CrCl2)]-LPMSN)分別做為催化劑，並應用在纖維素、纖維雙糖、葡萄糖及果糖在DMSO系統下的轉化反應中。高效能液相層析儀的分析結果顯示，在[HSO3+(ILs/CrCl2)]-LPMSN或ILs/CrCl2-LPMSN的催化下，可從果糖、葡萄糖、纖維雙糖和纖維素的轉化中分別得到產率最高的HMF (亦即80.64%, 6.86%, 4.94%和7.42%)。這是第一次有研究報告在DMSO系統中，利用官能化的中孔洞矽奈米粒子催化各種生質原料(纖維素、纖維雙糖、葡萄糖和果糖)直接轉化為HMF。

關鍵字

中孔洞矽奈米粒子 ； 雙官能化 ； 5-羥甲基糠醛 ； 纖維素轉化 ； 離子液體 ； 磺酸 ； 二甲基亞碸

並列摘要

This study focuses on the direct conversion of cellulose to 5-hydroxymethylfurfural (HMF) in dimethylsulfoxide (DMSO) systems by utilizing a series of sulfonic group (HSO3) and ionic liquid (ILs) functionalized mesoporous silica nanoparticles (MSNs) as heterogeneous solid catalysts. We first synthesized MSNs with pore size of 40 nm, namely large-pored MSN (LPMSN), and then functionalized LPMSN with acid groups (HSO3-) and ILs to form bi-functionalized LPMSN through a co-condensation method. Additionally, we also synthesized LPMSN with acidic or ionic liquids sites alone (i.e., HSO3-LPMSN and ILs/CrCl2-LPMSN, respectively). The amounts of functional groups on the MSN-based catalysts were characterized by solid-state NMR and elemental analysis. Moreover, the kinetics profiles of the systems with and without the catalysts were studied, and we derived that the reaction orders, activation energies and rate constants were alternated in the presence of catalysts. In particular, the Ea of the fructose-to-HMF conversion decreased from 80.05 kJ/mol to 67.5 kJ/mol. Finally, four materials (i.e., LPMSN, HSO3-LPMSN, ILs/CrCl2-LPMSN and bi-functionalized ([HSO3+(ILs/CrCl2)]-) LPMSN) were separately used as catalysts in the conversion of cellulose, cellobiose, glucose and fructose to HMF in the DMSO system. The HPLC results indicated that the highest yields of HMF converted from fructose, glucose, cellobiose and cellulose (i.e., 80.64%, 6.86%, 4.94% and 7.42%, respectively) could be obtained in the presence of [HSO3+(ILs/CrCl2)]-LPMSN or ILs/CrCl2-LPMSN catalysts. This is the first report of the generation of HMF directly from various sources (cellulose, cellobiose, glucose, and fructose) using funtionalized MSN as catalysts in DMSO systems.

並列關鍵字

mesoporous silica nanoparticle ； bifunctional ； HMF ； cellulose conversion ； ionic liquid ； sulfonic acid ； DMSO

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