製備具有酸性官能基之中孔洞矽材與生物質衍生碳材應用於有機催化反應

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题名:	製備具有酸性官能基之中孔洞矽材與生物質衍生碳材應用於有機催化反應
作者:	吳聲維;Wu, Sheng-Wei
贡献者:	化學學系
关键词:	異相催化劑;中孔洞矽材;酯化反應;香豆素;生物質衍生碳材
日期:	2024-07-11
上传时间:	2024-10-09 15:21:50 (UTC+8)
出版者:	國立中央大學
摘要:	本研究分為兩個部分。在第一部分研究中，利用中孔洞矽材具高比表面積、可調控的孔洞大小及孔洞體積等優點，透過直接合成法，將磺酸官能基修飾在一系列的三維中孔洞矽材表面。經過多種鑑定後，確認合成出S16SX(X = 10, 15, 20, 25, 30 )系列催化劑的結構與穩定性。此系列催化劑具有高比表面積、孔洞一致性和富有酸性位點，期望能應用於催化雙(三羥甲基)丙烷(Di-TMP)酯化反應。透過探討不同結構之中孔洞矽材、修飾上磺酸官能基的比例、不同催化劑量及不同丙烯酸與雙(三羥甲基)丙烷比例對於選擇性產生雙(三羥甲基)丙烷二丙烯酸酯(Di-TMPDA)的影響，得知最佳反應條件為以1.8 g S16S20當作催化劑，在起始物AA與Di-TMP莫耳比為2:1時進行反應。在溫度維持95℃，並持續除水的條件下，反應24小時後產生Di-TMPDA的比例約佔總產物的65%，並能減少雙(三羥甲基)丙烷三丙烯酸酯(Di-TMPTriA)與雙(三羥甲基)丙烷四丙烯酸酯(Di-TMPTetraA)的產生，因此，使用此催化劑S16S20是具有高催化活性並能選擇性產生特定產物 Di-TMPDA。第二部分研究中，透過水熱及KOH化學活化的方式，在高溫鍛燒下將咖啡渣製備成具孔洞性質的生質碳材。活化後的生質碳材透過4-benzene-diazoniumsulfonate與次磷酸反應，修飾上磺酸官能基，並透過元素分析、XPS、TEM等鑑定，證明成功製備出酸性生質碳材（S-WCG）。將此催化劑用於間苯二酚與乙醯乙酸乙酯的佩希曼縮合反應（Pechmann condensation），合成7-羥基-4-甲基香豆素。研究中探討鍛燒溫度、KOH比例、催化劑用量和反應溫度對催化劑催化活性的影響。最後在鍛燒溫度800°C，KOH與碳源比例為2:1條件下，所製備出的酸性咖啡渣碳材（S-WCG-800-21）在溫度130°C反應20分鐘時，得到最高的香豆素產率88%。 ;This study is divided into two parts. In the first part, taking advantage of mesoporous silica materials with high specific surface area, tunable pore size, and pore volume, sulfonic acid functional groups were directly synthesized on the surface of a series of three-dimensional mesoporous silica materials. Through SAXRD, BET, TEM, and XPS characterization, the structure and stability of the S16SX (X = 10, 15, 20, 25, 30) series catalysts were confirmed. This series of catalysts possesses high specific surface area, pore uniformity, and abundant acidic sites, and is expected to be applied in the catalytic Fischer esterification reaction of di(trimethylolpropane) (Di-TMP). By exploring the effects of different mesoporous silica structures, the ratio of sulfonic acid functional groups, different catalyst loading, and different ratios of acrylic acid to Di-TMP on the selective production of Di-TMPDA, it was found that the optimal reaction conditions were using 1.8 g of S16S20 as the catalyst with a starting material molar ratio of AA to Di-TMP of 2:1. Under the conditions of maintaining the temperature at 95°C and continuous water removal, after 24 hours of reaction, the proportion of Di-TMPDA in the total product was about 65%, and the production of Di-TMPTriA and Di-TMPTetraA was reduced. Therefore, the catalyst S16S20 exhibits high catalytic activity and can selectively produce the product Di-TMPDA. In the second part, wasted coffee grounds were transformed into porous biochar materials through hydrothermal acidic hydrolysis and KOH chemical activation methods under high-temperature calcination. The activated biochar was functionalized with sulfonic acid groups by reacting with 4-benzene-diazoniumsulfonate and hypophosphorous acid. Elemental analysis, XPS, TEM, and other characterizations confirmed the successful preparation of acidic biochar (S-WCG). This catalyst was applied in the Pechmann condensation reaction of resorcinol with ethyl acetoacetate to synthesize 7-hydroxy-4-methylcoumarin. The study explored the effects of calcination temperature, KOH ratio, catalyst loading, and reaction temperature on the catalytic activity. Finally, under the conditions of a calcination temperature of 800°C and a KOH-to-carbon source ratio of 2:1, the acidic wasted coffee ground-derived biochar (S-WCG-800-21) achieved the highest coumarin yield of 88% at 130°C in 20 minutes.
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