蜂窩狀整體式催化劑 Cordierite@MOFs 應用於二氧化碳環加成反應研究

Abstract

本論文旨在將金屬有機骨架材料塗布於蜂窩狀堇青石之催化劑載體，藉此製備整體式異相催化劑，應用於二氧化碳之環加成反應; 以整體式催化劑之形式相比於粉末型態催化劑，擁有提升催化劑在反 應後續處理之回收性及可重複利用性。本研究嘗試數種金屬有機骨架粉末，ZIF-67、PCN-222、PCN- 333(Al, Fe, Cr)、MIL-101 (Cr)、Al-TCPP、Al-TzDB、Al-TzDB-ZnPP 等，應用於 300 psi 的二氧化碳環加成反應。篩選出經由環加成反應 後，仍保有結晶性之 ZIF-67 及 Al-TCPP;並將兩者塗布於蜂窩狀堇 青石，後續成功合成出 Cordierite@ZIF-67 之金屬有機骨架複合材料， 將其用於二氧化碳還加成反應中。由實驗結果得知，相比於純 ZIF-67 粉末，Cordierite@ZIF-67 擁有較佳的轉化率(45 % v.s. 70 %) 及 TOF 值( 7 h-1 v.s. 90 h-1 )。且在環氧化物衍生物的催化中，也具有高度之催 化活性，擁有較高的轉換率(65 % - 89 %)。後續，將催化劑應用於 重複性測試中，在十次的循環催化實驗，平均轉換率仍保有 56 %。尤 其，此催化劑在後續回收上，並不需要複雜的分離動作，只需藉由簡 單溶劑清洗及乾燥，即可將其回收，可見其在工業領域中的發展潛力。This study aims to synthesize monolithic heterogeneous catalysts by coating metal-organic frameworks materials on honeycomb cordierite for CO2 cycloaddition; the recycling and reusability of catalysts in post- reaction treatment can be enhanced in the form of monolithic catalysts compared to powder catalysts.In this study, several metal-organic frameworks, ZIF-67, PCN-222, PCN-333 (Al, Fe, Cr), MIL-101 (Cr), Al-TCPP, Al-TzDB, Al-TzDB-ZnPP, were applied to the CO2 cycloaddition at 300 psi. ZIF-67 and Al-TCPP were retain their crystallinity after the reaction, and we tried to coat ZIF- 67 and Al-TCPP on honeycomb cordierite. Compared with the pure ZIF- 67 powder, Cordierite@ZIF-67 had a better conversion rate ( 45 % v.s. 70 % ) and TOF ( 7 h-1 v.s. 90 h-1 ). It also had high activity in the catalysis of epoxide derivatives with high conversion ( 65 % - 89 % ). Subsequently, the catalyst was applied to the reusability measurement, and the average conversion rate remained 56 % in ten cycles. In particular, this catalyst does not require complicated separation for recycle, and can be recovered by solvent wash and drying, which shows its potential for industrial development.