混合基質薄膜（mixed-matrix membranes， MMMs）結合了傳統高分子薄膜的加工性與多孔填料之氣體選擇性，是一種具備高度氣體分離潛力之材料。在眾多填料中，金屬有機框架材料（metal organic frameworks， MOFs）因具有高比表面積、可彈性調控的孔洞結構與對特定氣體的親和性，常被選為MMMs的填料。然而，MOFs的合成與洗滌以及MMMs的製備常需依賴具高溶解力的極性非質子溶劑像是 N，N-dimethylformamide（DMF）與 N-methyl-2-pyrrolidone（NMP），這些溶劑具有環境與安全疑慮。加上近年來環保法規日益嚴峻，尋找合適的替代溶劑已成為材料合成領域的重要課題。 為提升 MOFs 基MMM製程之永續性，本研究不使用任何高度關注清單上之化學物質，並且以生質來源之極性非質子溶劑 Cyrene 作為綠色溶劑，應用於 HKUST-1 之合成與 HKUST-1/聚碸（polysulfone， PSF）MMMs之製備。HKUST-1 具有高比表面積與開放的Cu 金屬位點，可提供豐富的氣體傳輸路徑並提升對 CO2 的親和性，因此被選為本研究之 MOF 填料，所製備之薄膜進一步用於 CO2/N2 煙道氣體分離。 FTIR與XRD鑑定結果顯示，成功的以Cyrene合成純淨且無殘留配體的HKUST-1。氮氣吸脫附分析顯示，Cyrene合成之 HKUST-1 具有 1109 m2/g 之 BET 比表面積，並主要保有微孔結構。SEM結果顯示Cyrene 合成之 HKUST-1 具有部分形貌缺陷與顆粒堆疊，將 HKUST-1 導入 PSF 聚合物後，透過FTIR 與 XRD 鑑定，證實了 HKUST-1 成功的摻入薄膜中，且其晶體結構於薄膜製備後仍可維持。SEM-EDX 分析顯示，HKUST-1 在混合基質薄膜中有著良好的分散性，未觀察到嚴重大範圍團聚或明顯填料沉澱現象，此現象得益於Cyrene的高黏度與高密度。氣體滲透測試結果顯示，10 wt% HKUST-1/PSF 混合基質薄膜具有最佳 CO2/N2 分離表現，其 CO2 滲透率為 8.193 Barrer，CO2/N2 理想選擇性為 32.00，相較於純 PSF 薄膜分別提升 35.8% 與 25.2%。 這項研究證實 Cyrene 可同時作為 HKUST-1 合成與MMMs製備之綠色溶劑，並為氣體分離薄膜提供一條可兼具分離效能與製程永續性的可行路徑。;Mixed-matrix membranes (MMMs) are composed of polymer and porous fillers. This combination allows MMMs to keep the processability of conventional polymer membranes while introducing the gas selectivity of porous fillers. Among various fillers， metal-organic frameworks (MOFs) are often selected for MMM preparation because they have adjustable porous structures， large surface area， and interaction sites for specific gas molecules. However， the synthesis and washing of MOFs， as well as the fabrication of MMMs， often rely on polar aprotic solvents with strong solvency， such as N，N-dimethylformamide (DMF) and N-methyl-2-pyrrolidone (NMP)， which raise environmental and safety concerns. In addition， with increasingly stringent environmental regulations in recent years， finding suitable alternative solvents has become an important issue in material synthesis and membrane fabrication. To improve the sustainability of MOF-based MMMs fabrication， this study avoided the use of any substances of very high concern (SVHCs) listed under REACH throughout the entire process and employed Cyrene， a biodegradable polar aprotic solvent， as a green solvent for the synthesis of HKUST-1 and the preparation of HKUST-1/polysulfone MMMs. HKUST-1 was selected as the MOF filler because its porous framework and open Cu sites can provide additional gas transport pathways and enhance CO2 affinity. The prepared membranes were then applied to CO2/N2 flue gas separation. The results confirmed that HKUST-1 was successfully synthesized using Cyrene and retained its characteristic chemical structure and crystalline framework. N2 adsorption-desorption analysis showed that the synthesized HKUST-1 possessed a BET specific surface area of 1109 m2/g and retained a predominantly microporous structure. After incorporation into the PSF matrix， FTIR and XRD results verified the presence of HKUST-1 in the MMMs， while SEM-EDX analysis showed acceptable filler distribution without severe large-scale agglomeration or obvious filler sedimentation. This favorable filler distribution may have benefited from the high viscosity of Cyrene. Performance evaluations revealed that incorporating 10 wt% HKUST-1 yielded the most favorable CO2/N2 separation properties. This optimal formulation demonstrated a CO2 permeability of 8.193 Barrer and a selectivity of 32.00， corresponding to respective enhancements of 35.8% and 25.2% over the pristine PSF polymer. Overall， this work demonstrates that Cyrene can be used as a greener solvent for both HKUST-1 synthesis and PSF-based MMM fabrication. The improved CO2/N2 separation performance of the HKUST-1/PSF MMMs suggests that this Cyrene-assisted route provides a feasible and more sustainable approach for preparing MOF-based membranes for CO2/N2 separation.
