金屬有機骨架（Metal–organic frameworks, MOFs）是一系列由規律排列的金屬節點和有機小分子連接器透過配位鍵自組裝而成的奈米孔洞材料，具有高比表面積和規律排列且互相連通的孔洞結構，可調控的孔徑大小以及可修飾官能基的特性。這些特點使得MOF近年來被廣泛應用於氣體捕捉與分離的領域。在應對全球氣候變遷的背景下，有效從空氣中捕捉極低濃度的二氧化碳（CO2）成爲一項重要且具挑戰的研究方向。本篇研究內容為探討MOF用於直接空氣捕捉二氧化碳（Direct Air Capture, DAC）的效用。首先選用具水穩定性的鋯基金屬有機骨架（Zirconium-based MOF, Zr-MOF） MOF-808為基底，透過溶劑輔助配體結合法分別成功在六鋯金屬節點上後修飾末端羥基/水基團（-OH/-OH2）、甲酸（FA）、三氟乙酸（TFA）、五氟丙酸（PFPA）、七氟丁酸（HFBA）等配體，得到一系列具有不同親疏水特性、相同骨架結構的Zr-MOFs材料。隨後將不同比例的四乙烯五胺(TEPA)以物理浸漬法引入一系列合成的Zr-MOFs中，使胺分子固定於MOF的奈米孔洞中形成固體吸附劑。接著為了評估吸附劑材料在DAC條件下對CO2的捕捉能力，測量這些固體吸附劑於298 K、0.3 mmHg 的CO2吸附等溫線。結果顯示，當TEPA浸漬比例為0.25時，以三氟乙酸修飾之MOF-808（MOF-808-TFA）擁有最佳的CO2吸附表現，吸附量可達1.02 mmol /g，相當於每個TEPA分子能夠捕獲約0.97個CO2分子。此結果表明MOF材料中金屬節點上引入的官能基對胺固定的固體吸附劑用於DAC捕捉有關鍵性的影響。顯示透過合理設計MOF孔洞表面的化學環境有助於開發更高效且可應用於實際DAC場域的固體吸附劑。

Metal–organic frameworks (MOFs) are nanoporous materials composed of metal nodes and organic linkers connected through coordination bonds. They possess high specific surface areas, well-ordered and interconnected pore structures, as well as tunable frameworks with modifiable functional groups. These unique characteristics make MOFs widely applicable in the fields of gas capture and storage. In this study, a water-stable MOF constructed from six-connected hexa-zirconium nodes, MOF-808, is subjected to various post-synthetic modifications to synthesize a series of isostructural frameworks with terminal hydroxo/aquo ligands, formate ligands, trifluoroacetate ligands, perfluoropropionate ligands, and heptafluorobutyrate ligands coordinated on its nodes, respectively. Tetraethylenepentamine (TEPA) impregnation is thereafter performed to immobilize the amine within nanopores of these MOFs, thereby forming solid adsorbents. Carbon dioxide (CO2) adsorption isotherms of these adsorbents are measured to examine their capabilities in capturing CO2 under a simulated condition of direct air capture, i.e., 0.3 mmHg CO2 at 298 K. The ratio between the amine and MOF during the impregnation is engineered, and findings suggest that both the chemical functional group present on the MOF nodes and the amine-to-MOF ratio are effective in adjusting the resulting adsorption capacity toward CO2. TEPA impregnated within the MOF-808 coordinated with trifluoroacetate ligands exhibits the highest CO2 adsorption capacity. Under the optimal amine-to-MOF ratio 0.25, the composite adsorbent can adsorb 1.02 mmol/g CO2 in 0.3 mmHg of CO2, equal to 0.97 CO2 captured by each impregnated TEPA molecule. The findings highlight the critical role of chemical functional groups on the porous supports used for amine impregnation in designing effective adsorbents for direct air capture.

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