Reticular Synthesis of HKUST-like tbo-MOFs with Enhanced CH4 Storage

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• 作者：Ioannis Spanopoulos ; Constantinos Tsangarakis ; Emmanuel Klontzas ; Emmanuel Tylianakis ; George Froudakis ; Karim Adil ; Youssef Belmabkhout ; Mohamed Eddaoudi ; Pantelis N. Trikalitis
• 刊名：Journal of the American Chemical Society
• 出版年：2016
• 出版时间：February 10, 2016
• 年：2016
• 卷：138
• 期：5
• 页码：1568-1574
• 全文大小：431K
• ISSN：1520-5126

文摘

Successful implementation of reticular chemistry using a judiciously designed rigid octatopic carboxylate organic linker allowed the construction of expanded HKUST-1-like tbo-MOF series with intrinsic strong CH₄ adsorption sites. The Cu-analogue displayed a concomitant enhancement of the gravimetric and volumetric surface area with the highest reported CH₄ uptake among the tbo family, comparable to the best performing metal organic frameworks (MOFs) for CH₄ storage. The corresponding gravimetric (BET) and volumetric surface areas of 3971 m² g^–1 and 2363 m² cm^–3 represent an increase of 115% and 47%, respectively, in comparison to the corresponding values for the prototypical HKUST-1 (tbo-MOF-1), and are 42% and 20% higher than that of tbo-MOF-2. High-pressure methane adsorption isotherms revealed a high total gravimetric and volumetric CH₄ uptakes, reaching 372 cm³ (STP) g^–1 and 221 cm³ (STP) cm^–3, respectively, at 85 bar and 298 K. The corresponding working capacities between 5 and 80 bar were found to be 294 cm³ (STP) g^–1 and 175 cm³ (STP) cm^–3 and are placed among the best performing MOFs for CH₄ storage particularly at relatively low temperature. To gain insight on the mechanism accounting for the resultant enhanced CH₄ storage capacity, molecular simulation study was performed and revealed the presence of very strong CH₄ adsorption sites near the organic linker with similar adsorption energetics as the open metal sites. The present findings support the potential of tbo-MOFs based on the supermolecular building layer (SBL) approach as an ideal platform to further enhance the CH₄ storage capacity via expansion and functionalization of the quadrangular pillars.