Modulated Hydrothermal Synthesis of UiO-66(Hf)-Type Metal–Organic Frameworks for Optimal Carbon Dioxide Separation

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• 作者：Zhigang Hu ; Anjaiah Nalaparaju ; Yongwu Peng ; Jianwen Jiang ; Dan Zhao
• 刊名：Inorganic Chemistry
• 出版年：2016
• 出版时间：February 1, 2016
• 年：2016
• 卷：55
• 期：3
• 页码：1134-1141
• 全文大小：618K
• ISSN：1520-510X

文摘

Recently, there has been growing interest in hafnium (Hf) metal–organic frameworks (MOFs). These MOFs may perform better as gas adsorbents than zirconium (Zr) MOFs due to the presence of Br?nsted acid sites with high affinity toward adsorbates, together with the outstanding chemical and hydrothermal stabilities similar to their Zr analogues. However, Hf-MOFs have been rarely reported due to the lack of effective synthetic methods. We herein report a modulated hydrothermal synthesis of UiO-66(Hf)-type MOFs. Among these MOFs, UiO-66(Hf)-(OH)₂ possesses a very high CO₂ gravimetric uptake of 1.81 mmol g^–1 at 0.15 bar and 298 K, which is 400% higher than that of UiO-66(Hf) (0.36 mmol g^–1). It also exhibits a record-high volumetric CO₂ uptake of 167 v/v at 1 bar and 298 K. Ideal adsorbed solution theory calculations showed a CO₂/N₂ (molar ratio 15:85) selectivity of 93 and CO₂/H₂ (molar ratio 30:70) selectivity above 1700. Breakthrough simulations also confirmed its optimal CO₂ separation attribute. Our results have demonstrated for the first time the strong potential of Hf-MOFs for advanced adsorbents for high-performance CO₂-related separations.