Direct Evidence of CO2 Capture under Low Partial Pressure on a Pillared Metal-Organic Framework with Improved Stabilization through Intramolecular Hydrogen Bonding

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• 作者：Zizhu Yao ; Yuan Chen ; Lizhen Liu ; Xiaonan Wu ; Shunshun Xiong ; Zhangjing Zhang and Shengchang Xiang
• 刊名：ChemPlusChem
• 出版年：2016
• 出版时间：August 2016
• 年：2016
• 卷：81
• 期：8
• 页码：850-856
• 全文大小：1720K
• ISSN：2192-6506

文摘

Direct structural observation of CO₂-loaded MOFs is helpful for revealing the specific binding interactions to allow the design of better CO₂ sorbents, but such direct structural evidence is almost always observed for pure-component CO₂ under a pressure of 1 atm or more, which does not really represent practical CO₂ capture and separation under low partial pressure (≤1 atm) in the presence of other gases. Herein, a series of isoreticular MOFs [Zn(Trz)(R-BDC)_1/2] (FJU-40-R, R=H, NH₂, Br, or OH) are synthesized. Among them, FJU-40-NH₂ exhibits the highest robustness, and good heat and water resistance, attributed to its intramolecular hydrogen-bonding interactions. A CO₂/N₂ (15:85, v/v) mixture can be separated efficiently through a column packed bed of FJU-40-NH₂ solid. The structures of CO₂-loaded FJU-40-NH₂ at 1 atm under various atmosphere conditions, including pure CO₂, CO₂/N₂ (15:85, v/v), and air, are observed, and it is found that: 1) the mechanism for CO₂ loading into the cages depends on the CO₂ partial pressure; 2) FJU-40-NH₂ can capture CO₂ directly from air, and CO₂ will have priority to occupy hydrophobic cage-I, whereas hydrophilic cage-II containing the amino group is occupied by H₂O molecules; 3) the triazolate C−H groups, rather than the amino groups in past observations in dry ice, act as predominant functional sites here under low CO₂ partial pressure.