Pyrene-Based Zinc-Organic Framework for Catalyzing Two Types of CO<sub>2</sub> Chemical Fixation
Gui Xiong, Mao Xu, Xiaohan Qin, Chaodan Xiong, Kun Huang, Xiang‐Yu Zhang
Abstract
Developing efficient metal–organic frameworks (MOFs) for catalytic CO 2 transformation has attracted significant interest worldwide, as it is crucial for environmental sustainability and sustainable development. Herein, we present a two-dimensional (2D) MOF {[Zn(Tip) 0.5 (nia 2– )]·H 2 O} n, namely, Zn-TN, based on 1, 3, 6, 8 - tetraimidazolyl-pyrene (Tip) and 5-(1,8-naphthalimido)-isophthalic acid (H 2 nia). Zn-TN has a (4, 4)-connected {4·6 4 ·8} 2 {4 2 ·6 4 } network and exhibits good thermal and solvent stability as well as a wide pH durability. In addition, Zn-TN can catalyze the fixation of CO 2 with propargylic amines to produce 2-oxazolidinones under mild conditions (60 °C, 1 atm of CO 2 ), and a gram-scale experiment has been successfully achieved. 1 H NMR data indicate that Zn-TN presents the capability of activating the acetylene bond of propargylic amine, together with 1, 4-diazabicyclo [2.2.2] octane (DABCO) to activate amine proton, which synergistically promotes the reaction. Besides, Zn-TN can promote CO 2 conversion with epoxides to produce cyclic carbonates under mild conditions (60 °C, 1 atm of CO 2 ) due to the activation of epoxides by Zn nodes in the framework. Notably, the catalyst Zn-TN can be reused five times in the two reactions mentioned above, demonstrating good reusability.