Guanidyl-implanted UiO-66 as an efficient catalyst for the enhanced conversion of carbon dioxide into cyclic
Aijia Gao1, Fangfang Li1, Zhi Xu1
1The Key Laboratory of Functional Molecular Solids, Ministry of Education, Anhui Laboratory of Molecule-Based Materials (State Key Laboratory Cultivation Base), College of Chemistry and Materials Science, Anhui Normal University, Wuhu, Anhui 241002, P.R. China. yhzhou@ahnu.edu.cn.
Abstract:
The development of heterogeneous catalysts for promoting epoxide cycloaddition with carbon dioxide is highly desirable for recycling CO2 and achieving the goal of carbon neutrality. Herein, we designed and synthesized Zr-based metal organic frameworks (MOFs) by implanting functional guanidyl into the framework via mixing different molar ratios of 4-guanidinobenzoic acid (Gua) with 1,4-benzenedicarboxylic acid (BDC). Consequently, a small sized Zr-MOF (∼350 nm) can be prepared by implanting Gua with 20% molar ligands, denoted as UiO-66-Gua0.2(s). Compared to large sized and different guanidyl Zr-MOFs, UiO-66-Gua0.2(s) exhibited an optimal activity on catalyzing epoxide cycloaddition with CO2 in the presence of the Bu4NBr cocatalyst. A yield of 97% for the product of chloropropene carbonate was achieved at 90 °C under 1 atm CO2. The great performance of UiO-66-Gua0.2(s) might be attributed to the synergistic effect of guanidyl groups as hydrogen-bond donors and Zr centers acting as Lewis-acidic sites. In addition, the heterogeneous catalyst of UiO-66-Gua0.2(s) exhibited a great versatility towards converting other epoxides and a satisfactory recyclability for five consecutive runs. Moreover, a plausible reaction mechanism has been proposed for UiO-66-Gua0.2(s) in promoting CO2 epoxide cycloaddition reactions.
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