Lab-to-Multigram-Scale Synthesis of a Zn(II) Metal–Organic Framework for Catalytic Carbon Dioxide Conversion at Atmospheric Pressure

Excessive CO 2 emissions primarily drive the Earth’s climate change, which can seriously endanger all living organisms. To alleviate the impact of CO 2 emissions, various approaches have been practiced. The conversion of CO 2 into value-added compounds is one of the effective methods to mitigate CO 2 emissions. Metal–organic frameworks (MOFs) have shown potential for transforming CO 2 into valuable cyclic carbonates. However, developing MOFs on a large scale remains challenging, particularly for dual-linker systems compared to single-linker systems. Herein, we present a scalable Zn-MOF1 [[Zn 2 (DHTPA) 1.5 (DATZ)(HDATZ)(DMF)] n (DHTPA = 2,5-dihydroxyterephthalate; HDATZ = 3,5-diamino-1,2,4-triazole; and DMF = N, N ′-dimethylformamide)], featuring abundant Brønsted and Lewis acidic sites and Lewis basic sites. The unsaturated Zn(II) centers adopt trigonal bipyramidal and tetrahedral geometries. Zn-MOF1 was synthesized via the reflux method using 20 g of precursors, achieving 83% yield within 4.5 h at 120 °C. Zn-MOF1 exhibits excellent catalytic performance, yielding 4-(chloromethyl)-1,3-dioxolan-2-one from CO 2 and 2-(chloromethyl)oxirane with 96% yield under atmospheric pressure in small-scale reactions (10 mmol). Zn-MOF1 achieved a 68% yield for the same product in large-scale reactions (230 mmol). This work presents the potential of Zn-MOF1 as an efficient, scalable catalyst for CO 2 conversion under atmospheric pressure for the large-scale synthesis of cyclic carbonates, paving the way for practical environmental applications.