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

Excessive CO2 emissions primarily drive the Earth's climate change, which can seriously endanger all living organisms. To alleviate the impact of CO2 emissions, various approaches have been practiced. The conversion of CO2 into value-added compounds is one of the effective methods to mitigate CO2 emissions. Metal-organic frameworks (MOFs) have shown potential for transforming CO2 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 [[Zn2(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 CO2 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 CO2 conversion under atmospheric pressure for the large-scale synthesis of cyclic carbonates, paving the way for practical environmental applications.