Evaluating Solvothermal and Mechanochemical Routes towards the Metal–Organic Framework Mg2(m-dobdc)

Abstract

Metal–organic frameworks bearing coordinatively unsaturated Mg(II) sites are promising materials for gas storage, chemical separations, and drug delivery due to their low molecular weights and lack of toxicity. However, there remains a limited number of such MOFs reported in the literature. Herein, we investigate the gas sorption properties of the understudied framework Mg2(m-dobdc) (dobdc4− = 4,6-dioxido-1,3-benzenedicarboxylate) synthesized under both solvothermal and mechanochemical conditions. Both materials are found to be permanently porous, as confirmed by 77 K N2 adsorption measurements. In particular, Mg2(m-dobdc) synthesized under mechanochemical conditions using exogenous organic base displays one of the highest capacities reported to date (6.14 mmol/g) for CO2 capture in a porous solid under simulated coal flue gas conditions (150 mbar, 40 °C). As such, mechanochemically synthesized Mg2(m-dobdc) represents a promising new framework for applications requiring high gas adsorption capacities in a porous solid.

Trapping of Photoluminescent Kinetic Intermediates During High-Concentration Synthesis of Non-Emissive Metal-Organic Frameworks

“…The large scales at which these two-step syntheses furnish high-quality M2(dobdc) without the requirement for specialized equipment gives this method an edge over state-of-the-art alternatives, such as mechanochemical syntheses that require ball mills. 39,45,78,79 A break in this trend was observed for the Zn congener (SI Section 13). Although CORN-MOF-1 (Zn) was not observed, its attempted synthesis at a linker concentration of 1.0 M yielded the known one-dimensional polymer Zn2(H2dobdc) instead (SI Figure S77).…”