Extended MOF-74-Type Variant with an Azine Linkage: Efficient Direct Air Capture and One-Pot Synthesis.

Direct air capture (DAC) shows considerable promise for the effective removal of CO; however, materials applicable to DAC are lacking. Among metal-organic framework (MOF) adsorbents, diamine-Mg(dobpdc) (dobpdc = 4,4-dioxidobiphenyl-3,3'-dicarboxylate) effectively removes low-pressure CO, but the synthesis of the organic ligand requires high temperature, high pressure, and a toxic solvent. Besides, it is necessary to isolate the ligand for utilization in the synthesis of the framework. In this study, we synthesized a new variant of extended MOF-74-type frameworks, M(hob) (M = Mg, Co, Ni, and Zn; hob = 5,5'-(hydrazine-1,2-diylidenebis(methanylylidene))bis(2-oxidobenzoate)), constructed from an azine-bonded organic ligand obtained through a facile condensation reaction at room temperature. Functionalization of Mg(hob) with -methylethylenediamine, -ethylethylenediamine, and ,'-dimethylethylenediamine (mmen) enables strong interactions with low-pressure CO, resulting in top-tier adsorption capacities of 2.60, 2.49, and 2.91 mmol g at 400 ppm of CO, respectively. Under humid conditions, the CO capacity was higher than under dry conditions due to the presence of water molecules that aid in the formation of bicarbonate species. A composite material combining mmen-Mg(hob) and polyvinylidene fluoride, a hydrophobic polymer, retained its excellent adsorption performance even after 7 days of exposure to 40% relative humidity. In addition, the one-pot synthesis of Mg(hob) from a mixture of the corresponding monomers is achieved without separate ligand synthesis steps; thus, this framework is suitable for facile large-scale production. This work underscores that the newly synthesized Mg(hob) and its composites demonstrate significant potential for DAC applications.