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The properties and applications of metal-organic frameworks (MOFs) are strongly dependent on the nature of the metals and linkers, along with the specific conditions employed during synthesis. Al-fumarate, trademarked as Basolite A520, is a porous MOF that incorporates aluminum centers along with fumarate linkers and is a promising material for applications involving adsorption of gases such as CO 2 . In this work, the solvothermal synthesis and detailed characterization of the gallium- and indium-fumarate MOFs (Ga-fumarate, In-fumarate) are described. Using a combination of powder X-ray diffraction, Rietveld refinements, solid-state NMR spectroscopy, IR spectroscopy, and thermogravimetric analysis, the topologies of Ga-fumarate and In-fumarate are revealed to be analogous to Al-fumarate. Ultra-wideline 69 Ga, 71 Ga, and 115 In NMR experiments at 21.1 T strongly support our refined structure. Adsorption isotherms show that the Al-, Ga-, and In-fumarate MOFs all exhibit an affinity for CO 2 , with Al-fumarate being the superior adsorbent at 1 bar and 273 K. Static direct excitation and cross-polarized 13 C NMR experiments permit investigation of CO 2 adsorption locations, binding strengths, motional rates, and motional angles that are critical to increasing adsorption capacity and selectivity in these materials. Conducting the synthesis of the indium-based framework in methanol demonstrates a simple route to introduce porous hydrophobicity into a MIL-53-type framework by incorporation of metal-bridging -OCH 3 groups in the MOF pores.

acs applied materials and interfaces

Welcoming Gallium- and Indium-Fumarate MOFs to the Family: Synthesis, Comprehensive Characterization, Observation of Porous Hydrophobicity, and CO<sub>2</sub> Dynamics

Welcoming Gallium- and Indium-Fumarate MOFs to the Family: Synthesis, Comprehensive Characterization, Observation of Porous Hydrophobicity, and CO2 Dynamics

Welcoming Gallium- and Indium-Fumarate MOFs to the Family: Synthesis, Comprehensive Characterization, Observation of Porous Hydrophobicity, and CO₂ Dynamics