UC Berkeley

Diamine-appended variants of the metal-organic framework M₂(dobpdc) (M = Mg, Mn, Fe, Co, Zn; dobpdc^4- = 4,4'-dioxidobiphenyl-3,3'-dicarboxylate) exhibit exceptional CO₂ capture properties owing to a unique cooperative adsorption mechanism, and thus hold promise for use in the development of energy- and cost-efficient CO₂ separations. Understanding the nature of thermal transport in these materials is essential for such practical applications, however, as temperature rises resulting from exothermic CO₂ uptake could potentially offset the energy savings offered by such cooperative adsorbents. Here, molecular dynamics (MD) simulations are employed in investigating thermal transport in bare and e-2-appended Zn₂(dobpdc) (e-2 = N-ethylethylenediamine), both with and without CO₂ as a guest. In the absence of CO₂, the appended diamines function to enhance thermal conductivity in the ab-plane of e-2-Zn₂(dobpdc) relative to the bare framework, as a result of noncovalent interactions between adjacent diamines that provide additional heat transfer pathways across the pore channel. Upon introduction of CO₂, the thermal conductivity along the pore channel (the c-axis) increases due to the cooperative formation of metal-bound ammonium carbamates, which serve to create additional heat transfer pathways. In contrast, the thermal conductivity of the bare framework remains unchanged in the presence of zinc-bound CO₂ but decreases in the presence of additional adsorbed CO₂.