Cooperative Carbon Dioxide Capture in Diamine-Appended Magnesium–Olsalazine Frameworks

Abstract

High Resolution Image Download MS PowerPoint Slide Diamine-appended Mg 2 (dobpdc) (dobpdc 4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) metal–organic frameworks have emerged as promising candidates for carbon capture owing to their exceptional CO 2 selectivities, high separation capacities, and step-shaped adsorption profiles, which arise from a unique cooperative adsorption mechanism resulting in the formation of ammonium carbamate chains. Materials appended with primary, secondary -diamines featuring bulky substituents, in particular, exhibit excellent stabilities and CO 2 adsorption properties. However, these frameworks display double-step adsorption behavior arising from steric repulsion between ammonium carbamates, which ultimately results in increased regeneration energies. Herein, we report frameworks of the type diamine–Mg 2 (olz) (olz 4– = ( E )-5,5′-(diazene-1,2-diyl)bis(2-oxidobenzoate)) that feature diverse diamines with bulky substituents and display desirable single-step CO 2 adsorption across a wide range of pressures and temperatures. Analysis of CO 2 adsorption data reveals that the basicity of the pore-dwelling amine─in addition to its steric bulk─is an important factor influencing adsorption step pressure; furthermore, the amine steric bulk is found to be inversely correlated with the degree of cooperativity in CO 2 uptake. One material, ee-2–Mg 2 (olz) (ee-2 = N, N -diethylethylenediamine), adsorbs >90% of the CO 2 from a simulated coal flue stream and exhibits exceptional thermal and oxidative stability over the course of extensive adsorption/desorption cycling, placing it among top-performing adsorbents to date for CO 2 capture from a coal flue gas. Spectroscopic characterization and van der Waals-corrected density functional theory calculations indicate that diamine–Mg 2 (olz) materials capture CO 2 via the formation of ammonium carbamate chains. These results point more broadly to the opportunity for fundamentally advancing materials in this class through judicious design.