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Controlling Cooperative CO2 Adsorption in Diamine-Appended Mg2(dobpdc) Metal–Organic Frameworks

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posted on 02.07.2017, 00:00 authored by Rebecca L. Siegelman, Thomas M. McDonald, Miguel I. Gonzalez, Jeffrey D. Martell, Phillip J. Milner, Jarad A. Mason, Adam H. Berger, Abhoyjit S. Bhown, Jeffrey R. Long
In the transition to a clean-energy future, CO2 separations will play a critical role in mitigating current greenhouse gas emissions and facilitating conversion to cleaner-burning and renewable fuels. New materials with high selectivities for CO2 adsorption, large CO2 removal capacities, and low regeneration energies are needed to achieve these separations efficiently at scale. Here, we present a detailed investigation of nine diamine-appended variants of the metal–organic framework Mg2(dobpdc) (dobpdc4– = 4,4′-dioxidobiphenyl-3,3′-dicarboxylate) that feature step-shaped CO2 adsorption isotherms resulting from cooperative and reversible insertion of CO2 into metal–amine bonds to form ammonium carbamate chains. Small modifications to the diamine structure are found to shift the threshold pressure for cooperative CO2 adsorption by over 4 orders of magnitude at a given temperature, and the observed trends are rationalized on the basis of crystal structures of the isostructural zinc frameworks obtained from in situ single-crystal X-ray diffraction experiments. The structure–activity relationships derived from these results can be leveraged to tailor adsorbents to the conditions of a given CO2 separation process. The unparalleled versatility of these materials, coupled with their high CO2 capacities and low projected energy costs, highlights their potential as next-generation adsorbents for a wide array of CO2 separations.