IL5. Interactions of CO₂ with metal organic frameworks and metal oxide nanoclusters

Acid gases, especially CO₂, play an important role in a range of large-scale energy applications. Acid gas conversion can make use of reactive sorbents and catalysts, but these materials must not substantially degrade under operating conditions. Metal oxides, metal organic frameworks, and clays may be used for these purposes, but interactions of acid gases with these complex materials are poorly understood. In order to improve our understanding of such materials, we have been using electronic structure methods to better understand these interactions in terms of ‘physisorption’ and ‘chemisorption’ type processes. The interactions of CO₂ with models of MOF-2 (M₂BDC₄ for M = Co²⁺, Cu²⁺, and Zn²⁺), Group II oxide nanoclusters, Group IV and Group VI transition metal oxide nanoclusters, and actinide oxides have been predicted with density functional theory benchmarked by correlated molecular orbital theory calculations at the CCSD(T) level. The results are being correlated in terms of molecular properties such as Lewis acidities, redox capability, bond energies, and complexation energies. The work is supported by the Department of Energy, Basic Energy Sciences EFRC (UNCAGE-ME) and Geochemistry programs.