Development of Materials-by-Design for CO2 Capture Applications

"The efficient separation and storage of CO2 from power plant flue gases can reduce the amount of CO2 released into the atmosphere and mitigate global warming. Potential candidates for industrial applications are solid sorbent materials. Crucial factors to control the efficiency of porous sorbent materials include the framework and pore structure, and the chemical and physical reactivity of CO2 within the pores. Computational modeling approaches, based on density functional theory (DFT) and van der Waals-DFT, have been applied to nanoporous solid – manganese dioxide a-MnO2. We found that the types and charges of cations as dopants in the a-MnO2 and the concentration of CO2 influence the structural features of a-MnO2, which control its CO2 selectivity performance within the flue gases.IntroductionCarbon capture and storage is a technique to separate large quantities of CO2 from power plant flue gases before being released into the atmosphere. Porous solids are a potential candidate as sorbents to “trap” CO2 through chemical or physical adsorption on their porous surfaces[1]. Such separation efficiency is determined by the size and shape of its pores and by the interaction between the porous surface and the gas adsorbates. The incorporation of cations into the pore can act as a means of structural support and alter the pore diameter to be comparable to the kinetic diameter of the gas adsorbate, such as CO2.A porous solid of particular interest for CCS is manganese dioxide a-MnO2, an octahedral molecular sieve (OMS) composed of edge-sharing MnO6 octahedra that are linked into a nanoporous framework[2]. The framework consists of (1×1) and (2×2) tunnels, referred to as OMS-2. Due to the larger tunnel size, cations and gas adsorbates prefer to reside along the (2×2) tunnel axis of the OMS-2. As seen in Figure 1, a potassium cation K+ is located in the (2×2) tunnel, known as cryptomelane-type MnO2. Its pore diameter of ~ 4.6 Å gives it a good CO2 selectivity performance, because the diameter is comparable to the kinetic diameter of 3.3 Å for CO2[3]. Alternatively, replacing potassium K+ with other cations, e.g. barium Ba2+, sodium Na+ or lithium Li+, in the OMS-2 tunnel is of great research interest, due to the effects of their concentrations, types and charges on the CO2 selectivity efficiency and sorption hysteresis phenomenon[2,4]."