(46d) First-Principles Modeling of Carbon Dioxide Capture and Conversion in Metal Organic Frameworks

The development of novel porous materials for CO2 capture from flue gas and other waste streams coupled with the conversion of CO2 into useful materials constitutes a grand challenge problem in today’s world. Capture of CO2 is critical to achieve in the short-term because fossil fuel use is expected to remain high for the next several decades. However, capturing CO2 is only half of the problem. What to do with the enormous quantities of CO2 generated from coal-fired power plants alone is a major challenge. The only alternative to sequestration is conversion of CO2 into fuel through hydrogenation. Ideally, one would have a technology that used a renewable energy source, such as solar or wind, to provide the reducing agent (e.g., hydrogen) to drive the conversion of CO2 into hydrogen-rich fuels.

In this work we provide examples of how electronic structure density functional theory (DFT) can be used to provide insight into the problems of CO2 capture and subsequent reduction through the addition of hydrogen to create value-added products. We report calculations on adsorption of CO2 and other small molecules in metal organic framework (MOF) materials using both classical and quantum mechanical simulations. We show that quantum mechanical DFT calculations provide important information about spin transitions and geometric relaxations in the MOFs that affect adsorption. We also demonstrate the utility of DFT methods for designing catalytically active MOFs for the reduction of CO2.