Electrostatically tunable interaction of CO₂ with MgO surfaces and chemical switching: first-principles theory

Electric field-assisted CO₂ capture using solid adsorbents based on basic oxides can immensely reduce the required energy consumption compared to the conventional processes of temperature or pressure swing adsorption. In this work, we present first-principles density functional theoretical calculations to investigate the effects of an applied external electric field (AEEF) within the range from -1 to 1 V Å^-1 on the CO₂ adsorption behavior on various high and low-index facets of MgO. When CO₂ is strongly adsorbed on MgO surfaces to form carbonate species, the coupling of electric fields with the resulting intrinsic dipole moment induces a 'switch' from a strongly chemisorbed state to a weakly chemisorbed or physisorbed state at a critical value of AEEF. We demonstrate that such 'switching' enables access to different metastable states with variations in the AEEF. On polar MgO(111) surfaces, we find a distinct feature of the adsorptive dissociation of CO₂ towards the formation of CO in contrast to that on the non-polar MgO(100) and MgO(110) surfaces. In some cases, we observe broken inversion symmetry because of the AEEF that results in induced polarity at the interaction site of CO₂ on MgO surfaces. Our results provide fundamental insights into the possibility of using AEEFs in novel solid adsorbent systems for CO₂ capture and reduction.