Accurate descriptions of molecule-surface interactions for understanding CO2 capture by MgO-based sorbents in wet conditions

Abstract

MgO shows promise as a CO2 sorbent material for the intermediate temperature range. Here, a hybrid computation scheme, xDH:GGA that combines the XYG3-type of doubly hybrid (xDH) and the generalized gradient approximation (GGA) functionals, is applied. It aims to provide an accurate description of molecular-surface interactions to reduce calculation uncertainties in exploring CO2 capture mechanisms for MgO-based systems. After validating the accuracy of the hybrid scheme by modeling CO adsorption on both MgO(100) and NaCl(100) surfaces against the experimental results, CO2 capture in wet conditions is examined. The results highlight the importance of competitive adsorption between CO2 and water, which undermines the significance of the conventionally identified active sites on MgO surfaces. In contrast, the intermediate Mg(OH)2 layer emerges as a more viable active phase, whose presence was experimentally observed, where the layered structure of Mg(OH)2 is found to kinetically retard water dissociative adsorption. In addition to surface areas and pore structures, our study emphasizes the pivotal role played by selective CO2 chemical adsorption in the development of effective CO2 sorbent materials.