Surface sulfur functionalized defects on the synergistic and competitive effects of CO2 and H2O adsorption: Density functional theory study

• This study systematically elucidates the co-adsorption mechanisms of H 2 O and CO 2 . • Sulfur-doped defects enhance CO 2 adsorption primarily through van der Waals interactions . • Basal plane defects enhance adsorption by altering surface structures and increasing electron density. • The adsorption of water molecules is primarily driven by their strong polarity and hydrogen bonding interactions. • Under humid conditions, hydrogen bonding interactions with H 2 O enhance the adsorption of CO 2 . Heteroatom doping can significantly enhance the CO 2 adsorption capacity of carbon-based materials, but it also increases the hydrophilicity of the carbon matrix. This can lead to the competitive adsorption of CO 2 and H 2 O becoming more pronounced in humid environments. In this study, the co-adsorption behaviors of H 2 O and CO 2 on carbon surfaces modified with various sulfur functional groups were investigated at the molecular level using density functional theory. The adsorption mechanisms were comprehensively analyzed through IGMH, QTAIM, EDA-FF, and charge transfer analysis. ESP analysis revealed that the absolute values of the local maxima and minima of the water molecules’ electrostatic potential were higher than those of CO 2 , indicating that water molecules exhibit greater adsorption stability and hydrogen bonding capability on highly polar functional groups. QTAIM analysis identified the specific interaction pathways and strengths between the atoms of CO 2 and H 2 O, while IGMH analysis showed that the interactions between CO 2 , H 2 O, and the porous carbon are primarily weak van der Waals forces. EDA-FF results indicate that electrostatic and dispersive interactions are the dominant forces in the co-adsorption of CO 2 and H 2 O. The enhanced adsorption stability of CO 2 in the co-adsorption system is mainly due to the additional unsaturated carbon sites created by basal defects, which significantly strengthen the van der Waals interactions of CO 2 . Additionally, hydrogen bonding between CO 2 and H 2 O further promotes CO 2 adsorption energy. This study underscores the critical role of sulfur functionalization in modulating adsorption behavior on carbon surfaces and provides valuable theoretical insights for designing advanced adsorbent materials capable of synergistically adsorbing multi-component gases.