Fe-Catalyzed CO₂ Adsorption over Hexagonal Boron Nitride with the Presence of H₂O

The energy barrier of CO₂ chemically adsorbed on hexagonal boron nitride (h-BN) is relatively big. In order to cut down the energy barriers and facilitate fast adsorption of CO₂, it is necessary to apply catalysts as a promoter. In this study, single-atom iron is introduced as the catalyst to reduce the energy barriers of CO₂ adsorbed on pure/doped h-BN. Through density functional theory calculations, catalytic reaction mechanisms, stability of single-atom iron fixed on adsorbents, CO₂ adsorption characteristics, and features of thermodynamics/reaction dynamics during adsorption processes are fully investigated to explain the catalytic effects of single-atom iron on CO₂ chemisorption. According to calculations, when CO₂ and OH^- get into activated states (i.e., CO₂^•- and ^•OH) with the help of single-atom iron, their chemical activities will be promoted to a large degree, which makes the transition state (TS) energy barrier of HCO₃^- to decrease by 92.54%. In the meantime, it is proved that single-atom iron could be stably fixed on doped h-BN with the binding energy larger than 2 eV to achieve sustainable catalysis. With the presence of single-atom iron, TS energy barriers of CO₂ adsorbed on h-BN with the presence of H₂O decreased by 94.39, 78.87, and 30.63% over pure h-BN, 3C-doped h-BN, and 3N-doped h-BN, respectively. In the meantime, thermodynamic analyses indicate that TS energy barriers are mainly determined by element doping and temperatures are a little beneficial to the reduction of TS energy barriers. With the above aspects combined, the results of this study could supply crucial information for massively and quickly capturing CO₂ in real industries.