CO2 activation on pristine and defected honeycomb lattice 2D Fe2O3 monolayer: A DFT study
Abhishek Dhasmana1, Kamal Kumar1, Sravendra Rana1
1Applied Science Cluster, School of Advanced Engineering, UPES, Dehradun, Uttarakhand 248007, India.
Abstract:
Two-dimensional (2D) transition metal oxides (TMOs) have emerged as promising catalysts for carbon capture and utilization (CCU) by efficiently converting carbon dioxide (CO2) into C1 and C2+ chemicals and fuels. Here, we have employed density functional theory (DFT) calculations to investigate CO2 activation on pristine and defect-engineered 2D Fe2O3 monolayers (MLs). CO2 binds to pristine 2D Fe2O3 ML with an adsorption energy (Eads) of -1.09 eV, indicating moderate chemisorption. The presence of vacancies significantly modifies CO2 adsorption behavior. Oxygen (VO) and iron (VFe) monovacancies, and O and Fe (VO-Fe) divacancy, strengthen CO2 binding. Among these, VO exhibit the most favorable activation characteristics. Vibrational frequency analysis reveals a pronounced shift in vibrational modes at the VO site, along with substantial molecular bending (∠O-C-O∼128°), indicating bond weakening and enhanced reactivity. In contrast, VFe maximizes adsorption strength but stabilizes a nearly linear CO2 geometry, limiting activation.
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