Construction of a BC3-based TM single-atom catalyst for efficient reduction of CO2 to CH4: a computational study

Abstract

The electrocatalytic conversion of CO₂ into fuels or chemicals presents an effective approach to mitigate greenhouse gas emissions and address the traditional fuel crisis. Based on density functional theory, we systematically investigate a series of transition metal atoms bound to a BC₃ monolayer as novel single-atom catalysts (SACs) for the CO₂ reduction reaction (CO₂RR). Our results demonstrate that most of the constructed SACs exhibit superior selectivity for the CO₂RR over the hydrogen evolution reaction, with CH₄ as the dominant product. Notably, the Pt@BC₃ monolayer emerges as the best CO₂RR catalyst with a low limiting potential of −0.36 V, surpassing many previously reported catalysts. Additionally, we explore the correlations between the SAC's catalytic activity and both ΔG_*OCHO and the structural descriptor φ, revealing volcano relationships. A catalyst with better performance is constructed with the aid of the volcano diagram. These findings are beneficial for understanding the CO₂RR mechanism and designing efficient catalysts.