Cu@Phosphorene as a Promising Catalyst for CO₂ to Formic Acid Conversion: A Mechanistic DFT Approach

Carbon dioxide is naturally present in the Earth’s atmosphere and plays a role in regulating and balancing the planet’s temperature. However, due to various human activities, the amount of carbon dioxide is increasing beyond safe limits, disrupting the Earth’s natural temperature regulation system. Today, CO₂ is the most prevalent greenhouse gas; as its concentration rises, significant climate change occurs. Therefore, there is a need to utilize anthropogenically released carbon dioxide in valuable fuels, such as formic acid (HCOOH). Single-atom catalysts are widely used, where a single metal atom is anchored on a surface to catalyze chemical reactions. In this study, we investigated the potential of Cu@Phosphorene as a single-atom catalyst (SAC) for CO₂ reduction using quantum chemical calculations. All computations for Cu@Phosphorene were performed using density functional theory (DFT). Mechanistic studies were conducted for both bimolecular and termolecular pathways. The bimolecular mechanism involves one CO₂ and one H₂ molecule adsorbing on the surface, while the termolecular mechanism involves two CO₂ molecules adsorbing first, followed by H₂. Results indicate that the termolecular mechanism is preferred for formic acid formation due to its lower activation energy. Further analysis included charge transfer assessment via NBO, and interactions between the substrate, phosphorene, and the Cu atom were confirmed using quantum theory of atoms in molecules (QTAIM) and non-covalent interactions (NCI) analysis. Ab initio molecular dynamics (AIMD) calculations examined the temperature stability of the catalytic complex. Overall, Cu@Phosphorene appears to be an effective catalyst for converting CO₂ to formic acid and remains stable at higher temperatures, supporting efforts to mitigate climate change.