CO2 reduction to CH4 on Cu-doped phosphorene: a first-principles study

Optimizing the electrochemical carbon dioxide reduction reaction (CRR) to fuels is one of the most significant challenges in materials science and chemistry. Recently, single metal atom catalysts based on 2D materials have shown promise to improve the electroreduction performance of pristine 2D materials in the CRR. The physical origins of such performance enhancements are still poorly understood. Herein, we report the potential of a single Cu atom doped phosphorene catalyst for CO2 electroreduction based on density functional theory (DFT) calculations. The doping sites (hollow, bridge, and on-top) of Cu on phosphorene are investigated first. Phosphorene with a Cu atom anchored on the hollow site is chosen for further study. The pathways for different CRR products, including HCOOH, CO, CH3OH, and CH4, are examined via constructing free energy diagrams and via comparing the limiting potentials. CH4 is the most likely product after analysis of the adsorption energies and free energy pathways. Cu-Doped phosphorene in general shows improved CRR performance with lower limiting potential values. Cu doping leads to a decrease in the band gap value (about 0.2 eV), which is likely to be the physical origin of the CRR performance enhancement. Our study provides a novel promising CRR candidate catalyst based on phosphorene.