Viability of transition metal decorated phosphorene nanoflakes as catalysts for carbon dioxide reduction: A theoretical study

The reduction of CO₂ using transition metal-decorated phosphorene catalysts was investigated via computational methods. Calculations revealed that metal-phosphorene interactions modulate catalytic activity. Phosphorene nanoflakes decorated with metals exhibited Gibbs free binding energies between −73.3 and − 83.2 kcal/mol, with Mn showing the highest binding energy. Reaction pathway studies indicated that CO₂ reduction with H₂ favors HCOOH formation over CO. Subsequent reduction of HCOOH to CH₂O and CH₃OH displayed lower energy barriers for Mn and Fe, while Ni showed inferior efficacy. CH₄ formation from MeOH required high activation energies, becoming viable only under moderate heating (400 K). Results highlighted selectivity toward HCOOH and CH₃OH, avoiding direct CH₄ formation from CH₂O due to prohibitive kinetic barriers. Mn- and Fe-decorated phosphorene systems emerged as promising catalysts for CO₂ reduction, offering high activity and selectivity at ambient or moderately heated conditions, whereas Ni exhibited limitations.