Comparative study of CO2 activation on alkali metals encapsulated III-V hollow nanocages: An insight from first-principles calculations

Density functional theory calculations have been applied to explore a series of 12 selected nano-hollow cages A12X12for catalysis of CO2 to hydrogenated products. The reactivity order among the nanocages is found to be A(12)N(12)> A(12)P(12)> A(12)As(12). Among the 12 selected nano-hollow cages, only six nanocages are able to activate CO2 molecule. Surprisingly, endohedral doping of alkali metals (Li, Na, K) leads to a decrease in band gap, increases charge separation and hereby increases the adsorption energies. Additionally, while the undoped A(12)As(12) nanocages remain inert for CO2 activation alkali metal doped A(12)As(12) nanocages showed an increased level of CO2 activation. Furthermore, among the alkali metals, potassium doped endohedral nanocages showed increased adsorption energy and the least energy barrier for CO2 activation. These findings have immense importance to provide new ideas for the design of potential nanocages catalyst for CO2 reduction. (C) 2021 Elsevier B.V. All rights reserved.

Automated summary

Density functional theory calculations have revealed the influence of alkali metal doping on the activation of CO2 in nano-hollow cages A12X12, with potassium-doped endohedral nanocages showing the lowest energy barrier for CO2 activation. These findings provide new insights for the design of potential nanocage catalysts for CO2 reduction.