Computational investigation of CO2 activation on pristine and Al/Si-doped Ga12N12 and Ga12P12 nanoclusters.

Abstract

The catalytic conversion of CO2 remains a major challenge for achieving sustainable carbon utilization due to its higher thermodynamic stability and kinetic inertness. In this study, we employ density functional theory to examine the adsorption and activation of CO2 on atomically well-defined Ga12N12 and Ga12P12 nanoclusters, with emphasis on the influence of substitutional doping on their structural, electronic, and CO2 interaction characteristics. The observed results demonstrate that pristine Ga12N12 shows a moderate interaction with CO2 molecule, while substitutional doping substantially improves the interaction strength, with adsorption energy reaching up to -135.7 kJ/mol for Al-doped system. In contrast, Ga12P12 displays weak interaction with Eads of -13.2 kJ/mol, while doping leads to only a limited enhancement in adsorption strength. Charge transfer analysis reveals significant electronic redistribution at the CO2-nanocluster interface, providing insight into their electronic interactions. Overall, these findings provide insight into the relationship between nanocluster structure and CO2 activation, highlighting the role of electronic structure tuning in modulating CO2-nanocluster interactions. Therefore, these results provide a basis for the rational design of nanoclusters with tailored electronic characteristics to promote CO2 activation.

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