The interplay between structural perfectness and CO oxidation catalysis on aluminum, phosphorous and silicon complexes of corroles

Catalytic oxidation of carbon monoxide on perfect and defective structures of corrole complexes with aluminum, phosphorous and silicon have been investigated by performing density functional theory calculations. The main objective is to highlight the effect of structural defects on the catalytic activity of corrole complexes for the CO oxidation reaction. Moreover, we also study how phenyl substitution at the meso or axial position of the corrole will affect its catalytic efficiency. It is shown that a vacancy defect leads to the formation of an interior cavity inside the corrole structure which hinders proper orientation of reacting O2 and CO molecules. While corrole complexes with aluminum may serve as potential catalysts for CO oxidation with a moderate energy barrier, phosphorous corrole displays superior catalytic activity with a very low energy barrier. We also demonstrate that phenyl substitution at the axial position reduces the catalytic activity of corrole complexes, whereas phenyl substitution at the meso sites does not change the activity of corrole complexes toward O2 and CO molecules. The results of the present study are promising to develop highly efficient single atom phosphorous–nitrogen–carbon catalysts for low temperature CO oxidation.