A comparison of CO oxidation on cleaned ZnO $$(10\overline{1 }0)$$ surface and defective ZnO $$(10\overline{1 }0)$$ surface using density functional theory studies

Abstract

In this work, we employed continuously the DFT calculations to study CO oxidation reaction on the defective ZnO [Formula: see text] surface. The oxygen (O) atom was removed from cleaned surface ZnO [Formula: see text] (CS-ZnO) to form the defective ZnO [Formula: see text] surface (DS-ZnO), which contained an O vacancy defect. Hereafter, the formation of oxygen vacancy was found to increase the adsorption abilities of O2 and CO on DS-ZnO, in comparison to those on CS-ZnO. Many steps of elementary reactions including O2 and CO adsorption, reacting between CO and O to form CO2, and CO2 desorption on DS-ZnO were investigated and calculated in terms of the configurations, activation energy, and reaction energy, to which the reaction pathway of CO oxidation has been found. Based on this pathway, the calculation results of the rate controlling step of 0.84eV corresponding to the exothermic reaction energy of 4.11eV on DS-ZnO indicated that the CO oxidation on DS-ZnO was more thermodynamically favorable and less kinetically desirable than that on CS-ZnO. In addition, the natural bonds of O2 and CO adsorptions on DS-ZnO were also analyzed by the partial density of state (PDOS) and the electron density difference (EDD) contour plots.