CO oxidation over defective and nonmetal doped MoS₂monolayers

Defective (missing S atoms) and nonmetal (C- and N-) doped MoS₂monolayers in the 2H and 1T' phases have been evaluated for catalyzing CO oxidation based on first-principles calculations. For the reaction 2CO + O₂→ 2CO₂, the oxidization of the first CO molecule is fairly easy and sometimes is even spontaneous, as the O₂ molecule is highly activated or dissociates upon adsorption. However, for the defective (2H-), C-doped (1T'-), and N-doped (2H- and 1T'-) MoS₂monolayers, the remaining O^*adatom often refuses to react with other CO molecules and is hard to be removed (barrier > 1.20 eV). Only when over the C-doped 2H- and defective 1T'-MoS₂monolayers, the removal of the second O^*adatom requires to overcome moderate barriers (0.74 and 0.88 eV, respectively) by reacting with another CO molecule via the Eley-Rideal mechanism and the catalysts are recovered. The barriers can be further reduced by applying either tensile or compressive strain to the MoS₂nanosheet. In contrast, the Langmuir-Hinshelwood mechanism is followed over the metal-containing MoS₂nanosheets, as the bigger size of metal dopants allow the co-adsorption of CO and O₂. Therefore, the C-doped 2H- and defective 1T'-MoS₂monolayers are promising nonmetal-doped catalysts for CO oxidation.