DFT investigation of Ni-doped graphene: catalytic ability to CO oxidation

Herein, CO oxidation on Ni-doped graphene ( Ni-Gr) is investigated by first-principle calculations. The strong binding energy ( -7.57 eV) of the Ni atom at a single vacancy in graphene and high energy barrier ( 3.41 eV) for Ni atom mobility in graphene suggest that graphene is stable even after Ni doping, which avoids the problem of metal clustering. The stronger binding interaction between Ni-Gr and O-2 than that between Ni-Gr and CO can prevent CO poisoning to Ni-Gr. To explore the catalytic effect of CO oxidation on Ni-Gr, both the Eley-Rideal ( ER) and Langmuir-Hinshelwood ( LH) mechanisms are investigated. The overall energy barrier at 0 K for the LH and ER mechanisms is 0.63 and 0.77 eV, respectively. At 298.15 K, the overall energy barrier for the LH mechanism decreases to 0.58 eV, whereas that for the ER mechanism increases to 0.88 eV, which implies that CO oxidation on Ni-Gr prefers to proceed via the LH mechanism kinetically. Our results show that the studied system, Ni-Gr, has chemical stability against metal clustering and CO poisoning, and it is a promising catalyst for CO oxidation at mild temperatures. This study provides a good theoretical guideline for the development of Ni-Gr based CO oxidation catalysts.