Ni-Doping Effects on Oxygen Removal from an Orthorhombic Mo2C (001) Surface: A Density Functional Theory Study

Density functional theory (DFT) calculations were used to investigate the effect of Ni dopants on the removal of chemisorbed oxygen (O*) from the Mo-terminated (TMo) and C-terminated (TC) Mo2C(001) surfaces. The removal of adsorbed oxygen from the catalytic site is essential to maintain the long-term activity and selectivity of the carbide catalysts in the deoxygenation process related to bio-oil stabilization and upgrading. In this contribution, the computed reaction energetics and reaction barriers of O* removal were compared among undoped and Ni-doped Mo2C(001) surfaces. The DFT calculations indicate that selected Ni-doped surfaces such as Ni adsorbed on TMo and TC Mo2C(001) surfaces enable weaker binding of important reactive intermediates (O*, OH*) compared to the undoped counterparts, which is beneficial for the O* removal from the catalyst surface. This study thus confirms the promoting effect of the Ni dopant on O* removal reaction on the TMo Mo2C(001) and TC Mo2C(001) surfaces. This computational...