Acta Phys. -Chim. Sin. ›› 2017, Vol. 33 ›› Issue (9): 1796-1802.

• ARTICLE •

### Effect of Ni Doping on Electron Transfer in Ni/MgO Catalysts

Yun-Peng GUO,Jie FENG,Wen-Ying LI*()

• Received:2017-04-03 Published:2017-07-05
• Contact: Wen-Ying LI E-mail:ying@tyut.edu.cn

Abstract:

First-principles calculations based on density functional theory (DFT) have been used to investigate how Ni doping in the supporter impacts CH4/CO2 reforming over Ni/MgO catalysts. Ni8 clusters supported on different NixMgyO27(100) slabs (x+y= 27) have been selected to model Ni/MgO catalysts with different Ni : Mg ratio. The CH4/CO2 reforming mechanisms on different Ni8/NixMgyO27(100) slabs indicate that the energy barriers of CH4 dissociated adsorption and CHx oxidation both increase with an increase in the Ni : Mg ratio of the supporter. CH would be easily generated from the pyrolytic carbon. The electron structure analysis shows that the direction of electron transfer changes to "between metal and supporter" with increasing Ni : Mg ratio of the supporter, but not to "from supporter to metal" on pure Ni/MgO. When the Ni cluster is negative, electron transfer occurs between adsorbed species and Ni atoms in the surface layer of the Ni cluster, and CH2 is the main species for CHx oxidation. When the Ni cluster is positive, its Hirshfeld is stable, electron transfer occurs between adsorbed species and Ni atoms in the surface layer of the NiO-MgO solid solution, and CH is the main oxidative species. The electron deficiency of the Ni cluster is the reason for the poor catalytic performance of Ni/MgO with a high Ni doping ratio.

MSC2000:

• O641