First-row transition metal atoms adsorption on rutile TiO2(110) surface

作者：Helali Zeineb; Markovits Alexis; Minot Christian^*; Abderrabba Manef

来源：Structural Chemistry, 2012, 23(5): 1309-1321.

DOI：10.1007/s11224-012-0058-3

• DFT
• TiO2 rutile
• Metal-oxide interface
• Reduction
• Charge transfer

We performed periodic DFT calculations for adsorption of metal atoms on a perfect rutile TiO2(110) surface (at low coverage, theta = 1/3) to investigate the interaction of an individual metal atom with TiO2 and to compare it with a study previously done on MgO(100). We considered partial period of Mendeleev's table from K to Zn. The overall evolution of the adsorption energies shows two maxima as for MgO(100). Two main differences, however, exist: the adsorption energy is much stronger and the first maximum is enhanced relative to the second one. This is attributed to the reducibility of the surface titanium cation. When the adsorbed metal is electropositive, it is oxidized under adsorption transferring electrons to titanium cations. We present the effect of introducing a Hubbard term to the gradient-corrected approximation band-structure Hamiltonian (GGA + U). The introduction of a reasonable Hubbard correction preserves the trends and allows localizing the electron of the reduction on Ti atoms in the near surface region. Finally, our results conclude that for heavier M atoms of the period, insertion is energetically favored relative to adsorption.

• 出版日期2012-10