The chemical nature of surface point defects on MoO3(010):: Adsorption of hydrogen and methyl

We report density functional theory calculations using the Adaptive Coordinate Real-space Electronic structure (ACRES) method of the terminal oxygen vacancy on the (010) surface of MoO3, within a (2 x 2) ordered array of vacancies on the surface. Analysis of the electronic structure of this surface shows that there are unoccupied dangling d(xz) and d(z)(2) orbitals perpendicular to the surface that are created by the removal of terminal oxygen. The Mo-oxygen bonds surrounding the vacancy contract; however, the overall morphology of the surface is not drastically distorted. The vacancies alter the chemical character of the surface, as shown by studies of hydrogen and methyl binding. On both the perfect and vacancy surfaces, hydrogen was most strongly adsorbed over the terminal oxygen and most weakly bound over the symmetric bridging oxygen. Hydrogen is bound over the Mo atom, with a slightly smaller binding energy than hydrogen over the asymmetric bridging oxygen. The most favorable binding site for methyl on the vacancy surface is over the Mo atom exposed by removal of a terminal oxygen, whereas methyl bound to terminal oxygen is most stable on the perfect surface. There is no local minimum for adsorption over the symmetric bridging oxygen; instead, a methyl placed over this site moves toward the terminal oxygen vacancy. Anaylysis of the bonding shows that methyl is bound more strongly than hydrogen over the Mo atom because the C 2p orbital has better overlap with the Mo d(z2) orbital than the hydrogen Is. In addition, the steric repulsion observed for methyl over the perfect MoO3(010) surface is more easily relieved with the presence of the terminal oxygen vacancy.