Creating self-assembled arrays of mono-oxo (MoO3)1 species on TiO2(101) via deposition and decomposition of (MoO3)n oligomers.

Hierarchically ordered oxides are of critical importance in material science and catalysis. Unfortunately, the design and synthesis of such systems remains a key challenge to realizing their potential. In this study, we demonstrate how the deposition of small oligomeric (MoO3)1-6 clusters-formed by the facile sublimation of MoO3 powders-leads to the self-assembly of locally ordered arrays of immobilized mono-oxo (MoO3)1 species on anatase TiO2(101). Using both high-resolution imaging and theoretical calculations, we reveal the dynamic behavior of the oligomers as they spontaneously decompose at room temperature, with the TiO2 surface acting as a template for the growth of this hierarchically structured oxide. Transient mobility of the oligomers on both bare and (MoO3)1-covered TiO2(101) areas is identified as key to the formation of a complete (MoO3)1 overlayer with a saturation coverage of one (MoO3)1 per two undercoordinated surface Ti sites. Simulations reveal a dynamic coupling of the reaction steps to the TiO2 lattice fluctuations, the absence of which kinetically prevents decomposition. Further experimental and theoretical characterizations demonstrate that (MoO3)1 within this material are thermally stable up to 500 K and remain chemically identical with a single empty gap state produced within the TiO2 band structure. Finally, we see that the constituent (MoO3)1 of this material show no proclivity for step and defect sites, suggesting they can reliably be grown on the (101) facet of TiO2 nanoparticles without compromising their chemistry.