Quantitative Attachment of Bimetal Combinations of Transition-Metal Ions to the Surface of TiO₂ Nanorods

We report the sequential, quantitative loading of transition-metal ions (Cr³⁺, Mn²⁺, Fe²⁺, Co²⁺, Ni²⁺, and Cu²⁺) onto the surface of rod-shaped anatase TiO₂ nanocrystals in bimetallic combinations (₆C₂ = 15) to form M,M′-TiO₂ nanocrystals. The materials were characterized with transmission electron microscopy (TEM), powder X-ray diffraction (XRD), elemental analysis, X-ray photoelectron spectroscopy (XPS), and UV-visible spectroscopy. TEM and XRD data indicate that the sequential adsorption of metal ions occurs with the retention of the phase and morphology of the nanocrystal. Atomistic models of the M,M′-TiO₂ nanocrystals were optimized with density functional theory calculations. Calculated UV-visible absorption spectra and partial charge density maps of the donor and acceptor states for the electronic transitions indicate the importance of metal-to-metal charge transfer (MMCT) processes.