Diffusion doping of cobalt in rod-shape anatase TiO\u3csub\u3e2\u3c/sub\u3e nanocrystals leads to antiferromagnetism†

Cobalt(II) ions were adsorbed to the surface of rod-shape anatase TiO2 nanocrystals and subsequently heated to promote ion diffusion into the nanocrystal. After removal of any remaining surface bound cobalt, a sample consisting of strictly cobalt-doped TiO2 was obtained and characterized with powder Xray diffraction, transmission electron microscopy, UV-visible spectroscopy, fluorescence spectroscopy, X-ray photoelectron spectroscopy, SQUID magnetometry, and inductively-coupled plasma atomic emission spectroscopy. The nanocrystal morphology was unchanged in the process and no new crystal phases were detected. The concentration of cobalt in the doped samples linearly correlates with the initial loading of cobalt(II) ions on the nanocrystal surface. Thin films of the cobalt doped TiO2 nanocrystals were prepared on indium-tin oxide coated glass substrate, and the electrical conductivity increased with the concentration of doped cobalt. Magnetic measurements of the cobalt-doped TiO2 nanocrystals reveal paramagnetic behavior at room temperature, and antiferromagnetic interactions between Co ions at low temperatures. Antiferromagnetism is atypical for cobalt-doped TiO2 nanocrystals, and is proposed to arise from interstitial doping that may be favored by the diffusional doping mechanism

Kirkendall Growth of Hollow Mn₃O₄ Nanoparticles upon Galvanic Reaction of MnO with Cu²⁺ and Evaluation as Anode for Lithium-Ion Batteries

We report the formation of high surface area hollow Mn₃O₄ nanoparticles that form as a result of the galvanic reaction of Cu²⁺ with MnO nanocrystals concomitant with a nanoscale Kirkendall effect. The MnO nanocrystals were prepared according to the ultralarge scale synthesis reported by Hyeon, which allowed the preparation of hollow Mn₃O₄ in multigram quantities. Ex-situ analyses with transmission electron microscopy and powder X-ray diffraction show the morphology and phase stability of the hollow particles correlate with DSC-TGA data and show collapse of the hollow particles at temperatures greater than 200 °C. Electrodes fabricated from hollow Mn₃O₄ exhibited excellent initial Li ion storage capability (initial discharge capacity = 1324 mAh/g) but poor cycling performance (97% loss of discharge capacity after 10th cycle), whereas Mn₃O₄-MWCNT electrodes exhibited good reversibility and discharge capacity of 760 mAh/g after 100 cycles

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 (₆<i>C</i>₂ = 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