Higher charge/discharge rates of lithium-ions across engineered TiO2 surfaces leads to enhanced battery performance.

Anatase TiO(2) having different percentages of (001)/(101) surface demonstrated different behaviors for Li(+) ions insertion and much enhanced rate performance of Li-ion batteries.

Growth velocity and direct length-sorted growth of short single-walled carbon nanotubes by a metal-catalyst-free chemical vapor deposition process.

We report on the observation of a very low growth velocity of single-walled carbon nanotubes (SWNTs) and consequently the direct length-sorted growth and patterned growth of SWNTs by using a metal-catalyst-free chemical vapor deposition (CVD) process proposed recently by our group, in which SiO(2) serves as catalyst. We found that the growth velocity of the SWNTs from SiO(2) catalyst is only 8.3 nm/s, which is about 300 times slower than that of the commonly used iron group catalysts (Co as a counterpart catalyst in this study). Such a slow growth velocity renders direct length-sorted growth of SWNTs, especially for short SWNTs with hundreds of nanometers in length. By simply adjusting the growth duration, SWNTs with average lengths of 149, 342, and 483 nm were selectively obtained and SWNTs as short as approximately 20 nm in length can be grown directly. Moreover, comparative studies indicate that the SiO(2) catalyst possesses a much longer catalytic active time, showing sharp contrast with the commonly used Co catalyst which quickly loses its catalytic activity. Taking advantage of the very slow growth velocity of the SiO(2) catalyst, patterned growth of SWNT networks confined in a narrow region of <5 microm was also achieved. The short SWNTs may show intriguing physics owing to their finite length effect and are attractive for various practical applications.

Solvothermal synthesis and photoreactivity of anatase TiO(2) nanosheets with dominant {001} facets.

Owing to wide-ranging industrial applications and fundamental importance, tailored synthesis of well-faceted single crystals of anatase TiO(2) with high percentage of reactive facets has attracted much research interest. In this work, high-quality anatase TiO(2) single-crystal nanosheets mainly dominated by {001} facets have been prepared by using a water-2-propanol solvothermal synthetic route. The synergistic functions of 2-propanol and HF on the growth of anatase TiO(2) single-crystal nanosheets were studied by first-principle theoretical calculations, revealing that the addition of 2-propanol can strengthen the stabilization effect associated with fluorine adsorption over (001) surface and thus stimulate its preferred growth. By measuring the (*)OH species with terephthalic acid scavenger, the as-prepared anatase TiO(2) single-crystal nanosheets having 64% {001} facets show superior photoreactivity (more than 5 times), compared to P25 as a benchmarking material.

Computational study of methyl derivatives of ammonia borane for hydrogen storage.

The structures and thermodynamic properties of methyl derivatives of ammonia-borane (BH3NH3, AB) have been studied with the frameworks of density functional theory and second-order Møller-Plesset perturbation theory. It is found that, with respect to pure, methyl ammonia-boranes show higher complexation energies and lower reaction enthalpies for the release of H2, together with a slight increment of the activation barrier. These results indicate that the methyl substitution can enhance the reversibility of the system and prevent the formation of BH3/NH3, but no enhancement of the release rate of H2 can be expected.

Anatase TiO2 single crystals with a large percentage of reactive facets.

Owing to their scientific and technological importance, inorganic single crystals with highly reactive surfaces have long been studied. Unfortunately, surfaces with high reactivity usually diminish rapidly during the crystal growth process as a result of the minimization of surface energy. A typical example is titanium dioxide (TiO2), which has promising energy and environmental applications. Most available anatase TiO(2) crystals are dominated by the thermodynamically stable {101} facets (more than 94 per cent, according to the Wulff construction), rather than the much more reactive {001} facets. Here we demonstrate that for fluorine-terminated surfaces this relative stability is reversed: {001} is energetically preferable to {101}. We explored this effect systematically for a range of non-metallic adsorbate atoms by first-principle quantum chemical calculations. On the basis of theoretical predictions, we have synthesized uniform anatase TiO(2) single crystals with a high percentage (47 per cent) of {001} facets using hydrofluoric acid as a morphology controlling agent. Moreover, the fluorated surface of anatase single crystals can easily be cleaned using heat treatment to render a fluorine-free surface without altering the crystal structure and morphology.

Functional anion concept: effect of fluorine anion on hydrogen storage of sodium alanate.

Doping NaAlH(4) with Ti-catalyst has produced a promising hydrogen storage system that can be reversibly operated at moderate temperature conditions. Of the various dopant precursors, TiCl(3) was well recognized due to its pronounced catalytic effect on the reversible dehydrogenation processes of sodium aluminium hydrides. Quite recently we experimentally found that TiF(3) was even better than TiCl(3) in terms of the critical hydrogen storage properties of the doped hydrides, in particular the dehydriding performance at Na(3)AlH(6)/NaH + Al step at moderate temperature. We present here the DFT calculation results of the TiF(3) or TiCl(3) doped Na(3)AlH(6). Our computational studies have demonstrated that F(-) and Cl(-) anions differ substantially from each other with regard to the state and function in the doped sodium aluminium hydride. In great contrast to the case of chloride doping where Cl(-) anion constitutes the "dead weight" NaCl, the fluoride doping results in a substitution of H(-) by F(-) anion in the hydride lattice and accordingly, a favorable thermodynamics adjustment. These results well explain the observed dehydriding performance associated with TiF(3)/TiCl(3)-doping. More significantly, the coupled computational and experimental efforts allow us to put forward a "functional anion" concept. This renews the current mechanism understanding in the catalytically enhanced sodium alanate.