Problems related to tremendous volume changes associated with cycling and the low electron conductivity and ion diffusivity of Si represent major obstacles to its use in high-capacity anodes for lithium ion batteries. We have developed a group IVA based nanotube heterostructure array, consisting of a high-capacity Si inner layer and a highly conductive Ge outer layer, to yield both favorable mechanics and kinetics in battery applications. This type of Si/Ge double-layered nanotube array electrode exhibits improved electrochemical performances over the analogous homogeneous Si system, including stable capacity retention (85% after 50 cycles) and doubled capacity at a 3C rate. These results stem from reduced maximum hoop strain in the nanotubes, supported by theoretical mechanics modeling, and lowered activation energy barrier for Li diffusion. This electrode technology creates opportunities in the development of group IVA nanotube heterostructures for next generation lithium ion batteries.

We combined first-principles calculations with several experimental studies to investigate the complex role for high oxygen storage capacity (OSC) in multivalent Pr-doped ceria. TPR and Raman spectra were measured for confirming oxygen vacancy concentration and oxygen mobility. The coordination number was fitted via EXAFS spectra, and it was the correlated DFT calculation that has been corrected as effective U (5.3 eV) to well express the reducing state (4+ → 3+) for both Ce and Pr elements. In our study, when Pr is incorporated into pure ceria, Pr3+ and Pr4+ ions are incorporated as majority and minority ions, respectively. Pr3+ ions play a key role to create oxygen vacancies and induce a local distortion, which improves oxygen mobility, and Pr4+ can contribute to diminishing reduction energy and a respectable OSC via the formation of an additional redox couple.

The effect of substituting sodium for calcium on enhanced osteoconductivity of hydroxyapatite was newly investigated. Sodium-substituted hydroxyapatite was synthesized by reacting calcium hydroxide and phosphoric acid with sodium nitrate followed by sintering. As a control, pure hydroxyapatite was prepared under identical conditions, but without the addition of sodium nitrate. Substitution of calcium with sodium in hydroxyapatite produced the structural vacancies for carbonate ion from phosphate site and hydrogen ion from hydroxide site of hydroxyapatite after sintering. The total system energy of sodium-substituted hydroxyapatite with structural defects calculated by ab initio methods based on quantum mechanics was much higher than that of hydroxyapatite, suggesting that the sodium-substituted hydroxyapatite was energetically less stable compared with hydroxyapatite. Indeed, sodium-substituted hydroxyapatite exhibited higher dissolution behavior of constituent elements of hydroxyapatite in simulated body fluid (SBF) and Tris-buffered deionized water compared with hydroxyapatite, which directly affected low-crystalline hydroxyl-carbonate apatite forming capacity by increasing the degree of apatite supersaturation in SBF. Actually, sodium-substituted hydroxyapatite exhibited markedly improved low-crystalline hydroxyl-carbonate apatite forming capacity in SBF and noticeably higher osteoconductivity 4 weeks after implantation in calvarial defects of New Zealand white rabbits compared with hydroxyapatite. In addition, there were no statistically significant differences between hydroxyapatite and sodium-substituted hydroxyapatite on cytotoxicity as determined by BCA assay. Taken together, these results indicate that sodium-substituted hydroxyapatite with structural defects has promising potential for use as a bone grafting material due to its enhanced osteoconductivity compared with hydroxyapatite.

The effect of chloride-substitution on bioactivity and osteoconductivity of hydroxyapatite (OHAp) was newly investigated. Chloride-substituted hydroxyapatites (ClAp) with low and high chloride concentrations were synthesized by reacting Ca(OH)2 and H3 PO4 with NH4 Cl of low and high concentrations, with subsequent sintering. As a control, pure OHAp was prepared under the same conditions but without addition of NH4 Cl. The ClAp showed markedly enhanced bioactivity in simulated body fluid (SBF) as the chloride substitution was increased. In contrast, OHAp did not show any bioactivity at all within the testing period. The solubility tests in deionized water also showed that the higher the chloride-substituting amount, the higher the dissolution amounts of the constituent elements of apatite, which directly affect bioactivity by increasing the degree of supersaturation of apatite in SBF. In addition, ClAp also showed noticeably higher osteoconductivity within the 4 weeks of implantation in calvarial defects of New Zealand white rabbits, compared with that of OHAp. The total system energy of the apatite calculated by the ab initio method showed that the higher the chloride-substituting amount, the higher the total system energy, which suggests that the ClAp was energetically less stable compared with OHAp. This result demonstrates the higher solubility of ClAp over that of OHAp in SBF and deionized water. The improved solubility of the OHAp enhances its bioactivity and consequent osteoconductivity. Taken together, it can be concluded that ClAp has encouraging potential for use as a bone grafting material due to its highly enhanced bioactivity and osteoconductivity compared with pure OHAp.

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