Jeng Han Wang

Enhancing Sodium Ion Battery Performance by Strongly Binding Nanostructured Sb2S3 on Sulfur-Doped Graphene Sheets

Sodium ion batteries (SIBs) have been considered a promising alternative to lithium ion batteries for large-scale energy storage. However, their inferior electrochemical performances, especially cyclability, become the major challenge for further development of SIBs. Large volume change and sluggish diffusion kinetics are generally considered to be responsible for the fast capacity degradation. Here we report the strong chemical bonding of nanostructured Sb2S3 on sulfur-doped graphene sheets (Sb2S3/SGS) that enables a stable capacity retention of 83% for 900 cycles with high capacities and excellent rate performances. To the best of our knowledge, the cycling performance of the Sb2S3/SGS composite is superior to those reported for any other Sb-based materials for SIBs. Computational calculations demonstrate that sulfur-doped graphene (SGS) has a stronger affinity for Sb2S3 and the discharge products than pure graphene, resulting in a robust composite architecture for outstanding cycling stability. Our study shows a feasible and effective way to solve the long-term cycling stability issue for SIBs.

Reaction dynamics of O(1D)+H2, D2, and HD: Direct evidence for the elusive abstraction pathway and the estimation of its branching

The dependencies of the integral cross sections for the title reactions on collision energies were determined from 0.6 kcal/mol to nearly 6 kcal/mol. The result provides, for the first time, direct and unambiguous experimental evidence for the existence of an abstraction pathway, in addition to the widely accepted inserted one. A reaction barrier of about 1.8 kcal/mol was found for this elusive abstraction channel. The branching of these two microscopic pathways was estimated. An intriguing H/D isotope effect was revealed, which called for further studies.

Electronic and vibrational properties of nickel sulfides from first principles

We report the results of first-principles calculations (generalized gradient approximation-Perdew Wang 1991) on the electronic and vibrational properties of several nickel sulfides that are observed on Ni-based anodes in solid oxide fuel cells (SOFCs) upon exposure to H2S contaminated fuels: heazlewoodite Ni3S2, millerite NiS, polydymite Ni3S4, and pyrite NiS2. The optimized lattice parameters of these sulfides are within 1% of the values determined from x-ray diffraction. The electronic structure analysis indicates that all Ni-S bonds are strongly covalent. Furthermore, it is found that the nickel d orbitals shift downward in energy, whereas the sulfur p orbitals shift upward with increasing sulfur content; this is consistent with the decrease in conductivity and catalytic activity of sulfur-contaminated Ni-based electrodes (or degradation in SOFC performance). In addition, we systematically analyze the classifications of the vibrational modes at the point from the crystal symmetry and calculate the corresponding vibrational frequencies from the optimized lattice constants. This information is vital to the identification with in situ vibrational spectroscopy of the nickel sulfides formed on Ni-based electrodes under the conditions for SOFC operation. Finally, the effect of thermal expansion on frequency calculations for the Ni3S2 system is also briefly examined.

Surface Modification of Ni-YSZ Using Niobium Oxide for Sulfur-Tolerant Anodes in Solid Oxide Fuel Cells

The surface of a dense Ni–yttria-stabilized zirconia YSZ anode for solid oxide fuel cells SOFCs was modified with niobium oxide Nb2O5 in order to achieve sulfur tolerance. Results suggest that Nb2O5 was reduced to NbO2 under SOFC operating conditions, which has high electrical conductivity and catalytic activity toward hydrogen oxidation. The NbOx-coated dense Ni-YSZ cermet anode showed sulfur tolerance when exposed to 50 ppm H2S at 700°C over 12 h. Raman spectroscopy and X-ray diffraction analysis suggest that different phases of niobium sulfides NbSx were formed on the surfaces of niobium oxides. Furthermore, density of state DOS analysis of NbO2, NbS, and NbS2 indicates that the electronic structure of niobium sulfides are similar to that of NbO2; they are electrically conductive and catalytically active for hydrogen oxidation in H2S containing fuels under the conditions studied.

Histone deacetylase inhibitors increase microRNA-146a expression and enhance negative regulation of interleukin-1β signaling in osteoarthritis fibroblast-like synoviocytes

OBJECTIVE MiR-146a exerts negative control on inflammatory responses by suppressing cytokine-induced expression of interleukin-1 receptor-associated kinase-1 (IRAK1) and tumor necrosis factor receptor-associated factor 6 (TRAF6) by impairing NF-κB activity and inhibiting the expression of target genes. Recent study suggests that histone deacetylases (HDACs) are involved in the regulation of microRNA (miRNA) expression. Therefore, we determined whether HDAC inhibitors can increase miR-146a expression, thereby inhibiting interleukin-1β (IL-1β)-induced signaling in osteoarthritis fibroblast-like synoviocytes (OA-FLS). METHOD MiRNA expression was analyzed using real-time PCR. IL-1β-induced downstream signals and cytokine expression were evaluated using Western blotting and ELISA. Transcription factors regulating promoter activation were identified using chromatin immunoprecipitation assays. RESULTS IL-1β treatment of OA-FLS induced a mild (1.7-fold) increase in miR-146a expression that was unable to appropriately downregulate IRAK1 and TRAF6 expression. HDAC inhibitors, SAHA (vorinostat), and LBH589 (panobinostat) significantly (6.1- and 5.4-fold) elevated miR-146a expression by increasing the binding of the transcription factor NF-κB to the miR-146a promoter, and negatively regulated IL-1β-induced IKK/IκB/p65 phosphorylation signaling and IL-6 secretion. The increase in miR-146a expression induced by the HDAC inhibitors was prevented by transfection of miR-146a inhibitor or HDAC1 (class I HDAC), HDAC4 (class IIa HDAC), and HDAC6 (class IIb HDAC) overexpression, suggesting that they were due to inhibition of HDAC activity. CONCLUSIONS Our study demonstrated that HDAC inhibitor treatment in OA-FLS significantly increased miR-146a expression and mediated markedly negative regulation to inhibit IL-1β-induced signaling and cytokine secretion. Our results indicate the potential rationale of anti-inflammatory effects for HDAC inhibitors.

Tetrazole-based, anhydrous proton exchange membranes for fuel cells.

A tetrazole-based polymer electrolyte membrane showed high conductivity at 20-120°C under dry conditions, offering the potential to dramatically simplify fuel cells for many applications over a wide temperature range without the need for cumbersome humidification and pressurization.

Direct mapping of vibrational‐specific angular distributions of the polyatomic reaction product: CN+D2→DCN+D

A newly developed Doppler‐selected time‐of‐flight (a 3D) method was applied to map out for the first time the vibrational‐specific angular distributions of the DCN product from the title reaction. A tentative vibrational assignment was given for the observed structures. It was found that the nascent DCN is formed with substantial excitations in both C–D stretch and DCN bend modes. While the pure C–D stretch and those associated with low bend excitations are predominantly backward scattered, the highly excited DCN in both modes also exhibit a substantial forward scattered component in the angular distribution.

Enhanced Magnetic Anisotropy via Quasi-Molecular Magnet at Organic-Ferromagnetic Contact

To realize the origin of efficient spin injection at organic-ferromagnetic contact in organic spintronics, we have implemented the formation of quasi-molecular magnet via surface restructuring of a strong organic acceptor, tetrafluoro-tetracyano-quinodimethane (F4-TCNQ), in contact with ferromagnetic cobalt. Our results demonstrate a spin-polarized F4-TCNQ layer and a remarkably enhanced magnetic anisotropy of the Co film. The novel magnetic properties are contributed from strong magnetic coupling caused by the molecular restructuring that displays an angular anchoring conformation of CN and upwardly protruding fluorine atoms. We conclude that the π bonds of CN, instead of the lone-pair electrons of N atoms, contribute to the hybridization-induced magnetic coupling between CN and Co and generate a superior magnetic order on the surface.

Chemoselective synthesis of tetrasubstituted furans via intramolecular Wittig reactions: mechanism and theoretical analysis

An efficient synthesis of tetrasubstituted furans was achieved from the corresponding α,β-unsaturated ketone derivatives, acid chlorides, and Bu3P in the presence of Et3N via a chemoselective intramolecular Wittig reaction as the key step. The presence of an additional electron-withdrawing group in the α-position of Michael acceptors controlled the chemoselectivities of presumable phosphorus ylides in the intramolecular Wittig reactions, and their mechanisms were also investigated by DFT calculations.

Unraveling the Nature of Anomalously Fast Energy Storage in T-Nb2O5

While T-Nb2O5 has been frequently reported to display an exceptionally fast rate of Li-ion storage (similar to a capacitor), the detailed mechanism of the energy storage process is yet to be unraveled. Here we report our findings in probing the nature of the ultrafast Li-ion storage in T-Nb2O5 using both experimental and computational approaches. Experimentally, we used in operando Raman spectroscopy performed on a well-designed model cell to systematically characterize the dynamic evolution of vibrational band groups of T-Nb2O5 upon insertion and extraction of Li ions during repeated cycling. Theoretically, our model shows that Li ions are located at the loosely packed 4g atomic layers and prefer to form bridging coordination with the oxygens in the densely packed 4h atomic layers. The atomic arrangement of T-Nb2O5 determines the unique Li-ion diffusion path topologies, which allow direct Li-ion transport between bridging sites with very low steric hindrance. The proposed model was validated by computational and experimental vibrational analyses. A comprehensive comparison between T-Nb2O5 and other important intercalation-type Li-ion battery materials reveals the key structural features that lead to the exceptionally fast kinetics of T-Nb2O5 and the cruciality of atomic arrangements for designing a new generation of Li-ion conduction and storage materials.