Novel Engineered Nanostructured Complex Oxide for High Temperature Thermoelectric Power Generation

Thermoelectric power generators are a promising technology that can produce electrical power directly from waste heat emitted in energy production and consumption systems. The essential component of thermoelectric generators is the thermoelectric material which performs the energy conversion process. In order to make thermoelectric devices to be considered a significant contributor to US energy infrastructure, it is essential first to foster improvements in high performance thermoelectric materials. They must possess not only a high conversion efficiency, but also need be composed of nontoxic and abundantly available elemental materials having high chemical stability in air up to 800-1000 K. In comparison with the conventional thermoelectric materials (intermetallic compounds); the layered oxide materials, such as the newly developed nontoxic p-type Ca3Co4O9, are particularly promising for thermoelectric applications because of their high stability at high temperatures in air.;In recent years, the layered cobalt oxide Ca3Co4O 9 system has gained great attention due to its outstanding thermoelectric performance (ZT=0.83 at 973 K) for the single crystal. Single crystals, however, are too small and expensive for practical applications. The current challenge for developing oxide thermoelectric materials is to improve the conversion efficiency of the polycrystalline Ca3Co 4O9 ceramic, which is currently lower than that of the conventional thermoelectric materials. The distinctive objective in this research is to optimize the energy inter-conversion properties of p-type Ca3Co 4O9 ceramic, through nano-structure engineering approaches. Novel methods of introducing the appropriate dopants and other nano-structures into the oxide were investigated, and the effect of dopants and nano-structure engineering on the thermoelectric performance of the Ca3Co 4O9 system was evaluated. The above study will be instrumental for fabricating polycrystalline Ca3Co4O9 with optimized microstructure and enhanced thermoelectric properties

Edge state on hydrogen-terminated graphite edges investigated by scanning tunneling microscopy

The edge states that emerge at hydrogen-terminated zigzag edges embedded in dominant armchair edges of graphite are carefully investigated by ultrahigh-vacuum scanning tunneling microscopy (STM) measurements. The edge states at the zigzag edges have different spatial distributions dependent on the $\alpha$- or $\beta$-site edge carbon atoms. In the case that the defects consist of a short zigzag (or a short Klein) edge, the edge state is present also near the defects. The amplitude of the edge state distributing around the defects in an armchair edge often has a prominent hump in a direction determined by detailed local atomic structure of the edge. The tight binding calculation based on the atomic arrangements observed by STM reproduces the observed spatial distributions of the local density of states.Comment: 9 pages, 11 figures, accepted for Physical Review

Halogen bonding stabilizes a cis-azobenzene derivative in the solid state: A crystallographic study

Crystals of trans- and cis-isomers of a fluorinated azobenzene derivative have been prepared and characterized by single-crystal X-ray diffraction. The presence of F atoms on the aromatic core of the azobenzene increases the lifetime of the metastable cis-isomer, allowing single crystals of the cis-azobenzene to be grown. Structural analysis on the cis-azobenzene, complemented with density functional theory calculations, highlights the active role of the halogen-bond contact (N...I synthon) in promoting the stabilization of the cis-isomer. The presence of a long aliphatic chain on the azobenzene unit induces a phase segregation that stabilizes the molecular arrangement for both the trans- and cis-isomers. Due to the rarity of cis-azobenzene crystal structures in the literature, our paper makes a step towards understanding the role of non-covalent interactions in driving the packing of metastable azobenzene isomers. This is expected to be important in the future rational design of solid-state, photoresponsive materials based on halogen bonding. We show by single-crystal X-ray diffraction studies and computational analysis that halogen bonding can stabilize a metastable cis-azobenzene derivative in the solid state

Coordination networks incorporating halogen-bond donor sites and azobenzene groups

Two Zn coordination networks, [Zn(1)(Py)2]2(2-propanol)n (3) and [Zn(1)2(Bipy)2](DMF)2n (4), incorporating halogen-bond (XB) donor sites and azobenzene groups have been synthesized and fully characterized. Obtaining 3 and 4 confirms that it is possible to use a ligand wherein its coordination bond acceptor sites and XB donor sites are on the same molecular scaffold (i.e., an aromatic ring) without interfering with each other. We demonstrate that XBs play a fundamental role in the architectures and properties of the obtained coordination networks. In 3, XBs promote the formation of 2D supramolecular layers, which, by overlapping each other, allow the incorporation of 2-propanol as a guest molecule. In 4, XBs support the connection of the layers and are essential to firmly pin DMF solvent molecules through I⋯O contacts, thus increasing the stability of the solvated systems

Rhapso : automatic stitching of mass segments from fourier transform ion cyclotron resonance mass spectra

Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) provides the resolution and mass accuracy needed to analyze complex mixtures such as crude oil. When mixtures contain many different components, a competitive effect within the ICR cell takes place that hampers the detection of a potentially large fraction of the components. Recently, a new data collection technique, which consists of acquiring several spectra of small mass ranges and assembling a complete spectrum afterward, enabled the observation of a record number of peaks with greater accuracy compared to broadband methods. There is a need for statistical methods to combine and preprocess segmented acquisition data. A particular challenge of quadrupole isolation is that near the window edges there is a drop in intensity, hampering the stitching of consecutive windows. We developed an algorithm called Rhapso to stitch peak lists corresponding to multiple different m/z regions from crude oil samples. Rhapso corrects potential edge effects to enable the use of smaller windows and reduce the required overlap between windows, corrects mass shifts between windows, and generates a single peak list for the full spectrum. Relative to a stitching performed manually, Rhapso increased the data processing speed and avoided potential human errors, simplifying the subsequent chemical analysis of the sample. Relative to a broadband spectrum, the stitched output showed an over 2-fold increase in assigned peaks and reduced mass error by a factor of 2. Rhapso is expected to enable routine use of this spectral stitching method for ultracomplex samples, giving a more detailed characterization of existing samples and enabling the characterization of samples that were previously too complex to analyze

Survival Regression Models With Dependent Bayesian Nonparametric Priors

We present a novel Bayesian nonparametric model for regression in survival analysis. Our model builds on the classical neutral to the right model of Doksum and on the Cox proportional hazards model of Kim and Lee. The use of a vector of dependent Bayesian nonparametric priors allows us to efficiently model the hazard as a function of covariates while allowing nonproportionality. The model can be seen as having competing latent risks. We characterize the posterior of the underlying dependent vector of completely random measures and study the asymptotic behavior of the model. We show how an MCMC scheme can provide Bayesian inference for posterior means and credible intervals. The method is illustrated using simulated and real data. Supplementary materials for this article are available online

The response of taxonomic and functional diversity of the seed bank to agricultural intensification and soil properties in two Mediterranean cereal areas

Weed seed bank diversity has been severely impacted by agriculture intensifi cation. However, the functional consequences have been poorly studied in highly intensifi ed agro-ecosystems.Postprint (published version