Bournonite PbCuSbS3 : Stereochemically Active Lone-Pair Electrons that Induce Low Thermal Conductivity.

An understanding of the structural features and bonding of a particular material, and the properties these features impart on its physical characteristics, is essential in the search for new systems that are of technological interest. For several relevant applications, the design or discovery of low thermal conductivity materials is of great importance. We report on the synthesis, crystal structure, thermal conductivity, and electronic-structure calculations of one such material, PbCuSbS3 . Our analysis is presented in terms of a comparative study with Sb2 S3 , from which PbCuSbS3 can be derived through cation substitution. The measured low thermal conductivity of PbCuSbS3 is explained by the distortive environment of the Pb and Sb atoms from the stereochemically active lone-pair s(2) electrons and their pronounced repulsive interaction. Our investigation suggests a general approach for the design of materials for phase-change-memory, thermal-barrier, thermal-rectification and thermoelectric applications, as well as other functions for which low thermal conductivity is purposefully sought.

Selective synthesis of Cu2SnSe3 and Cu2SnSe4 nanocrystals.

The selective synthesis of Cu2SnSe3 and Cu2SnSe4 nanocrystals was achieved by a one-step solvothermal synthesis method. We also investigated the effects of different precursor sources and starting material concentrations on the phase purity of the products. Powder X-ray diffraction, elemental analysis, and magnetic susceptibility measurements were used to investigate the phase, purity, and homogeneity of the nanocrystals. This solvothermal approach is broadly applicable and may also be employed for the synthesis of other ternary or quaternary chalcogenide nanocrystals.

Conversion efficiency of skutterudite-based thermoelectric modules.

Presently, the only commercially available power generating thermoelectric (TE) modules are based on bismuth telluride (Bi2Te3) alloys and are limited to a hot side temperature of 250 °C due to the melting point of the solder interconnects and/or generally poor power generation performance above this point. For the purposes of demonstrating a TE generator or TEG with higher temperature capability, we selected skutterudite based materials to carry forward with module fabrication because these materials have adequate TE performance and are mechanically robust. We have previously reported the electrical power output for a 32 couple skutterudite TE module, a module that is type identical to ones used in a high temperature capable TEG prototype. The purpose of this previous work was to establish the expected power output of the modules as a function of varying hot and cold side temperatures. Recent upgrades to the TE module measurement system built at the Fraunhofer Institute for Physical Measurement Techniques allow for the assessment of not only the power output, as previously described, but also the thermal to electrical energy conversion efficiency. Here we report the power output and conversion efficiency of a 32 couple, high temperature skutterudite module at varying applied loading pressures and with different interface materials between the module and the heat source and sink of the test system. We demonstrate a 7% conversion efficiency at the module level when a temperature difference of 460 °C is established. Extrapolated values indicate that 7.5% is achievable when proper thermal interfaces and loading pressures are used.

Multiple-filled skutterudites: high thermoelectric figure of merit through separately optimizing electrical and thermal transports.

Skutterudites CoSb(3) with multiple cofillers Ba, La, and Yb were synthesized and very high thermoelectric figure of merit ZT = 1.7 at 850 K was realized. X-ray diffraction of the densified multiple-filled bulk samples reveals all samples are phase pure. High-resolution scanning transmission electron microscopy (STEM) and energy dispersive X-ray spectroscopy (EDS) analysis confirm that multiple guest fillers occupy the nanoscale-cages in the skutterudites. The fillers are further shown to be uniformly distributed and the Co-Sb skutterudite framework is virtually unperturbed from atomic scale to a few micrometers. Our results firmly show that high power factors can be realized by adjusting the total filling fraction of fillers with different charge states to reach the optimum carrier density, at the same time, lattice thermal conductivity can also be significantly reduced, to values near the glass limit of these materials, through combining filler species of different rattling frequencies to achieve broad-frequency phonon scattering. Therefore, partially filled skutterudites with multiple fillers of different chemical nature render unique structural characteristics for optimizing electrical and thermal transports in a relatively independent way, leading to continually enhanced ZT values from single- to double-, and finally to multiple-filled skutterudites. The idea of combining multiple fillers with different charge states and rattling frequencies for performance optimization is also expected to be valid for other caged TE compounds.

New intermetallics YbAu2In4 and Yb2Au3In5.

The intermetallic compounds YbAu(2)In(4) and Yb(2)Au(3)In(5) were obtained as single crystals in high yield from reactions run in liquid indium. Single crystal X-ray diffraction data of YbAu(2)In(4) showed that it crystallizes as a new structure type in the monoclinic space group P2(1)/m and lattice constants a = 7.6536(19) Å, b = 4.5424(11) Å, c = 9.591(2) Å and ß = 107.838(4)°. The YbAu(2)In(4) compound is composed of a complex [Au(2)In(4)](3-) polyanionic network in which the rare-earth ions are embedded. Yb(2)Au(3)In(5) crystallizes in the polar space group Cmc2(1) with the Y(2)Rh(3)Sn(5) type structure and lattice constants a = 4.5351(9) Å, b = 26.824(5) Å, and c = 7.4641(15) Å. The gold and indium atoms define a complex three-dimensional [Au(3)In(5)] network with a broad range of Au-In (2.751(2) Å-3.0518(16) Å) and In-In (3.062(3) Å-3.3024(19) Å) distances. Magnetic susceptibility measurements of YbAu(2)In(4) revealed a transition at 25 K. Below the transition, the susceptibility of YbAu(2)In(4) follows Curie-Weiss behavior with an effective paramagnetic moment of 0.79 µ(B)/Yb. Magnetic susceptibility measurements on Yb(2)Au(3)In(5) show a mixed valent ytterbium and the magnetic moment within the linear region (<100 K) of 1.95 µ(B)/Yb. Heat capacity data for YbAu(2)In(4) and Yb(2)Au(3)In(5) give Debye temperatures of 185 and 153 K, respectively.

Zero thermal expansion in YbGaGe due to an electronic valence transition.

Most materials expand upon heating. Although rare, some materials expand on cooling, and are said to exhibit negative thermal expansion (NTE); but the property is exhibited in only one crystallographic direction. Such materials include silicon and germanium at very low temperature (<100 K) and, at room temperature, glasses in the titania-silica family, Kevlar, carbon fibres, anisotropic Invar Fe-Ni alloys, ZrW2O3 (ref. 4) and certain molecular networks. NTE materials can be combined with materials demonstrating a positive thermal expansion coefficient to fabricate composites exhibiting an overall zero thermal expansion (ZTE). ZTE materials are useful because they do not undergo thermal shock on rapid heating or cooling. The need for such composites could be avoided if ZTE materials were available in a pure form. Here we show that an electrically conductive intermetallic compound, YbGaGe, can exhibit nearly ZTE--that is, negligible volume change between 100 and 400 K. We suggest that this response is due to a temperature-induced valence transition in the Yb atoms. ZTE materials are desirable to prevent or reduce resulting strain or internal stresses in systems subject to large temperature fluctuations, such as in space applications and thermomechanical actuators.

Nano- and Microstructure Engineering: An Effective Method for Creating High Efficiency Magnesium Silicide Based Thermoelectrics.

Considering the effect of CO2 emission together with the depletion of fossil fuel resources on future generations, industries in particular the transportation sector are in deep need of a viable solution to follow the environmental regulation to limit the CO2 emission. Thermoelectrics may be a practical choice for recovering the waste heat, provided their conversion energy can be improved. Here, the high temperature thermoelectric properties of high purity Bi doped Mg2(Si,Sn) are presented. The samples Mg2Si1-x-ySnxBiy with x(Sn) ≥ 0.6 and y(Bi) ≥ 0.03 exhibited electrical conductivities and Seebeck coefficients of approximately 1000 Ω-1 cm-1 and -200 µV K-1 at 773 K, respectively, attributable to a combination of band convergence and microstructure engineering through ball mill processing. In addition to the high electrical conductivity and Seebeck coefficient, the thermal conductivity of the solid solutions reached values below 2.5 W m-1 K-1 due to highly efficient phonon scattering from mass fluctuation and grain boundary effects. These properties combined for zT values of 1.4 at 773 K with an average zT of 0.9 between 400 and 773 K. The transport properties were both highly reproducible across several measurement systems and were stable with thermal cycling.

Temperature-induced abrupt volume inflation in the mixed-valence ternary Zintl phase Yb8Ge3Sb5.

The Zintl phase, Yb8Ge3Sb5 exhibits a complex lattice response and an abrupt negative thermal expansion below 15 K - subtle structural changes before and after the transition are consistent with temperature-induced electron transfer from (to) Yb 4f bands to (from) Sb 5p and Ge 4p bands.

Band Structure Engineering and Thermoelectric Properties of Charge-Compensated Filled Skutterudites.

Thermoelectric properties of semiconductors are intimately related to their electronic band structure, which can be engineered via chemical doping. Dopant Ga in the cage-structured skutterudite Co4Sb12 substitutes Sb sites while occupying the void sites. Combining quantitative scanning transmission electron microscopy and first-principles calculations, we show that Ga dual-site occupancy breaks the symmetry of the Sb-Sb network, splits the deep triply-degenerate conduction bands, and drives them downward to the band edge. The charge-compensating nature of the dual occupancy Ga increases overall filling fraction limit. By imparting this unique band structure feature, and judiciously doping the materials by increasing the Yb content, we promote the Fermi level to a point where carriers are in energetic proximity to these features. Increased participation of these heavier bands in electronic transport leads to increased thermopower and effective mass. Further, the localized distortion from Ga/Sb substitution enhances the phonon scattering to reduce the thermal conductivity effectively.

Alkyl halide charge transfer complexes with hard Lewis bases.

The unusual charge transfer complexes formed between alkyl halide acceptors and hard Lewis base donors (amines and alcohols) in low dielectric solvent were examined using ultraviolet spectroscopy. The lambda(max) of the complex decreases with increasing ionization potential of the donor. The complex formation equilibria were probed by thermodynamic analysis and concentration variation. At ambient temperatures complex formation is generally slightly exergonic with a negative complexation entropy. The complex extinction coefficients are much lower (<10 l mol(-1) cm(-1)) than for typical charge transfer complexes. These complexes are extraordinary within a classical context since the halide acceptors have a negative electron affinity. They exhibited an atypical hypsochromic shift with increasing solvent dielectric constant.

Sb- and Bi-doped Mg2Si: location of the dopants, micro- and nanostructures, electronic structures and thermoelectric properties.

Due to increasing global energy concerns, alternative sustainable methods to create energy such as thermoelectric energy conversion have become increasingly important. Originally, research into thermoelectric materials was focused on tellurides of bismuth and lead because of the exemplary thermoelectric properties of Bi2Te3 and PbTe. These materials, however, contain toxic lead and tellurium, which is also scarce and thus expensive. A viable alternative material may exist in Mg2Si, which needs to be doped and alloyed in order to achieve reasonable thermoelectric efficiency. Doping is a major problem, as p-type doping has thus far not produced competitive efficiencies, and n-type doping is problematic because of the low solubility of the typical dopants Sb and Bi. This investigation shows experimentally that these dopants can indeed replace Si in the crystal lattice, and excess Sb and Bi atoms are present in the grain boundaries in the form of Mg3Sb2 and Mg3Bi2. As a consequence, the carrier concentration is lower than the formal Sb/Bi concentration suggests, and the thermal conductivity is significantly reduced. DFT calculations are in good agreement with the experimental data, including the band gap and the Seebeck coefficient. Overall, this results in competitive efficiencies despite the low carrier concentration. While ball-milling was previously shown to enhance the solubility of the dopants and thus the carrier concentration, this did not lead to enhanced thermoelectric properties.

Commercially viable resolution of ibuprofen.

Ibuprofen belongs to the non-steroidal anti-inflammatory drug (NSAID) family known as profens. Studies demonstrate that (S-ibuprofen is 160 times more potent than (R-ibuprofen in vitro, while the accumulation of (R-ibuprofen can cause serious side effects such as gastrointestinal pain. Candida rugosa lipase was used to enantioselectively esterify racemic ibuprofen with decan-1-ol and butan-1-ol in cyclohexane with an enantiomeric ratio (E) of 130 and 46, respectively, in up to 46% conversion. Separation by bulb-to-bulb distillation of (R)-ibuprofen and unreacted alcohol from the corresponding (S)-alkyl ibuprofen ester was possible for the decyl but not the butyl case. The enantioselective hydrolysis of (S)-alkyl ibuprofen esters with the same biocatalyst in aqueous phosphate buffer was twice as slow for the decyl alcohol versus the butyl example. The combined environmentally friendly enantioselective esterification and hydrolysis of ibuprofen insured the isolation of (S)-ibuprofen with a greater than 99% enantiomeric excess.

Atomic ordering and gap formation in Ag-Sb-based ternary chalcogenides.

Novel semiconductors with tailored properties can be designed theoretically based on our understanding of the interplay of atomic and electronic structures and the nature of the electronic states near the band-gap region. We discuss here the realization of this idea in Ag-Sb-based ternary chalcogenides, which are important optical phase change and thermoelectric materials. Based on our studies we propose new systems for high-performance thermoelectrics.

REAu2In4 (RE = La, Ce, Pr, Nd): polyindides from liquid indium.

The series of compounds REAu2In4 (RE = La, Ce, Pr, Nd) crystallize from excess In as rod-shaped single crystals. All members adopt the orthorhombic space group Pnma with a = 18.506(2) A, b = 4.6865(6) A, and c = 7.3414(9) A for LaAu2In4, a = 18.514(3) A, b = 4.6624(8) A, and c = 7.389(1) A for CeAu2In4, a = 18.420(4) A, b = 4.6202(9) A, and c = 7.376(2) A for the Pr analogue, and a = 18.406(2) A, b = 4.6114(5) A, and c = 7.4073(7) A for NdAu2In4. The REAu2In4 series can be regarded as polar intermetallic phases composed of a complex [Au2In4]3- polyanion network in which the rare-earth ions are embedded. The [Au2In4]3- network features In tetramer units, which defines the compounds as polyindides. Magnetic measurements found no magnetic ordering down to 2 K for any of the compounds. In addition, LaAu2In4 was found to be Pauli paramagnetic with a small susceptibility. Ab initio density functional methods were used to carry out electronic structure calculations to explore the bonding, the role of gold, and the contributions of different atoms to the density of states near the Fermi energy. We find that the density of states decreases slowly near Ef and reaches a minimum at about 0.5 eV above Ef.

Indium flux synthesis of RE4Ni2InGe4 (RE = Dy, Ho, Er, and Tm): an ordered quaternary variation on the binary phase Mg5Si6.

The quaternary compounds RE4Ni2InGe4 (RE = Dy, Ho, Er, and Tm) were obtained as large single crystals in high yields from reactions run in liquid In. The title compounds crystallize in the monoclinic C2/m space group with the Mg(5)Si(6) structure type with lattice parameters a = 15.420(2) A, b = 4.2224(7) A, c = 7.0191(11) A, and beta = 108.589(2) degrees for Dy4Ni2InGe4, a = 15.373(4) A, b = 4.2101(9) A, c = 6.9935(15) A, and beta = 108.600(3) degrees for Ho4Ni2InGe4, a = 15.334(7) A, b = 4.1937(19) A, c = 6.975(3) A, and beta =108.472(7) degrees for Er4Ni2InGe4, and a = 15.253(2) A, b = 4.1747(6) A, c = 6.9460(9) A, and beta = 108.535(2) degrees for Tm4Ni2InGe4. RE4Ni2InGe4 formed in liquid In from a melt that was rich in the rare-earth component. These compounds are polar intermetallic phases with a cationic rare-earth substructure embedded in a transition metal and main group matrix. The rare-earth atoms form a highly condensed network, leading to interatomic distances that are similar to those found in the elemental lanthanides themselves. The Dy and Ho analogues display two maxima in the susceptibility, suggesting antiferromagnetic ordering behavior and an accompanying spin reorientation. The Er analogue shows only one maximum in the susceptibility, and no magnetic ordering was observed for the Tm compound down to 2 K.

Intermetallic compounds with near Zintl phase behavior: RE2Zn3Ge6 (RE = La, Ce, Pr, Nd) grown from liquid indium.

A series of compounds has been discovered while investigating reactions of rare earth, transition metals, and Ge in excess indium. These compounds, RE2Zn3Ge6 (RE = La, Ce, Pr, Nd), are isostructural, crystallizing in the orthorhombic space group Cmcm with lattice parameters a = 5.9691(9) angstroms, b = 24.987(4) angstroms, and c = 5.9575(9) angstroms for La2Zn3Ge6, a = 5.9503(5) angstroms, b = 24.761(2) angstroms, and c = 5.9477(5) angstroms for the Ce analogue, a =5.938(2) angstroms, b = 24.708(8) angstroms, and c = 5.936(2) angstroms for Pr2Zn3Ge6, and a = 5.9094(7) angstroms, b = 24.619(3) angstroms, and c = 5.9063(5) angstroms for the Nd analogue. The structure is composed of PbO-like ZnGe layers and ZnGe4 cage layers and is related to the Ce4Zn8Ge(11-x) structure type. The bonding in the system can be rationalized using the Zintl concept resulting in a material that is expected to be a valence precise semiconductor, although its behavior is more consistent with it being a semimetal, making it an intermediate case. The results of band structure calculations and magnetic measurements of these compounds are discussed.

Photoinduced electron-transfer substitution reactions via unusual charge-transfer intermediates.

The photoinduced substitution reactions of halogenated alkanes (1-haloadamantanes, 1-haloronorbornanes, menthyl chloride) with a homologous series of amines or alcohols (methylamine, 2-methyl-2-aminopropane, methanol, or 2-methyl-2-propanol) to form the corresponding alkane-substituted amines or ethers and HCl were investigated. The geometry of the bridgehead carbons made S(N)2 reactions impossible. Nonpolar reaction conditions were employed which made classical and nonclassical carbocation S(N)1 reaction pathways unlikely. The reaction rates were measured. Trapping experiments indicated that free radical reactions were uninvolved in the substitution product formation. A novel, photoinduced electron-transfer reaction mechanism involving a charge-transfer intermediate is proposed to explain the observed production of secondary amines and ethers. The excitation wavelength dependence (action spectrum) was measured and found to be comparable to the ultraviolet absorption spectra of the charge-transfer complexes. The stereochemical implications of the reaction mechanism were investigated. The formation of the methyl ether of (1R,2S,5R)-menthol was the only organic reaction product observed in the photoreaction between (1R,2S,5R)-menthyl chloride and methanol.

Valence instabilities, phase transitions, and abrupt lattice expansion at 5 K in the YbGaGe system.

The powder synchrotron X-ray diffraction technique was used to study the thermal expansion behavior of the mixed valence layered compound, YbGa1.05Ge0.95 in the temperature range 3-1123 K. A surprising abrupt isosymmetric phase transition, accompanied by a dramatic volume increase (negative thermal expansion), was found at 5 K induced by a sudden Yb valence transition from +(2 + epsilon) toward +2. At high temperatures, the material undergoes a transformation to a highly disordered structure until it eventually collapses at 1123 K to a structure with isovalent Yb ions and flat Ga/Ge planes (AlB2 type).