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Pursuing efficient thermoelectricity from low-dimensional materials has been highly motivated since the seminal work of Hicks and Dresselhaus. In fact, many superior thermoelectric materials like Bi2Te3, Mg3Sb2/Mg3Bi2 and SnSe are quasi-two-dimensional (q2D), though the advantages of two-dimensionality appear to be diverse and sometimes controversial. Here, we report on a remarkably high thermoelectric performance in TlCu3Te2, which is quasi-one-dimensional (q1D) with a further reduced dimension. The thermoelectric figure of merit zT along its q1D axis amounts to 1.3 (1.5) at 300 (400) K, rivaling the best ever reported at these temperatures. The high thermoelectric performances benefit from, on one hand, large power factors derived from a center-hollowed, pancake-like Fermi pocket with q1D dispersion at the edge of a narrow band gap, and on the other hand, small lattice thermal conductivities caused by the large and anharmonic q1D lattice consisting of heavy, lone-pair-electron bearing (Tl+) and weakly-bonded (Cu+) ions. This compound represents the first bulk material with quasi-uniaxial thermoelectric transport of application level, offering a renewed opportunity to exploit reduced dimensionality for high-performance thermoelectricity.
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How magnetism affects the Seebeck effect is an important issue of wide concern in the thermoelectric community but remains elusive. Based on a thermodynamic analysis of spin degrees of freedom on varied d-electron-based ferromagnets and antiferromagnets, we demonstrate that in itinerant or partially itinerant magnetic compounds there exists a generic spin contribution to the Seebeck effect over an extended temperature range from slightly below to well above the magnetic transition temperature. This contribution is interpreted as resulting from transport spin entropy of (partially) delocalized conducting d electrons with strong thermal spin fluctuations, even semiquantitatively in a single-band case, in addition to the conventional diffusion part arising from their kinetic degrees of freedom. As a highly generic effect, the spin-dependent Seebeck effect might pave a feasible way toward efficient "magnetic thermoelectrics."
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Spent resins generated from the nuclear industrial processes are still difficult to be treated and disposed. Fenton-like processes have great application potential in the treatment of spent resins, but the Fenton reaction mechanisms and resin degradation pathways remain challenging. In this study, nanoscale Fe0/Cu0 bimetallic catalysts were prepared and characterized for the Fenton-like degradation of the mixture of cationic and anionic resins. High catalytic property of Fe0/Cu0 bimetallic nanoparticles activated by H2O2 was evaluated, according to the effects of various nanoparticles, temperature, catalyst amount, H2O2 concentration and the mixing ratio of cationic and anionic resins. Combined the shape and color changes of mixed resins with the experimental and calculated characterization results, different degradation difficulty of cationic and anionic resins and their degradation mechanisms were studied. According to the density functional theory calculations of the optimized resin molecules with the Fe0/Cu0 catalyst, the mechanisms of Fenton-like reactions and the degradation of mixed resins through the synergistic effect of Fe and Cu species were proposed. The comprehensive Fenton-like reactions and degradation mechanisms provide new insights to advance the treatment of spent resins and organic polymers by Fenton-like processes.
Assuntos
Peróxido de Hidrogênio , Ferro , Resinas de Troca Aniônica , Catálise , Cobre , OxirreduçãoRESUMO
Nanoscale zero-valent iron (nZVI) was prepared and used as a heterogeneous Fenton-like catalyst for the degradation of nuclear-grade cationic exchange resin. The properties of nZVI before and after reaction were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and Brunauer-Emmett-Teller (BET) surface area analysis. The results showed that nZVI-H2O2 system exhibited the enhanced degradation of cationic resins, compared with Fe2+-H2O2, Cu0-H2O2, and Fe0/Cu0-H2O2 systems. The effects of initial temperature, nZVI dose, and H2O2 concentration were studied, and the higher temperature and nZVI dose with relatively low H2O2 concentration brought faster degradation rate. The degradation of cationic resins followed the pseudo-first-order kinetics with the apparent activation energy of 53.29 kJ/mol. According to the experimental and calculated infrared and UV-visible spectra, the carbon skeleton of cationic resins was broken with the detachment of benzene ring and the desulfonation of resin polymer by hydroxyl radicals (â¢OH), generating long-chain alkenes. These intermediates were further oxidized through the hydroxyl substitution, hydrogen abstraction, ring cleavage, or carbonylation reactions, finally forming carboxylic acids remained in solution.
Assuntos
Ferro , Poluentes Químicos da Água/análise , Resinas de Troca de Cátion , Teoria da Densidade Funcional , Peróxido de Hidrogênio , Difração de Raios XRESUMO
We report on anisotropic electrical, thermal as well as thermoelectric properties of the prototypical Weyl semimetal TaAs. Compared to the normal metallic behavior along a axis, TaAs is more electrically resistive along c axis and exhibits a semiconductor-like resistivity upturn below [Formula: see text] K. In the same temperature range, the thermal conductivity along c axis shows a pronounced maximum of 183 [Formula: see text] characteristic of a crystalline solid, three times higher than that of a axis. The thermoelectric power, while exhibiting enhanced values around room temperature, becomes diminished in a substantial range of temperature ([Formula: see text] K) for both axes. Together with the enhanced Nernst signals, this hints at a dominating ambipolar diffusion as is frequently seen in a compensated semimetal. An in-depth investigation of the anisotropic transport quantities is expected to yield deep insights into the propagating Weyl fermions in TaAs.
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The magnetoelectric (ME) effect originating from the effective coupling between electric field and magnetism is an exciting frontier in nanoscale science such as magnetic tunneling junction (MTJ), ferroelectric/piezoelectric heterojunctions etc. The realization of switchable ME effect under external electric field in d0 semiconducting materials of single composition is needed especially for all-silicon spintronics applications because of its natural compatibility with current industry. We employ density functional theory (DFT) to reveal that the pristine Si(111)-3×3 R30° (Si3 hereafter) reconstructed surfaces of thin films with a thickness smaller than eleven bilayers support a sizeable linear ME effect with switchable direction of magnetic moment under external electric field. This is achieved through the interlayer exchange coupling effect in the antiferromagnetic regime, where the spin-up and spin-down magnetized density is located on opposite surfaces of Si3 thin films. The obtained coefficient for the linear ME effect can be four times larger than that of ferromagnetic Fe films, which fail to have the reversal switching capabilities. The larger ME effect originates from the spin-dependent screening of the spin-polarized Dirac fermion. The prediction will promote the realization of well-controlled and switchable data storage in all-silicon electronics.
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SmB6 has been a well-known Kondo insulator for decades, but recently attracts extensive new attention as a candidate topological system. Studying SmB6 under pressure provides an opportunity to acquire the much-needed understanding about the effect of electron correlations on both the metallic surface state and bulk insulating state. Here we do so by studying the evolution of two transport gaps (low temperature gap El and high temperature gap Eh) associated with the Kondo effect by measuring the electrical resistivity under high pressure and low temperature (0.3â¯K) conditions. We associate the gaps with the bulk Kondo hybridization, and from their evolution with pressure we demonstrate an insulator-to-metal transition at â¼4â¯GPa. At the transition pressure, a large change in the Hall number and a divergence tendency of the electron-electron scattering coefficient provide evidence for a destruction of the Kondo entanglement in the ground state. Our results raise the new prospect for studying topological electronic states in quantum critical materials settings.
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The "failed Kondo insulator" CeNiSn has long been suspected to be a nodal metal, with a node in the hybridization matrix elements. Here we carry out a series of Nernst effect experiments to delineate whether the severely anisotropic magnetotransport coefficients do indeed derive from a nodal metal or can simply be explained by a highly anisotropic Fermi surface. Our experiments reveal that despite an almost twentyfold anisotropy in the Hall conductivity, the large Nernst signal is isotropic. Taken in conjunction with the magnetotransport anisotropy, these results provide strong support for an isotropic Fermi surface with a large anisotropy in quasiparticle mass derived from a nodal hybridization.
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The Seebeck effect describes the generation of an electric potential in a conducting solid exposed to a temperature gradient. In most cases, it is dominated by an energy-dependent electronic density of states at the Fermi level, in line with the prevalent efforts towards superior thermoelectrics through the engineering of electronic structure. Here we demonstrate an alternative source for the Seebeck effect based on charge-carrier relaxation: a charge mobility that changes rapidly with temperature can result in a sizeable addition to the Seebeck coefficient. This new Seebeck source is demonstrated explicitly for Ni-doped CoSb3, where a marked mobility change occurs due to the crossover between two different charge-relaxation regimes. Our findings unveil the origin of pronounced features in the Seebeck coefficient of many other elusive materials characterized by a significant mobility mismatch. When utilized appropriately, this effect can also provide a novel route to the design of improved thermoelectric materials.
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The Nernst effect and thermopower of the prototypical Yb-based intermediate valence compound YbAl(3) were investigated. Different to the thermopower whose absolute values are enhanced with increasing temperature and assume a broad maximum at 175 K, the Nernst coefficient of YbAl(3) is enhanced only below T ≈ 75 K. While the two quantities in the heavy-fermion compound CeCu(2)Si(2) were recently found to be related by the anomalous Hall mobility due to the local asymmetric Kondo scattering, this theorem fails when being applied to YbAl(3). Rather, the thermopower of YbAl(3) is well described by a simple narrow-band model. We discuss the reason for this in terms of the intermediate valence nature of YbAl(3) that is conceptually different from the local Kondo physics.
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A distinctly temperature-dependent Nernst coefficient, ν, which is strongly enhanced over that of LaCu(2)Si(2), is observed between T=2 and 300 K for CeCu(2)Si(2) and Ce(0.8)La(0.2)Cu(2)Si(2). The enhanced ν(T) is determined by the asymmetry of the on-site Kondo (conduction electron -4f electron) scattering rate. Taking into account the measured Hall mobility, µ(H), the highly unusual thermopower, S, of these systems can be semiquantitatively described by S(T)=-ν(T)/µ(H)(T), which explicitly demonstrates that the thermopower originates from the local Kondo scattering process over a wide temperature range from far above to well below the coherence temperature (≈20 K for CeCu(2)Si(2)). Our results suggest that the Nernst effect can act as a proper probe of local charge-carrier scattering. This promises to impact on exploring the unconventional enhancement of the thermopower in correlated materials suited for potential applications.
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A quantum critical point (QCP) arises when a continuous transition between competing phases occurs at zero temperature. Collective excitations at magnetic QCPs give rise to metallic properties that strongly deviate from the expectations of Landau's Fermi-liquid description, which is the standard theory of electron correlations in metals. Central to this theory is the notion of quasiparticles, electronic excitations that possess the quantum numbers of the non-interacting electrons. Here we report measurements of thermal and electrical transport across the field-induced magnetic QCP in the heavy-fermion compound YbRh(2)Si(2) (refs 2, 3). We show that the ratio of the thermal to electrical conductivities at the zero-temperature limit obeys the Wiedemann-Franz law for magnetic fields above the critical field at which the QCP is attained. This is also expected for magnetic fields below the critical field, where weak antiferromagnetic order and a Fermi-liquid phase form below 0.07 K (at zero field). At the critical field, however, the low-temperature electrical conductivity exceeds the thermal conductivity by about 10 per cent, suggestive of a non-Fermi-liquid ground state. This apparent violation of the Wiedemann-Franz law provides evidence for an unconventional type of QCP at which the fundamental concept of Landau quasiparticles no longer holds. These results imply that Landau quasiparticles break up, and that the origin of this disintegration is inelastic scattering associated with electronic quantum critical fluctuations--these insights could be relevant to understanding other deviations from Fermi-liquid behaviour frequently observed in various classes of correlated materials.
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The thermoelectric properties of a PtSb(2) single crystal containing a stoichiometric gradient were investigated. The gradient was produced by employing a Stockbarger synthesis technique. The gradient was observed through the use of spatial resolved Seebeck coefficient measurements and verified utilizing X-Ray Diffraction and Energy Dispersive X-Ray Spectroscopy. The correlation between Pt/Sb ratio and physical property parameters--Seebeck coefficient, mobility, resistivity and charge carrier concentration--was studied. Elemental analysis by Energy Dispersive X-Ray Spectroscopy, X-Ray Fluorescence and Inductively Coupled Plasma revealed Sb deficiency in the crystal, which explains the observed high charge carrier concentration and metallic properties. The transport properties were measured in the temperature range T = 20-300 K on a polycrystalline sample. Furthermore, ab initio theoretical calculations have been conducted to support the interpretation of the measurements.
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FeSb(2) was recently identified as a narrow-gap semiconductor with indications of strong electron-electron correlations. In this manuscript, we report on systematic thermoelectric investigation of a number of FeSb(2) single crystals with varying carrier concentrations, together with two isoelectronically substituted FeSb(2-x)As(x) samples (x = 0.01 and 0.03) and two reference compounds FeAs(2) and RuSb(2). Typical behaviour associated with narrow bands and narrow gaps is only confirmed for the FeSb(2) and the FeSb(2-x)As(x) samples. The maximum absolute thermopower of FeSb(2) spans from 10 to 45 mV/K at around 10 K, greatly exceeding that of both FeAs(2) and RuSb(2). The relation between the carrier concentration and the maximum thermopower value is in approximate agreement with theoretical predictions of the electron-diffusion contribution which, however, requires an enhancement factor larger than 30. The isoelectronic substitution leads to a reduction of the thermal conductivity, but the charge-carrier mobility is also largely reduced due to doping-induced crystallographic defects or impurities. In combination with the high charge-carrier mobility and the enhanced thermoelectricity, FeSb(2) represents a promising candidate for thermoelectric cooling applications at cryogenic temperatures.
