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1.
In this work, a zT value as high as 1.2 at room temperature for n‐type Ag2Se films is reported grown by pulsed hybrid reactive magnetron sputtering (PHRMS). PHRMS is a novel technique developed in the lab that allows to grow film of selenides with different compositions in a few minutes with great quality. The improved zT value reported for room temperature results from the combination of the high power factors, similar to the best values reported for bulk Ag2Se (2440 ± 192 µW m?1 K?2), along with a reduced thermoelectric conductivity as low as 0.64 ± 0.1 W m?1 K?1. The maximum power factor for these films is of 4655 ± 407 µW m?1 K?2 at 103 °C. This material shows promise to work for room temperature applications. Obtaining high zT or, in other words, high power factor and low thermal conductivity values close to room temperature for thin films is of high importance to develop a new generation of wearable devices based on thermoelectric heat recovery.  相似文献   

2.
PbS shares several features with the other lead chalcogenides PbX (X: Te, Se), which are good thermoelectric materials. PbS has a potential advantage in that it is quite earth abundant and inexpensive. In this work we tune the transport properties in n‐type, single‐phase polycrystalline PbS1‐xClx (x ≤ 0.008) with different carrier densities. Lead chloride provides a nearly 100% efficient doping control up to 1.2 × 1020 cm?3. The maximum zT achieved at 850 K is 0.7 with a predicted zT ~ 1 at 1000 K. This is about twice as high as what was previously reported (~0.4) for binary PbS. Compared with the other lead chalcogenides the higher effective mass and higher lattice thermal conductivity makes binary PbS an inferior thermoelectric material. However this study also predicts greater potential of zT improvement in PbS by material engineering such as alloying or nanostructuring compared to PbSe or PbTe. Considering their abundance and low cost, PbS based materials are quite competitive among the lead chalcogenides for thermoelectric applications.  相似文献   

3.
Noting the steadily worsening problem of depleted fossil fuel sources, alternate energy sources have become increasingly important; these include thermoelectrics, which may use waste heat to generate electricity. To be economically viable, the thermoelectric figure‐of‐merit, zT, which is related to the energy conversion efficiency, needs to be in excess of unity (zT > 1). Tl4SnTe3 and Tl4PbTe3 were reported to attain a thermoelectric figure‐of‐merit zT max = 0.74 and 0.71, respectively, at 673 K. Here, the thermoelectric properties of both materials are presented as a function of x in Tl10–x Sn x Te6 and Tl10–x Pb x Te6, with x varying between 1.9 and 2.05, culminating in zT values in excess of 1.2. These materials are charge balanced when x = 2, according to (Tl+)8(Sn2+)2(Te2?)6 and (Tl+)8(Pb2+)2(Te2?)6 (or: (Tl+)4Pb2+(Te2?)3). Increasing x causes an increase in valence electrons, and thus a decrease in the dominating p‐type charge carriers. Larger x values occur with a smaller electrical conductivity and a larger Seebeck coefficient. In each case, the lattice thermal conductivity remains under 0.5 W m?1 K?1, resulting in several samples attaining the desired zT max > 1. The highest values thus far are exhibited by Tl8.05Sn1.95Te6 with zT = 1.26 and Tl8.10Pb1.90Te6 with zT = 1.46 around 685 K.  相似文献   

4.
Recent discoveries of novel thermoelectric materials largely rely on an intrinsic low lattice thermal conductivity. This results from various mechanisms including low sound velocity, complex crystal structure, liquid‐like ions, and lattice anharmonicity. Here semiconducting Ag9AlSe6 with many weakly bonded and highly disordered cations is shown to be a promising novel thermoelectric material, due to its ultralow lattice thermal conductivity (κL) of ≈0.3 W m?1 K?1 in the entire temperature range. Such a low κL is believed to be a result of its (1) complex crystal structure for a small population of acoustic phonons, (2) soft bonding for an overall low sound velocity (1300 m s?1), and (3) massive disordering of Ag ions. Its electronic transport properties can be well understood by a single parabolic band model with acoustic scattering. The achieved thermoelectric figure of merit (zT) can be as high as unity, which is unlike conventional thermoelectric materials, which rely heavily on a high power factor. This work not only demonstrates Ag9AlSe6 as a promising thermoelectric material, but also paves the way for the exploration of novel thermoelectrics with a complex crystal structure with weakly bonded and highly disordered constituent elements in the structure.  相似文献   

5.
High ZT of 1.34 at 766 K and a record high average ZT above 1 in the temperature range of 300‐864 K are attained in n‐type PbTe by engineering the temperature‐dependent carrier concentration and weakening electron–phonon coupling upon Ga doping. The experimental studies and first principles band structure calculations show that doping with Ga introduces a shallow level impurity contributing extrinsic carriers and imparts a deeper impurity level that ionizes at higher temperatures. This adjusts the carrier concentration closer to the temperature‐dependent optimum and thus maximizes the power factor in a wide temperature range. The maximum power factor of 35 µW cm−1 K−2 is achieved for the Pb0.98Ga0.02Te compound, and is maintained over 20 µWcm−1 K−2 from 300 to 767 K. Band structure calculations and X‐ray photoelectron spectroscopy corroborate the amphoteric role of Ga in PbTe as the origin of shallow and deep levels. Additionally, Ga doping weakens the electron–phonon coupling, leading to high carrier mobilities in excess of 1200 cm2 V−1 s−1. Enhanced point defect phonon scattering yields a reduced lattice thermal conductivity. This work provides a new avenue, beyond the conventional shallow level doping, for further improving the average ZT in thermoelectric materials.  相似文献   

6.
A high ZT (thermoelectric figure of merit) of ≈1.4 at 900 K for n‐type PbTe is reported, through modifying its electrical and thermal properties by incorporating Sb and S, respectively. Sb is confirmed to be an amphoteric dopant in PbTe, filling Te vacancies at low doping levels (<1%), exceeding which it enters into Pb sites. It is found that Sb‐doped PbTe exhibits much higher carrier mobility than similar Bi‐doped materials, and accordingly, delivers higher power factors and superior ZT . The enhanced electronic transport is attributed to the elimination of Te vacancies, which appear to strongly scatter n‐type charge carriers. Building on this result, the ZT of Pb0.9875Sb0.0125Te is further enhanced by alloying S into the Te sublattice. The introduction of S opens the bandgap of PbTe, which suppresses bipolar conduction while simultaneously increasing the electron concentration and electrical conductivity. Furthermore, it introduces point defects and induces second phase nanostructuring, which lowers the lattice thermal conductivity to ≈0.5 W m?1 K?1 at 900 K, making this material a robust candidate for high‐temperature (500–900 K) thermoelectric applications. It is anticipated that the insights provided here will be an important addition to the growing arsenal of strategies for optimizing the performance of thermoelectric materials.  相似文献   

7.
NbFeSb‐based half‐Heusler alloys have been recently identified as promising high‐temperature thermoelectric materials with a figure of merit zT > 1, but their thermal conductivity is still relatively high. Alloying Ta at the Nb site would be highly desirable because the large mass fluctuation between them could effectively scatter phonons and reduce the lattice thermal conductivity. However, practically it is a great challenge due to the high melting point of refractory Ta. Here, the successful synthesis of Ta‐alloyed (Nb1?xTax)0.8Ti0.2FeSb (x = 0 – 0.4) solid solutions with significantly reduced thermal conductivity by levitation melting is reported. Because of the similar atomic sizes and chemistry of Nb and Ta, the solid solutions exhibit almost unaltered electrical properties. As a result, an overall zT enhancement from 300 to 1200 K is realized in the single‐phase Ta‐alloyed solid solutions, and the compounds with x = 0.36 and 0.4 reach a maximum zT of 1.6 at 1200 K. This work also highlights that the isoelectronic substitution by atoms with similar size and chemical nature but large mass difference should reduce the lattice thermal conductivity but maintain good electrical properties in thermoelectric materials, which can be a guide for optimizing the figure of merit by alloying.  相似文献   

8.
This study investigates Ga-doped n-type PbTe thermoelectric materials and the dynamic phase conversion process of the second phases via Cu2Se alloying. Introducing Cu2Se enhances its electrical transport properties while reducing its lattice thermal conductivity (κlat) via weak electron–phonon coupling. Cu2Te and CuGa(Te/Se)2 (tetragonal phase) nanocrystals precipitate during the alloying process, resulting in Te vacancies and interstitial Cu in the PbTe matrix. At room temperature, Te vacancies and interstitial Cu atoms serve as n-type dopants, increasing the carrier concentration and electrical conductivity from ≈1.18 × 1019 cm−3 and ≈1870 S cm−1 to ≈2.26 × 1019 cm−3 and ≈3029 S cm−1, respectively. With increasing temperature, the sample exhibits a dynamic change in Cu2Te content and the generation of a new phase of CuGa(Te/Se)2 (cubic phase), strengthening the phonon scattering and obtaining an ultralow κlat. Pb0.975Ga0.025Te-3%CuSe exhibits a maximum figure of merit of ≈1.63 at 823 K, making it promising for intermediate-temperature device applications.  相似文献   

9.
Little is currently known about the potential impact of silver nanoparticles (AgNPs) on estuarine microbial communities. The Colne estuary, UK, is susceptible to oil pollution through boat traffic, and there is the potential for AgNP exposure via effluent discharged from a sewage treatment works located in close proximity. This study examined the effects of uncapped AgNPs (uAgNPs), capped AgNPs (cAgNPs) and dissolved Ag2SO4, on hydrocarbon-degrading microbial communities in estuarine sediments. The uAgNPs, cAgNPs and Ag2SO4 (up to 50 mg L−1) had no significant impact on hydrocarbon biodegradation (80–92% hydrocarbons were biodegraded by day 7 in all samples). Although total and active cell counts in oil-amended sediments were unaffected by silver exposure; total cell counts in non-oiled sediments decreased from 1.66 to 0.84 × 107 g−1 dry weight sediment (dws) with 50 mg L−1 cAgNPs and from 1.66 to 0.66 × 107 g−1 dws with 0.5 mg L−1 Ag2SO4 by day 14. All silver-exposed sediments also underwent significant shifts in bacterial community structure, and one DGGE band corresponding to a member of Bacteroidetes was more prominent in non-oiled microcosms exposed to 50 mg L−1 Ag2SO4 compared to non-silver controls. In conclusion, AgNPs do not appear to affect microbial hydrocarbon-degradation but do impact on bacterial community diversity, which may have potential implications for other important microbial-mediated processes in estuaries.  相似文献   

10.
Half‐Heusler (HH) alloys are among the best promising thermoelectric (TE) materials applicable for the middle‐to‐high temperature power generation. Despite of the large thermoelectric power factor and decent figure‐of‐merit ZT (≈1), their broad applications and enhancement on TE performance are limited by the high intrinsic lattice thermal conductivity (κL) due to insufficiencies of phonon scattering mechanisms, and the fewer powerful strategies associated with the microstructural engineering for HH materials. This study reports a bottom‐up nanostructure synthesis approach for these HH materials based on the displacement reaction between metal chlorides/bromides and magnesium (or lithium), followed by vacuum‐assisted spark plasma sintering process. The samples are featured with dense dislocation arrays at the grain boundaries, leading to a minimum κL of ≈1 W m?1 K?1 at 900 K and one of the highest ZT (≈1) and predicted η (≈11%) for n‐type Hf0.25Zr0.75NiSn0.97Sb0.03. Further manipulation on the dislocation defects at the grain boundaries of p‐type Nb0.8Ti0.2FeSb leads to enhanced maximum power factor of 47 × 10?4 W m?1 K?2 and the predicted η of ≈7.5%. Moreover, vanadium substitution in FeNb0.56V0.24Ti0.2Sb significantly promotes the η to ≈11%. This strategy can be extended to a broad range of advanced alloys and compounds for improved properties.  相似文献   

11.
Mono Lake sediment slurries incubated with lactate and tellurite [Te(IV)] turned progressively black with time because of the precipitation of elemental tellurium [Te(0)]. An enrichment culture was established from these slurries that demonstrated Te(IV)-dependent growth. The enrichment was purified by picking isolated black colonies from lactate/Te(IV) agar plates, followed by repeated streaking and picking. The isolate, strain MLTeJB, grew in aqueous Te(IV)-medium if provided with a small amount of sterile solid phase material (e.g., agar plug; glass beads). Strain MLTeJB grew at high concentrations of Te(IV) (~8 mM) by oxidizing lactate to acetate plus formate, while reducing Te(IV) to Te(0). Other electron acceptors that were found to sustain growth were tellurate, selenate, selenite, arsenate, nitrate, nitrite, fumarate and oxygen. Notably, growth on arsenate, nitrate, nitrite and fumarate did not result in the accumulation of formate, implying that in these cases lactate was oxidized to acetate plus CO2. Strain MLTeJB is a low G + C Gram positive motile rod with pH, sodium, and temperature growth optima at 8.5–9.0, 0.5–1.5 M, and 40°C, respectively. The epithet Bacillus beveridgei strain MLTeJBT is proposed.  相似文献   

12.
A water‐soluble, high‐output fluorescent sensor, based on a lumazine ligand with a thiophene substituent for Cd2+, Hg2+ and Ag+ metal ions, is reported. The sensor displays fluorescence enhancement upon Cd2+ binding (log  β = 2.79 ± 0.08) and fluorescence quenching by chelating with Ag+ and Hg2+ (log β = 4.31 ± 0.15 and 5.42 ± 0.1, respectively). The mechanism of quenching is static and occurs by formation of a ground‐state non‐fluorescent complex followed by rapid intersystem crossing. The value of the Stern–Volmer quenching rate constant (kq) by Ag+ ions is close to 6.71 × 1012 mol/L/s at 298 K. The thermodynamic parameters (ΔG, ΔH and ΔS) were also evaluated and indicated that the complexation process is spontaneous, exothermic and entropically favourable. The quantitative linear relationship between the softness values of Klopman (σK) or Ahrland (σA) and the experimental binding constants (β) being in the order of Hg2+ > Ag+ > Cd2+ suggests that soft–soft interactions are the key for the observed sensitivity and selectivity in the presence of other metal ions, such as: Pb2+, Ni2+, Mn2+, Cu2+, Co2+, Zn2+ and Mg2+ ions. Copyright © 2008 John Wiley & Sons, Ltd.  相似文献   

13.
To monitor the specificity of Staphylococcus aureus aptamer (SA‐31) against its target cell, we used enzyme‐linked aptamer assay. In the presence of target cell, horseradish peroxidase–conjugated streptavidin bound to biotin‐labeled SA‐31 showed specific binding to S   aureus among 3 different bacteria with limit of detection of 103 colony‐forming unit per milliliter. The apparent K a was 1.39 μM−1 ± 0.3 μM−1. The binding of SA‐31 to membrane proteins extracted from cell surface was characterized using isothermal titration calorimetry, and the effect of changes in binding temperature and salt concentrations of binding buffer was evaluated based on thermodynamic parameters (K a, ΔH , and ΔG ). Since binding of aptamer to its targets solely depends on its 3‐dimensional structure under experimental conditions used in selection process, the change in temperature and ion concentration changed the affinity of SA‐31 to its target on surface of bacteria. At 4°C, SA‐31 did not show an affinity to its target with poor heat change upon injection of membrane fraction to aptamer solution. However, the apparent association constants of SA‐31 slightly varied from K a = 1.56 μM−1 ± 0.69 μM−1 at 25°C to K a = 1.03 μM−1 ± 0.9 μM−1 at 37°C. At spontaneously occurring exothermic binding reactions, affinities of S  aureus aptamer to its target were also 9.44 μM−1 ± 0.38 μM−1 at 50mM, 1.60 μM−1 ± 0.11 μM−1 at 137mM, and 3.28 μM−1 ± 0.46 μM−1 at 200 mM of salt concentration. In this study, it was demonstrated that enzyme‐linked aptamer assay and isothermal titration calorimetry were useful tools for studying the fundamental binding mechanism between a DNA aptamer and its target on the outer surface of S  aureus .  相似文献   

14.

The marine diatom Thalassiosira pseudonana grown under air (0.04% CO2) and 1 and 5% CO2 concentrations was evaluated to determine its potential for CO2 mitigation coupled with biodiesel production. Results indicated that the diatom cultures grown at 1 and 5% CO2 showed higher growth rates (1.14 and 1.29 div day−1, respectively) and biomass productivities (44 and 48 mgAFDWL−1 day−1) than air grown cultures (with 1.13 div day−1 and 26 mgAFDWL−1 day−1). The increase of CO2 resulted in higher cell volume and pigment content per cell of T. pseudonana. Interestingly, lipid content doubled when air was enriched with 1–5% CO2. Moreover, the analysis of the fatty acid composition of T. pseudonana revealed the predominance of monounsaturated acids (palmitoleic-16:1 and oleic-18:1) and a decrease of the saturated myristic acid-14:0 and polyunsaturated fatty acids under high CO2 levels. These results suggested that T. pseudonana seems to be an ideal candidate for biodiesel production using flue gases.

  相似文献   

15.
Thermoelectric materials can be optimized by tuning the carrier concentration with chemical doping. However, because the optimum dopant concentration typically increases with temperature, the optimum efficiency can not normally be achieved for a uniform material in a temperature gradient. Here, we show Ag‐doped PbTe/Ag2Te composites exhibit high thermoelectric performance (~50% greater than La‐doped composites) because of a temperature induced gradient in the doping concentration caused by the temperature‐dependent solubility of Ag in the PbTe matrix. This demonstrates a new mechanism to achieve a higher thermoelectric efficiency afforded by a given material system, and should be applicable to other thermoelectric materials.  相似文献   

16.
Bioluminescent bacteria in the form of a cell suspension for on-site hazard analysis are not suitable as in vivo luminescence in free cells fluctuates and may lead to erroneous results. Furthermore, the culture broth cannot be stored for long durations to continue sensing analytes as the luminescence ceases over time. Factors that affect luminescence response include growth dynamism, and ambient environmental conditions. The present study investigated the effect of storage conditions such as temperature (25 ± 2°C, room temperature; 4°C; and −20°C) and ambient aqueous environment (M1: sucrose, 1.02 M; M2, bioluminescent media [tryptone, 10 g L−1; NaCl, 28.5 g L−1; MgCl2.7H2O, 4.5 g L−1; CaCl2, 0.5 g L−1; KCl 0.5 g L−1; yeast extract, 1 g L−1; H2O, 1 L]; M3, bioluminescent media and 95% glycerol, 1:1 ratio) on the luminescence emission from the calcium alginate-immobilized Photobacterium phosphoreum (Sb) against the cells in free suspension for an extended period. The results indicated that both the parameters that were undertaken markedly affected the luminescence. In the study, Sb showed an enhanced luminescence emission than the control up to 18.5-fold and for a prolonged period which can be efficiently utilized for rapid biosensing of hazardous materials.  相似文献   

17.
Microstructure manipulation plays an important role in enhancing physical and mechanical properties of materials. Here a high figure of merit zT of 1.2 at 357 K for n‐type bismuth‐telluride‐based thermoelectric (TE) materials through directly hot deforming the commercial zone melted (ZM) ingots is reported. The high TE performance is attributed to a synergistic combination of reduced lattice thermal conductivity and maintained high power factor. The lattice thermal conductivity is substantially decreased by broad wavelength phonon scattering via tuning multiscale microstructures, which includes microscale grain size reduction and texture loss, nanoscale distorted regions, and atomic scale lattice distotions and point defects. The high power factor of ZM ingots is maintained by the offset between weak donor‐like effect and texture loss during the hot deformation. The resulted high zT highlights the role of multiscale microstructures in improving Bi2Te3‐based materials and demonstrates the effective strategy in enhancing TE properties.  相似文献   

18.
The ultrahigh thermoelectric performance of SnSe‐based single crystals has attracted considerable interest in their polycrystalline counterparts. However, the temperature‐dependent structural transition in SnSe‐based thermoelectric materials and its relationship with their thermoelectric performance are not fully investigated and understood. In this work, nanolaminar SnSe polycrystals are prepared and characterized in situ using neutron and synchrotron powder diffraction measurements at various temperatures. Rietveld refinement results indicate that there is a complete inter‐orthorhombic evolution from Pnma to Cmcm by a series of layer slips and stretches along the a‐ and b‐axes over a 200 K temperature range. This phase transition leads to drastic enhancement of the carrier concentration and phonon scattering above 600 K. Moreover, the unique nanolaminar structure effectively enhances the carrier mobility of SnSe. Their grain and layer boundaries further improve the phonon scattering. These favorable factors result in a high ZT of 1.0 at 773 K for pristine SnSe polycrystals. The thermoelectric performances of polycrystalline SnSe are further improved by p‐type and n‐type dopants (i.e., doped with Ag and SnCl2, respectively), and new records of ZT are achieved in Ag0.015Sn0.985Se (ZT of 1.3 at 773 K) and SnSe0.985Cl0.015 (ZT of 1.1 at 773 K) polycrystals.  相似文献   

19.
Li-CO2 batteries with a high theoretical energy density (1876 Wh kg−1) have unique benefits for reversible carbon fixation for energy storage systems. However, due to lack of stable and highly active catalysts, the long-term operation of Li-CO2 batteries is limited to low current densities (mainly <0.2 mA cm−2) that are far from practical conditions. In this work, it is discovered that, with an ionic liquid-based electrolyte, highly active and stable transition metal trichalcogenide alloy catalysts of Sb0.67Bi1.33X3 (X = S, Te) enable operation of the Li-CO2 battery at a very high current rate of 1 mA cm−2 for up to 220 cycles. It is revealed that: i) the type of chalcogenide (Te vs S) significantly affects the electronic and catalytic properties of the catalysts, ii) a coupled cation-electron charge transfer process facilitates the carbon dioxide reduction reaction (CO2RR) occurring during discharge, and iii) the concentration of ionic liquid in the electrolyte controls the number of participating CO2 molecules in reactions. A combination of these key factors is found to be crucial for a successful operation of the Li-CO2 chemistry at high current rates. This work introduces a new class of catalysts with potential to fundamentally solve challenges of this type of batteries.  相似文献   

20.
Half‐Heusler (HH) compounds have shown great potential in waste heat recovery. Among them, p‐type NbFeSb and n‐type ZrNiSn based alloys have exhibited the best thermoelectric (TE) performance. However, TE devices based on NbFeSb‐based HH compounds are rarely studied. In this work, bulk volumes of p‐type (Nb0.8Ta0.2)0.8Ti0.2FeSb and n‐type Hf0.5Zr0.5NiSn0.98Sb0.02 compounds are successfully prepared with good phase purity, compositional homogeneity, and matchable TE performance. The peak zTs are higher than 1.0 at 973 K for Hf0.5Zr0.5NiSn0.98Sb0.02 and at 1200 K for (Nb0.8Ta0.2)0.8Ti0.2FeSb. Based on an optimal design by a full‐parameters 3D finite element model, a single stage TE module with 8 n‐p HH couples is assembled. A high conversion efficiency of 8.3% and high power density of 2.11 W cm?2 are obtained when hot and cold side temperatures are 997 and 342 K, respectively. Compared to the previous TE module assembled by the same materials, the conversion efficiency is enhanced by 33%, while the power density is almost the same. Given the excellent mechanical robustness and thermal stability, matchable thermal expansion coefficient and TE properties of NbFeSb and ZrNiSn based HH alloys, this work demonstrates their great promise for power generation with both high conversion efficiency and high power density.  相似文献   

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