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1.
Oxygen‐containing compounds are promising thermoelectric (TE) materials for their chemical and thermal stability. As compared with the high‐performance p‐type counterparts (e.g., ZT ≈1.5 for BiCuSeO), the enhancement of the TE performance of n‐type oxygen‐containing materials remains challenging due to their mediocre electrical conductivity and high thermal conductivity. Here, n‐type layered Bi2O2Se is reported as a potential TE material, of which the thermal conductivity and electrical transport properties can be effectively tuned via carrier engineering and hierarchical microstructure. By selective modification of insulating [Bi2O2]2+ layers with Ta dopant, carrier concentration can be increased by four orders of magnitude (from 1015 to 1019 cm?3) while relatively high carrier mobility can be maintained, thus greatly enhancing the power factors (≈451.5 µW K?2 m?1). Meanwhile, the hierarchical microstructure can be induced by Ta doping, and the phonon scattering can be strengthened by atomic point defects, nanodots of 5–10 nm and grains of sub‐micrometer level, which progressively suppresses the lattice thermal conductivity. Accordingly, the ZT value of Bi1.90Ta0.10O2Se reaches 0.36 at 773 K, a ≈350% improvement in comparison with that of the pristine Bi2O2Se. The average ZT value of 0.30 from 500 to 823 K is outstanding among n‐type oxygen‐containing TE materials. This work provides a desirable way for enhancing the ZT values in oxygen‐containing compounds.  相似文献   

2.
Grain or phase boundaries play a critical role in the carrier and phonon transport in bulk thermoelectric materials. Previous investigations about controlling boundaries primarily focused on the reducing grain size or forming nanoinclusions. Herein, liquid phase compaction method is first used to fabricate the Yb‐filled CoSb3 with excess Sb content, which shows the typical feature of low‐angle grain boundaries with dense dislocation arrays. Seebeck coefficients show a dramatic increase via energy filtering effect through dislocation arrays with little deterioration on the carrier mobility, which significantly enhances the power factor over a broad temperature range with a high room‐temperature value around 47 μW cm?2 K?1. Simultaneously, the lattice thermal conductivity could be further suppressed via scattering phonons via dense dislocation scattering. As a result, the highest average figure of merit ZT of ≈1.08 from 300 to 850 K could be realized, comparable to the best reported result of single or triple‐filled Skutterudites. This work clearly points out that low‐angle grain boundaries fabricated by liquid phase compaction method could concurrently optimize the electrical and thermal transport properties leading to an obvious enhancement of both power factor and ZT .  相似文献   

3.
The layered oxyselenide BiCuSeO system is known as one of the high‐performance thermoelectric materials with intrinsically low thermal conductivity. By employing atomic, nano‐ to mesoscale structural optimizations, low thermal conductivity coupled with enhanced electrical transport properties can be readily achieved. Upon partial substitution of Bi3+ by Ca2+ and Pb2+, the thermal conductivity can be reduced to as low as 0.5 W m?1 K?1 at 873 K through dual‐atomic point‐defect scattering, while a high power factor of ≈1 × 10?3 W cm?1 K?2 is realized over a broad temperature range from 300 to 873 K. The synergistically optimized power factor and intrinsically low thermal conductivity result in a high ZT value of ≈1.5 at 873 K for Bi0.88Ca0.06Pb0.06CuSeO, a promising candidate for high‐temperature thermoelectric applications. It is envisioned that the all‐scale structural optimization is critical for optimizing the thermoelectricity of quaternary compounds.  相似文献   

4.
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   

5.
A rapid solvent evaporation method based on the triple point of a processing solvent is presented to prepare carbon nanotube (CNT) foam with a porous structure for thermoelectric (TE) power generators. The rapid solvent evaporation process allows the preparation of CNT foam with various sizes and shapes. The obtained highly porous CNT foam with porosity exceeding 90% exhibits a low thermal conductivity of 0.17 W m?1 K?1 with increased phonon scattering, which is 100 times lower than that of a CNT film with a densely packed network. The aforementioned structural and thermal properties of the CNT foam are advantageous to develop a sufficient temperature gradient between the hot and cold parts to enhance TE output characteristics. To improve the electrical conductivity and Seebeck coefficient further, p‐ and n‐molecular dopants are easily introduced into the CNT foam, and the optimized condition is investigated based on the TE properties. Finally, optimized p‐ and n‐doped CNT foams are used to fabricate a vertical and flexible TE power generator with a combination of series and parallel mixed circuits. The maximum output power and output power per weight of the TE generator reach 1.5 µW and 82 µW g?1, respectively, at a temperature difference of 13.9 K.  相似文献   

6.
The effects of phloretin, H2DIDS (4,4′-diisothiocyano-1,2-diphenylethane-2,2′-disulfonate) and SO4?2 on anion transport in Ehrlich ascites tumor cells was studied in an effort to determine whether Cl? and SO4?2 share a common transport mechanism. Sulfate, in the presence of constant extracellular Cl? (100 mM), reduces Cl? self-exchange by 43% (40 mM SO4?2) and Cl??SO4?2 exchange by 36% (25 mM Cl?/O SO4?2) compared to 25 mM Cl?/50 mM SO4?2. Phloretin blocks without delay and to the same extent the self-exchange of both Cl? and SO4?2. For example, at 10?4 M phloretin, anion transport is inhibited 28% which increases to 78% at 5 × 10?4 M. Reversibly bound H2DIDS also inhibits the self-exchange of both Cl? and SO4?2. However, at all H2DIDS concentrations tested (0.5 ? 10 × 10?5 M) SO4?2 transport was far more susceptible to inhibition than that of Cl?. H2DIDS when irreversibly bound to the cell inhibits SO4?2 but not Cl? transport The results of these experiments are consistent with the postulation that both Cl? and SO4?2 are transported by a common mechanism possessing two reactive sites.  相似文献   

7.
Abstract The purported blocker of anion transport 4, 4′ di-isothiocyano-2-2′ stilbene disulfonate (DIDS) has been shown to partially inhibit 36Cl? influx, 36CIO?3 influx and 35SO2?4 influx into Pisum salivum L. cv. Feltham First seedlings. This inhibitory effect could be prevented by pretreatment with the respective unlabelled medium. There was no effect of DIDS on 14C methylamine influx. The results are consistent with the hypothesis that the binding of DIDS to the site of anion-carrier interaction is responsible for its observed inhibitory effects on anion fluxes. The fluorescent properties of DIDS upon binding to membrane proteins was exploited in an attempt to examine the major sites of anion pumping in whole roots. The results show clearly that in the presence of DIDS the epidermal layers became brightly fluorescent, while cortical layers did not fiuoresce. Lycopersicum esculentum cells taken from locular fluid were plasmolysed using sucrose solution, and the patterns of fluorescence in the presence of DIDS showed in an unambiguous way that the fluorescence is associated with cell membranes. The potential usefulness of this technique to probe sites of anion transport in whole plants and tissues is discussed.  相似文献   

8.
Thermoelectric (TE) materials are important for the sustainable development because they enable the direct harvesting of low‐quality heat into electricity. Among them, conducting polymers have attracted great attention arising from their advantages, such as flexibility, nontoxicity, easy availability, and intrinsically low thermal conductivity. In this work, a novel and facile method is reported to significantly enhance the TE property of poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) films through sequential post‐treatments with common acids and bases. Compared with the as‐prepared PEDOT:PSS, both the Seebeck coefficients and electrical conductivities can be remarkably enhanced after the treatments. The oxidation level, which significantly impacts the TE property of the PEDOT:PSS films, can also be well tuned by controlling the experimental conditions during the base treatment. The optimal PEDOT:PSS films can have a Seebeck coefficient of 39.2 µV K?1 and a conductivity of 2170 S cm?1 at room temperature, and the corresponding power factor is 334 µW (m?1 K?2). The enhancement in the TE properties is attributed to the synergetic effect of high charge mobility by the acid treatment and the optimal oxidation level tuned by the base treatment.  相似文献   

9.
Until now, many works have shown that the hydrogen evolution reaction (HER) performance can be improved by anion or cation substitution into the crystal lattice of pyrite‐structure materials. However, the synergistic effects of anion–cation double substitution for overall enhancement of the catalytic activity remains questionable. Here, the simultaneous incorporation of vanadium and phosphorus into the CoS2 moiety for preparing 3D mesoporous cubic pyrite‐metal Co1‐xVxSP is presented. It is demonstrated that the higher catalytic activity of CoS2 after V incorporation can be primarily attributed to abundance active sites, whereas P substitution is responsible for improving HER kinetics and intrinsic catalyst. Interestingly, due to the synergistic effect of P–V double substitution, the 3D Co1‐xVxSP shows superior electrocatalysis toward the HER with a very small overpotential of 55 mV at 10 mA cm?2, a small Tafel slope of 50 mV dec?1, and a high turnover frequency of 0.45 H2 s?1 at 10 mA cm?2, which is very close to commercial 20% Pt/C. Density functional theory calculation reveals that the superior catalytic activity of the 3D Co1‐xVxSP is contributed by the reduced kinetic energy barrier of rate‐determining HER step as well as the promotion of the desorption H2 gas process.  相似文献   

10.
The effects of a variety of chemically diverse, reversibly acting inhibitors have been measured on both Cl? and SO42? equilibrium exchange across the human red cell membrane. The measurements were carried out under the same conditions (pH 6.3, 8°C) and in the same medium for both the Cl? and SO24 tracer fluxes. Under these conditions the rate constant for Cl?-Cl? exchange is about 20 000 times larger than that for SO42?-SO42? exchange. Despite this large difference in the rates of transport of the two anions, eight different reversibly acting inhibitors have virtually the same effect on the Cl? and SO42? transport. The proteolytic enzyme papain also has the same inhibitory effect on both the Cl? and SO42? self-exchange. In addition, the slowly penetrating disulfonate 2-(4′-aminophenyl)-6-methylbenzenethiazol-3′,7-disulfonic acid (APMB) is 5-fold more effective from the outer than from the inner membrane surface in inhibiting both Cl? and SO42? self-exchange. We interpret these results as evidence that the rapidly penetrating monovalent anion Cl? and the slowly penetrating divalent anion SO42? are transported by the same system.  相似文献   

11.
A method was developed for study of β-hydroxybutyrate transport in erythrocytes and thymocytes. Critical to the method was a centrifugal separation of cells from medium which took advantage of β-hydroxybutyrate transport's temperature dependence and inhibition by phloretin and methylisobutylxanthine, all of which are demonstrated in this work. These properties suggested mediated transport, as did saturation kinetics and inhibition by several agents including pyruvate and α-cyanocinnamate. Most conclusive in this regard was a 2-fold preference for d- over l-β-hydroxybutyrate. Entry was not Na+ dependent. It was stimulated by substitution of SO42? for most of the Cl?. The equilibrium β-hydroxybutyrate space was much higher than the Cl? space of thymocytes, suggesting that β-hydroxybutyrate entry is not associated with net inward negative current and is not coupled to outward Cl? or inward K+ movement (assuming that K+ is at electrochemical equilibrium). Coupling to H+ entry or OH? exit is compatible with the result. These findings are consistent with β-hydroxybutyrate entry by the carboxylate transport site which has been studied extensively with pyruvate and lactate as permeants. The Cl?/HCO3? exchange carrier did not appear to contribute significantly to β-hydroxybutyrate transport.  相似文献   

12.
H2DIDS, the dihydro analog of DIDS (4,4′-diisothiocyanostilbene-2,2′-disulfonic acid) can interact covalently with membrane sites, resulting in an irreversible inhibition of anion exchange. At low temperatures (0°C) and for relatively short times, however, its interaction is largely reversible, so that a kinetic analysis of the nature of its inhibitory effect on Cl? self exchange can be performed. The effects of variations in the chloride concentration on the inhibitory potency of H2DIDS are consistent with the concept that Cl? and H2DIDS compete for the transport site of the anion exchange system. The value of Ki for H2DIDS is 0.046 μM, indicating that H2DIDS has a higher affinity for the transport system than any other inhibitor so far examined. If, as seems probable, the covalent labelling of H2DIDS occurs at the same site as the reversible binding, H2DIDS can be used as a covalent label for the transport site. The specific localization of H2DIDS in the band-3 protein thus indicates that this protein participates directly in anion exchange.  相似文献   

13.
The Ag and In co‐doped PbTe, AgnPb100InnTe100+2n (LIST), exhibits n‐type behavior and features unique inherent electronic levels that induce self‐tuning carrier density. Results show that In is amphoteric in the LIST, forming both In3+ and In1+ centers. Through unique interplay of valence fluctuations in the In centers and conduction band filling, the electron carrier density can be increased from ≈3.1 × 1018 cm?3 at 323 K to ≈2.4 × 1019 cm?3 at 820 K, leading to large power factors peaking at ≈16.0 µWcm?1 K?2 at 873 K. The lone pair of electrons from In+ can be thermally continuously promoted into the conduction band forming In3+, consistent with the amphoteric character of In. Moreover, with rising temperature, the Fermi level shifts into the conduction band, which enlarges the optical band gap based on the Moss–Burstein effect, and reduces bipolar diffusion and thermal conductivity. Adding extra Ag in LIST improves the electrical transport properties and meanwhile lowers the lattice thermal conductivity to ≈0.40 Wm?1 K?1. The addition of Ag creates spindle‐shaped Ag2Te nanoprecipitates and atomic‐scale interstitials that scatter a broader set of phonons. As a result, a maximum ZT value ≈1.5 at 873 K is achieved in Ag6Pb100InTe102 (LIST).  相似文献   

14.
Movements of ions are considered to be governed by the electroneutrality rule. Therefore, a cation moving across the cell membrane into the cell either passively or actively should move together with its counterion, an anion, in equal amounts of charge or in exchange for another cation inside the cell. This means that the net influx of the cation in question should be affected by the permeability of its counterion and/or another cation inside the cell. To examine osmotic and ionic regulation in Chara cells, cell fragments of Chara having a lower osmotic pressure than normal (L-cell fragments) were prepared. The L-cell fragments were individually put into various dilute electrolyte solutions and their osmotic potentials were measured with a turgor balance. Concentrations of K+, Na+, Ca2+, Mg2+, Cl?, NO?3. and SO2?4. in the external electrolyte solutions in which L-cells had been incubated were also analysed by ion chromatography. The results showed that in 0.5 mM KCL + 0.1 mM CaCl2 solution, Chara L-cell fragments absorbed K+ and Cl? to maintain electroneutrality and then regained their osmotic potential very rapidly. When the anion was Cl, the cation absorbed at the highest rate was K+ On the other hand, when the cation was K, the anion absorbed at the highest rate was Cl, Other ions Ca2+, SO2?4 and NO?3 showed much less permeability than K+ and Cl ?for the Chara plasma membrane. The conclusion from these findings was that due to the constraint of electroneutral transport, the uptake rate of a salt into L-cells is limited by the permeability of the least permeable ion.  相似文献   

15.
In view of the importance of Pi in the control of cell metabolism, it was of interest to study the mechanism and regulation of Pi uptake by ascites tumor cells. For this purpose, the incorporation of 32Pi into Ehrlich Lettré cells was compared when competitive anions and inhibitors which alter cation movements were present. Anions such as sulfanilate (35 mm) and succinate (30 mm) decrease 32Pi uptake by ca. 35%, suggesting that transport is mediated by a protein similar to the 100,000 Mr anion carrier isolated from erythrocyte membranes. Furosemide, a diuretic which bears a structural analogy to sulfanilate inhibitors of anion transport, also decreases 32Pi incorporation at concentrations as low as 2 × 10?5m. This inhibitor blocks cation exchange in ascites tumor cells, and from the present data, it is suggested that a possible function of the furosemidesensitive cation exchange protein is to facilitate anion transport. Ouabain, known to inhibit (Na+ + K+)-ATPase and its dephosphorylation, stimulates the rate of incorporation of 32Pi into cells and also raises the net inorganic phosphate level. The stimulation of 32Pi incorporation is decreased by sulfanilate or succinate. In contrast to the effects of ouabain, addition of 10 mm K+, which is known to stimulate (Na+ + K+)-ATPase and its dephosphorylation, decreases 32Pi incorporation. These observations suggest that anion transport and energy-dependent Na+ and K+ movements may be closely coupled to the intact cell.  相似文献   

16.
Despite the unfavorable band structure with twofold degeneracy at the valence band maximum, MgAgSb is still an excellent p‐type thermoelectric material for applications near room temperature. The intrinsically weak electron–phonon coupling, reflected by the low deformation potential Edef ≈ 6.3 eV, plays a crucial role in the relatively high power factor of MgAgSb. More importantly, Li is successfully doped into Mg site to tune the carrier concentration, leading to the resistivity reduction by a factor of 3 and a consequent increase in power factor by ≈30% at 300 K. Low lattice thermal conductivity can be simultaneously achieved by all‐scale hierarchical phonon scattering architecture including high density of dislocations and nanoscale stacking faults, nanoinclusions, and multiscale grain boundaries. Collectively, much higher average power factor ≈25 μW cm?1 K?2 with a high average ZT ≈ 1.1 from 300 to 548 K is achieved for 0.01 Li doping, which would result in a high output power density ≈1.56 W cm?2 and leg efficiency ≈9.2% by calculations assuming cold‐side temperature Tc = 323 K, hot‐side temperature Th = 548 K, and leg length = 2 mm.  相似文献   

17.
A series of artificial 2,2′-bipyridine receptors (1, 2, 3) containing phenol group have been designed and synthesized. Their anion-binding properties are evaluated for various anions (F?, Cl?, Br?, I?, AcO? and H2PO4?) by UV-vis titration experiment in order to research the impact of different substituents on anion-recognition properties. Results indicate that the anion binding abilities can be tuned by electron push-pull properties of substituents on the phenyl ortho- or para-position of the receptors. In addition, receptor 1 is sensitive for F? detection without the interference of other studied anions, and receptors 2 and 3 are sensitive for H2PO4? detection.  相似文献   

18.
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   

19.
The role of cAMP in regulation of intracellular pH in the confluent LLC-PK1 cells was investigated. DibutyrylcAMP and forskolin induce intracellular acidification. This acidification is inhibited by DIDS and ethacrynic acid, inhibitors of Na+-independent Cl?/HCO3? exchange, and by removal of extracellular Cl?. In addition, Bt2 cAMP causes Cl? entry into LLC-PK1 cells. These results suggest that cAMP activates Cl? transport, namely Na+-independent Cl?/HCO3? exchange, which participates in pHi regulation.  相似文献   

20.
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   

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