Remarkable enhancement of photo-allylation of aromatic carbonyl compounds with a hypervalent allylsilicon reagent by donor molecules

Photo-allylation of various aromatic carbonyl compounds with a penta-coordinated allylsiliconate reagent was remarkably accelerated by the addition of a donor molecule. As the oxidation potential of the allylsiliconate was significantly decreased in the presence of a donor molecule, the more efficient photo-induced electron transfer from the allylsiliconate to the excited substrate was enabled by the hexa-coordination of the silicon atom.     

Nanostructures boost the thermoelectric performance of PbS

In situ nanostructuring in bulk thermoelectric materials through thermo-dynamic phase segregation has established itself as an effective paradigm for optimizing the performance of thermoelectric materials. In bulk PbTe small compositional variations create coherent and semicoherent nanometer sized precipitates embedded in a PbTe matrix, where they can impede phonon propagation at little or no expense to the electronic properties. In this paper the nanostructuring paradigm is for the first time extended to a bulk PbS based system, which despite obvious advantages of price and abundancy, so far has been largely disregarded in thermoelectric research due to inferior room temperature thermoelectric properties relative to the pristine fellow chalcogenides, PbSe and PbTe. Herein we report on the synthesis, microstructural morphology and thermoelectric properties of two phase (PbS)(1-x)(PbTe)(x)x = 0-0.16 samples. We have found that the addition of only a few percent PbTe to PbS results in a highly nanostructured material, where PbTe precipitates are coherently and semicoherently embedded in a PbS matrix. The present (PbS)(1-x)(PbTe)(x) nanostructured samples show substantial decreases in lattice thermal conductivity relative to pristine PbS, while the electronic properties are left largely unaltered. This in turn leads to a marked increase in the thermoelectric figure of merit. This study underlines the efficiency of the nanostructuring approach and strongly supports its generality and applicability to other material systems. We demonstrate that these PbS-based materials, which are made primarily from abundant Pb and S, outperform optimally n-type doped pristine PbTe above 770 K.     

Nanostructured Bi(2-x)Cu(x)S3 bulk materials with enhanced thermoelectric performance

Nanostructured Bi(2-x)Cu(x)S(3) (x = 0, 0.002, 0.005, 0.007, 0.01, 0.03) thermoelectric polycrystals were fabricated by combining mechanical alloying (MA) and spark plasma sintering (SPS) methods. The effect of Cu content on the microstructure and thermoelectric property of Bi(2-x)Cu(x)S(3) bulk samples was investigated. It was found that the subtle tailoring of Cu content could reduce both the electrical resistivity and the thermal conductivity at the same time, and consequently enhancing the thermoelectric property. A low electrical resistivity of 1.34 × 10(-4)Ω m(-1) and a low thermal conductivity of 0.52 W m(-1) K(-1) were obtained for the Bi(1.995)Cu(0.005)S(3) sample at 573 K. The low thermal conductivity is supposed to be due to the nanoscopic Cu-rich regions embedded in the host matrix. A peak ZT value of 0.34 at 573 K was achieved for the Bi(1.995)Cu(0.005)S(3) composition, which is the highest value in the Bi(2)S(3) system reported so far.     

Remarkable enhancement of reactivity of carbonyl compounds for polymerizations with non-activated aromatic hydrocarbons

Reaction of carbonyl compounds bearing electron-withdrawing substituents with non-activated aromatic hydrocarbons proceeds selectively in trifluoromethanesulfonic acid (TFSA) at room temperature to give linear, high-molecular-weight polymers.     

Remarkable enhancement effect of potassium tert-butoxide/THF solution in base-induced Sommelet-Hauser rearrangements

A solution of potassium tert-butoxide in THF was shown to remarkably enhance the base-induced Sommelet-Hauser rearrangement of N-benzylic amino acid-derived ammonium ylides.     

Enhanced thermoelectric performance of hydrothermally synthesized polycrystalline Te-doped SnSe

In this study,large-scale Te-doped polycrystalline SnSe nanopowders were synthesized by a facile hydrothermal approach and the effect of Te doping on the thermoelectric properties of SnSe was fully investigated.It is found that the carrier concentration increases due to the reduction of band gap by alloying with Te,which contributes to significant enhancement of electrical conductivity especially at room temperature.Combined with the moderated Seebeck coefficient,a high power factor of 4.59μW cm ~1 K ~2 is obtained at 773 K.Furthermore,the lattice the rmal conductivity is greatly reduced upon Te substitution owing to the atomic point defect scattering.Benefiting from the synergistically optimized both electrical-and thermal-transport properties by Te-doping,thermoelectric performance of polycrystalline SnSe is enhanced in the whole temperature range with a maximum ZT of-0.79 at a relatively low temperature(773 K) for SnSe_(0.85)Te_(0.15).This study provides a low-cost and simple lowtemperature method to mass production of SnSe with high thermoelectric performance for practical applications     

Paper: An effective substrate for the enhancement of thermoelectric properties in PEDOT:PSS

A novel strategy via paper as an effective substrate has been introduced as a thermoelectric material in this work. Free‐standing poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS)/paper composite films are conveniently prepared by a one‐step method of directly writing PEDOT:PSS solution on paper, making the process simple, rapid, and facile. The free‐standing composite films display excellent flexibility, light weight, soaking stability in water, and great potential in large‐scale production. Improved thermoelectric properties are obtained in PEDOT:PSS/paper composite films, owing to the simultaneously enhanced Seebeck coefficient (30.6 μV K^?1) and electrical conductivity, and a low thermal conductivity (0.16 W m^?1 K^?1) compared with pristine PEDOT:PSS films. The results indicate that paper as an effective substrate is suitable for the preparation of high‐performance and flexible thermoelectric materials. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 737–742     

Enhanced thermoelectric performance and novel nanopores in AgSbTe2 prepared by melt spinning

We report a melt-spinning spark-plasma-sintering synthesis process of the polycrystalline p-type material composed of AgSbTe₂ coarse grains and evenly formed 5-10 nm pores that occur primarily on the surface of matrix grains. The formation mechanism of nanopores and their influences on the thermoelectric properties have been studied and correlated. Microstructure analysis shows that the as-prepared sample can be regarded as a nanocomposite of matrix and in situ generated nanopores evenly coated on matrix grains. For the single-phase component and the possible energy-filter effect caused by the nanopores, the electrical transport properties are improved. Moreover, the thermal conductivity is significantly reduced by strong phonon scattering effect resulted from the nanopores. The thermoelectric performance of the as prepared sample enhances greatly and a ZT of 1.65 at 570 K is achieved, increasing∼200% compared with the sample prepared by traditional melt and slow-cooling method.     

Superionic phase transition in silver chalcogenide nanocrystals realizing optimized thermoelectric performance

Thermoelectric has long been recognized as a potentially transformative energy conversion technology due to its ability to convert heat directly into electricity. However, how to optimize the three interdependent thermoelectric parameters (i.e., electrical conductivity σ, Seebeck coefficient S, and thermal conductivity κ) for improving thermoelectric properties is still challenging. Here, we put forward for the first time the semiconductor-superionic conductor phase transition as a new and effective way to selectively optimize the thermoelectric power factor based on the modulation of the electric transport property across the phase transition. Ultra low value of thermal conductivity was successfully retained over the whole investigated temperature range through the reduction of grain size. As a result, taking monodisperse Ag(2)Se nanocrystals for an example, the maximized ZT value can be achieved around the temperature of phase transition. Furthermore, along with the effective scattering of short-wavelength phonons by atomic defects created by alloying, the alloyed ternary silver chalcogenide compounds, monodisperse Ag(4)SeS nanocrystals, show better ZT value around phase transition temperature, which is cooperatively contributed by superionic phase transition and alloying at nanoscale.     

Efficient enhancement of the thermoelectric performance of vapor phase polymerized poly(3,4‐ethylenedioxythiophene) films with poly(ethyleneimine)

Tuning the molecular rearrangement and oxidation level has been proven to be effective strategies for optimizing the thermoelectric (TE) performance of PEDOT. It is difficult to achieve these effects simultaneously via a one‐step process, however. In this work, we combined vapor phase polymerization (VPP) and H₂SO₄ post‐treatment to obtain a highly conductive PEDOT film. A novel strategy using polyethylenemine (PEI) as an effective reducing agent was employed to enhance the thermopower of the PEDOT film. Grazing‐Incidence Wide‐Angle X‐ray Scattering analysis and the changes in the oxidation level allow us to elucidate the role of PEI and its transport mechanism. It is demonstrated that the thermopower of well‐ordered crystallites in the PEDOT film significantly increases more than five times (from 11 to 59 μV K^?1) by the PEI‐DMF solution immersion process, while the electrical conductivity is maintained at 100 S cm^?1. The promising method connecting VPP, H₂SO₄, and PEI shows great potential for effectively tuning the thermopower of organic TE materials. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 257–265     

Unveiling the origin of performance enhancement of photovoltaic devices by upconversion nanoparticles

To better utilize the infrared(IR)region in sunlight for photovoltaic devices(PVs),upconversion nanoparticles(UCNPs)have been proposed to improve power conversion efficiency(PCE).However,researchers recently have found that the upconversion(UC)effect is negligible in PVs performance improvement for their ultra-low UC photoluminescence quantum yields of UCNPs solid film,while the real mechanism of UCNPs in PVs has not been clearly studied.Herein,based on the material inorganic perovskitesγ-CsPbI₃,NaYF₄:20%Yb³⁺,2%Er³⁺UCNPs were integrated into different transport layer to optimize device performance.Compared with reference device,the short-circuit current density and PCE of optimized device reached 20.87 mA/cm²(20.39 mA/cm²)and 18.34%(17.72%),respectively,without sacrificing open-circuit voltage and filling factor.Further experimental characterizations verified that the improved performance was attributable to enhanced visible light absorption instead of IR.To theoretically explain the statement,the light field distribution in device was simulated and the absorption in different layers was calculated.The results revealed that the introduction of UCNPs with different refractive index from other layers caused light field disturbance,and improved visible light captured by γ-CsPbI₃.Importantly,through experiments and theoretical calculation,the research deeply explored the potential mechanism of UCNPs in optimizing PVs performance.     

Heating performance enhancement for a road unit by using sectorial-finned pipe

Journal of Thermal Analysis and Calorimetry - This study proposes a sectorial-finned pipe in the hydronic road heating system with a three-dimensional road model to enhance the road heating...     

Te/Cr共掺提高PbSe的热电性能

采用高温固相法和快速热压工艺在PbSe的Pb位掺入Cr以调节载流子有效质量、在Se位掺入Te以调节载流子浓度,协同优化载流子迁移率以提高基体材料的热电优值ZT。最终获得的Pb0.97Cr0.03Se0.94Te0.06热电材料在673 K时ZT为0.44,是未掺杂样品PbSe的4.89倍。     

Remarkable reactivity enhancement with Sb?N inter-coordination of ethynyl-1,5-azastibocines in Pd-catalyzed cross-coupling reactions with organic halides

The reaction of 12-arylethynyl-6-methyl-5,6,7,12-tetrahydrodibenzo[c,f][1,5]-azastibocines with organic halides such as acyl halides and aryl halides in the presence of PdCl₂(PPh₃)₂ as a catalyst led to the formation of cross-coupling products, alkynyl ketones and diaryl acetylenes, in good yields. The reactivity of the ethynyl group on the 1,5-azastibocines was far superior to that on diphenyl(phenylethynyl)stibane, which brought about marked improvement in the reaction conditions (lower temperature and shorter reaction time) and in the yields of the cross-coupling products. Single-crystal X-ray analysis of the ethynyl-1,5-azastibocine showed the presence of intramolecular Sb?N interaction which should be responsible for the remarkable reactivity enhancement of the 1,5-azastibocines for this type of reaction.     

Colloidal synthesis of Cu2CdSnSe4 nanocrystals and hot-pressing to enhance the thermoelectric figure-of-merit

We report a solution-based synthesis of monodispersed Cu(2)CdSnSe(4) nanocrystals and a study on the thermoelectric properties of these wide-band-gap dense materials compacted from nanocrystals for the first time. With the help of copper dopants and selenium vacancies generated during wet-chemistry synthesis, a large increment in the power factor is observed, and the dimensionless figure-of-merit ZT reaches a peak value of 0.65 at 450 °C.     

Synthesis and transport property of Cu(1.8)S as a promising thermoelectric compound

Polycrystalline Cu(1.8)S compounds were fabricated by using a combined process of mechanical alloying and spark plasma sintering. The Cu(1.8)S sample with a second Cu(1.96)S phase and a lot of micro pores shows its maximum ZT value 0.5 at 673 K which is the highest value for p-type sulfide thermoelectric materials so far.     

The effect of Cu substitution on microstructure and thermoelectric properties of LaCoO(3) ceramics

La(Co, Cu)O(3-δ) ceramics were prepared by pressureless sintering of citrate precursor powders, and their thermoelectric properties were investigated with an emphasis on the influence of Cu doping and phase structure as well as microstructure. It was found that a secondary phase first appeared in the form of a network along the grain boundaries and then changed to dispersion with increasing Cu content, which effectively reduced the lattice thermal conductivity of the materials. The thermal conductivity was only 1.21 W m(-1) K(-1) for the sample LaCo(0.75)Cu(0.25)O(3-δ), being much lower as for the thermoelectric oxide materials. In addition, a small amount of Cu substitution for Co increased the electrical conductivity greatly and the absolute Seebeck coefficient, whose sign was also reversed from negative to positive. The dimensionless figure of merit, ZT, of LaCoO(3-δ) oxides at low and middle temperatures can be remarkably enhanced by substituting Co with Cu.     

Highly enhanced thermoelectric performance of WS2 nanosheets upon embedding PEDOT:PSS

Two‐dimensional (2D) WS₂ nanosheets (NSs) as a promising thermoelectric (TE) material have gained great concern recently. The low electrical conductivity significantly limits its further development. Herein, we reported an effective method to enhance the TE performance of WS₂ NSs by combining poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS). The restacked WS₂ NSs thin film with 1T phase structure obtained by a common chemical lithium intercalation show a high Seebeck coefficient of 98 μV K^?1 and a poor electrical conductivity of 12.5 S cm^?1. The introduction of PEDOT:PSS with different contents obviously improve the electrical conductivity of WS₂ NSs thin films. Although a declining Seebeck coefficient was observed, an optimized TE power factor of 45.2 μW m^?1 k^?1 was achieved for WS₂/PEDOT:PSS composite thin film. Moreover, the as‐prepared WS₂/PEDOT:PSS thin film can be easily peeled off and transferred to other substrate leading to a more promising application. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55 , 997–1004     

Phase-engineered high-entropy metastable FCC Cu2−yAgy(InxSn1−x)Se2S nanomaterials with high thermoelectric performance

Crystal-phase engineering to create metastable polymorphs is an effective and powerful way to modulate the physicochemical properties and functions of semiconductor materials, but it has been rarely explored in thermoelectrics due to concerns over thermal stability. Herein, we develop a combined colloidal synthesis and sintering route to prepare nanostructured solids through ligand retention. Nano-scale control over the unconventional cubic-phase is realized in a high-entropy Cu_2−yAg_y(In_xSn_1−x)Se₂S (x = 0–0.25, y = 0, 0.07, 0.13) system by surface-ligand protection and size-driven phase stabilization. Different from the common monoclinic phase, the unconventional cubic-phase samples can optimize electrical and thermal properties through phase and entropy design. A high power factor (0.44 mW m⁻¹ K⁻²), an ultralow thermal conductivity (0.25 W m⁻¹ K⁻¹) and a ZT value of 1.52 are achieved at 873 K for the cubic Cu_1.87Ag_0.13(In_0.06Sn_0.94)Se₂S nanostructured sample. This study highlights a new method for the synthesis of metastable phase high-entropy materials and gives insights into stabilizing the metastable phase through ligand retention in other research communities.

The retention in size caused by the residual ligands drives the stability of metastable phase, enhancing structure symmetry and leading to good electrical transport. The distorted lattice and multidimensional defects intensify phonon scattering.