Progress on Material Design and Device Fabrication via Coupling Photothermal Effect with Thermoelectric Effect.

Recovery and utilization of low-grade thermal energy is a topic of universal importance in today's society. Photothermal conversion materials can convert light energy into heat energy, which can now be used in cancer treatment, seawater purification, etc., while thermoelectric materials can convert heat energy into electricity, which can now be used in flexible electronics, localized cooling, and sensors. Photothermoelectrics based on the photothermal effect and the Seebeck effect provide suitable solutions for the development of clean energy and energy harvesting. The aim of this paper is to provide an overview of recent developments in photothermal, thermoelectric, and, most importantly, photothermal-thermoelectric coupling materials. First, the research progress and applications of photothermal and thermoelectric materials are introduced, respectively. After that, the classification of different application areas of materials coupling photothermal effect with thermoelectric effect, such as sensors, thermoelectric batteries, wearable devices, and multi-effect devices, is reviewed. Meanwhile, the potential applications and challenges to be overcome for future development are presented, which are of great reference value in waste heat recovery as well as solar energy resource utilization and are of great significance for the sustainable development of society. Finally, the challenges of photothermoelectric materials as well as their future development are summarized.

Elevating Thermoelectric Performance by Compositing Dibromo-Substituted Thienoacene with SWCNTs.

Composites of organic small molecules (OSMs) and single-walled carbon nanotubes (SWCNTs) have drawn great attention as flexible thermoelectric (TE) materials in recent years. Here, we synthesized thieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA) and 2,6-dibromothieno[2',3':4,5]thieno[3,2-b]thieno[2,3-d]thiophene (TTA-2Br) and compounded them with SWCNTs, obtaining thermoelectric TTA/SWCNT and TTA-2Br/SWCNT composites. The introduction of the electron-withdrawing Br group was found to decrease the highest molecular orbital energy level and bandgap (Eg) of TTA-2Br. As a result, the Seebeck coefficient (S) and power factor (PF) of the OSM/SWCNT composite films were significantly improved. Moreover, suitable energy barrier between TTA-2Br and SWCNTs facilitates the energy filtering effect, which further enhances thermoelectric properties of the 40 wt % TTA-2Br/SWCNT composite film with optimum thermoelectric properties (PF = 242.59 ± 9.42 µW m-1 K-2 at room temperature), good thermal stability, and mechanical flexibility. In addition, the thermoelectric generator (TEG) prepared using 40 wt % TTA-2Br/SWCNT composite films and n-type SWCNT films can generate an output power of 102.8 ± 7.4 nW at a temperature difference of 20 °C. This work provides new insights into the preparation of OSM/SWCNT composites with significantly enhanced thermoelectric properties.

Design and Optimization Strategies for Flexible Quasi-Solid-State Thermo-Electrochemical Cells.

Currently, efficient utilization of low-grade thermal energy is a great challenge. Thermoelectricity is an extremely promising method of generating electrical energy from temperature differences. As a green energy conversion technology, thermo-electrochemical cells (TECs) have attracted much attention in recent years for their ability to convert thermal energy directly into electricity with high thermal power. Within TECs, anions and cations gain and lose electrons, respectively, at the electrodes, using the potential difference between the hot and cold terminals of the electrodes by redox couples. Additionally, the anions and cations therein are constantly circulating and mobile via concentration diffusion and thermal diffusion, providing an uninterrupted supply of power to the exterior. This review article focuses mainly on the operation of TECs and recent advances in redox couples, electrolytes, and electrodes. The outlook for optimization strategies regarding TECs is also outlined in this paper.

Compositing Benzothieno[3,2-b]Benzofuran Derivatives with Single-Walled Carbon Nanotubes for Enhanced Thermoelectric Performance.

Although numerous thermoelectric (TE) composites of organic materials and single-walled carbon nanotubes (SWCNTs) have been developed in the past decade, most of the research has been related to polymers without much on organic small molecules (OSMs). In this work, benzothieno[3,2-b]benzofuran (BTBF) and its derivatives (BTBF-Br and BTBF-2Br) were synthesized and their TE composites with SWCNTs were prepared. It is found that the highest molecular orbital level and band gap (Eg) of BTBF, BTBF-Br, and BTBF-2Br gradually decrease upon the introduction of electron-withdrawing Br group on BTBF. These changes significantly improve the Seebeck coefficient and power factor (PF) of OSM/SWCNT composites. An appropriate energy barrier between BTBF-2Br and SWCNTs promotes the energy filtering effect, which further contributes to the enhancement of composites' thermoelectric properties. The composites of SWCNTs and BTBF-2Br with the smallest Eg (4.192 eV) afford the best thermoelectric performance with the room temperature power factor of 169.70 ± 3.46 µW m-1 K-2 in addition to good mechanical flexibility and thermal stability. This study provides a feasible strategy for the preparation of OSM/SWCNT composites with improved thermoelectric properties.

Solvent- and Co-Catalyst-Free Cycloaddition of Carbon Dioxide and Epoxides Catalyzed by Recyclable Bifunctional Niobium Complexes.

CO2, as a cheap and abundant renewable C1 resource, can be used to synthesize high value-added chemicals. In this paper, a series of bifunctional metallic niobium complexes were synthesized and their structures were characterized by IR, NMR and elemental analysis. All of these complexes have been proved to be efficient catalysts for the coupling reaction of CO2 and epoxides to obtain cyclic carbonates under solvent- and co-catalyst-free conditions. By using CO2 and propylene oxide as a model reaction, the optimal reaction conditions were systematically screened as: 100 °C, 1 MPa, 2 h, ratio of catalyst to alkylene oxide 1:100. Under the optimal reaction conditions, the bifunctional niobium catalysts can efficiently catalyze the coupling reaction with high yield and excellent selectivity (maximum yield of >99% at high pressure and 96.8% at atmospheric pressure). Moreover, this series of catalysts can also catalyze the coupling reaction at atmospheric pressure and most of them showed high conversion of epoxide. The catalysts have good substrate suitability and are also applicable to a variety of epoxides including diepoxides and good catalytic performances were achieved for producing the corresponding cyclic carbonates in most cases. Furthermore, the catalysts can be easily recovered by simple filtration and reused for at least five times without obvious loss of catalytic activity and selectivity. Kinetic studies were carried out preliminarily for the bifunctional niobium complexes with different halogen ions (3a(Cl-), 3b(Br-), 3c(I-)) and the formation activation energies (Ea) of cyclic carbonates were obtained. The order of apparent activation energy Ea is 3a (96.2 kJ/mol) > 3b (68.2 kJ/mol) > 3c (37.4 kJ/mol). Finally, a possible reaction mechanism is proposed.

Solvent-Free Coupling Reaction of Carbon Dioxide and Epoxides Catalyzed by Quaternary Ammonium Functionalized Schiff Base Metal Complexes under Mild Conditions.

A series of bifunctional Schiff base metal catalysts (Zn-NPClR, Zn-NPXH, and M-NPClH) with two quaternary ammonium groups were prepared for carbon dioxide (CO2) and epoxide coupling reactions. The effects of the reaction variables on the catalytic activity were systematically investigated, and the optimal reaction conditions (120 °C, 1 MPa CO2, 3 h) were screened. The performances of different metal-centered catalysts were evaluated, and Co-NPClH showed excellent activity. This kind of bifunctional catalyst has a wide range of substrate applicability, excellent stability, and can be reused for more than five runs. A relatively high TOF could reach up to 1416 h-1 with Zn-NPClH as catalyst by adjusting reaction factors. In addition, the kinetic study of the coupling reaction catalyzed by three catalysts (Zn, Co, and Ni) was carried out to obtain the activation energy (Ea) for the formation of cyclic carbonates. Finally, a possible mechanism for this cyclization reaction was proposed.

Advances in Thermoelectric Composites Consisting of Conductive Polymers and Fillers with Different Architectures.

Stretchable wireless power is in increasingly high demand in fields such as smart devices, flexible robots, and electronic skins. Thermoelectric devices are able to convert heat into electricity due to the Seebeck effect, making them promising candidates for wearable electronics. Therefore, high-performance conductive polymer-based composites are urgently required for flexible wearable thermoelectric devices for the utilization of low-grade thermal energy. In this review, mechanisms and optimization strategies for polymer-based thermoelectric composites containing fillers of different architectures will be introduced, and recent advances in the development of such thermoelectric composites containing 0- to 3-dimensional filler components will be presented and outlooked.

Self-Healable and Robust PE/PEDOT/SWCNT Thermoelectric Composites.

With increasing popularity and great application prospects of flexible wearable electronics, organic thermoelectric (TE)materials have become one hotspot in view of energy recycling and environment protection. However, diversifying application scenarios and frequent movements impose inevitable damage to materials. Herein, the polyethylene (PE) matrix is used in compositing with poly(3,4-ethylenedioxythiophene) and single-walled carbon nanotubes, forming a unique conductive penetration network and endowing the composites with a maximal room-temperature power factor of 158.81 µW m-1 K-2 with 20 wt % of PE. The introduction of PE not only reduces thermal conductivity (out-of-plane) but also provides the composites with self-healing and good mechanical properties. The compounding method and penetration structure reported in this work are universal and enlightening in developing highly efficient TE composites with cost-effectiveness and good comprehensive properties for low-grade waste heat utilization.

Functionalized ß-Cyclodextrins Catalyzed Environment-Friendly Cycloaddition of Carbon Dioxide and Epoxides.

Ammonium, imidazole, or pyridinium functionalized ß-cyclodextrins (ß-CDs) were used as efficient one-component bifunctional catalysts for the coupling reaction of carbon dioxide (CO2) and epoxide without the addition of solvent and metal. The influence of different catalysts and reaction parameters on the catalytic performance were examined in detail. Under optimal conditions, Im-CD1-I catalysts functionalized with imidazole groups were able to convert various epoxides into target products with high selectivity and good conversion rates. The one-component bifunctional catalysts can also be recovered easily by filtration and reused at least for five times with only slight decrease in catalytic performance. Finally, a possible process for hydroxyl group-assisted ring-opening of epoxide and functionalized group- induced activation of CO2 was presented.

Enhancing Thermoelectric Performance of Polyaniline/Single-Walled Carbon Nanotube Composites via Dimethyl Sulfoxide-Mediated Electropolymerization.

The fabrication of flexible high-performance organic/inorganic thermoelectric (TE) composite films has been a hot spot for researchers in recent years. In this work, dynamic 3-phase interfacial electropolymerization of aniline, together with physical mixing with single-walled carbon nanotubes (SWCNTs), was adopted to prepare polyaniline/SWCNT (PANI/SWCNT) TE composites. The dimethyl sulfoxide (DMSO) added into the electrochemical polymerization system affords strong capability in improving the TE performance of composite films. Moreover, varying loadings of SWCNTs can also conveniently tune the TE performance of composites. Hence, the resultant composites afford the highest power factor (PF) of 236.4 ± 5.9 µW m-1 K-2 at room temperature. This work demonstrates that the introduction of DMSO into the electrolyte and the electrochemical polymerization are highly effective in fabricating high-performance PANI/SWCNT TE composites.

Poly(3,4-ethylenedioxythiophene)/Te/Single-Walled Carbon Nanotube Composites with High Thermoelectric Performance Promoted by Electropolymerization.

Electrochemical polymerization has proven very effective in fabricating flexible organic/inorganic composite films with high thermoelectric (TE) performance. In this work, dynamic three-phase interfacial electropolymerization of 3,4-ethylenedioxythiophene (EDOT) combined with physical mixing of single-walled carbon nanotubes (SWCNT) and tellurium nanowires was employed to prepare PEDOT/Te/SWCNT thermoelectric composites. When the loadings of Te and SWCNT were changed, the electropolymerized PEDOT exhibited great capability of improving TE properties of the resultant composites with a highest electrical conductivity (σ) of 900.3 ± 20.5 S cm-1 and Seebeck coefficient (S) of 43.4 ± 0.6 µV K-1, affording maximum power factor (PF) of 169.8 ± 7.8 µW m-1 K-2 at room temperature.

ß-Cyclodextrin/Quaternary Ammonium Salt as an Efficient Catalyst System for Chemical Fixation of CO2.

The environmental friendly biomaterial ß-cyclodextrin (ß-CD) was used for the synthesis of cyclic carbonates from CO2 with epoxides in the presence of quaternary ammonium salts as co-catalyst. The factors affecting the activity of this binary catalyst system, such as reaction temperature, time, CO2 pressure and the mole ratio of reactants, were investigated systematically. The excellent yield of cyclic carbonate (100%) was obtained at 130 °C, 3 MPa after 5 h with the catalyst system of ß-CD/tetrabutylammonium bromine (TBABr). The catalyst system of ß-CD/TBABr can also be applied to a wide substrates of epoxides with good to excellent yield and high selectivity (>99%). Recyclable ability of ß-CD/TBABr can also be detected and there was no significant decline in activity after five recycles. Finally, reaction mechanism was proposed based on the reaction results and literatures.

Copper-Phenylacetylide Nanobelt/Single-Walled Carbon Nanotube Composites: Mechanochromic Luminescence Phenomenon and Thermoelectric Performance.

We report flexible films of organic-inorganic thermoelectric (TE) composites based on organometallic coordination compound [copper-phenylacetylide (PhC2Cu)] nanobelts and single-walled carbon nanotubes (SWCNTs). Interestingly, an unusual mechanochromic luminescence phenomenon from bright green to dark red is clearly observed after grinding the PhC2Cu crystalline nanobelts. The PhC2Cu/SWCNT composites display high mechanical flexibility and excellent TE performance. The maximum power factor at room temperature can reach as high as 200.2 ± 10.9 µW m-1 K-2. The present study opens an avenue to fabricate novel organic-inorganic TE composite materials using organometallic coordination compounds such as PhC2Cu.

Raising the N-aryl fluoride content in unsymmetrical diaryliminoacenaphthylenes as a route to highly active nickel(ii) catalysts in ethylene polymerization.

Five examples of selectively fluorinated unsymmetrical diiminoacenaphthylenes, 1-[2,6-{(4-FC6H4)2CH}2-4-FC6H4N]-2-(ArN) C2C10H6 (Ar = 2,6-Me2C6H3L1, 2,6-Et2C6H3L2, 2,6-iPr2C6H3L3, 2,4,6-Me3C6H2L4, 2,6-Et2-4-MeC6H2L5), have been synthesized and used to prepare their corresponding nickel(ii) halide complexes, LNiBr2 (Ni1-Ni5) and LNiCl2 (Ni6-Ni10). Both 1H and 19F NMR spectroscopy techniques have been employed to characterize paramagnetic Ni1-Ni10; an inequivalent fluorine environment is a feature of the tetrahedral complexes in solution. Upon activation with relatively low ratios (ca. 600 equiv.) of ethylaluminum sesquichloride (Et3Al2Cl2, EASC), all the nickel complexes displayed high activities toward ethylene polymerization at 30 °C with precatalyst Ni4 the standout performer at 2.20 × 107 g of PE per mol of Ni per h, producing highly branched polyethylenes. In comparison with related diiminoacenaphthylene-nickel catalysts, these current systems, incorporating a high fluorine content on one N-aryl group, display superior productivity. In addition, the molecular structures of Ni2 and Ni4 are reported and the active catalyst is probed using 19F NMR spectroscopy.

Synthesis biological screening and molecular docking studies of some tin (IV) Schiff base adducts.

The search for an alternative to platinum anticancer agents is a major motivation for continuing investigations concerning the antitumor properties of other transition metal-based compounds. Keeping this in view, synthesis, antitumor and antimicrobial activity of diorganotin (IV) complexes was studied. A novel series of diorganotin (IV) complexes of the Schiff base ligand derived from 7-methoxy-2-hydroxy-1-naphthaldehyde, 1,2-phenylenediamine, Salicylaldehyde were synthesized. Physical and spectral examination was done through various techniques using elemental analyses, IR, 1H, 13C, 119Sn NMR, and 119mSn Mössbauer techniques respectively. The results obtained are in good agreement with 1:1:1 stoichiometry of Schiff base and 2:1 stoichiometry of the complexes. Octahedral geometry was assigned to all the synthesized complexes within six (6) coordination number around the tin. Antitumor activity was screened against human oral epidermoid carcinoma (KB) cell line. The diethyltin (IV) complex 2 showed the most promising cytotoxic results (IC50=0.35µM) against the cell line which is comparable with cisplatin (IC50=0.37µM). Docking studies revealed that these complexes can bind favorably within cisplatin binding site and the binding energy of complex 2 is more than that of cisplatin. Furthermore, binding of these complexes on human topoisomerase IIα enzyme and revealed that these complexes intercalating within the inter-strand of DNA showing interactions with DNA as well as protein that may results in DNA damage and cell death.

Methylene-bridged bimetallic α-diimino nickel(II) complexes: synthesis and high efficiency in ethylene polymerization.

A series of 1,2-bis(arylimino)acenaphthylidenes (L1-L5) and their corresponding 4,4'-methylenebis(1-(2,6-diisopropylphenylimino)-2-(arylimino)acenaphthylene) derivatives (L6-L10) were synthesized and used to form mono-nuclear nickel bromides LnNiBr2 (n = 1-5, Ni1-Ni5) and bi-nuclear nickel halides LnNi2X4 (n = 6-10: X = Br, Ni2-1-Ni2-5; n = 4, X = Cl, Ni2-6). All the organic compounds were fully characterized by FT-IR spectra, NMR measurements and elemental analysis. The nickel complexes were characterized by FT-IR spectra and elemental analysis and the molecular structures of the representative complexes Ni1, Ni2-1 and Ni2-3 were confirmed by single-crystal X-ray diffraction. Upon activation with either Et2AlCl or MAO, all the nickel complex pre-catalysts exhibited high activity toward ethylene polymerization over the temperature range from ambient to 50 °C. In general, the bi-nuclear complexes showed a positive synergetic effect with higher activity than their mono nuclear analogs. The resultant polyethylene possessed higher molecular weight and a high degree of branching.