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111.
Alia Jouhara Eric Quarez Franck Dolhem Michel Armand Nicolas Dupr Philippe Poizot 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(44):15827-15831
The ever‐increasing demand for rechargeable batteries induces significant pressure on the worldwide metal supply, depleting resources and increasing costs and environmental concerns. In this context, developing the chemistry of anion‐inserting electrode organic materials could promote the fabrication of molecular (metal‐free) rechargeable batteries. However, few examples have been reported because little effort has been made to develop such anionic‐ion batteries. Here we show the design of two anionic host electrode materials based on the N‐substituted salts of azaaromatics (zwitterions). A combination of NMR, EDS, FTIR spectroscopies coupled with thermal analyses and single‐crystal XRD allowed a thorough structural and chemical characterization of the compounds. Thanks to a reversible electrochemical activity located at an average potential of 2.2 V vs. Li+/Li, the coupling with dilithium 2,5‐(dianilino)terephthalate (Li2DAnT) as the positive electrode enabled the fabrication of the first all‐organic anionic rechargeable batteries based on crystallized host electrode materials capable of delivering a specific capacity of ≈27 mAh/gelectrodes with a stable cycling over dozens of cycles (≈24 Wh/kgelectrodes). 相似文献
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113.
Sergey Vyazovkin Alice Mititelu Nicolas Sbirrazzuoli 《Macromolecular rapid communications》2003,24(18):1060-1065
The curing of a mesomorphic epoxy has been studied by polarized light microscopy (PLM) and differential scanning calorimetry. PLM in combination with wide‐angle X‐ray diffraction proves the formation of a liquid crystalline (LC) structure. An advanced isoconversional method reveals that the formation of the LC structure is accompanied by a dramatic decrease in the effective activation from ∼60 to ∼10 kJ · mol−1. A kinetic model of the phenomenon has been discussed.
114.
The initial stages of the heterogeneous photoreduction of quinone species by self-assembled porphyrin ion pairs at the water|1,2-dichloroethane (DCE) interface have been studied by ultrafast time-resolved spectroscopy and dynamic photoelectrochemical measurements. Photoexcitation of the water-soluble ion pair formed by zinc meso-tetrakis(p-sulfonatophenyl)porphyrin (ZnTPPS(4)(-)) and zinc meso-tetrakis(N-methylpyridyl)porphyrin (ZnTMPyP(4+)) leads to a charge-separated state of the form ZnTPPS(3)(-)-ZnTMPyP(3+) within 40 ps. This charge-separated state is involved in the heterogeneous electron injection to acceptors in the organic phase in the microsecond time scale. The heterogeneous electron transfer manifests itself as photocurrent responses under potentiostatic conditions. In the case of electron acceptors such as 1,4-benzoquinone (BQ), 2,6-dichloro-1,4-benzoquinone (DCBQ), and tetrachloro-1,4-benzoquinone (TCBQ), the photocurrent responses exhibit a strong decay due to back electron transfer to the oxidized porphyrin ion pair. Interfacial protonation of the radical semiquinone also contributes to the photocurrent relaxation in the millisecond time scale. The photocurrent responses are modeled by a series of linear elementary steps, allowing estimations of the flux of heterogeneous electron injection to the acceptor species. The rate of electron transfer was studied as a function of the thermodynamic driving force, confirming that the activation energy is controlled by the solvent reorganization energy. This analysis also suggests that the effective redox potential of BQ at the liquid|liquid boundary is shifted by 0.6 V toward positive potentials with respect to the value in bulk DCE. The change of the redox potential of BQ is associated with the formation of hydrogen bonds at the liquid|liquid boundary. The relevance of this approach toward modeling the initial processes in natural photosynthetic reaction centers is briefly discussed. 相似文献
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117.
Ting Quan Dr. Nicolas Goubard-Bretesché Dr. Eneli Härk Dr. Zdravko Kochovski Dr. Shilin Mei Prof. Dr. Nicola Pinna Prof. Dr. Matthias Ballauff Prof. Dr. Yan Lu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(18):4757-4766
MoS2, a typical layered transition-metal dichalcogenide, is promising as an electrode material in supercapacitors. However, its low electrical conductivity could lead to limited capacitance if applied in electrochemical devices. Herein, a new nanostructure composed of hollow carbon–MoS2–carbon was successfully synthesized through an l -cysteine-assisted hydrothermal method by using gibbsite as a template and polydopamine as a carbon precursor. After calcination and etching of the gibbsite template, uniform hollow platelets, which were made of a sandwich-like assembly of partial graphitic carbon and two-dimensional layered MoS2 flakes, were obtained. The platelets showed excellent dispersibility and stability in water, and good electrical conductivity due to carbon provided by the calcination of polydopamine coatings. The hollow nanoplate morphology of the material provided a high specific surface area of 543 m2 g−1, a total pore volume of 0.677 cm3 g−1, and fairly small mesopores (≈5.3 nm). The material was applied in a symmetric supercapacitor and exhibited a specific capacitance of 248 F g−1 (0.12 F cm−2) at a constant current density of 0.1 A g−1; thus suggesting that hollow carbon–MoS2–carbon nanoplates are promising candidate materials for supercapacitors. 相似文献
118.
Dr. Massimo Rigo Evi R. M. Habraken Dr. Koyel Bhattacharyya Manuela Weber Dr. Andreas W. Ehlers Dr. Nicolas Mézailles Dr. J. Chris Slootweg Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8769-8779
A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur) was calculated to get insight into the steric properties, [LNi(CO)3] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts. 相似文献
119.
Dr. Ting Liang Dr. Dominique Collin Melodie Galerne Dr. Gad Fuks Dr. Andreas Vargas Jentzsch Prof. Dr. Mounir Maaloum Alain Carvalho Prof. Dr. Nicolas Giuseppone Dr. Emilie Moulin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14341-14348
C3-Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π–π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude. 相似文献
120.
Clement ND Routaboul L Grotevendt A Jackstell R Beller M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2008,14(25):7408-7420
The following account summarises recent developments in the area of palladium-catalysed telomerisation and dimerisation reactions of 1,3-dienes. The most active types of catalyst, palladium-carbene complexes, were tested in pilot plant and proved to be industrially viable. 相似文献