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991.
992.
Wei Fang Dr. Fangyi Liang Dr. Zhengwen Cao Frank Steinbach Prof. Dr. Armin Feldhoff 《Angewandte Chemie (International ed. in English)》2015,54(16):4847-4850
To combine good chemical stability and high oxygen permeability, a mixed ionic‐electronic conducting (MIEC) 75 wt % Ce0.85Gd0.1Cu0.05O2?δ‐25 wt % La0.6Ca0.4FeO3?δ (CGCO‐LCF) dual‐phase membrane based on a MIEC–MIEC composite has been developed. Copper doping into Ce0.9Gd0.1O2?δ (CGO) oxide enhances both ionic and electronic conductivity, which then leads to a change from ionic conduction to mixed conduction at elevated temperatures. For the first time we demonstrate that an intergranular film with 2–10 nm thickness containing Ce, Ca, Gd, La, and Fe has been formed between the CGCO grains in the CGCO‐LCF one‐pot dual‐phase membrane. A high oxygen permeation flux of 0.70 mL min?1 cm?2 is obtained by the CGCO‐LCF one‐pot dual‐phase membrane with 0.5 mm thickness at 950 °C using pure CO2 as the sweep gas, and the membrane shows excellent stability in the presence of CO2 even at lower temperatures (800 °C) during long‐term operation. 相似文献
993.
Dr. Eva Alvarez de Eulate Dr. Debbie S. Silvester Prof. Dr. Damien W. M. Arrigan 《Angewandte Chemie (International ed. in English)》2015,54(49):14903-14906
At the water–trihexyl(tetradecyl)phosphonium tris(pentafluoroethyl)trifluorophosphate ([P14,6,6,6][FAP]) ionic liquid interface, the unusual electrochemical transfer behavior of protons (H+) and deuterium ions (D+) was identified. Alkali metal cations (such as Li+, Na+, K+) did not undergo this transfer. H+/D+ transfers were assisted by the hydrophobic counter anion of the ionic liquid, [FAP]?, resulting in the formation of a mixed capacitive layer from the filling of the latent voids within the anisotropic ionic liquid structure. This phenomenon could impact areas such as proton‐coupled electron transfers, fuel cells, and hydrogen storage where ionic liquids are used as aprotic solvents. 相似文献
994.
Dr. Ulrich P. Preiss Dr. Dzmitry H. Zaitsau Dr. Witali Beichel Dr. Daniel Himmel Dr. Alexander Higelin Dr. Klaus Merz Niklas Caesar Prof. Dr. Sergey P. Verevkin 《Chemphyschem》2015,16(13):2890-2898
New measurements of vaporization enthalpies for 15 1:1 ionic liquids are performed by using a quartz‐crystal microbalance. Collection and analysis of 33 available crystal structures of organic salts, which comprise 13 different cations and 12 anions, is performed. Their dissociation lattice enthalpies are calculated by a combination of experimental and quantum chemical quantities and are divided into the relaxation and Coulomb components to give an insight into elusive short‐range interaction enthalpies. An empirical equation is developed, based on interaction‐specific Hirshfeld surfaces and solvation enthalpies, which enables the estimation of the lattice enthalpy by using only the crystal‐structure data. 相似文献
995.
Triphilic Ionic‐Liquid Mixtures: Fluorinated and Non‐fluorinated Aprotic Ionic‐Liquid Mixtures
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Dr. Oldamur Hollóczki Dr. Marina Macchiagodena Henry Weber Martin Thomas Dr. Martin Brehm Prof. Dr. Annegret Stark Dr. Olga Russina Dr. Alessandro Triolo Prof. Dr. Barbara Kirchner 《Chemphyschem》2015,16(15):3325-3333
We present here the possibility of forming triphilic mixtures from alkyl‐ and fluoroalkylimidazolium ionic liquids, thus, macroscopically homogeneous mixtures for which instead of the often observed two domains—polar and nonpolar—three stable microphases are present: polar, lipophilic, and fluorous ones. The fluorinated side chains of the cations indeed self‐associate and form domains that are segregated from those of the polar and alkyl domains. To enable miscibility, despite the generally preferred macroscopic separation between fluorous and alkyl moieties, the importance of strong hydrogen bonding is shown. As the long‐range structure in the alkyl and fluoroalkyl domains is dependent on the composition of the liquid, we propose that the heterogeneous, triphilic structure can be easily tuned by the molar ratio of the components. We believe that further development may allow the design of switchable, smart liquids that change their properties in a predictable way according to their composition or even their environment. 相似文献
996.
Susana Chatzipapadopoulos Tobias Zentel Prof. Dr. Ralf Ludwig Matthias Lütgens Prof. Dr. Stefan Lochbrunner Prof. Dr. Oliver Kühn 《Chemphyschem》2015,16(12):2519-2523
Understanding both structure and dynamics is crucial for producing tailor‐made ionic liquids (ILs). We studied the vibrational and structural dynamics of medium versus weakly hydrogen‐bonded C?H groups of the imidazolium ring in ILs of the type [1‐alkyl‐3‐methylimidazolium][bis(trifluoromethanesulfonyl)imide] ([Cnmim][NTf2]), with n=1, 2, and 8, by time‐resolved coherent anti‐Stokes Raman scattering (CARS) and quantum‐classical hybrid (QCH) simulations. From the time series of the CARS spectra, dephasing times were extracted by modeling the full nonlinear response. From the QCH calculations, pure dephasing times were obtained by analyzing the distribution of transition frequencies. Experiments and calculations reveal larger dephasing rates for the vibrational stretching modes of C(2)?H compared with the more weakly hydrogen‐bonded C(4,5)?H. This finding can be understood in terms of different H‐bonding motifs and the fast interconversion between them. Differences in population relaxation rates are attributed to Fermi resonance interactions. 相似文献
997.
The Effect of C4H and C5H on the Microstructure of Aqueous Solutions of 1‐Alkyl‐3‐methylimidazolium Tetrafluoroborate Ionic Liquids
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As is well‐known, the C2?H proton of 1‐ethyl‐3‐methylimidazolium tetrafluoroborate ([Emim]BF4) and 1‐butyl‐3‐methylimidazolium tetrafluoroborate ([Bmim]BF4) has a strong ability to form hydrogen bonds. The purpose of this work is to evaluate the effect of the interactions of the C4?H and C5?H protons on the microstructure of [Emim]BF4 and [Bmim]BF4 with water by using 1H NMR spectroscopy. The differences between the relative 1H NMR chemical shifts of C2?H, C4?H, and C5?H and between the interaction‐energy parameters obtained from these chemical shifts are minor, thus suggesting that the interactions of C4?H and C5?H may have a considerable effect on the microstructure. To confirm this, the viscosities of the systems are estimated by using the interaction‐energy parameters obtained from the 1H NMR chemical shifts of the three studied aromatic protons and water, showing that the interactions of C4?H and C5?H also play an important role in the microstructure. 相似文献
998.
999.
Ionic Liquids as Precursors for Efficient Mesoporous Iron‐Nitrogen‐Doped Oxygen Reduction Electrocatalysts
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Dr. Zelong Li Dr. Guanglan Li Prof. Luhua Jiang Jinlei Li Prof. Gongquan Sun Prof. Chungu Xia Prof. Fuwei Li 《Angewandte Chemie (International ed. in English)》2015,54(5):1494-1498
A ferrocene‐based ionic liquid (Fe‐IL) is used as a metal‐containing feedstock with a nitrogen‐enriched ionic liquid (N‐IL) as a compatible nitrogen content modulator to prepare a novel type of non‐precious‐metal–nitrogen–carbon (M‐N‐C) catalysts, which feature ordered mesoporous structure consisting of uniform iron oxide nanoparticles embedded into N‐enriched carbons. The catalyst Fe10@NOMC exhibits comparable catalytic activity but superior long‐term stability to 20 wt % Pt/C for ORR with four‐electron transfer pathway under alkaline conditions. Such outstanding catalytic performance is ascribed to the populated Fe (Fe3O4) and N (N2) active sites with synergetic chemical coupling as well as the ordered mesoporous structure and high surface area endowed by both the versatile precursors and the synthetic strategy, which also open new avenues for the development of M‐N‐C catalytic materials. 相似文献
1000.
Thiol–Ene “Click” Reaction Triggered by Neutral Ionic Liquid: The “Ambiphilic” Character of [hmim]Br in the Regioselective Nucleophilic Hydrothiolation
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Rajesh Kumar Saima Amit Shard Nitin H. Andhare Richa Dr. Arun K. Sinha 《Angewandte Chemie (International ed. in English)》2015,54(3):828-832
Thiol–ene “click” chemistry has emerged as a powerful strategy to construct carbon–heteroatom (C? S) bonds, which generally results in the formation of two regioisomers. To this end, the neutral ionic liquid [hmim]Br has been explored as a solvent cum catalyst for the synthesis of linear thioethers from activated and inactivated styrene derivatives or secondary benzyl alcohols and thiols without the requirement of using a metal complex, base, or free radical initiator. Furthermore, detailed mechanistic investigations using 1H NMR spectroscopy and quadrupole time‐of‐flight electrospray ionization mass spectrometry (Q‐TOF ESI‐MS) revealed that the “ambiphilic” character of the ionic liquid promotes the nucleophilic addition of thiol to styrene through an anti‐Markovnikov pathway. The catalyst recyclability and the extension of the methodology for thiol–yne click chemistry are additional benefits. A competitive study among thiophenol, styrene, and phenyl acetylene revealed that the rate of reaction is in the order of thiol–yne>thiol–ene>dimerization of thiol in [hmim]Br. 相似文献