@article{7288, abstract = {Nowadays commercial supercapacitors are based on purely capacitive storage at the porous carbons that are used for the electrodes. However, the limits that capacitive storage imposes on energy density calls to investigate new materials to improve the capacitance of the device. This new type of electrodes (e.g., RuO2, MnO2…) involves pseudo-capacitive faradaic redox processes with the solid material. Ion exchange with solid materials is, however, much slower than the adsorption process in capacitive storage and inevitably leads to significant loss of power. Faradaic process in the liquid state, in contrast can be similarly fast as capacitive processes due to the fast ion transport. Designing new devices with liquid like dynamics and improved specific capacitance is challenging. We present a new approach to increase the specific capacitance using biredox ionic liquids, where redox moieties are tethered to the electrolyte ions, allowing high redox concentrations and significant pseudo-capacitive storage in the liquid state. Anions and cations are functionalized with anthraquinone (AQ) and 2,2,6,6-tetramethylpiperidinyl-1-oxyl (TEMPO) moieties, respectively. Glassy carbon, carbon-onion, and commercial activated carbon electrodes that exhibit different double layer structures and thus different diffusion dynamics were used to simultaneously study the electrochemical response of biredox ionic liquids at the positive and negative electrode.}, author = {Bodin, C. and Mourad, E. and Zigah, D. and Le Vot, S. and Freunberger, Stefan Alexander and Favier, F. and Fontaine, O.}, issn = {1359-6640}, journal = {Faraday Discussions}, pages = {393--404}, publisher = {Royal Society of Chemistry}, title = {{Biredox ionic liquids: New opportunities toward high performance supercapacitors}}, doi = {10.1039/c7fd00174f}, volume = {206}, year = {2017}, } @article{7290, abstract = {We report a family of Pt and Pd benzoporphyrin dyes with versatile photophysical properties and easy access from cheap and abundant chemicals. Attaching 4 or 8 alkylsulfone groups onto a meso-tetraphenyltetrabenzoporphyrin (TPTBP) macrocylcle renders the dyes highly soluble in organic solvents, photostable, and electron-deficient with the redox potential raised up to 0.65 V versus the parent porphyrin. The new dyes intensively absorb in the blue (Soret band, 440–480 nm) and in the red (Q-band, 620–650 nm) parts of the electromagnetic spectrum and show bright phosphorescence at room-temperature in the NIR with quantum yields up to 30% in solution. The small singlet–triplet energy gap yields unusually efficient thermally activated delayed fluorescence (TADF) at elevated temperatures in solution and in polymeric matrices with quantum yields as high as 27% at 120 °C, which is remarkable for benzoporphyrins. Apart from oxygen sensing, these properties enable unprecedented simultaneous, self-referenced oxygen and temperature sensing with a single indicator dye: whereas oxygen can be determined either via the decay time of phosphorescence or TADF, the temperature is accessed via the ratio of the two emissions. Moreover, the dyes are efficient sensitizers for triplet–triplet annihilation (TTA)-based upconversion making possible longer sensitization wavelength than the conventional benzoporphyrin complexes. The Pt-octa-sulfone dye also features interesting semireversible transformation in basic media, which generates new NIR absorbing species.}, author = {Zach, Peter W. and Freunberger, Stefan Alexander and Klimant, Ingo and Borisov, Sergey M.}, issn = {1944-8252}, journal = {ACS Applied Materials & Interfaces}, number = {43}, pages = {38008--38023}, publisher = {ACS}, title = {{Electron-deficient near-infrared Pt(II) and Pd(II) benzoporphyrins with dual phosphorescence and unusually efficient thermally activated delayed fluorescence: First demonstration of simultaneous oxygen and temperature sensing with a single emitter}}, doi = {10.1021/acsami.7b10669}, volume = {9}, year = {2017}, } @article{7292, abstract = {Rechargeable Li–O2 batteries have amongst the highest formal energy and could store significantly more energy than other rechargeable batteries in practice if at least a large part of their promise could be realized. Realization, however, still faces many challenges than can only be overcome by fundamental understanding of the processes taking place. Here, we review recent advances in understanding the chemistry of the Li–O2 cathode and provide a perspective on dominant research needs. We put particular emphasis on issues that are often grossly misunderstood: realistic performance metrics and their reporting as well as identifying reversibility and quantitative measures to do so. Parasitic reactions are the prime obstacle for reversible cell operation and have recently been identified to be predominantly caused by singlet oxygen and not by reduced oxygen species as thought before. We discuss the far reaching implications of this finding on electrolyte and cathode stability, electrocatalysis, and future research needs.}, author = {Mahne, Nika and Fontaine, Olivier and Thotiyl, Musthafa Ottakam and Wilkening, Martin and Freunberger, Stefan Alexander}, issn = {2041-6539}, journal = {Chemical Science}, number = {10}, pages = {6716--6729}, publisher = {RSC}, title = {{Mechanism and performance of lithium–oxygen batteries – a perspective}}, doi = {10.1039/c7sc02519j}, volume = {8}, year = {2017}, } @article{7291, abstract = {Na battery chemistries show poor passivation behavior of low voltage Na storage compounds and Na metal with organic carbonate‐based electrolytes adopted from Li‐ion batteries. Therefore, a suitable electrolyte remains a major challenge for establishing Na batteries. Here we report highly concentrated sodium bis(fluorosulfonyl)imide (NaFSI) in dimethoxyethane (DME) electrolytes and investigate them for Na metal and hard carbon anodes and intercalation cathodes. For a DME/NaFSI ratio of 2, a stable passivation of anode materials was found owing to the formation of a stable solid electrolyte interface, which was characterized spectroscopically. This permitted non‐dentritic Na metal cycling with approximately 98 % coulombic efficiency as shown for up to 300 cycles. The NaFSI/DME electrolyte may enable Na‐metal anodes and allows for more reliable assessment of electrode materials in Na‐ion half‐cells, as is demonstrated by comparing half‐cell cycling of hard carbon anodes and Na3V2(PO4)3 cathodes with a widely used carbonate and the NaFSI/DME electrolyte.}, author = {Schafzahl, Lukas and Hanzu, Ilie and Wilkening, Martin and Freunberger, Stefan Alexander}, issn = {1864-5631}, journal = {ChemSusChem}, number = {2}, pages = {401--408}, publisher = {Wiley}, title = {{An electrolyte for reversible cycling of sodium metal and intercalation compounds}}, doi = {10.1002/cssc.201601222}, volume = {10}, year = {2017}, } @article{731, abstract = {Genetic variations in the oxytocin receptor gene affect patients with ASD and ADHD differently.}, author = {Novarino, Gaia}, issn = {19466234}, journal = {Science Translational Medicine}, number = {411}, publisher = {American Association for the Advancement of Science}, title = {{The science of love in ASD and ADHD}}, doi = {10.1126/scitranslmed.aap8168}, volume = {9}, year = {2017}, }