Revealing the CO2 Conversion at Electrode/Electrolyte Interfaces in Li-CO2 Batteries via Nanoscale Visualization Methods.

Lithium-carbon dioxide (Li-CO2 ) battery technology presents a promising opportunity for carbon capture and energy storage. Despite tremendous efforts in Li-CO2 batteries, the complex electrode/electrolyte/CO2 triple-phase interfacial processes remain poorly understood, in particular at the nanoscale. Here, using in situ atomic force microscopy and laser confocal microscopy-differential interference contrast microscopy, we directly observed the CO2 conversion processes in Li-CO2 batteries at the nanoscale, and further revealed a laser-tuned reaction pathway based on the real-time observations. During discharge, a bi-component composite, Li2 CO3 /C, deposits as micron-sized clusters through a 3D progressive growth model, followed by a 3D decomposition pathway during the subsequent recharge. When the cell operates under laser (λ=405 nm) irradiation, densely packed Li2 CO3 /C flakes deposit rapidly during discharge. Upon the recharge, they predominantly decompose at the interfaces of the flake and electrode, detaching themselves from the electrode and causing irreversible capacity degradation. In situ Raman shows that the laser promotes the formation of poorly soluble intermediates, Li2 C2 O4 , which in turn affects growth/decomposition pathways of Li2 CO3 /C and the cell performance. Our findings provide mechanistic insights into interfacial evolution in Li-CO2 batteries and the laser-tuned CO2 conversion reactions, which can inspire strategies of monitoring and controlling the multistep and multiphase interfacial reactions in advanced electrochemical devices.

Revealing the Correlations between Morphological Evolution and Surface Reactivity of Catalytic Cathodes in Lithium-Oxygen Batteries.

Lithium-oxygen batteries suffer from the degradation of the catalytic cathode during long-term operation, which limits their practical use. Understanding the direct correlations between the surface morphological evolution of catalytic cathodes at nanoscale and their catalytic activity during cycling has proved challenging. Here, using in situ electrochemical atomic force microscopy, the dynamic evolution of the Pt nanoparticles electrode in a working Li-O2 battery and its effects on the Li-O2 interfacial reactions are visualized. In situ views show that repeated oxidation-reduction cycles (ORCs) trigger the increase in the size of Pt nanoparticles, eventually causing the Pt nanoparticles to fall off the electrode. In 0-80 ORCs, the grown Pt nanoparticles promote the conversion of the Li-O2 reaction route from the surface-mediated pathway to the solution-mediated pathway during discharging and significantly increase the discharge capacity. After 250 ORCs, accompanied by the part of the Pt nanoparticles detaching from the electrode, the nucleation potential of reaction product decreases, and the reaction dynamic slows down, which cause the performance to degrade. Modification of a proper amount of Au nanoparticle on the Pt nanoparticles electrode could improve its stability and maintain the high catalytic activity. These results provide a direct evidence for clarifying the correlations between morphological evolution and surface reactivity of catalytic cathodes during cycling, which is critical for developing high-performance catalysts.

Efficacy and safety of sublingual dust mite drops in children with mono- or polysensitized allergic rhinitis.

OBJECTIVE: To explore the efficacy and safety of sublingual house dust mite (HDM) drops in children with mono- or polysensitized allergic rhinitis. METHODS: We conducted a retrospective cohort study of 65 children with monosensitized AR and 118 children with polysensitized AR who were scheduled for sublingual administration of HDM drops from January 2015 to June 2016. Interleukin (IL)-2, IL-4, and IL-17α, transforming growth factor-ß1 (TGF-ß1), specific immunoglobulin E (IgE), and specific IgG4 were detected by ELISA. The efficacies were assessed using symptoms score and medication score. All the outcomes were measured 1 month before the study and 1 month after the end of the 2-year treatment. RESULTS: The total nasal symptoms score (TNSS) decreased significantly from 11.27 (9.81 ±â€¯12.73) at baseline to 3.48(1.98 ±â€¯4.98) at the end of sublingual treatment for the monosensitized AP group (t = 30.00, P < 0.01), and from 11.54(10.04 ±â€¯13.04) to 3.56 (2.00 ±â€¯5.16) for the polysensitized AR group (t = 40.05, P < 0.01), respectively. IL-2 and TGF-ß1 increased significantly after treatment in contrast with before treatment in both the monosensitized group and the polysensitized group (both P < 0.01). In contrast, IL-4 and IL-17α decreased significantly after treatment compared with the baseline in both groups (both P < 0.01). Sublingual HDM drops were generally safe and well tolerant in both groups. CONCLUSIONS: This study confirmed the efficacy and safety of sublingual AIT in both monosensitized and polysensitized AR patients (Chinese children).

Optical-Dielectric Duple Bistable Switches: Photoluminescence of Reversible Phase Transition Molecular Material.

Molecular optical-dielectric duple bistable switches are photoelectric (dielectric and fluorescent) multifunctional materials that can simultaneously convert optical and electrical signals in one device for seamless integration. However, exploring optical-dielectric duple channels of dielectric and photoluminescence is still a bigger challenge than single dielectric or photoluminescence bistable ones, which are hardly reported but probably will be heavily researched owing to the new generation artificial intelligence development needs in the future. Herein, a new optical-dielectric duple bistable switches material, [(CH3 )3 NCH2 CH3 ]2 MnCl4 (I), was obtained by a simple method for volatilization of solvents. Variable temperature single crystal X-ray analysis indicates that material I has a reversible bistable structure (order-disorder structure phase transition) corresponding to switching "ON'' and "OFF''. Unlike the single dielectric bistable structures that were previously reported, material I also own bistable features in terms of fluorescence property. This material enriches the specific examples of photoelectric duple function switch materials and facilitates the development of required devices.

Above room-temperature dielectric and nonlinear optical switching materials based on [(CH3)3S]2[MBr4] (M = Cd, Mn and Zn).

In this paper, three zero-dimensional organic-inorganic hybrid compounds [(CH3)3S]2[CdBr4] (1), [(CH3)3S]2[MnBr4] (2) and [(CH3)3S]2[ZnBr4] (3) were synthesized. The phase transition behavior of 1, 2 and 3 was well characterized by differential scanning calorimetry (DSC) and variable temperature single crystal diffraction measurements. The phase transition temperature of 1, 2 and 3 was at ca. 315 K in the heating process. The vigorous ordered-disordered reorientation and displacement motion of [(Me3)3S]+ and [MBr4]2- of 1, 2 and 3 induce the structural phase transition from the centrosymmetric (CS) space group Pnma to the non-centrosymmetric (NCS) space group P212121. The apparent second-harmonic generation (SHG) switching responses further confirm this CS to NCS symmetry breaking. Moreover, dielectric studies illustrate that 1, 2 and 3 display distinctly switchable dielectric behavior, revealing their potential application in dielectric switches. This finding suggests that sulfonium-based organic-inorganic hybrids can be used to build phase transition materials, broadening the way for exploring dielectric and nonlinear optical (NLO) switching materials.

A Semiconducting Organic-Inorganic Hybrid Perovskite-type Non-ferroelectric Piezoelectric with Excellent Piezoelectricity.

Piezoelectric materials are a class of important functional materials applied in high-voltage sources, sensors, vibration reducers, actuators, motors, and so on. Herein, [(CH3 )3 S]3 [Bi2 Br9 ](1) is a brilliant semiconducting organic-inorganic hybrid perovskite-type non-ferroelectric piezoelectric with excellent piezoelectricity. Strikingly, the value of the piezoelectric coefficient d33 is estimated as ≈18 pC N-1 . Such a large piezoelectric coefficient in non-ferroelectric piezoelectric has been scarcely reported and is comparable with those of typically one-composition non-ferroelectric piezoelectrics such as ZnO (3pC N-1 ) and much greater than those of most known typical materials. In addition, 1 exhibits semiconducting behavior with an optical band gap of ≈2.58 eV that is lower than the reported value of 3.37 eV for ZnO. This discovery opens a new avenue to exploit molecular non-ferroelectric piezoelectric and should stimulate further exploration of non-ferroelectric piezoelectric due to their high stability and low loss characteristics.