An experimental and theoretical study on mechanistic insights into urolithin-based ratiometric fluorescent probe for instant quantitative detection of fluoride ions.

Fluoride detection has been playing an important role in chemical, biological, and medicinal field, especially for keeping physical health and resisting environmental pollution. Herein, a urolithin B fluorescent probe has been successfully developed with good sensitivity, selectivity, anti-interference ability. The low limit of detection (LOD) refers to 0.156 µM, and the instant response time to F- is less than 1 s. The probe is suitable for quantitatively and qualitatively ratiometric detection for F- in solution with two distinct emission bands at 425 (blue) and 566 nm (orange), with the coordinate change of CIE from (0.38, 0.41) to (0.22, 0.11). Urolithin B displayed a remarkable ratiometric fluorescence response towards F-. The detection mechanistic was further proposed by NMR and electronic spectroscopic experiments combining with time-dependent density functional theoretical calculation.

Operando characterization of cathodic reactions in a liquid-state lithium-oxygen micro-battery by scanning transmission electron microscopy.

Rechargeable non-aqueous lithium-oxygen batteries with a large theoretical capacity are emerging as a high-energy electrochemical device for sustainable energy strategy. Despite many efforts made to understand the fundamental Li-O2 electrochemistry, the kinetic process of cathodic reactions, associated with the formation and decomposition of a solid Li2O2 phase during charging and discharging, remains debate. Here we report direct visualization of the charge/discharge reactions on a gold cathode in a non-aqueous lithium-oxygen micro-battery using liquid-cell aberration-corrected scanning transmission electron microscopy (STEM) combining with synchronized electrochemical measurements. The real-time and real-space characterization by time-resolved STEM reveals the electrochemical correspondence of discharge/charge overpotentials to the nucleation, growth and decomposition of Li2O2 at a constant current density. The nano-scale operando observations would enrich our knowledge on the underlying reaction mechanisms of lithium-oxygen batteries during round-trip discharging and charging and shed lights on the strategies in improving the performances of lithium-oxygen batteries by tailoring the cathodic reactions.

Direct Observations of the Formation and Redox-Mediator-Assisted Decomposition of Li2 O2 in a Liquid-Cell Li-O2 Microbattery by Scanning Transmission Electron Microscopy.

Operando scanning transmission electron microscopy observations of cathodic reactions in a liquid-cell Li-O2 microbattery in the presence of the redox mediator tetrathiafulvalene (TTF) in 1.0 m LiClO4 dissolved dimethyl sulfoxide electrolyte are reported. It is found that the TTF addition does not obviously affect the discharge reaction for the formation of a solid Li2 O2 phase. The coarsening of Li2 O2 nanoparticles occurs via both conventional Ostwald ripening and nonclassical crystallization by particle attachment. During charging, the oxidation reaction at significantly reduced charge potentials mainly takes place at Li2 O2 /electrolyte interfaces and has obvious correspondence with the oxidized TTF+ distributions in the electric fields of the charged electrode. This study provides direct evidence that TTF truly plays a role in promoting the decomposition of Li2 O2 as a soluble charge-transfer agent between the electrode and the Li2 O2 .

In Situ Investigation of Li and Na Ion Transport with Single Nanowire Electrochemical Devices.

In the past decades, Li ion batteries are widely considered to be the most promising rechargeable batteries for the rapid development of mobile devices and electric vehicles. There arouses great interest in Na ion batteries, especially in the field of static grid storage due to their much lower production cost compared with Li ion batteries. However, the fundamental mechanism of Li and Na ion transport in nanoscale electrodes of batteries has been rarely experimentally explored. This insight can guide the development and optimization of high-performance electrode materials. In this work, single nanowire devices with multicontacts are designed to obtain detailed information during the electrochemical reactions. This unique platform is employed to in situ investigate and compare the transport properties of Li and Na ions at a single nanowire level. To give different confinement for ions and electrons during the electrochemical processes, two different configurations of nanowire electrode are proposed; one is to fully immerse the nanowire in the electrolyte, and the other is by using photoresist to cover the nanowire with only one end exposed. For both configurations, the conductivity of nanowire decreases after intercalation/deintercalation for both Li and Na ions, indicating that they share the similar electrochemical reaction mechanisms in layered electrodes. However, the conductivity degradation and structure destruction for Na ions is more severe than those of Li ions during the electrochemical processes, which mainly results from the much larger volume of Na ions and greater energy barrier encountered by the limited layered spaces. Moreover, the battery performances of coin cells are compared to further confirm this conclusion. The present work provides a unique platform for in situ electrochemical and electrical probing, which will push the fundamental and practical research of nanowire electrode materials for energy storage applications.