Switching between local and global aromaticity in a conjugated macrocycle for high-performance organic sodium-ion battery anodes

Aromatic organic compounds can be used as electrode materials in rechargeable batteries and are expected to advance the development of both anode and cathode materials for sodium-ion batteries (SIBs). However, most aromatic organic compounds assessed as anode materials in SIBs to date exhibit significant degradation issues under fast-charge/discharge conditions and unsatisfying long-term cycling performance. Now, a molecular design concept is presented for improving the stability of organic compounds for battery electrodes. The molecular design of the investigated compound, [2.2.2.2]paracyclophane-1,9,17,25-tetraene (PCT), can stabilize the neutral state by local aromaticity and the doubly reduced state by global aromaticity, resulting in an anode material with extraordinarily stable cycling performance and outstanding performance under fast-charge/discharge conditions, demonstrating an exciting new path for the development of electrode materials for SIBs and other types of batteries

Functional group introduction and aromatic unit variation in a set of π‑conjugated macrocycles: revealing the central role of local and global aromaticity

π-Conjugated macrocycles are molecules with unique properties that are increasingly exploited for applications and the question of whether they can sustain global aromatic or antiaromatic ring currents is particularly intriguing. However, there are only a small number of experimental studies that investigate how the properties of π‑conjugated macrocycles evolve with systematic structural changes. Here, we present such a systematic experimental study of a set of [2.2.2.2]cyclophanetetraenes, all with formally Hückel antiaromatic ground states, and combine it with an in-depth computational analysis. The study reveals the central role of local and global aromaticity for rationalizing the observed optoelectronic properties, ranging from extremely large Stokes shifts of up to 1.6 eV to reversible fourfold reduction, a highly useful feature for charge storage/accumulation applications. A recently developed method for the visualization of chemical shielding tensors (VIST) is applied to provide unique insight into local and global ring currents occurring in different planes along the macrocycle. Conformational changes as a result of the structural variations can further explain some of the observations. The study contributes to the development of structure–property relationships and molecular design guidelines and will help to understand, rationalize, and predict the properties of other π‑conjugated macrocycles

Electrochemical Nanoprobes for Single-Cell Analysis

The measurement of key molecules in individual cells with minimal disruption to the biological milieu is the next frontier in single-cell analyses. Nanoscale devices are ideal analytical tools because of their small size and their potential for high spatial and temporal resolution recordings. Here, we report the fabrication of disk-shaped carbon nanoelectrodes whose radius can be precisely tuned within the range 5–200 nm. The functionalization of the nanoelectrode with platinum allowed the monitoring of oxygen consumption outside and inside a brain slice. Furthermore, we show that nanoelectrodes of this type can be used to impale individual cells to perform electrochemical measurements within the cell with minimal disruption to cell function. These nanoelectrodes can be fabricated combined with scanning ion conductance microscopy probes, which should allow high resolution electrochemical mapping of species on or in living cells

Charge Orderings and Phase Separations in Itinerant Fermion Systems at Half Filling

We analyse the ground state phase diagrams of the charge orderings in narrow band materials using two effective models: (1) the spinless fermion model (t - W) with repulsive intersite interaction ($W_{ij}$ > 0) and (2) the molecular crystal model with the coupling of electrons to intramolecular (crystal field) vibrations. We present results for the case of half filled bands for d = 2 square lattice. The calculations are performed within the (broken symmetry) Hartree-Fock approximation. The study takes into consideration the effects of frustrating next-nearest-neighbour hopping $(t_2)$ on the charge ordered states in these systems. We focus on the two cases: (i) homogeneous phases and phase separations involving checkerboard charge ordering with the nesting vector Q= (π,π) only and (ii) homogeneous phases and phase separations involving two types of charge ordering: (a) checkerboard charge ordering with the nesting vector Q = (π,π), and (b) collinear (CL) charge ordering with Q = (0,π) or Q = (π,0)

Effects of Frustrating Hopping on Charge Ordered States in Itinerant Fermion Systems for Arbitrary Concentration in 2D Lattice

There is ongoing, intense, research in the field of electron charge orderings (CO) and charge density waves phenomena, due to experimental discovery of such phases in numerous important compounds. The aim of this work is to extend recent advances in the field by studying two simple effective paradigmatic models used to describe CO in narrow band materials i.e. (i) a model of correlated electrons: the so-called t-W model of spinless fermions with repulsive interaction W and (ii) the molecular crystal model with the coupling of electrons to intramolecular (crystal field) vibrations in the static limit. The finite temperature phase diagrams are evaluated at arbitrary carriers concentration for several representative cases. Our calculations are performed within the (broken symmetry) HFA for d=2 square lattice and arbitrary carriers concentration. In this contribution we focus on the effects of next-nearest-neighbor hopping on the CO states in these systems and the problem of phase separations involving checkerboard CO with the nesting vector Q=(π,π). The results we show here are an extension of our previous work on the subject

Fabrication of electrochemical nanoelectrode for sensor application Rusing focused ion beam technology

The capabilities and applications of the focused ion beam (FIB) technology for detection of an electrochemical signal in nanoscale area are shown. The FIB system, enabling continuous micro- and nanofabrication within only one equipment unit, was used to produce a prototype of electrochemical nanometer-sized electrode for sensor application. Voltammetric study of electrochemically active compound (ferrocenemethanol) revealed the diffusion limiting current (12 pA), corresponding to a disc (planar) nanoelectrode with about 70 nm diameter of contact area. This size is in a good accordance with the designed contact-area (50 nm × 100 nm for width × thickness) of the FIB-produced nanoelectrode. It confi rms that produced nanoelectrode is working properly in liquid solution and may enable correct measurements in nanometer-sized regions

Scanning electrochemical microscopy activity mapping of electrodes modified with laccase encapsulated in sol-gel processed matrix

Electrodes modified with sol-gel encapsulated laccase (isolated from Cerrena unicolor) exhibiting mediated or mediatorless bioelectrocatalytic dioxygen reduction activity were inspected using confocal laser scanning microscopy, atomic force microscopy and scanning electrochemical microscopy. Potential-driven leaching of the redox mediator 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) from carbon ceramic electrodes covered by hydrophilic silicate-encapsulated laccase was detected during electrocatalytic action. Strongly non-homogeneous lateral distribution of the activity towards dioxygen reduction was found by redox competition mode of scanning electrochemical microscopy using a similar electrode with syringaldazine as redox mediator. Hydrogen peroxide formation at these electrodes is detected at potentials lower than 0.05 V. It is ascribed to the electrochemical oxygen reduction at the carbon material while laccase-catalyzed oxygen reduction occurs below 0.35 V without hydrogen peroxide formation. The scanning electrochemical microscopy images of electrodes consisting of single-walled carbon nanotubes non-covalently modified with pyrenesulfonate and laccase encapsulated in a sol-gel processed silicate film confirm direct electron transfer electrocatalysis in redox competition mode experiments and show that the enzyme is evenly distributed in the composite film. In conclusion scanning electrochemical microscopy proved to be useful for mapping of enzyme activity on different materials