Self-assembly of pendant functional groups grafted PEDOT as paracetamol detection material.

In this paper, pendant functional group grafted EDOTs, such as EDOTCH2NH2, EDOTCH2OH and EDOTCH2SH, were selected as monomers for the preparation of their respective polymers via a common chemical oxidative polymerization method in the absence of CTAB by varying the [monomer]/[oxidant] ratios. The self-assembly mechanism of the polymers was systematically studied by discussing the hydrogen bonding effect, acidity and electron-donating ability, as well as the chain initiation and chain growth of the chemically oxidated polymerized monomers. These functional group grafted PEDOTs were applied to the electrochemical determination of paracetamol (PAR) to further investigate the effect of the pendant functional groups (-SH, -OH, -NH2) on the electrochemical sensing behaviour of the polymers. The results indicated that the hydrogen bonding effect of the pendant functional groups was vital to the self-assembly of the polymer chains, and the PEDOTs with -OH and -SH groups had a tendency to self-assemble into a spherical structure, while the PEDOT with an -NH2 group exhibited a fibrous structure. The electrochemical response of PEDOTs with functional groups was better than that that of PEDOT alone, and the highest electrochemical response was observed in PEDOT with an -SH group ([monomer]/[oxidant] = 1 : 8).

Electrochemical synthesis of multilayered PEDOT/PEDOT-SH/Au nanocomposites for electrochemical sensing of nitrite.

A multilayered film of poly(3,4-ethylenedioxythiophene)/poly(thiomethyl 3,4- ethylenedioxythiophene)/gold nanoparticle (PEDOT/PEDOT-SH/Au) nanocomposites was successfully synthesized on indium tin oxide (ITO) and glassy carbon electrode (GCE) via an electrochemical technique. The structure and morphology of the composite was characterized by FT-IR, UV-vis, EDS, XPS, and SEM analyses. The prepared multilayered PEDOT/PEDOT-SH/Au nanocomposite was used for the electrochemical catalytic oxidation of nitrite by amperometry. The results showed that the microstructures of PEDOT/PEDOT-SH/Au nanocomposites are not strongly dependent on the substrate. Fibrous PEDOT as hard template absorbed EDOT-SH on it to form porous PEDOT/PEDOT-SH. Porous structure had the advantages of large specific surface area and high porosity for nitrite ion adsorption. The thiol group in PEDOT/PEDOT-SH stabilized Au nanoparticles (NPs) effectively through Au-S bond and allowed Au NPs to have high dispersion and excellent electrocatalytic activity. The PEDOT/PEDOT-SH/Au composite prepared on GCE had a good performance in its electrochemical response to nitrite ions. PEDOT/PEDOT-SH/Au/GCE displayed a low oxidation potential (0.74 V), a fast response time (< 3 s), a low detection limit (0.051 µM), two linear ranges (0.15-1 mM and 1-16 mM), good sensitivity (0.301 µA µM-1 cm-2 and 0.133 µA µM-1 cm-2) with good reproducibility, stability, and selectivity. Graphical abstract Schematic representation of the preparation process of the nitrite ion electrochemical sensor.

Rational electrolyte design and electrode regulation for boosting high-capacity Zn-iodine fiber-shaped batteries with four-electron redox reactions.

Aqueous Zn ion-based fiber-shaped batteries (AZFBs) with the merits of high flexibility and safety have received much attention for powering wearable electronic devices. However, the relatively low specific capacity provided by cathode materials limits their practical application. Herein, we first propose a simple strategy for fabricating high-capacity Zn-iodine fiber-shaped batteries with a high concentration electrolyte and a reduced graphene oxide fiber (GF) cathode. It was found that oxygen functional groups in the graphene sheet demonstrate strong interaction with polyiodides but hinder electron conductivity; thus, the optimal balance between the specific capacity and coulombic efficiency of the GF electrode can be a function of the surface properties at different hydrothermal temperatures. Besides, the regulated high concentration electrolyte effectively suppresses the diffusion of polyiodides, which is attributed to the constrained freedom of water. More importantly, a four-electron redox mechanism was experimentally revealed through in situ Raman spectra. As a result, this fiber-shaped battery delivers a superior high reversible capacity of 390 mA h cm-3 at 1 A cm-3, an excellent rate performance of 125.7 mA h cm-3 at a high current density of 8 A cm-3 and outstanding cycling life with 82% capacitance retention after 2500 cycles.

Synergistic Ion Sieve and Solvation Regulation by Recyclable Clay-Based Electrolyte Membrane for Stable Zn-Iodine Battery.

The high dissolution of polyiodides and unstable interface at the anode/electrolyte severely restrict the practical applications of rechargeable aqueous Zn-iodine batteries. Herein, we develop a zinc ion-based montmorillonite (ZMT) electrolyte membrane for synergizing ion sieve and solvation regulation to achieve highly stable Zn-iodine batteries. The rich M-O band and special cation-selective transport channel in ZMT locally tailor the solvation sheath around Zn2+ and therefore achieve high transference number (t+ = 0.72), benefiting for uniform and reversible deposition/stripping of Zn. Meanwhile, the mechanisms for three-step polyiodide generation and shuttle-induced Zn corrosion are highlighted by in situ characterization techniques. It is confirmed that the strong chemical adsorption between O atoms in ZMT and polyiodides species is the key to effectively inhibit the shuffle effect and side reactions. Consequently, the ZMT-based Zn-iodine battery delivers a high capacity of 0.45 mAh cm-2 at 1 mA cm-2 with a much improved Coulombic efficiency of 99.5% and outstanding capacity retention of 95% after 13 500 cycles at 10 mA cm-2. Moreover, owing to its high durability and chemical inertness and structural stability, ZMT-based electrolyte membranes can be recycled and applied in double-sided pouch cells, delivering a high areal capacity of 2.4 mAh cm-2 at 1 mA cm-2.