Direct electrochemistry of horseradish peroxidase in gelatin-hydrophobic ionic liquid gel films

The direct electrochemistry and electrocatalysis of horseradish peroxidase (HRP) immobilized on a gelatin - N, N-dimethylformamide (DMF) - hydrophobic ionic liquid (i.e. 1-octyl-3-methylimidazolium hexafluorophsohate) gel film coated glassy carbon electrode has been studied for the first time. The immobilized HRP exhibits a pair of well-defined quasi-reversible peaks in pH 7.0 phosphate buffer solutions, which results from the direct electron transfer between the enzyme and the underlying electrode. In this case there is about 2.7% of the immobilized HRP undergoing the electrochemical reaction, which corresponds to multi-layer of HRP on the electrode surface. The HRP immobilized has higher thermal stability than in gelatin hydrogel. Experiment results also show that the voltammetric behavior of the enzyme electrode depends on the type of room temperature ionic liquid (RTIL) used. When a more hydrophobic RTIL is adopted, the resulting enzyme electrode gives better performance. In the presence of hydrogen peroxide, the enzyme electrode shows sensitive response. The sensitivity of the catalytic peak is up to 1.38 A cm⁻² M⁻¹ and the Michaelis constant is down to 6.84 × 10⁻⁵ M, which are superior to that reported elsewhere. In addition, the UV-visible spectra of HRP entrapped in different films and the mass transfer of hydrogen peroxide are discussed as well.     

Electrochemical deposition of poly[N,N′‐ethylene–bis(salicylideneiminato)–nickel(II)] nanobelts as electrode materials for supercapacitors

N,N′‐ethylene–bis(salicylideneiminato)]–nickel(II) [Ni(salen)] was synthesized in situ onto the surface of multiwalled carbon nanotubes via a one‐step potentiostatic electrodeposition as one‐dimensional nanobelts. The synthetic process was free of any templates or additives. Potential played a key role in the formation of the poly[N,N′‐ethylene–bis(salicylideneiminato)]–nickel(II)] {poly[Ni(salen)]} nanobelts, and the electrical conductivities of the poly[Ni(salen)] decreased with increasing deposition time. The capacitance values of poly[Ni(salen)] were 272, 195, and 146 F/g at 0.05 mA/cm² for deposition times of 10, 20, and 30 min, respectively. The capacitance of the sample with a particle structure was much lower than that of poly[Ni(salen)] with a nanobelt structure. The poly[Ni(salen)] nanobelts exhibited a better capacitive behavior than the poly[Ni(salen)] particles because the nanobelt structure made access for the charge and ion to the inner part of the electrode easier. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 39561.     

Immobilization of multicopper oxidase from Pyrobaculum aerophilum onto an electrospun-aligned single-walled carbon nanotube surface via a carbon-nanotube-binding peptide for biocathode

Biofuel cells (BFCs) that produce electrical energy from organic resources through enzymatic reactions have been attracting significant attention. Owing to the high electrical conductivity of carbon nanotubes (CNTs), their modification on the electrode surface of a BFC is expected to increase the current, and their high specific surface area may be useful in increasing the power output. Previously, we constructed a biocathode by immobilizing multicopper oxidase from Pyrobaculum aerophilum (McoP) with a carbon nanotube binding peptide (CBP) sequence on the CNTs. This resulted in higher current densities than when using enzymes without CBP sequences. However, owing to the randomly stacked CNTs on the surface of the electrodes, their conductive properties were impaired and performance as biocathodes was poor. Herein, we constructed a biocathode in which single-walled CNTs (SWCNTs) were oriented one-dimensionally and McoP is immobilized on the surface of an SWNCT via CBP. The current density was successfully increased by two-fold by orienting the CNTs and orienting and immobilizing McoP on their surfaces. This technology provides insights into the development of biodevices with controlled orientation of both the SWCNTs and enzymes immobilized on their surfaces.     

Matched‐dual‐polymer electrochromic lenses,using new cathodically coloring conducting polymers,with exceptional performance and incorporated into automated sunglasses

Reported are syntheses of several new monomer precursors of cathodically coloring conducting polymers (CPs), based on a propylene dioxythiophene skeleton. These are shown to yield CPs—both as homopolymers and as copolymers—that are nearly “perfectly” matched electrochemically and electrochromically with a set of anodically coloring poly(aromatic amines), for use in dual‐polymer electrochromic lenses. Resulting dual‐polymer electrochromic lenses display very high light/dark contrast (typically up to 70/7% or 50/0.5% Transmission (integrated over visible spectrum, vs. air reference), Haze < 2%, very high cyclability (> 10 K cycles), multiyear shelf life, appealing transparent to dark‐blue‐black transition, and excellent optical memory. Dramatic lowering of switching time, from 8 to < 1 s, is demonstrated using unique applied‐potential algorithm resident on inexpensive Microcontroller chip. Working, practical dual‐polymer electrochromic spectacles are demonstrated with electrochromic lenses retrofitted to spectacles meeting ANSI Z87.1, GL‐PD 10–12 (U.S. military) specifications. These incorporate photosensor, rechargeable Li battery, Microcontroller, allow for automated operation. Ab‐initio‐design spectacles, also conforming to above specifications, are also demonstrated, with components seamlessly hidden within frame. To the best of our knowledge, the electrochromic lenses and sunglasses reported herein represent the best visible‐region electrochromic performance for dual‐polymer CP electrochromic systems to date and the first practical implementation in working sunglasses. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41043.     

Anhydrous proton conductor consisting of pectin–inorganic composite material

An organic–inorganic proton conductive composite material consisting of a biopolymer was prepared by mixing the pectin, tetraethyl titanate, and imidazole. Although the pectin material without the composite dissolved in water, the pectin–inorganic composite material did not show water solubility. In addition, in the composite material, the pectin and imidazole formed an acid–base structure by an electrostatic interaction, and as a result, these composite materials showed a thermal stability at intermediate temperatures (100–200°C). Furthermore, these composite materials indicated the proton conductivity of 5.6 × 10^?4 S cm^?1 at 180°C under anhydrous conditions. The activation energy of the proton conduction under anhydrous conditions was 0.32–0.22 eV and these values were one order of magnitude higher than that of the typical humidified perfluorinated membrane, such as Nafion^®. The organic–inorganic composite material consisting of a biocomponent may have the potential to be utilized as a novel proton conductor under anhydrous conditions. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42433.     

Fullerene-like Re-Doped MoS2 Nanoparticles as an Intercalation Host with Fast Kinetics for Sodium Ion Batteries

Sodium ion batteries (SIBs) are considered as a promising alternative to threaten the reign of lithium ion batteries (LIBs) among various next-generation rechargeable energy storage systems, including magnesium ion, metal air, and metal sulfur batteries. Since both sodium and lithium are located in Group 1 of the periodic table, they share similar (electro)chemical properties with regard to ionization pattern, electronegativity, and electronic configuration; thus the vast number of compounds developed from LIBs can provide guidance to design electrode materials for SIBs. However, the larger ionic radius of the sodium cation and unique (de)sodiation processes may also lead to uncertainties in terms of thermodynamic or kinetic properties. Herein, we present the first construction of SIBs based on inorganic fullerene-like (IF) MoS₂ nanoparticles. Closed-shell-type structures, represented by C₆₀ fullerene, have largely been neglected for studies of alkali-metal hosting materials due to their inaccessibility for intercalating ions into the inner spaces. However, IF-MoS₂, with faceted surfaces, can diffuse sodium ions through the defective channels, thereby allowing reversible sodium ion intercalation/deintercalation. Interestingly, Re-doped MoS₂ showed good electrochemical performances with fast kinetics (ca. 74 mA h g⁻¹ at 20 C). N-type doping caused by Re substitution of Mo in IF-MoS₂ revealed enhanced electrical conductivity and an increased number of diffusion defect sites. Thus, chemical modification of fullerene-like structures through doping is proven to be a promising synthetic strategy to prepare improved electrodes.     

Recent Advances in Counter Electrodes for Thiolate-mediated Dye-sensitized Solar Cells

Dye-sensitized solar cells (DSSCs) based on disulfide/thiolate (T₂/T⁻) redox couples have attracted remarkable attention due to their high efficiency and low cost. As an indispensible part of DSSCs, counter electrode (CE) design plays a crucial role in high efficiency DSSCs. This mini-review paper selectively reviews the recent advances in T-mediated DSSCs using novel CE (namely cathode) materials, mainly including noble metal platinum (Pt), carbon materials, transition metal compounds (TMCs), polymers, and hybrids, thus highlighting the merits and demerits of alternative Pt catalysts, and the prospects and challenges of Pt-free CEs for the development of high-performance and low-cost DSSCs.     

Electrochemical Impedance Spectroscopic Analysis of Sensitization-Based Solar Cells

Electrochemical impedance spectroscopy (EIS) is a very powerful tool for elucidation of charge transfer and transport processes in sensitization-based solar cells (e.g., dye-sensitized solar cells [DSSCs], quantum dot-sensitized solar cells [QDSSCs], and perovskite solar cells [PSCs]). EIS measures the electrochemical response to small amplitude AC signals over a wide range of frequencies. Analysis of the EIS response provides information about the corresponding parameters of the cells. Here, we review the fundamentals of EIS, charge transport kinetic processes, and equivalent circuit models of sensitization-based solar cells and use these concepts to explain the EIS spectra of DSSCs, QDSSCs, and PSCs. This review will be very useful for understanding the fundamental charge transfer and transport processes in different sensitization-based solar cells and the use of an equivalent circuit model to interpret the observed charge transfer and reactions.     

Novel composite nanofilm of electropolymerization and self‐assembling on AA5052 surface as anticorrosion coating

Electropolymerization nanofilm was prepared by cyclic voltammogram with 6N,N‐diallylamino‐1,3,5‐triazine‐2,4‐dithiol monosodium (DAN) on the AA5052 surface in 0.15M NaNO₂ at 10°C, then octyl‐triethoxysilane (OTES) film was fabricated on the poly(6N,N‐diallylamino‐1,3,5‐triazine‐2,4‐dithiol) nanofilm (PDA) covered AA5052 surface by self‐assembling method to obtain the composite polymeric nanofilm (C‐PDA/OTES). The composite polymeric nanofilm was characterized by means of FTIR spectra, scanning electron microscope (SEM), contact angle, and potentiodynamic polarization. The results showed that the C‐PDA/OTES covered surface was more homogenous, compact, hydrophobic compared with PDA covered surface and had excellent protection efficiency. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Coagulation and Electrocoagulation of Wastes Polluted with Colloids

Abstract

The goal of this work has been to compare for both, continuous and batch processes, the efficiencies of the chemical and the electrochemical coagulation processes with hydrolyzing aluminum salts, and to determine the similarities or differences that exist between both coagulation processes. To meet the objective, experiments of both coagulation technologies have been carried out in the same operation conditions and the results have been interpreted in terms of the mechanisms previously proposed in literature for kaolin coagulation. The charge neutralization by the adsorption of monomeric hydroxocations onto the kaolin surface can be the primary coagulation‐mechanism for low concentration of aluminum and acidic pHs (below 4). In the range of pH 4–7, two primary mechanisms can explain the experimental behavior of the system: sweep flocculation for high concentration of aluminum, and a combination of precipitation‐charge‐neutralization and charge neutralization by adsorption of monomeric or polymeric aluminum, for low concentration of aluminum. In the continuously‐operated processes, the efficiency in the turbidity‐removal seems to be much related to the aluminum species present in the treated waste, and not to the way of adding aluminum to the reaction system. For the same steady‐state pH and aluminum concentration, the same turbidity removal is obtained in both, the chemical and the electrochemical coagulation processes. For high aluminum/kaolin ratios, kaolin suspensions which contain sulfate as electrolyte, achieve better removals of turbidity than those containing chloride ions. The operation mode (continuous or discontinuous) influences greatly on the efficiency of the electrocoagulation processes. Similar efficiencies are obtained for low (below 5 mg dm^?3) and high doses of aluminum (above 20 mg dm^?3). However, at intermediate doses a strong difference is observed, with a more marked decrease in the efficiency in the discontinuous process. This observation has been explained considering that the addition of aluminum in the continuous process is instantaneous (and not progressive as in the discontinuous one), and thus, the sweep coagulation mechanism is more favored in this operation mode.