Electrochemical methods for analysing and controlling charge transfer at the electrode–tissue interface

There have been rapid advances in the development of new materials for use in electrode–tissue interfacing. The development of conducting polymers, conducting hydrogels, carbon nanotubes, graphene and other conducting materials has provided a rich landscape for controlling charge transfer at the electrode–tissue interface and hence to monitor and manipulate cell behaviour. These materials have been used in tissue-engineered constructs to direct and control cell proliferation, growth and differentiation. However, their translation to clinical devices has been less successful. In this review, the use of electroanalytical techniques to develop an understanding of charge transfer at the electrode–tissue interface is discussed. In particular, the impact of solution and electrode conditions on charge injection capacity is demonstrated. The importance of standardised testing methods and the correlation of electrochemical and electrophysiological performance show the limitations of empirical studies and help define key electrode properties for clinical devices. The development of a sound theoretical basis for charge transfer at this increasingly important interface is being advocated to improve clinical outcomes and device lifetime and reduce power usage.     

Synthesis and properties of novel N,C,N terdentate skeleton based on 1,3-di(pyridin-2-yl)benzene moiety-new tricks for old dogs

Utilization of intermolecular Friedel-Crafts and intramolecular condensation reaction,novel 1,3-di-(pyridine-2-yl)benzene(N,C,N terdentate) skeleton with electro-withdrawing group in 6' position of pyridyl and a cyclization between 6' position of pyridyl and 6 position of benzyl ring were firstly designed and synthesized.The structures of these novel N,C,N terdentate were confirmed by NMR,MS and X-ray single crystalanalyses.The photophysical properties of these compounds were briefly explored.     

Nickel (II) tetrapyridyl complexes as electrocatalysts and precatalysts for water oxidation

Two nickel complexes, [Ni(tpen)](ClO₄)₂.0.5CH₃COCH₃ ( 1 ) and [Ni(tpbn)](ClO₄)₂ ( 2 ), of tetrapyridyl ligands N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,2-ethanediamine (tpen) and N,N,N′,N′-tetrakis(2-pyridyl-methyl)-1,4-butanediamine (tpbn) were prepared and their catalysis for water oxidation reaction (WOR) studied. In 0.1 M phosphate buffer solution (PBS) of pH 8.0, complex 1 is a homogeneous molecular catalyst with an overpotential of ~440 mV and a Faradaic efficiency of 89%. At pH ≥ 9.0, complex 1 degraded gradually during the catalytic process and formed NiO_x composite (nickel oxide with general formula Ni_xO_yH_z) active for WOR. In contrast, complex 2 deteriorated under measured conditions (pH 8.0–12.0) and formed NiO_x composite active for WOR. The NiO_x composite derived from 1 in 0.1 M PBS at pH 11.0 showed an activity with an overpotential of ~500 mV, a Tafel slope of ~90 mV/decade and a Faradaic efficiency of 97%. Mechanisms were proposed for water oxidation catalyzed by 1 and 2 . This work revealed that the catalytic activity of the nickel complexes was related to the flexibility of the tetrapyridyl ligands and the adaptability of the coordination sphere of the nickel(II) center.     

Voltammetric study of the behaviour of N-acetyl-p-aminophenol in aqueous solutions at a platinum electrode

The electrochemical oxidation of N-acetyl-p-aminophenol (PAR) was investigated at a Pt electrode with the application of cyclic (CV) and differential pulse (DPV) voltammetry methods. An effect of scan rate, substrate concentration and pH on electrode reactions was determined. The parameters of substrate electro-oxidation, i.e. heterogeneous rate constant, charge transfer coefficient, and diffusion coefficient, were calculated. Our investigation's results prove the exchange of two electrons and one proton in the first step, followed by a chemical reaction. PAR electro-oxidation occurs according to an EC mechanism.     

Electrocatalytic Oxidation of Ethanol on the Surface of Graphene Based Nanocomposites: An Introduction and Review to it in Recent Studies

This review gives an overview of the electrochemical investigations about the properties of various types of graphene composites in the ethanol oxidation. Various routes to provide appropriate graphene‐based materials required electrochemical techniques for investigation of different types of the materials as well as their performance and efficacy in ethanol oxidation are discussed in detail. Furthermore, it is demonstrated that the incorporation of suitable materials, e. g. noble metals (graphene‐supported binary and ternary metal nanoparticles), metal oxides, conductive polymer, etc, with graphene results in excellent electrocatalytic activity, superb durability and selectivity in ethanol oxidation. Immobilization of electrocatalytically active NPs on graphene supports using physical approaches is considered as an effective route to prepare direct ethanol fuel cell (DEFC) anode catalysts.     

Cobalt Based Nanoparticles Embedded Reduced Graphene Oxide Aerogel for Hydrogen Evolution Electrocatalyst

Efficient water electrolysis catalyst is highly demanded for the production of hydrogen as a sustainable energy fuel. It is reported that cobalt derived nanoparticle (CoS₂, CoP, CoS|P) decorated reduced graphene oxide (rGO) composite aerogel catalysts for highly active and reliable hydrogen evolution reaction electrocatalysts. 7 nm level cobalt derived nanoparticles are synthesized over graphene aerogel surfaces with excellent surface coverage and maximal expose of active sites. CoS|P/rGO hybrid aerogel composites show an excellent catalytic activity with overpotential of ≈169 mV at a current density of ≈10 mA cm^?2. Accordingly, efficient charge transfer is attained with Tafel slope of ≈52 mV dec^?1 and a charge transfer resistance (R_ct) of ≈12 Ω. This work suggests a viable route toward ultrasmall, uniform nanoparticles decorated graphene surfaces with well‐controlled chemical compositions, which can be generally useful for various applications commonly requiring large exposure of active surface area as well as robust interparticle charger transfer.     

X-ray photoelectron spectroscopy and Raman microscopy of a ferroan platinum crystal from the Kondyor Massif,Russian Far East

X-ray Photoelectron Spectroscopy was used to study a ferroan platinum crystal from the Kondyor Massif, Russian Far East. Prior to the X-ray Photoelectron Spectroscopic analyses, the nature of the crystal was confirmed by X-ray diffraction. The survey scan showed mainly the presence of Pt and Fe, with smaller amounts of O and Si. The high resolutions spectra of the Pt 4f and Fe 2p showed 18.3 atom% Fe in the crystal, which puts the composition on the lower boundary for ferroan platinum and confirms earlier analyses using other methods such as Scanning Electron Microscopy-Energy Dispersive X-ray analysis/microprobe. The binding energy of the Pt 4f5/2 was 74.0?eV and Pt 4f7/2 70.5?eV, while the Fe 2p3/2 for metallic Fe was observed at 707.2?eV. The Fe 2p3/2 for metallic Fe was significantly sharper than that of Fe 2p3/2 at 710.7?eV associated with surface material. The Raman spectrum was dominated by the Pt–Pt stretching mode at 253?cm^?1. Changed orientation resulted in the observation of two bands at 127 and 139?cm^?1, interpreted as being due to stretching modes of two Pt–Pt bonds with the third bond to Fe and Pt fixed. The presence of Ca-Fe-Al-Mg-Si-O on the surface was probably associated with the presence of a clinopyroxene. These minerals can be expected since the crystal came originally from a clinopyroxenite-dunite matrix. The spectra showed a variety of interferences, e.g. Al 2p with Pt 4f, Mg 2p with Fe 3p, and Ca 2p1/2 with Mg Auger, making exact determinations of the ratios of these elements difficult.     

Assessment of the beneficial combination of electrochemical and ultrasonic activation of compounds originating from biomass

The electro-oxidation of organic molecules at the anode with simultaneous generation of hydrogen at the cathode in electrosynthesis reactors is considered as a promising and efficient process for the co-production of hydrogen and bio-sourced value-added chemicals. In this study and for the first time, we investigated the electro-oxidation of glucose and methylglucoside in 0.1 mol L⁻¹ NaOH on polycrystalline Pt (real surface area = 14.5 ± 0.5 cm², roughness ≈ 5) in the potential range [0; +1.20 V vs. rhe] under silent and ultrasonic (bath, 45 kHz, P_acous = 11.20 W) conditions. A series of linear sweep voltammograms, chronoamperograms and high-performance liquid chronoamperograms were generated. It was found that higher current densities were obtained under ultrasonic conditions over the potential range of +0.25 V to +1.10 V vs. rhe, indicating that higher oxidation rates were provided under ultrasonication. It was observed that the desorption of species from the Pt surface in the medium potential region was favoured, allowing free catalytic Pt sites for further adsorption and oxidation of reactants; and in the high potential region, high peak current densities in the presence of ultrasound was due to enhanced mass transport of the electroactive species from the bulk electrolyte to the Pt-polycrystalline electrode surface. HPLC studies confirmed that higher electrochemical activity was obtained in the presence of ultrasound than in the absence. In our conditions, it was also found that low frequency ultrasound did not change the selectivity of the glucose and methylglucoside electro-oxidation reactions but instead, a significant increase in the rate of conversion was observed.     

Phase-Selective Syntheses of Cobalt Telluride Nanofleeces for Efficient Oxygen Evolution Catalysts

Cobalt-based nanomaterials have been intensively explored as promising noble-metal-free oxygen evolution reaction (OER) electrocatalysts. Herein, we report phase-selective syntheses of novel hierarchical CoTe₂ and CoTe nanofleeces for efficient OER catalysts. The CoTe₂ nanofleeces exhibited excellent electrocatalytic activity and stablity for OER in alkaline media. The CoTe₂ catalyst exhibited superior OER activity compared to the CoTe catalyst, which is comparable to the state-of-the-art RuO₂ catalyst. Density functional theory calculations showed that the binding strength and lateral interaction of the reaction intermediates on CoTe₂ and CoTe are essential for determining the overpotential required under different conditions. This study provides valuable insights for the rational design of noble-metal-free OER catalysts with high performance and low cost by use of Co-based chalcogenides.     

Facile synthesis of ordered mesoporous molybdenum carbide electrocatalysts for high-performance hydrogen evolution reaction

In this study, a simple method was designed to prepare ordered mesoporous carbons embedded with molybdenum without any extreme conditions. We prepared three different ordered molybdenum carbide materials with mesoporous structures to explore the influence of the structure of molybdenum-based materials on the HER catalytic efficiency. The ordered mesoporous molybdenum carbide catalysts (CMK-3-MoCx, fCMK-3-MoCx, CMK-8-MoCx) were characterized by SEM, TEM, XRD, nitrogen adsorption-desorption and XPS. The HER is catalyzed efficiently on the three electrocatalysts, fCMK-3-MoCx shows the best HER electro-catalytic performance with a small onset potential of −0.06 V vs. RHE, a low tafel slope of 66 mV dec⁻¹ and a small over-potential value of 89 mV at 10 mA cm⁻². This excellent performance on HER is due to its high specific surface area and highly ordered mesoporous structure that resulted in excellent proton transport efficiency and high electron transfer rate. Our results provide a new research direction for the application of flat ordered mesoporous structures in catalysis.