Comparative Study of the Structural Features and Electrochemical Properties of Nitrogen-Containing Multi-Walled Carbon Nanotubes after Ion-Beam Irradiation and Hydrochloric Acid Treatment

Using a set of microscopic, spectroscopic, and electrochemical methods, a detailed study of the interrelation between the structural and electrochemical properties of the as-prepared nitrogen-containing multi-walled carbon nanotubes (N-MWCNTs) and their modified derivatives is carried out. It was found that after treatment of nanotubes with hydrochloric acid, their structure is improved by removing amorphous carbon from the outer layers of N-MWCNTs. On the contrary, ion bombardment leads to the formation of vacancy-type structural defects both on the surface and in the bulk of N-MWCNTs. It is shown that the treated nanotubes have an increased specific capacitance (up to 27 F·g−1) compared to the as-prepared nanotubes (13 F·g−1). This is due to an increase in the redox capacitance. It is associated with the reversible Faraday reactions with the participation of electrochemically active pyridinic and pyrrolic nitrogen inclusions and oxygen-containing functional groups (OCFG). Based on the comparison between cyclic voltammograms of N-MWCNTs treated in HCl and with an ion beam, the peaks on these curves were separated and assigned to specific nitrogen inclusions and OCFGs. It is shown that the rate of redox reactions with the participation of OCFGs is significantly higher than that of reactions with nitrogen inclusions in the pyridinic and pyrrolic forms. Moreover, it was established that treatment of N-MWCNTs in HCl is accompanied by a significant increase in the activity of nitrogen centers, which, in turn, leads to an increase in the rate of redox reactions involving OCFGs. Due to the significant contribution of redox capacitance, the obtained results can be used to develop supercapacitors with increased total specific capacitance.

Solid-Contact Ion-Selective Electrodes: Response Mechanisms, Transducer Materials and Wearable Sensors

Wearable sensors based on solid-contact ion-selective electrodes (SC-ISEs) are currently attracting intensive attention in monitoring human health conditions through real-time and non-invasive analysis of ions in biological fluids. SC-ISEs have gone through a revolution with improvements in potential stability and reproducibility. The introduction of new transducing materials, the understanding of theoretical potentiometric responses, and wearable applications greatly facilitate SC-ISEs. We review recent advances in SC-ISEs including the response mechanism (redox capacitance and electric-double-layer capacitance mechanisms) and crucial solid transducer materials (conducting polymers, carbon and other nanomaterials) and applications in wearable sensors. At the end of the review we illustrate the existing challenges and prospects for future SC-ISEs. We expect this review to provide readers with a general picture of SC-ISEs and appeal to further establishing protocols for evaluating SC-ISEs and accelerating commercial wearable sensors for clinical diagnosis and family practice.

Coulometric response characteristics of solid contact ion-selective electrodes for divalent cations

The chronoamperometric and coulometric response of solid contact ion-selective electrodes (SCISEs) for the detection of divalent cations was investigated in order to provide a more complete description of the mechanism of the recently introduced coulometric transduction method for SCISEs. The coulometric transduction method has earlier been employed only for SCISEs that were selective to monovalent ions. The SCISEs utilized poly(3,4-ethylenedioxythiophene) (PEDOT) doped with poly(styrene sulfonate) (PSS−) as the solid contact (ion-to-electron transducer). PEDOT(PSS) was electrodeposited on glassy carbon and covered with plasticized PVC-based ion-selective membranes (ISMs) that were selective towards divalent cations (Ca2+, Pb2+). In contrast to earlier studies, the results obtained in this work show that the coulometric response for the Pb2+-SCISE was limited mainly by ion transport in the PEDOT(PSS) layer, which was not the case for the Ca2+-SCISE, nor was it observed earlier for the monovalent ions. The exceptional behavior of the Pb2+-SCISE was explored further by electrochemical impedance spectroscopy, and it was shown that the effective redox capacitance of PEDOT(PSS) was significantly higher for the Pb2+-SCISE than for the Ca2+-SCISE although the polymerization charge of PEDOT(PSS) was the same. The slow transport of Pb2+ in PEDOT(PSS) was tentatively related to complexation between Pb2+ and PEDOT(PSS).

Effect of Synthesis Conditions on Pseudocapacitance Properties of Nitrogen-Doped Porous Carbon Materials

The electrochemical properties of the nitrogen-enriched carbons obtained by plant raw treatment as electrode material for supercapacitors were investigated by electrochemical impedance spectroscopy, cycling voltammetry and galvanostatic charge-discharge cycling in KOH aqueous electrolyte. The effect of activation agent (NaOH) concentration and carbonization temperature were analyzed. The separation of double layer and redox capacitance components was done. The dominating role of microporosity for capacitive properties was demonstrated. The capacitance of model capacitors based on carbons obtained at different modes was calculated from both from cycling voltammetry and galvanostatic charge-discharge data. The maximal values of specific capacitance of carbon materials carbonized at 600°C and 900°C are about 100 and 120 F/g, respectively.

Preparation of Nickel and Manganese Dioxide by Co-Precipitation and its Electrochemical Capacitive Properties

The precursor nickel and manganese carbonates were synthesized by co-precipitation with sodium carbonate as precipitant, and then nickel and manganese oxides were gained after calcination. The phase and morphology of the synthesized product were characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM), and the electrochemical characterization was performed using cyclic voltammetry (CV), galvanostatic charge–discharge tests (GCD) and electrochemical impedance spectroscopy (EIS) in a 6mol/L KOH aqueous solution electrolyte. The result showed that the products were the mixture of nickel and manganese oxides and solid solution. nanoparticles and spherical particles were gained by controlling the molar ratio of nickel and manganese. All of the samples exhibited typical Faradic redox capacitance. The specific capacitance was different with the change of nickel and manganese molar ratio. The specific capacitance (Cs) reached 130F/g at 1A/g when the ratio was 2:1.

Capacitance spectroscopy and density functional theory

We relate capacitance spectroscopy with density functional theory, providing a theoretical description of redox capacitance and its electrostatic and quantum terms.