Metallic impurity free carbon nanotube paste electrodes

Electrodes modified with carbon nanomaterials find wide ranging applications in electrochemistry such as in energy generation and storage through to applications in electroanalysis. A substantial limitation is the presence of metallic impurities which vary between batches and can produce erroneous results. Consequently we have explored the electrochemical properties of metallic impurity free carbon nanotube paste electrodes using potassium ferrocyanide and hydrogen peroxide as model compounds. In terms of the latter utilising cyclic voltammetry, a linear range from 0.75 to 3 mM with a limit of detection of 0.19 mM is possible using the electrochemical oxidation of hydrogen peroxide while using the electrochemical reduction of the target analyte, a linear range from 0.5 to 249 mM is possible with a detection limit of 0.43 mM.The ultra-small size of the carbon nanotubes and fabrication methodology result in a tightly bound carbon nanotube electrode surface which does not exhibit thin-layer behaviour resulting in highly reproducible electrodes with the %RSD found to be 5.5%. These analytical ranges, detection limits and reproducibility are technologically useful.The carbon nanotubes utilised are completely free from metallic impurities and do not require lengthy processing to remove impurities and consequently have no variation in the purity of the nanomaterial between batches as is commonly the case for other available carbon nanotube material. The impurity free nature of this nanomaterial allows for highly reproducible and intelligent sensors based on carbon nanotubes to be understood and realised for the first time.     

Disposable paper-based electrochemical sensor based on stacked gold nanoparticles supported carbon nanotubes for the determination of bisphenol A

This work reports a new type of disposable electrochemical sensor for the determination of bisphenol A (BPA). The working electrodes were fabricated by sputtering gold nanoparticles on commercial art paper and then modifying the gold layer with multi-walled carbon nanotubes (MWCNTs). The electrode in their intermediated and final stage was characterized by atomic force microscope, scanning electron microscope and electrochemical techniques. To perform electrochemical analysis, the resulting electrode was integrated with a homemade paper-based analytical device, which could also ensure the immobilization of MWCNTs on the electrode surface without any functionalization. The determination of BPA was investigated by linear sweep voltammetry (LSV). A wide linearity in the range from 0.2 to 20 mg/L with a detection limit of 0.03 mg/L (S/N = 3) was obtained. The between-sensor reproducibility was 5.7% (n = 8) for 0.5 mg/L BPA. The proposed sensor showed good resistance against interferences and was applied to detect BPA leached from real plastic samples with satisfying results. This disposable sensor is readily mass-produced and has been verified to serve as an attractive alternative to screen-printed electrodes for practical applications.     

Comparative study of different types of graphenes as electrocatalysts for ascorbic acid

A comparative study regarding the electrocatalytic activity of graphene oxide (GO), chemically-reduced graphene oxide (crGO) and graphene produced by direct liquid exfoliation (dG) is presented. Sensors were developed by modifying glassy carbon (GC) electrodes with GO, crGO and dG and ascorbic acid was used as a pilot analyte. GC/GO electrodes offer substantially lower oxidation overpotential, up to 350 mV, compared with GC/crGO, GC/dG and unmodified GC electrodes. In addition, the different carbon-to-oxygen atomic ratios in GO, as it occurs depending on the synthetic route, were found to have a remarkable effect on the performance of the sensors. Reduction of GO was achieved by immersing the modified electrodes into a stirred solution of NaBH₄ for 10 min at room temperature. This process was used alternatively of the time consuming and laborious process of hydrazine, and its effectiveness was confirmed by cyclic voltammetry and electrochemical impedance spectroscopy. Analytical utility of the sensors is demonstrated.     

Sodium dodecyl sulfate modified carbon nanotubes paste electrode as a novel sensor for the simultaneous determination of dopamine,ascorbic acid,and uric acid

A novel modified multiwall carbon nanotubes paste electrode with sodium dodecyl sulfate as a surfactant (SDS) has been fabricated through an electrochemical oxidation procedure and was used to electrochemically detect dopamine (DA), ascorbic acid (AA), uric acid (UA), and their mixture by cyclic voltammetry (CV) and differential voltammetry (DPV) methods. Several factors affecting the electrocatalytic activity of the hybrid material, such as the effect of pH, of the scan rate and of the concentration were studied. The bare carbon nanotubes paste electrode (BCNTPE) and SDS-modified carbon nanotubes paste electrode (SDSMCNTPE) were characterized using Field Emission Scanning Electron Microscopy (FESEM) and Energy-Dispersive X-ray spectroscopy (EDX). Using the CV procedure, a linear analytical curve was observed in the 1 × 10⁻⁶–2.8 × 10⁻⁵ M range with a detection limit at 3.3 × 10⁻⁷ M in pH 6.5, 0.2 M phosphate buffer solutions (PBS).     

Preparation of activated carbon from Turbinaria turbinata seaweeds and its use as supercapacitor electrode materials

Turbinaria turbinata brown seaweeds were tested as carbon electrode material in symmetric, electrochemical supercapacitors. The electrochemical properties of the carbon materials were characterised for their application as supercapacitors using cyclic voltammetry, galvanostatic charge/discharge method and electrochemical impedance spectroscopic analyses. Our initial results showed that the optimal behaviour was obtained for the sample prepared by pyrolysis at 800 °C. The average surface area of the carbon was 812 m²/g. Electrochemical tests with an organic electrolyte gave the following interesting results: a capacitance of 74.5 F/g, a specific series resistance of 0.5 Ω cm² and an ionic resistivity of 1.3 Ω cm². These results show the promising capacitive properties of carbon derived from seaweeds and their application in electrochemical supercapacitors.     

Gelatin-functionalized carbon nanotubes for the bioelectrochemistry of hemoglobin

In this paper, we compared the use of gelatin-functionalized carbon nanotubes (CNTs) as substrates for Hemoglobin (Hb) immobilization and as electrodes for electrochemical reduction of the absorbed Hb. The non-covalently gelatin-functionalized CNTs possessed an improved solubility in aqueous solution and may have an enhanced biocompatibility with Hb. The characteristics of Hb/gelatin-CNTs composite films were studied by using UV–vis spectroscopy, FTIR spectroscopy and electrochemical methods. The immobilized Hb showed a couple of quasi-reversible redox peaks with a formal potential of −0.35 V (vs. SCE) in 0.10 M pH 7.0 phosphate buffer solution (PBS). The surface concentration of electroactive Hb immobilized on gelatin-CNT/GC electrode was about 4.34 × 10⁻¹⁰ mol cm⁻².     

Selective determination of trichloroacetic acid using silver nanoparticle coated multi-walled carbon nanotubes

Silver nanoparticle coated multi-walled carbon nanotubes (Ag/MWCNT) were prepared and used to fabricate a modified electrode. The Ag/MWCNT composites were observed by a transmission electron microscope (TEM), and the electrochemical properties of the Ag/MWCNT composite modified glassy carbon electrode were characterized by electrochemical measurements. The results showed that these composites had a favorable catalytic ability for the reduction of trichloroacetic acid (TCAA). Square wave voltammetric (SWV) technique was applied to detect TCAA. Under optimum conditions, the voltammetric determination of TCAA was performed with a linear range of 5.0 × 10^? 6–1.2 × 10^? 4 mol L^? 1 and a detection limit of 1.9 × 10^? 6 mol L^? 1 (S/N = 3).     

Determination of nitrite with the electrocatalytic property to the oxidation of nitrite on thionine modified aligned carbon nanotubes

A thionine modified aligned carbon nanotubes (ACNTs) electrode was fabricated and was used to electrochemically determine nitrite. The thionine modified ACNTs electrode exhibited enhanced electrocatalytic behavior to the oxidation of nitrite. The electrochemical mechanism of the thionine/ACNTs electrode towards the oxidation of nitrite was discussed. The thionine modified ACNTs electrode exhibited fast response towards nitrite with a detection limit of 1.12 × 10⁻⁶ mol  L⁻¹ and a linear range of 3 × 10⁻⁶ – 5 × 10⁻⁴ mol  L⁻¹. The proposed method was successfully applied in the detection of nitrite in real samples.     

A dysprosium nanowire modified carbon paste electrode for determination of levodopa using fast Fourier transformation square-wave voltammetry method

A new detection technique called the fast Fourier transform square-wave voltammetry (FFT-SWV) is based on the measurements of electrode admittance as a function of potential. The response of the detector (microelectrode) is fast, which makes the method suitable for most applications involving flowing electrolytes. The carbon paste electrode was modified by nanostructures to improve better sensitivity. The response is generated by a redox processes. The redox property of L-dopa was used for determination of it in human serum and urine samples. The support electrolyte that provided a more defined and intense peak current for L-dopa determination was at 0.05 mol l^?1 acetate buffer pH 7.0. Synthesized dysprosium nanowires make more effective surface like nanotubes [1], [2], [3], [4] so they are good candidates for using as a modifier for electrochemical reactions. The drug presented one irreversible oxidation peaks at 360 mV versus Ag/AgCl by modified nanowire carbon paste electrode which produced high current and reduced the oxidation potential about 80 mV.Furthermore, signal-to-noise ratio has significantly increased by application of discrete fast Fourier transform (FFT) method, background subtraction and two-dimensional integration of the electrode response over a selected potential range and time window. To obtain the much sensitivity the effective parameters such as frequency, amplitude and pH was optimized. As a result, C_DL of 4.0 × 10^?9 M and an LOQ of 7.0 × 10^?9 M were found for determination for L-dopa. A good recovery was obtained for assay spiked urine samples and a good quantification of L-dopa was achieved in a commercial formulation.     

Controlled synthesis of MnSn(OH)6/graphene nanocomposites and their electrochemical properties as capacitive materials

We report the synthesis of novel MnSn(OH)₆/graphene nanocomposites produced by a co-precipitation method and their potential application for electrochemical energy storage. The hydroxide decorated graphene nanocomposites display better performance over pure MnSn(OH)₆ nanoparticles because the graphene sheets act as conductive bridges improving the ionic and electronic transport. The crystallinity of MnSn(OH)₆ nanoparticles deposited on the surface of graphene sheets also impacts the capacitive properties as electrodes. The maximum capacitance of 31.2 F/g (59.4 F/g based on the mass of MnSn(OH)₆ nanoparticles) was achieved for the sample with a low degree of crystallinity. No significant degradation of capacitance occurred after 500 cycles at a current density of 1.5 A/g in 1 M Na₂SO₄ aqueous solution, indicating an excellent electrochemical stability. The results serve as an example demonstrating the potential of integrating highly conductive graphene networks into binary metal hydroxide in improving the performance of active electrode materials for electrochemical energy storage applications.     

Novel poly (neutral red) nanowires as a sensitive electrochemical biosensing platform for hydrogen peroxide determination

Poly (neutral red) nanowires (PNRNWs) have been synthesized for the first time by the method of cyclic voltammetric electrodeposition using porous anodic aluminum oxide (AAO) template and were examined by scanning electron microscopy (SEM) and transmission electron microscope (TEM). Moreover, horseradish peroxidase (HRP) was encapsulated in situ in PNRNWs (denoted as PNRNWs–HRP) by electrochemical copolymerization for potential biosensor applications. The PNRNWs showed excellent efficiency of electron transfer between the HRP and the glassy carbon (GC) electrode for the reduction of H₂O₂ and the PNRNWs–HRP modified GC electrode showed to be excellent amperometric sensors for H₂O₂ at −0.1 V with a linear response range of 1 μM to 8 mM with a correlation coefficient of 0.996. The detection limit (S/N = 3) and the response time were determined to be 1 μM and <5 s and the high sensitivity is up to 318 μA mM⁻¹ cm⁻².     

Graphene oxide doped polyaniline for supercapacitors

A novel high-performance electrode material based on fibrillar polyaniline (PANI) doped with graphene oxide sheets was synthesized via in situ polymerization of monomer in the presence of graphene oxide, with a high conductivity of 10 S cm^?1 at 22 °C for the obtained nanocomposite with a mass ratio of aniline/graphite oxide, 100:1. Its high specific capacitance of 531 F/g was obtained in the potential range from 0 to 0.45 V at 200 mA/g by charge–discharge analysis compared to 216 F/g of individual PANI. The doping and the ratio of graphene oxide have a pronounced effect on the electrochemical capacitance performance of the nanocomposites.     

Electrochemical determination of nitrite based on poly(amidoamine) dendrimer-modified carbon nanotubes for nitrite oxidation

This study describes a simple and reliable method for the electrochemical determination of nitrite based on poly(amidoamine)-modified carbon nanotubes. Amine-terminated poly(amidoamine) (generation 4.0, G4-NH₄) were covalently attached onto multi-walled carbon nanotube (MWNT)-modified glass carbon (GC) electrodes (written as G4-NH₄/MWNT-modified GC) and which were used for the electrochemical determination of nitrite. The studies show that the G4-NH₄/MWNT-modified electrodes demonstrated significantly enhanced electrochemical activity towards nitrite oxidation. Chronoamperometry studies reveal that the amperometric response is rapid, stable, and offers a linear dependence over a wide range of nitrite concentrations from 5 μM to 1.5 mM. The proposed method can be used for the continuous monitoring of nitrite in real samples. The electrochemical properties of the G4-NH₄/MWNT nanocomposites are reasonably envisaged to be promising for providing a nanostructured platform in the development of electrochemical sensors or biosensors.     

Label-free electrochemical detection of Avian Influenza Virus genotype utilizing multi-walled carbon nanotubes–cobalt phthalocyanine–PAMAM nanocomposite modified glassy carbon electrode

A novel DNA electrochemical biosensor for label-free determination of DNA sequence related to the Avian Influenza Virus (AIV) genotype was demonstrated in this paper. First, the multi-walled carbon nanotubes–cobalt phthalocyanine (MWNTs–CoPc) nanocomposite and poly (amidoamine) (PAMAM) dendrimer (generation 4.0) were modified on the glassy carbon electrode (GCE) sequentially. Then, DNA probes were successfully immobilized on the modified electrode with G4 PAMAM dendrimer acting as the coupling agent. The hybridization events were monitored by differential pulse voltammetry (DPV) measurement based on the oxidation signals of guanine without any external labels. Under the optimal conditions, the difference in guanine oxidation signal of the probe modified GCE in the absence and presence of complementary target (ΔI_p) was linear with the logarithmic value of the complementary target concentration from 0.01 to 500 ng/ml with a correlation coefficient of 0.998 and a detection limit of 1.0 pg/ml.     

A novel network composite cathode of LiFePO4/multiwalled carbon nanotubes with high rate capability for lithium ion batteries

A novel network composite cathode was prepared by mixing LiFePO₄ particles with multiwalled carbon nanotubes for high rate capability. LiFePO₄ particles were connected by multiwalled carbon nanotubes to form a three-dimensional network wiring. The web structure can improve electron transport and electrochemical activity effectively. The initial discharge capacity was improved to be 155 mA h/g at C/10 rate (0.05 mA/cm²) and 146 mA h/g at 1C rate. The comparative investigation on MWCNTs and acetylene black as a conducting additive in LiFePO₄ proved that MWCNTs addition was an effective way to increase rate capability and cycle efficiency.     

Constructing a hierarchical graphene–carbon nanotube architecture for enhancing exposure of graphene and electrochemical activity of Pt nanoclusters

Stacking of individual graphene sheets (GS) is effectively inhibited by introducing one-dimensional carbon nanotubes to form a 3-D hierarchical structure which enhances the utilization of GS-based composites. From SEM images, CNTs are useful nanospacers for diminishing the face-to-face aggregation of GS. The specific electrochemically active surface area (SECSA) and specific double-layer capacitance (C_S,DL) of Pt/GS–CNTs (127.9 m²/g, 171.3 F/g) is much higher than that of Pt/GS (105.4 m²/g, 104.7 F/g) and Pt/CNTs (51.5 m²/g, 37.1 F/g), revealing the synergistic effects between GS and CNTs on enhancing the electrochemical activity of Pt nanoparticles and electrolyte-accessible surface area.     

Microwave plasma chemical vapor deposition of nano-composite C/Pt thin-films

Composite carbon–platinum thin-films of nano-crystalline graphitic carbon decorated with uniformly-dispersed 2–4 nm Pt nano-particles have been synthesized from a solid organic precursor by a one-step microwave plasma chemical vapor deposition (MPCVD). The fast Ar-plasma discharge and the presence of microwave radiation accelerate the formation of sites suitable for in situ heterogeneous nucleation, and consequently, the fine dispersion of metal in the carbonaceous matrix. The electrochemical response of the 2 μm C/Pt thin-film electrode displays electrochemical activity, which is attributed to the high ca. 18 m²/g effective surface area of Pt nano-particles.     

Multilayer graphene nanoribbons exhibit larger capacitance than their few-layer and single-layer graphene counterparts

This article demonstrates that it is not always beneficial to exfoliate graphitic structures to single-layer graphene to achieve maximum electrochemical performance. Using electrochemical impedance spectroscopy, we show that multilayer graphene nanoribbons with cross sections of 100 × 100 nm provide larger capacitance (15.6 F/g) than do few-layer graphene nanoribbons (14.9 F/g) and far larger capacitance than single-layer graphene nanoribbons (10.9 F/g) with the same cross section.     

Microwave-irradiated synthesized platinum nanoparticles/carbon nanotubes for oxidative determination of trace arsenic(III)

Platinum nanoparticles/carbon nanotubes (Pt_nano/CNTs) were rapidly synthesized by microwave radiation, and applied for the oxidative determination of arsenic(III). The transmission electron microscopy (TEM) revealed the size of synthesized Pt nanoparticles with nominal diameter of 15 ± 3 nm. Pt_nano/CNTs modified glassy carbon electrode (Pt_nano/CNTs/GCE) exhibited better performance for arsenic(III) analysis than that of Pt nanoparticles modified GCE (Pt_nano/GCE) by electrochemical deposition or Pt foil electrode. Excellent reproducibility of the Pt_nano/CNTs/GCE was obtained with the relative standard deviation (RSD) of 3.5% at 20 repeated analysis of 40 μM As(III), while the RSD was 9.8% for Pt_nano/GCE under the same conditions. The limit of determination (LOD) of the Pt_nano/CNTs/GCE was 0.12 ppb, which was 1–2 orders of magnitude lower than that of Pt_nano/GCE or Pt foil electrode.     

Graphene and carbon quantum dots electrochemistry

Graphene and carbon quantum (QDs) dots exhibit interesting and well-defined properties owing to their quantum confinement. In this work, graphene QDs (G-QDs) and carbon QDs of size ~ 6 nm and ~ 2 nm, respectively, were prepared and their potential uses in electrochemistry and electrochemical sensing were subsequently investigated. It was discovered that the C-QDs surface displayed a faster electron transfer rate compared to the G-QDs following analyses with the ferro/ferricyanide redox probe. Studies were also carried out with redox biomarkers such as uric acid (UA) and ascorbic acid (AA), and it was found that while the C-QDs displayed electrocatalytic properties toward the oxidation of both UA and AA, the G-QDs seemed to only have an impact on AA, from the decrease in the oxidation peak potential. This work provides direct electrochemical comparison of the two latest frontiers of carbon nanomaterials and opens the way for their electrochemical sensing applications.