Redox Response of Reduced Graphene Oxide-Modified Glassy Carbon Electrodes to Hydrogen Peroxide and Hydrazine.
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ABSTRACT: The surface of a glassy carbon (GC) electrode was modified with reduced graphene oxide (rGO) to evaluate the electrochemical response of the modified GC electrodes to hydrogen peroxide (H₂O₂) and hydrazine. The electrode potential of the GC electrode was repeatedly scanned from -1.5 to 0.6 V in an aqueous dispersion of graphene oxide (GO) to deposit rGO on the surface of the GC electrode. The surface morphology of the modified GC electrode was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). SEM and AFM observations revealed that aggregated rGO was deposited on the GC electrode, forming a rather rough surface. The rGO-modified electrodes exhibited significantly higher responses in redox reactions of H₂O₂ as compared with the response of an unmodified GC electrode. In addition, the electrocatalytic activity of the rGO-modified electrode to hydrazine oxidation was also higher than that of the unmodified GC electrode. The response of the rGO-modified electrode was rationalized based on the higher catalytic activity of rGO to the redox reactions of H₂O₂ and hydrazine. The results suggest that rGO-modified electrodes are useful for constructing electrochemical sensors.
Project description:A new thiosemicarbazone ligand was immobilized through a Cu(I)-catalyzed click reaction on the surface of glassy carbon (GC) and electrochemically reduced graphene oxide (GC-ERGO) electrodes grafted with phenylethynyl groups. Using the accumulation at open circuit followed by anodic stripping voltammetry, the modified electrodes showed a significant selectivity and sensibility for Hg(II) ions. A detection limit of 7 nM was achieved with the GC modified electrodes. Remarkably, GC-ERGO modified electrodes showed a significantly improved detection limit (0.8 nM), sensitivity, and linear range, which we attribute to an increased number of surface binding sites and better electron transfer properties. Both GC and GC-ERGO modified electrodes proved their applicability for the analysis of real water samples.
Project description:This study compares the sensing performance of glassy carbon electrodes (GCE) modified with graphene (GR), multiwalled carbon nanotubes (MWCNTs), and graphene-multiwalled carbon nanotube (GR-MWCNT) composites for the simultaneous detection of ascorbic acid (AA), dopamine (DA), and uric acid (UA). Among these electrodes, GR-MWCNT/GCE exhibited the highest sensitivity and the lowest detection limit. Using differential pulse voltammetry (DPV), AA, DA, and UA can be simultaneously detected at low potentials of -0.032, 0.206, and 0.34 V vs Ag/AgCl, with sensitivities of 0.076, 1.38, and 0.181 μA μM-1 and detection limits (LOD) of 6.71, 0.58, and 7.30 μM, respectively. The GR-MWCNT/GCE also demonstrated good stability, reproducibility, and excellent anti-interference capability. This newly fabricated sensor was confirmed to be applicable for the simultaneous detection of AA, DA, and UA in real serum and urine samples.
Project description:Four different graphene-based nanomaterials (htGO, N-htGO, htGONR, and N-htGONR) were synthesized, characterized, and used as a modifier of carbon paste electrode (CPE) in order to produce a reliable, precise, and highly sensitive non-enzymatic amperometric hydrogen peroxide sensor for complex matrices. CPE, with their robustness, reliability, and ease of modification, present a convenient starting point for the development of new sensors. Modification of CPE was optimized by systematically changing the type and concentration of materials in the modifier and studying the prepared electrode surface by cyclic voltammetry. N-htGONR in combination with manganese dioxide (1:1 ratio) proved to be the most appropriate material for detection of hydrogen peroxide in pharmaceutical and saliva matrices. The developed sensor exhibited a wide linear range (1.0-300 µM) and an excellent limit of detection (0.08 µM) and reproducibility, as well as high sensitivity and stability. The sensor was successfully applied to real sample analysis, where the recovery values for a commercially obtained pharmaceutical product were between 94.3% and 98.0%. Saliva samples of a user of the pharmaceutical product were also successfully analyzed.
Project description:In recent years, the electrochemical sensing approach has attracted electrochemists because of its excellent detection process, simplicity, high sensitivity, cost-effectiveness, and high selectivity. In this study, we prepared nitrogen doped reduced graphene oxide (N-rGO) and characterized it using various advanced techniques such as XRD, SEM, EDX, Raman, and XPS. Furthermore, we modified the active surface of a screen printed carbon electrode (SPCE) via the drop-casting of N-rGO. This modified electrode (N-rGO/SPCE) exhibited an excellent detection limit (LOD) of 0.83 µM with a decent sensitivity of 4.34 µAµM-1cm-2 for the detection of hydrogen peroxide (H2O2). In addition, N-rGO/SPCE also showed excellent selectivity, repeatability, and stability for the sensing of H2O2. Real sample investigations were also carried out that showed decent recovery.
Project description:Cadmium (Cd) and lead (Pb) are classified as category one toxicants. The provisional guideline values, according to the World Health Organization (WHO), for Cd and Pb are 3 and 10 ppb, respectively. An easy, quick, and cheap analytical technique is in demand for the determination of these toxic heavy metals in water. Hence, a novel electrochemical sensing platform is developed by modifying the glassy carbon electrode with ethylenediaminetetraacetic acid (EDTA)-functionalized reduced graphene oxide (ErGO) for the low-cost simultaneous quantitation of toxic heavy-metal ions, lead and cadmium, in real water samples. EDTA is grafted to the surface of graphene oxide, via amine linkage, and the oxygen functionality is reduced by a green agent, tyrosine. Various physical and electrochemical characterizations of the as-prepared electrocatalytic material were performed by X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), ζ-potential, ultraviolet diffuse reflectance spectroscopy (UV-DRS), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), etc. The glassy carbon electrode (GCE) is modified with ErGO by a simple drop-casting method for simultaneous metal-ion quantitation by differential pulse voltammetry (DPV). EDTA functionalization of graphene oxide and its further reduction using the green agent enhance the stability and sensitivity of the electrode substrate. The limits of detection for cadmium and lead ions calculated for ErGO/GCE are 1.02 and 2.52 ppb, while the limits of quantification for lead and cadmium ions are 3.41 and 8.4 ppb, and their sensitivities are 0.8 and 0.6 nA/ppb, respectively. Real river water contains 200.2 ± 0.38 ppb of Pb2+ ions (mean ± stdev, n = 3) by the DPV technique, which is validated by ICP-OES analysis.
Project description:The diversity of materials proposed for non-enzymatic glucose detection and the lack of standardized protocols for assessing sensor performance have caused considerable confusion in the field. Therefore, methods for pre-evaluation of working electrodes, which will enable their conscious design, are currently intensively sought. Our approach involved comprehensive morphologic and structural characterization of copper sulfides as well as drop-casted suspensions based on three different polymers-cationic chitosan, anionic Nafion, and nonionic polyvinylpyrrolidone (PVP). For this purpose, scanning electron microscopy (SEM), X-ray diffraction (XRD), and Raman spectroscopy were applied. Subsequently, comparative studies of electrochemical properties of bare glassy carbon electrode (GCE), polymer- and copper sulfides/polymer-modified GCEs were performed using electrochemical impedance spectroscopy (EIS) and voltammetry. The results from EIS provided an explanation for the enhanced analytical performance of Cu-PVP/GCE over chitosan- and Nafion-based electrodes. Moreover, it was found that the pH of the electrolyte significantly affects the electrocatalytic behavior of copper sulfides, indicating the importance of OHads in the detection mechanism. Additionally, diffusion was denoted as a limiting step in the irreversible electrooxidation process that occurs in the proposed system.
Project description:This study reports a detailed analysis of an electrode material containing poly(phenolphthalein), carbon nanotubes and gold nanoparticles which shows superior catalytic effect towards to hydrazine oxidation in Britton-Robinson buffer (pH 10.0). Glassy carbon electrode was modified by electropolymerization of phenolphthalein (PP) monomer (poly(PP)/GCE) and the multiwalled carbon nanotubes (MWCNTs) was dropped on the surface. This modified surface was electrodeposited with gold nanoparticles (AuNPs/CNT/poly(PP)/GCE). The fabricated electrode was analysed the determination of hydrazine using cyclic voltammetry, linear sweep voltammetry and amperometry. The peak potential of hydrazine oxidation on bare GCE, poly(PP)/GCE, CNT/GCE, CNT/poly(PP)/GCE, and AuNPs/CNT/poly(PP)/GCE were observed at 596 mV, 342 mV, 320 mV, 313 mV, and 27 mV, respectively. A shift in the overpotential to more negative direction and an enhancement in the peak current indicated that the AuNPs/CNT/poly(PP)/GC electrode presented an efficient electrocatalytic activity toward oxidation of hydrazine. Modified electrodes were characterized with High-resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and electrochemical impedance spectroscopy (EIS). Amperometric current responses in the low hydrazine concentration range of 0.25-13 µM at the AuNPs/CNT/poly(PP)/GCE. The limit of detection (LOD) value was obtained to be 0.083 µM. A modified electrode was applied to naturel samples for hydrazine determination.
Project description:Since peroxide-based explosives (PBEs) lack reactive functional groups, they cannot be determined directly by most detection methods and are often detected indirectly by converting them to H2O2. However, H2O2 may originate from many sources, causing false positives in PBE detection. Here, we developed a novel electrochemical sensor for the direct sensitive and selective determination of PBEs such as triacetone triperoxide (TATP) and hexamethylene triperoxide diamine (HMTD) using electrochemical modification of the glassy carbon (GC) electrode with PBE-memory polycarbazole (PCz) films decorated with gold nanoparticles (AuNPs) by cyclic voltammetry (CV). The prepared electrodes were named TATP-memory-GC/PCz/AuNPs (used for TATP determination) and HMTD-memory-GC/PCz/AuNPs (used for HMTD detection). The calibration lines of TATP and HMTD were found in the concentration range of 0.1-1.0 mg L-1 using the net current intensities of differential pulse voltammetry (DPV) versus analyte concentrations. The limit of detection (LOD) commonly found was 15 μg L-1 for TATP and HMTD. The sensor electrodes could separately determine intact TATP and HMTD in the presence of nitro-aromatic, nitramine, and nitrate ester energetic materials. The proposed electrochemical sensing method was not interfered by electroactive substances such as paracetamol, caffeine, acetylsalicylic acid, aspartame, d-glucose, and detergent (containing perborate and percarbonate) used as camouflage materials for PBEs. This is the first molecularly imprinted polymeric electrode for PBEs accomplishing such low LODs, and the DPV method was statistically validated in contaminated clay soil samples against the GC-MS method for TATP and a spectrophotometric method for HMTD using t- and F-tests.
Project description:A new electrochemical sensor based on a Nafion, aminated reduced graphene oxide and chitosan functional membrane-modified glassy carbon electrode was proposed for the simultaneous detection of adenine and guanine. Fourier transform-infrared spectrometry (FTIR), transmission electron microscopy (TEM), and electrochemical methods were utilized for the additional characterization of the membrane materials. The prepared electrode was utilized for the detection of guanine (G) and adenine (A). The anodic peak currents to G and A were linear in the concentrations ranging from 0.1 to 120 μM and 0.2 to 110 μM, respectively. The detection limits were found to be 0.1 μM and 0.2 μM, respectively. Moreover, the modified electrode could also be used to determine G and A in calf thymus DNA.
Project description:In the present work, we have developed a facile one-step route for preparing electrochemically reduced graphene oxide-cationic pillar[6]arene (ErGO-CP6) nanocomposite films on glassy carbon electrodes (GCEs) directly from graphene oxide-cationic pillar[6]arene (GO-CP6) colloidal solution by using a pulsed electrodeposition technique. The electrocatalytic activity of ErGO-CP6 was examined by studying the oxidations of five purine bases [adenine (A), guanine (G), xanthine (X), hypoxanthine (HX), and uric acid (UA)]. It enhanced the oxidation currents of A, G, X, HX, and UA when compared to unmodified ErGO films and bare GCE, which is considered to be the synergetic effects of the graphene (excellent electrical properties and large surface area) and CP6 molecules (high inclusion complexation and enrichment capability).