Preparation of carbon nanotubes supported platinum nanoparticles by an organic colloidal process for nonenzymatic glucose sensing

Multi-walled carbon nanotubes (MWNTs) supported platinum nanoparticles with narrow size distribution were prepared by an organic colloidal process with sodium citrate as the coordination reagent and stabilizer, and ethylene glycol as the reduction reagent. A nonenzymatic glucose sensor with high sensitivity based on the Pt/MWNTs electrode was demonstrated. Transmission electron microscopy (TEM) and X-ray diffraction (XRD) were employed to investigate the size distributions and the crystal structure of Pt nanoparticles on the MWNTs. The TEM images show that the Pt nanoparticles with about 2–4 nm in diameter are well dispersed on the MWNTs. The Pt/MWNTs shows high electrocatalytic activity towards the oxidation of glucose in 0.1 M NaOH solution. At +0.5 V, the Pt/MWNTs nanocomposite electrode exhibits linearity in the range of 1 mM to 23 mM (R > 0.998) glucose with a response time of 11.6 s. The detection limit is 50 μM (S/N = 3). It was demonstrated that the Pt/MWNTs electrode with high electrocatalytic activity to glucose oxidation could find application in nonenzymatic detection of glucose.     

Electrodeposition of Three‐Dimensional Porous Platinum Film on Removable Polyaniline Template for High‐Performance Electroanalysis

Three‐dimensional porous platinum (Pt_por) films are prepared based on Pt electrodeposition on polyaniline (PANI) modified electrodes followed by selective dissolution of PANI with HNO₃. Electrochemical quartz crystal microbalance data suggest that the PANI‐H₂PtCl₆ interaction involves redox and coordination reactions, depending on the working potential. The Pt_por shows better electrocatalytic performance than the Pt/PANI and conventionally electrodeposited Pt. The Pt_por modified glassy carbon electrode (GCE) can electrocatalyze the oxidation of H₂O₂ with a sensitivity of 414 µA cm^?2 mM^?1 and a detection limit of 9 nM, and the chitosan‐glucose oxidase/Pt_por/GCE can sense glucose with a sensitivity of 93.4 µA cm^?2 mM^?1.     

Electrocatalytic Oxidation of Glucose at Carbon Nanotubes Supported PtRu Nanoparticles and Its Detection

PtRu nanoparticles were supported on multiwall carbon nanotubes (MWNTs), which were further fabricated as an electrode for nonenzymatic glucose sensing. Transmission electron microscope and X‐ray diffraction patterns were used for characterization of the PtRu nanoparticles on MWNTs. Cyclic voltammetry and chronopotentiometry were applied to investigate the performance of the PtRu/MWNTs nanocomposite electrode for nonenzymatic oxidation of glucose. The PtRu/MWNTs electrode shows high electrocatalytic activity towards the oxidation of glucose in 0.1 M NaOH solution and thus can be used to selectively detect glucose. Under the optimal potential (+0.55 V vs. Ag/AgCl), the biosensor effectively performs a selective electrochemical analysis of glucose in the presence of common interferents, such as ascorbic acid (AA), dopamine (DP) and uric acid (UA). Wide linear calibration ranging from 1 mM to 15 mM, high sensitivity of 28.26 μA cm^?2 mM^?1, low detection limit of 2.5×10^?5 M, and fast response time of 10 s were achieved for the detection of glucose at the PtRu/MWNTs electrode.     

Electrochemical Determination of Uric Acid Using a Multiwalled Carbon Nanotube Platinum–Nickel Alloy Glassy Carbon Electrode

Platinum–nickel nanoparticles were synthesized by a reduction procedure. The Pt–Ni/C composite was characterized by X-ray diffraction, infrared spectroscopy, transmission electron microscopy, and electrochemical analysis. The measurements show that the Pt–Ni/multiwalled carbon nanotubes provided higher electrocatalytic activity for the oxidation of uric acid than Pt–Ni/carbon black. The sensor prepared from the characterized material provided a long linear dynamic range from 0.1 to 240.4?µM with a detection limit of 0.03?µM and a sensitivity of 41.21?µA?mM^?1?cm^?2. The reported modified electrode also provided excellent selectivity, good stability, and satisfactory reproducibility for the determination of uric acid.     

Direct electrochemistry of glucose oxidase immobilized on TiO2–graphene/nickel oxide nanocomposite film and its application

A novel electrochemical platform based on nickel oxide (NiO) nanoparticles and TiO₂–graphene (TiO₂–Gr) was developed for the direct electrochemistry of glucose oxidase (GOD). The electrochemical behavior of the sensor was studied using cyclic voltammetry and chronoamperometry. The experimental results demonstrated that the nanocomposite well retained the activity of GOD and the modified electrode GOD/NiO/TiO₂–Gr/GCE exhibited excellent electrocatalytic activity toward the redox of GOD as evidenced by the significant enhancement of redox peak currents in comparison with bare GCE. The biosensor responded linearly to glucose in the range of 1.0–12.0?mM, with a sensitivity of 4.129?μA?mM^?1 and a detection limit of 1.2?×?10^?6?M under optimized conditions. The response time of the biosensor was 3?s. In addition, the developed biosensor possessed good reproducibility and stability, and there was negligible interference from other electroactive components.     

CuNiO nanoparticles assembled on graphene as an effective platform for enzyme-free glucose sensing

We utilized CuNiO nanoparticles modified graphene sheets (CuNiO–graphene) to the application of enzymeless glucose sensing. The hydrothermal synthesized CuNiO nanoparticles were successfully assembled on graphene sheets. Distinct from general method, the high quality pristine graphene was produced by chemical vapor deposition (CVD) and bubbling transferred on the electrode. Incorporating the excellent electronic transport of graphene and high electrocatalytic activity of CuNiO nanoparticles, the CuNiO–graphene nanocomposite modified electrode possessed strong electrocatalytic ability toward glucose in alkaline media. The proposed nonenzymatic glucose sensor exhibited wide linear range up to 16 mM (two parts, from 0.05 to 6.9 mM and 6.9–16 mM) and high sensitivity (225.75 μA mM⁻¹ cm⁻² and 32.44 μA mM⁻¹ cm⁻², respectively). Excellent selectivity and acceptable stability were also achieved. Such an electrode would be attractive to sensor construction for its good properties, simple operation and low expense.     

Selective and sensitive electrochemical detection of glucose in neutral solution using platinum-lead alloy nanoparticle/carbon nanotube nanocomposites

Electrodeposition of Pt-Pb nanoparticles (PtPbNPs) to multi-walled carbon nanotubes (MWCNTs) resulted in a stable PtPbNP/MWCNT nanocomposite with high electrocatalytic activity to glucose oxidation in either neutral or alkaline medium. More importantly, the nanocomposite electrode with a slight modification exhibited high sensitivity, high selectivity, and low detection limit in amperometric glucose sensing at physiological neutral pH (poised at a negative potential). At +0.30 V in neutral solution, the nanocomposite electrode exhibited linearity up to 11 mM of glucose with a sensitivity of 17.8 μA cm⁻² mM⁻¹ and a detection limit of 1.8 μM (S/N = 3). Electroactive ascorbic acid (0.1 mM), uric acid (0.1 mM) and fructose (0.3 mM) invoked only 23%, 14% and 9%, respectively, of the current response obtained for 3 mM glucose. At −0.15 V in neutral solution, the electrode responded linearly to glucose up to 5 mM with a detection limit of 0.16 mM (S/N = 3) and detection sensitivity of ∼18 μA cm⁻² mM⁻¹. At this negative potential, ascorbic acid, uric acid, and fructose were not electroactive, therefore, not interfering with glucose sensing. Modification of the nanocomposite electrode with Nafion coating followed by electrodeposition of a second layer of PtPbNPs on the Nafion coated PtPbNP/MWCNT nanocomposite produced a glucose sensor (poised at −0.15 V) with a lower detection limit (7.0 μM at S/N = 3) and comparable sensitivity, selectivity and linearity compared to the PtPbNP/MWCNT nanocomposite. The Nafion coating lowered the detection limit by reducing the background noise, while the second layer of PtPbNPs restored the sensitivity to the level before Nafion coating.     

An Effective Non-Enzymatic Glucose Biosensor Based on Nanostructured CuxO/Cu Electrodes Synthesized in Situ by Copper Anodization

Potentiostatic anodization was developed to synthesize copper oxide/copper (Cu_xO/Cu, x=1,2) electrode with nano structure for sensitive non-enzymatic glucose detection. At a catalytic potential of 0.55 V, the CuO/Cu electrode presented a high sensitivity of 2954.38 μA mM⁻¹ cm⁻² to glucose and a linear range of 0.1 mM to 1.3 mM. The response time is less than 3 s with addition of 0.1 mM glucose. The CuO/Cu electrode above was anodized in 1M KOH solution at −100 mV and the morphology was compact nanoparticles and sparsely dispersed nanosheets, which enlarged the surface area and provided abundant electrocatalytic active sites. Compared the sensing property of electrodes with different morphologies, it indicated that nanostructure was significant to the efficient glucose catalytic oxidation process and it could be regulated by changing the potential and electrolyte concentration during anodization.     

Nonenzymatic Electrochemical Glucose Sensor Based on Pt Nanoparticles/Mesoporous Carbon Matrix

A nonenzymatic amperometric sensor for sensitive and selective detection of glucose has been constructed by using highly dispersed Pt nanoparticles supported onto mesoporous carbons (MCs). The Pt nanoparticles/mesoporous carbons (Pt/MCs) composites modified electrode displayed high electrocatalytic activity towards the oxidation of glucose. At an applied potential of 0.1 V, the Pt/MCs electrode has a linear dependence (R=0.996) in the glucose concentration up to 7.5 mM with a sensitivity of 8.52 mA M^?1 cm^?2. The Pt/MCs electrode has also shown highly resistant toward poisoning by chloride ions and without interference from the oxidation of common interfering species.     

Biosensor Based on Self‐Assembling Glucose Oxidase and Dendrimer‐Encapsulated Pt Nanoparticles on Carbon Nanotubes for Glucose Detection

A novel amperometric glucose biosensor based on layer‐by‐layer (LbL) electrostatic adsorption of glucose oxidase (GOx) and dendrimer‐encapsulated Pt nanoparticles (Pt‐DENs) on multiwalled carbon nanotubes (CNTs) was described. Anionic GOx was immobilized on the negatively charged CNTs surface by alternatively assembling a cationic Pt‐DENs layer and an anionic GOx layer. Transmission electron microscopy images and ζ‐potentials proved the formation of layer‐by‐layer nanostructures on carboxyl‐functionalized CNTs. LbL technique provided a favorable microenvironment to keep the bioactivity of GOx and prevent enzyme molecule leakage. The excellent electrocatalytic activity of CNTs and Pt‐DENs toward H₂O₂ and special three‐dimensional structure of the enzyme electrode resulted in good characteristics such as a low detection limit of 2.5 μM, a wide linear range of 5 μM–0.65 mM, a short response time (within 5 s), and high sensitivity (30.64 μA mM^?1 cm^?2) and stability (80% remains after 30 days).     

A highly sensitive nonenzymatic glucose sensor based on nickel oxide–carbon nanotube hybrid nanobelts

In this study, we demonstrated a highly sensitive electrochemical sensor for the determination of glucose in alkaline aqueous solution by using nickel oxide single-walled carbon nanotube hybrid nanobelts (NiO–SWCNTs) modified glassy carbon electrode (GCE). The hybrid nanobelts were prepared by the deposition of SWCNTs onto the Ni(SO₄)_0.3(OH)_1.4 nanobelt surface, followed by heat treatment at different temperatures ranging from 400 °C to 600 °C. The NiO–SWCNTs hybrid nanobelts modified electrode prepared at 500 °C displays enhanced electrocatalytic activity towards glucose oxidation, revealing a synergistic effect between the NiO and the deposited SWCNTs. The as-fabricated nonenzymatic glucose sensor exhibits excellent glucose sensitivity (2,980 μA cm^?2 mM^?1), lower detection limit (0.056 μM, signal/noise [S/N] ratio?=?3), and wider linear range (0.5–1,300 μM). Moreover, the sensor has been successfully used for the assay of glucose in serum samples with good recovery, ranging from 96.4 % to 102.4 %.     

Electropolymerized Diphenylamine on Functionalized Multiwalled Carbon Nanotube Composite Film and Its Application to Develop a Multifunctional Biosensor

Diphenylamine (DPA) monomers have been electropolymerized on the amino‐functionalized multiwalled carbon nanotube (AFCNT) composite film modified glassy carbon electrode (GCE) by cyclic voltammetry (CV). The surface morphology of PDPA‐AFCNT was studied using field‐emission scanning electron microscopy (FE‐SEM). The interfacial electron transfer phenomenon at the modified electrode was studied using electrochemical impedance spectroscopy (EIS). The PDPA‐AFCNT/GCE represented a multifunctional sensor and showed good electrocatalytic behavior towards the oxidation of catechol and the reduction of hydrogen peroxide. Rotating‐disk electrode technique was applied to detect catechol with a sensitivity of 1360 µA mM^?1 cm^?2 and a detection limit of 0.01 mM. Amperometric determination of hydrogen peroxide at the PDPA‐AFCNT film modified electrode results in a linear range from 10 to 800 µM, a sensitivity of 487.1 µA mM^?1 cm^?2 and detection limit of 1 µM. These results show that the nano‐composite film modified electrode can be utilized to develop a multifunctional sensor.     

A sensitive non-enzymatic glucose sensor in alkaline media based on Cu/MnO2-modified glassy carbon electrode

A novel and simple glucose sensor based on layer-by-layer (LBL) assembly of Cu and MnO₂ nanoparticles on the glassy carbon electrode (Cu/MnO₂/GCE) was constructed. The morphology and composition of the Cu and Cu/MnO₂ on the electrode surface were observed by scanning electron microscopy and X-ray diffraction. Electrochemical experiments showed that the proposed Cu/MnO₂/GCE exhibited excellent electrocatalytic properties to glucose. The oxidation peak currents of glucose on the Cu/MnO₂/GCE were linearly related to glucose concentration in a wider linearity range from 0.25???M to 1.02?mM with a correlation coefficient of 0.9977. The sensitivity and detection limit was 26.96???A?mM^?1 and 0.1???M (S/N?=?3), respectively. The Cu/MnO₂ nanocomposite-modified electrode presented attractive features such as high sensitivity, stability, reproducibility, and interference-free property. The applicability of the proposed method to the determination of glucose in serum samples was demonstrated with satisfactory results.     

Hydrothermal Synthesis of Titanium‐Supported Nickel Nanoflakes for Electrochemical Oxidation of Glucose

Titanium‐supported nanoscale flaky nickel electrode (nanoNi/Ti) was prepared by a hydrothermal process using hydrazine hydrate as a reduction agent. Its electrocatalytic activity as an electrocatalyst for the electrooxidation of glucose was evaluated in alkaline solutions using cyclic voltammetry (CV), chronoamperometric responses (CA) and electrochemical impedance spectra (EIS). The nanoNi/Ti electrode exhibits significantly high current density of glucose oxidation. A high catalytic rate constant of 1.67×10⁶ cm³ mol^?1 s^?1 was calculated from amperometric responses on the nanoNi/Ti electrode. Low charge transfer resistances on the nanoNi/Ti in 0.5 M NaOH containing various concentrations of glucose were obtained according to the analysis for EIS. Furthermore, amperometric data show a linear dependence of the current density for glucose oxidation upon glucose concentration in the range of 0.05–0.6 mM with a sensitivity of 7.32 mA cm^?2 mM^?1. A detection limit of 0.0012 mM (1.2 μM) M glucose was found. Results show that the prepared nanoNi/Ti electrode presents high electrocatalytic activity for glucose oxidation.     

Binder Free Modification of Glassy Carbon Electrode by Employing Reduced Graphene Oxide/ZnO Composite for Voltammetric Determination of Certain Nitroaromatics

Reduced Graphene oxide/ZnO nanoflowers ( rGO/ZnO‐NFs ) composite has been synthesized in‐situ using asymmetric Zn complex ( 1 ) as a single‐source molecular precursor (SSMP) with GO at 150 °C. The rGO/ZnO‐NFs composite was characterized by PXRD, UV‐vis, SEM, EDX mapping, TEM and SAED pattern to confirm its purity and morphology. The rGO/ZnO‐NFs composite shows uniform distribution of nanoflowers on graphene sheets. The modified glassy carbon electrode ( GCE ) was fabricated by drop wise layering of the rGO/ZnO‐NFs composite at the surface of the GCE without using binder. The binder free modified electrode ( GCE‐rGO/ZnO ) was explored for detection of nitroaromatics such as p‐nitro‐phenol ( p ‐NP ), 2,4‐dinitrophenol ( 2,4‐DNP ), 2,4‐dinitrotoluene ( 2,4‐DNT ) and 2,4,6‐trinitrophenol ( 2,4,6‐TNP ). The fabricated sensor showed remarkable response for the both toxicants and explosives. The LOD, sensitivity and linear range for the studied toxicants and explosives were found to be in a good range: p ‐NP= 0.93 μM, 240 μA mM⁻¹ cm⁻² and 0.2–0.9 mM; 2,4‐DNP= 6.2 μM, 203 μA mM⁻¹ cm⁻² and 0.1–0.9 mM; 2,4‐DNT= 10 μM, 371 μA mM⁻¹ cm⁻² and 0.2–0.9 mM; 2,4,6‐TNP= 16 μM, 514 μA mM⁻¹ cm⁻² and 0.2–0.9 mM, respectively.     

Carbon Nanotubes‐Ionic Liquid and Chloropromazine Modified Electrode for Determination of NADH and Fabrication of Ethanol Biosensor

Potential cycling was used for oxidation of chloropromazine and producing an electroactive redox couples which strongly adsorbed on the electrode surface modified with carbon nanotubes and ionic liquid nanocomposite. The modified electrode shows excellent electrocatalytic activity toward NADH oxidation. The differential pulse voltammetry detection provided high sensitivity, 0.5835 A M^?1, low detection limit, 80 nM at concentration range up to 20 μM. An ethanol biosensor was also developed by immobilizing alcohol dehydrogenase enzyme onto nanocomposite. Differential pulse voltammetric detection of ethanol gives linear responses over the concentration range 40 μM–1.5 mM with detection limit 5 μM and sensitivity 1.97 μA mM^?1.     

Binder-less and free-standing Co–Fe metal nanoparticles-decorated PVdF-HFP nanofiber membrane as an electrochemical probe for enzyme-less glucose sensors

Co–Fe bimetallic nanoparticles-affixed polyvinylidene fluoride-co-hexafluoropropylene (PVdF-HFP) nanofiber membrane is fabricated using the electrospinning and chemical reduction techniques. The semicrystalline polymeric backbone decorated with the highly crystalline Co–Fe bimetallic nanoparticles enunciates the mechanical integrity, while the incessant and swift electron mobility is articulated with the consistent dissemination of bimetallic nanoparticles on the intersected and multi-layered polymeric nanofibers. The diffusion and adsorption of glucose are expedited in the extended cavities and porosities of as-formulated polymeric nanofibers, maximizing the glucose utilization efficacy, while the uniformly implanted Co⁴⁺/Fe³⁺ active centers on PVdF-HFP nanofibers maximize the electrocatalytic activity toward glucose oxidation under alkaline regimes. Thus, the combinative sorts including nanofiber and nanocomposite strategies of PVdF-HFP/Co–Fe membrane assimilate the enzyme-less electrochemical glucose detection concerts of high sensitivity (375.01 μA mM^?1 cm^?2), low limit of detection (0.65 μm), and wide linear range (0.001 to 8 mM), outfitting the erstwhile enzyme-less glucose detection reports. Additionally, the endowments of high selectivity and real sample glucose-sensing analyses of PVdF-HFP/Co–Fe along with the binder-less and free-standing characteristics construct the state-of-the-art paradigm for the evolution of affordable enzyme-less electrochemical glucose sensors.

     

Pt Nanoparticle‐modified Carbon Fiber Microelectrode for Selective Electrochemical Sensing of Hydrogen Peroxide

We report a simple approach to the production of carbon fiber‐based amperometric microbiosensors for selective detection of hydrogen peroxide (H₂O₂), which was achieved by electrometallization of carbon fiber microelectrodes (CFMs) by electrodeposition of Pt nanoparticles. The Pt‐carbon hybrid sensing interface provided a sensitivity of 7711±587 μA ? mM^?1 ? cm^?2, a detection limit of 0.53±0.16 μM (S/N=3), a linear range of 0.8 μM–8.6 mM, and a response time of <2 sec. The morphologies of the Pt nanoparticle‐modified CFMs were characterized by scanning electron microscopy. To achieve selectivity, permseletive layers, polyphenylenediamine (PPD) and Nafion, were deposited resulting in exclusion of the anionic and cationic interferents, ascorbic acid and dopamine, respectively, at their physiologically relevant concentrations. The resultant sensors displayed a sensitivity to hydrogen peroxide of 1381±72 μA ? mM^?1 ? cm^?2, and a detection limit of 0.86±0.19 μM (S/N=3). This simple and rapid metallization method converts carbon fiber microelectrodes, which are readily accessible, to microscale Pt electrodes in 2 min, providing a platform for oxidase‐based amperometric biosensors with improved spatial resolution over more commonly used platinum electrode array microprobes.     

Nanocomposite based on depositing platinum nanostructure onto carbon nanotubes through a one-pot, facile synthesis method for amperometric sensing

Platinum nanoparticles (Pt NPs) were deposited onto multi-walled carbon nanotubes (MWNTs) through direct chemical reduction without any other stabilizing agents. Transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry were employed to characterize the morphology of the as-prepared nanocomposite (noted as Pt NPs-MWNTs) and further identify the Pt NPs on the surface of MWNTs. The nanocomposite demonstrated the ability to electrocatalyze the oxidation of hydrogen peroxide and substantially raises the response current. A sensitivity of 591.33 μA mM⁻¹ cm⁻² was obtained at Pt NPs-MWNTs modified electrode. Thus, we immobilized glucose oxidase (GOD) as a model enzyme on the nanocomposite-based electrode with a thin layer of Nafion to fabricate a glucose biosensor, which showed sensitive and fast response to glucose. The influence of the GOD loading was investigated and the biosensor with an enzyme loading concentration of 10 mg/mL shows optimal performance for glucose detection, that is, a detection limit of 3 μM and a response time of 3 s, respectively.     

Amperometric nonenzymatic glucose sensor based on a glassy carbon electrode modified with a nanocomposite made from nickel(II) hydroxide nanoplates and carbon nanofibers

We report on a highly sensitive and selective nonenzymatic glucose sensor based on a glassy carbon electrode modified with a composite prepared from nickel(II) hydroxide nanoplates and carbon nanofibers. The nanocomposite was characterized by scanning electron microscopy and powder X-ray diffraction. Electrodes modified with pure Ni(OH)₂ and with the nanocomposite were characterized by electrochemical impedance spectroscopy. Cyclic voltammetric and amperometric methods were used to investigate the catalytic properties of the modified electrodes for glucose electrooxidation in strongly alkaline solution. The sensor exhibits a wide linear range (from 0.001 to 1.2 mM), a low detection limit (0.76 μM), fast response time (< 5 s), high sensitivity (1038.6 μA?·?mM^?1?·?cm^?2), good reproducibility, and long operational stability. Application of the nonenzymatic sensor for monitoring glucose in real samples was also demonstrated.