Synthesis,characterization and the electrocatalytic application of prussian blue/titanate nanotubes nanocomposite

A novel kind of nanocomposite, titanate nanotubes (TNTs) decorated by electroactive Prussian blue (PB), was fabricated by a simple chemical method. The as-prepared nanocomposite was characterized by XRD, XPS, TEM, FT-IR and Cyclic voltammetry (CV). Experimental results revealed that PB was adsorbed on the surface of TNTs, and the adsorption capacity of TNTs was stronger than that of anatase-type TiO₂ powder (TNP). The PB-TNTs nanocomposite was modified onto a glassy carbon electrode and the electrode showed excellent electroactivity. The modified electrode also exhibited outstanding electrocatalytic activity towards the reduction of hydrogen peroxide and can serve as an amperometric sensor for H₂O₂ detection. The sensor fabricated by casting Nafion (NF) above the PB-TNTs composite film (NF/PB-TNTs/GCE) showed two linear ranges of 2 × 10^?5–5 × 10^?4 M and 2 × 10^?3–7 × 10^?3 M, with a detection limit of 1 × 10^?6 M. Furthermore, PB-TNTs modified electrode with Nafion (NF/PB-TNTs/GCE) showed wider linear range and better stability compared with PB-TNTs modified electrode without Nafion (PB-TNTs/GCE) and PB modified electrode with Nafion (NF/PB/GCE).     

Nonenzymatic Hydrogen Peroxide Electrochemical Sensor Based on Au‐HS/SO3H‐PMO (Et) Nanocomposite

A newly nonenzymatic sensor for hydrogen peroxide (H₂O₂) based on the (Au‐HS/SO₃H‐PMO (Et)) nanocomposite is demonstrated. The electrochemical properties of the as‐prepared nanocomposite were studied. It displayed an excellent performance towards H₂O₂ sensing in the linear response range from 0.20 µM to 4.30 mM (R=0.9999) with a sensitivity of 6.35×10² µA µM^?1 cm^?2 and a low detection limit of 0.0499 µM. Furthermore, it was not affected by electroactive interference species. These features proved that the modified electrode was suitable for determination of H₂O₂.     

Nickel hexacyanoferrate nanoparticles/nano silver coated multiwalled carbon nanotubes nanocomposite for the detection of hydrogen peroxide

A new nanocomposite was developed by combination of nickel hexacyanoferrate nanoparticles (NiNP) and nano silver coated multiwalled carbon nanotubes (nano Ag-MWNTs). The NiNP/nano Ag-MWNTs nanocomposite was charactered by scanning electron microscopy (SEM). The NiNP/nano Ag-MWNTs nanocomposite modified glassy carbon (GC) electrode was used to investigate the electrochemical reduction of hydrogen peroxide. The results showed that NiNP and nano Ag-MWNTs provided the synergistic effect toward this process. The obtained NiNP/nano Ag-MWNTs/GC electrode showed a wide linear response range of 1 × 10^?6 to 1 × 10^?4 and 5 × 10^?4 to 0.01 M hydrogen peroxide with correlation coefficients of 0.998 and 0.997, fast response time (2 s), and good selectivity toward the electrocatalytic reduction of hydrogen peroxide. The detection limit (S/N = 3) of hydrogen peroxide was 5 × 10^?7 M.     

Non-enzymatic hydrogen peroxide sensor based on a nanoporous gold electrode modified with platinum nanoparticles

A novel non-enzymatic electrochemical sensor based on a nanoporous gold electrode modified with platinum nanoparticles was constructed for the determination of hydrogen peroxide (H₂O₂). Platinum nanoparticles exhibit good electrocatalytic activity towards hydrogen peroxide. The nanoporous gold (NPG) increases the effective surface area and has the capacity to promote electron-transfer reactions. With electrodeposition of Pt nanoparticles (NPs) on the surface of the nanoporous gold, the modified Au electrode afforded a fast, sensitive and selective electrochemical method for the determination of H₂O₂. The linear range for the detection of H₂O₂ was from 1.0 × 10^?7 M to 2.0 × 10^?5 M while the calculated limit of detection was 7.2 × 10^?8 M on the basis of the 3σ/slope (σ represents the standard deviation of the blank samples). These findings could lead to the widespread use of electrochemical sensors to detect H₂O₂.     

Self-assembly of ultra-small gold nanoparticles on an indium tin oxide electrode for the enzyme-free detection of hydrogen peroxide

A novel enzyme-free electrochemical sensor for H₂O₂ was fabricated by modifying an indium tin oxide (ITO) support with (3-aminopropyl) trimethoxysilane to yield an interface for the assembly of colloidal gold. Gold nanoparticles (AuNPs) were then immobilized on the substrate via self-assembly. Atomic force microscopy showed the presence of a monolayer of well-dispersed AuNPs with an average size of ~4 nm. The electrochemical behavior of the resultant AuNP/ITO-modified electrode and its response to hydrogen peroxide were studied by cyclic voltammetry. This non-enzymatic and mediator-free electrode exhibits a linear response in the range from 3.0?×?10^?5 M to 1.0?×?10^?3 M (M?=?mol?·?L^?1) with a correlation coefficient of 0.999. The limit of detection is as low as 10 nM (for S/N?=?3). The sensor is stable, gives well reproducible results, and is deemed to represent a promising tool for electrochemical sensing.

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.     

Electrochemical DNA Biosensor Based on Graphene and TiO2 Nanorods Composite Film for the Detection of Transgenic Soybean Gene Sequence of MON89788

Based on graphene (GR), TiO₂ nanorods, and chitosan (CTS) nanocomposite modified carbon ionic liquid electrode (CILE) as substrate electrode, a new electrochemical DNA biosensor was effectively fabricated for the detection of the transgenic soybean sequence of MON89788. By using methylene blue (MB) as hybridization indicator for monitoring the hybridization with different ssDNA sequences, the differential pulse voltammetric response of MB on DNA modified electrodes were recorded and compared. Due to the synergistic effects of TiO₂ nanorods and GR on the electrode surface, the electrochemical responses of MB were greatly increased. Under optimal conditions the differential pulse voltammetric response of the target ssDNA sequence could be detected in the range from 1.0×10^?12 to 1.0×10^?6 mol/L with a detection limit of 7.21×10^?13 mol/L (3σ). This electrochemical DNA biosensor was further applied to the polymerase chain reaction (PCR) product of transgenic soybeans with satisfactory results.     

Trace Level Determination of Hydrogen Peroxide at a Carbon Ceramic Electrode Modified with Copper Oxide Nanostructures

An electrochemical sensor was developed for determination of hydrogen peroxide based on nanocopper oxides modified carbon sol‐gel or carbon ceramic electrode (CCE). The modified electrode was prepared by electrodeposition of metallic copper on the CCE surface and derivatized in situ to copper oxides nanostructures and characterized by scanning electron microscopy (SEM) and X‐ray diffraction (XRD) techniques. The modified electrode responded linearly to the hydrogen peroxide (H₂O₂) concentration over the range 0.78–193.98 µmol L^?1 with a detection limit of 71 nmol L^?1 (S/N=3) and the sensitivity of 0.697 A mol^?1 L cm^?2. This electrode was used as selective amperometric sensor for determination of H₂O₂ contents in hair coloring creams.     

Electrodeposition of TiO2 Nanoparticles on Multiwalled Carbon Nanotube Arrays for Hydrogen Peroxide Sensing

In this work, an amperometric H₂O₂ sensor based on TiO₂/MWCNTs electrode is reported. TiO₂ nanoparticles were synthesized on vertically aligned multiwalled carbon nanotube (MWCNT) arrays by electrodeposition. The morphology of the TiO₂/MWCNTs was characterized by scanning electron microscopy (SEM). The electrochemical performance of the TiO₂/MWCNTs electrode for detection of H₂O₂ was investigated by cyclic voltammetry (CV), differential pulse voltammetry (DPV) and chronoamperometry. The TiO₂/MWCNTs electrode displays high electrocatalytic activity towards oxidation of H₂O₂ in 0.1 M phosphate buffer solution (PBS, pH 7.4). At an applied potential of +0.40 V, the TiO₂/MWCNTs electrode exhibits a linear dependence (R=0.998) in the H₂O₂ concentration up to 15.0×10^?3 M with a sensitivity of 13.4 μA mM^?1 and detection limit of 4.0×10^?7 M with signal/noise=3. The optimal response time is less than 5 s with addition of 1 mM H₂O₂. The TiO₂/MWCNTs electrode presents stable, high sensitivity and also exhibits fast amperometric response to the detection of H₂O₂, which is promising for the development of H₂O₂ sensor.     

Sensitive and Selective Sensing of Hydrogen Peroxide with Iron‐Tetrasulfophthalocyanine‐Graphene‐Nafion Modified Screen‐Printed Electrode

We developed a novel iron‐tetrasulfophthalocyanine‐graphene‐Nafion (FeTSPc‐GR‐Nafion) modified screen‐printed electrode to determine hydrogen peroxide (H₂O₂) with high sensitivity and selectivity. The nanocomposite film (FeTSPc‐GR‐Nafion) exhibits an excellent electrocatalytic activity towards oxidation of H₂O₂ at a potential of +0.35 V in the absence of enzyme. A comparative study reveals that the FeTSPc‐GR complexes play a dual amplification role. Amperometric experiment indicates that the sensors possess good sensitivity and selectivity, with a linear range from 2.0×10^?7 M to 5.0×10^?3 M and a detection limit of 8.0×10^?8 M. This sensor has been successfully used to develop the glucose biosensor and has also been applied to determine H₂O₂ in sterile water.     

A carbon electrode sputtered with palladium and gold for the amperometric detection of hydrogen peroxide

A modified carbon electrode for the amperometric determination of hydrogen peroxide is described. By deposition of a 15-nm thick layer of a 40:60 mixture of palladium and gold on the surface of the electrode the overvoltages for both the oxidation and the reduction can be decreased by at least 800 mV. When applied as an electrochemical sensor in a flow-injection system, linear calibration graphs were obtained between 10^?7 and 5 × 10^?3 M hydrogen peroxide. The modified electrodes were stable for months.     

A Novel Hydrogen Peroxide Amperometric Sensor Based on Hierarchical 3D Porous MnO2−TiO2 Composites

A novel nanocomposite electrode based on hierarchical 3D porous MnO₂?TiO₂ for the application in hydrogen peroxide (H₂O₂) sensors has been explored. This electrode was fabricated by growing TiO₂ cross‐linked nanowires on a commercial fluorine tin oxide (FTO) glass via a hydrothermal process and subsequent deposition of 3D honeycomb‐like MnO₂ nanowalls using an electrodeposition method (denoted as 3D MNS‐TNW@FTO). The obtained 3D MNS‐TNW@FTO electrode was characterized by scanning electron microscopy (SEM), Raman spectroscopy, X‐ray diffraction (XRD), and X‐ray photoelectron spectroscopy (XPS). Based on such a unique 3D porous framework and the existence of MnO₂, the electrode demonstrates a good performance in the detection of H₂O₂, with two linear ranges from 9.8 to 125 μM and 125 μM–1.0 mM, a good selectivity of 8.02 μA mM^?1 cm^?2, and a low detection limit of 4.5 μM. In addition, the simplicity of the developed low‐cost fabrication process provides an efficient method for the mass production of electrocatalytical MnO₂?TiO₂ nanocomposites on commercial FTO glass for H₂O₂ sensing applications and can be adapted for other electrochemical sensors for various biochemical targets. It thus is beneficial for the practical usage in bioanalysis.     

Electrocatalytic Oxidation of Hydrogen Peroxide on Poly(m‐toluidine)‐Nickel Modified Carbon Paste Electrode in Alkaline Medium

The poly(m‐toluidine) film was prepared by using the repeated potential cycling technique in an acidic solution at the surface of carbon paste electrode. Then transition metal ions of Ni(II) were incorporated to the polymer by immersion of the modified electrode in a 0.2 M NiSO₄, also the electrochemical characterization of this modified electrode exhibits stable redox behavior of the Ni(III)/Ni(II) couple. The electrocatalytic ability of Ni(II)/poly(m‐toluidine)/modified carbon paste electrode (Ni/PMT/MCPE) was demonstrated by electrocatalytic oxidation of hydrogen peroxide with cyclic voltammetry and chronoamperometry methods in the alkaline solution. The effects of scan rate and hydrogen peroxide concentration on the anodic peak height of hydrogen peroxide oxidation were also investigated. The catalytic oxidation peak current showed two linear ranges with different slopes dependent on the hydrogen peroxide concentration and the lower detection limit was 6.5 μM (S/N=3). The catalytic reaction rate constant, (k_h), was calculated 5.5×10² M^?1 s^?1 by the data of chronoamperometry. This modified electrode has many advantages such as simple preparation procedure, good reproducibility and high catalytic activity toward the hydrogen peroxide oxidation. This method was also applied as a simple method for routine control and can be employed directly without any pretreatment or separation for analysis cosmetics products.     

A Non‐Enzymatic Glucose Sensor Based on Ni/MnO2 Nanocomposite Modified Glassy Carbon Electrode

A novel flower like 3D nickel/manganese dioxide (Ni/MnO₂) nanocomposite was synthesized by a kind of simple electrochemical method and the formation mechanism of flower like structure was also researched. In addition, morphology and composition of the nanocomposite were characterized by scanning electron microscope (SEM), transmission electron microscopy (TEM), and X‐ray photoelectron spectroscopy (XPS). Then the Ni/MnO₂ nanocomposites were applied to fabricate electrochemical non‐enzymatic glucose sensor. The electrochemical investigation for the sensor indicated that it possessed an excellent electrocatalytic property for glucose, and could applied to the quantification of glucose with a linear range from 2.5×10^?7 to 3.5×10^?3 M, a sensitivity of 1.04 mA mM^?1 cm^?2, and a detection limit of 1×10^?7 M (S/N=3). The proposed sensor also presented attractive features such as interference‐free, and long‐term stability. The present study provided a general platform for the one‐step synthesis of nanomaterials with novel structure and can be extended to other optical, electronic and magnetic nanocompounds.     

Self‐Assembled Prussian Blue Nanoparticles Based Electrochemical Sensor for High Sensitive Determination of H2O2 in Acidic Media

In this paper, self‐assembled Prussian blue nanoparticles (PBNPs) on carbon ceramic electrode (CCE) were developed as a high sensitive hydrogen peroxide (H₂O₂) electrochemical sensor. The PBNPs film was prepared by a simple dipping method. The morphology of the PBNPs‐modified CCE was characterized by scanning electron microscopy (SEM). The self‐assembled PB film exhibited sufficient mechanical, electrochemical stability and high sensitivity in compare with other PB based H₂O₂ sensors. The sensor showed a good linear response for H₂O₂ over the concentration range 1 μM–0.26 mM with a detection limit of ca. 0.7 μM (S/N=3), and sensitivity of 754.6 mA M^?1 cm^?2. This work demonstrates the feasibility of self‐assembled PBNPs‐modified CCE for practical sensing applications.     

Novel Hydrogen Peroxide Biosensor Based on Hemoglobin Combined with Electrospinning Composite Nanofibers

A facile strategy to construct an amperometric biosensor was described for the determination of hydrogen peroxide (H₂O₂). This biosensor relied on an electrospinning gold nanoparticle-chitosan-poly(vinyl alcohol) composite nanofibers modified ITO electrode, followed by immobilization of hemoglobin (Hb) on the surface. The introduction of nanofibers and gold nanoparticles in the modification of electrode surface not only enhanced the surface area of the modified electrode for enzyme immobilization but also facilitated the electron transfer rate. Under optimum conditions, the sensor was characterized in terms of its morphology by scanning electron microscopy and its electroactivity by cyclic voltammetry and chronoamperometry. Scanning electron microscopy revealed that the obtained nanofibers were uniform. The chronoamperometric behavior of the modified electrode indicated that the immobilized Hb retained electrochemical activity inside the electrospinning fibrous membranes. The electrode responded linearly to H₂O₂ in a wider concentration range of 5.6 × 10^?7 M to 5.2 × 10^?2 M with a low detection limit (S/N = 3) of 1.98 × 10^?7 M and a short response time of ～4 s, suggesting a much better performance than that of other sensors. Moreover, the biosensor achieved bulk production and exhibited superior properties for the sensitive determination of H₂O₂, studied namely, long-term stability, good reproducibility, and high selectivity.     

Self-assembling of Prussian blue nanocubic particles on nanoporous glassy carbon and its use in the electrocatalytic reduction of hydrogen peroxide

In this paper, self-assembled Prussian blue nanocubic particles on nanoporous glassy carbon was developed. The morphology of the PBNP-modified porous glassy carbon was characterized by scanning electron microscopy. The PBNP-GCE-red film-modified electrode was used for the sensitive detection of hydrogen peroxide. The electrochemical behavior of the resulting sensor was investigated using cyclic voltammetry and chronoamperometry. The value of α, k _cat, and D was calculated as 0.35, 1.7 × 10⁵ cm³ mol^?1 s^?1, and 2.6 × 10^?5 cm² s^?1, respectively. The calibration curve for hydrogen peroxide determination was linear over 0–600 μM with a detection limit (S/N = 3) of 0.51 μM.     

Titanium Dioxide/Multi-walled Carbon Nanotubes Composite Modified Pencil Graphite Sensor for Sensitive Voltammetric Determination of Propranolol in Real Samples

A very effective electrochemical sensor for the analysis of propranolol was constructed using TiO₂/MWCNT film deposited on the pencil graphite electrode as modifier. The modified electrode represented excellent electrochemical properties such as fast response, high sensitivity and low detection limit. The proposed sensor showed an excellent selective response to propranolol in the presence of foreign species and other drugs. The electrochemical features of the modified electrode were investigated by cyclic voltammetry and electrochemical impedance spectroscopy (EIS) technique which indicated a decrease in resistance of the modified electrode versus bare PGE and MWCNT/PGE. The surface morphology for the modified electrode was determined by scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDX) and Fourier transform infrared spectroscopy (FT-IR). Differential pulse technique (DPV) was used to determine propranolol which showed a good analytical response in the linear range of 8.5×10⁻⁸-6.5×10⁻⁶ M with a limit of detection 2.1×10⁻⁸ M. The TiO₂/MWCNT/PGE sensor was conveniently applied for the measurement of propranolol in biological and pharmaceutical media.     

Sensitive Electrochemical Determination of Hydrogen Peroxide Using Copper Nanoparticles in a Polyaniline Film on a Glassy Carbon Electrode

Rapid and accurate determination of hydrogen peroxide is necessary in biochemistry and environmental science. In this paper, a sensitive hydrogen peroxide electrochemical sensor was developed by cyclic voltammetry deposition of polyaniline–copper nanocomposite film on a glassy carbon electrode. The synthesized polyaniline/Cu composites were characterized by scanning electron microscopy and X-ray diffraction. With a typical working potential of 0.4?V (versus Ag/AgCl) and a pH value of 6.0, the prepared electrochemical sensor achieved linear range of 1.0–500?µM for hydrogen peroxide detection. A relative standard deviation of 4.9% for n?=?7 and 10.0?µM of H₂O₂ and a limit of detection of 0.33?µM at a signal-to-noise ratio?=?3 were observed. The sensor was successfully used for the analysis of tap water, and a spiked recovery of 93.0?±?2.1% was obtained, further confirming the sensor’s accuracy and feasibility.     

Sensitive Nonenzymatic Electrochemiluminescence Determination of Hydrogen Peroxide in Dental Products using a Polypyrrole/Polyluminol/Titanium Dioxide Nanocomposite

A layer-by-layer assembled of a polypyrrole and polyluminol was synthesized through the electrodeposition of pyrrole and luminol in acidic medium on a graphite electrode. The electrode was then modified by casting titanium dioxide (TiO₂) nanoparticles on its surface for enhancing electrochemiluminescence of luminol. The properties of this electrochemiluminescence sensor were studied by cyclic voltammetry, electrochemical impedance spectroscopy, field emission scanning electron microscopy, and energy dispersive X-ray spectroscopy. The results demonstrated that the modification of this electrochemiluminescence sensor shows sensitive response for the determination of hydrogen peroxide. Figures of merit include broad linearity from 1?pmol L^?1 to 4?µmol L^?1 (R²?=?0.996) with a limit of detection as low as 0.40?pmol L^?1 at a signal-to-noise ratio of three and good reproducibility with relative standard deviation of 4% for the determination of a 400?nmol L^?1 hydrogen peroxide solution (n?=?4), along with favorable long-term stability. The presence of glucose, citric acid, uric acid, dopamine, and ascorbic acid at concentrations as high as 100?nmol L^?1 of H₂O₂ did not produce any electrochemiluminescence signals, which demonstrates the selective nature of this modified electrode. The sensor was also used for the determination of H₂O₂ in mouthwash formulations and dental whitelight gels.