A Novel Hydrogen Peroxide Sensor Based on the Direct Electron Transfer of Catalase Immobilized on Nano‐Sized NiO/MWCNTs Composite Film

MWCNTs‐nanoNiO composite was used as a glassy carbon electrode modifier for construction of a novel catalase nanobiosensor for hydrogen peroxide. The immobilized catalase exhibited excellent electrocatalytic activity towards the reduction of H₂O₂. The resulting amperometric biosensor exhibited a linear response over a concentration range of 200 µM to 2.53 mM with a low detection limit of 19.0 µM. Electrochemical impedance measurements revealed that the modified electrode can be used for the sensitive detection of H₂O₂. The charge transfer resistance found to decrease significantly after enzymatic reaction of nanobiosensor with H₂O₂. The resulting impedance was highly sensitive to H₂O₂ over a linear range of 19–170 nM with a detection limit of 2.4 nM.     

Methylene Blue/Multiwall Carbon Nanotube Modified Electrode for the Amperometric Determination of Hydrogen Peroxide

A novel amperometric sensor based on the incorporation of multiwalled carbon nanotubes (MWCNT) into a poly(methylene blue) (PMB) film immobilized on carbon composite electrodes is described. Cyclic voltammetry indicated that at a surface covered by a MWCNT/PMB layer the cathodic reduction of hydrogen peroxide is facilitated and occurs already at 0.0 V versus SCE. The effect of the order of deposition of PMB and MWCNT, as well as its loading, on electrochemical behaviour was evaluated by cyclic voltammetry and electrochemical impedance spectroscopy. The influence of the various immobilised platforms on the electrocatalytic performance towards hydrogen peroxide was also examined.     

Fe2O3/CNT催化湿法H2O2氧化苯酚

通过化学沉积法和热处理得到多壁碳纳米管负载Fe2O3催化剂 Fe2O3/CNT, Fe2O3的负载质量分数约为15.1%,XRD表征显示,负载的Fe2O3存在α和γ这2种晶型。考察了Fe2O3/CNT催化湿式H2O2氧化去除废水中苯酚催化性能,通过苯酚的去除率及反应过程中催化剂活性组分的溶出总量,研究了催化剂制备过程中添加聚乙烯醇对催化剂性能的影响。在苯酚和H2O2初始浓度分别为350和1 500 mg/L、催化剂投加量为1.0 g/L、温度80 ℃条件下,经过240 min的反应,苯酚去除率达100％,COD去除率为86.1％。     

基于碳复合Fe3O4纳米粒子的过氧化氢电化学传感器研究

本文以碳纳米粒子复合Fe₃O₄磁性纳米粒子构建新型过氧化氢电化学传感器,该传感器对过氧化氢有良好的电催化性能,过氧化氢浓度在1.00×10^-6 ~ 1.00×10^-3 mol·L^-1范围内与其氧化峰电流之间呈良好线性关系(R = 0.9980),检出限为6.60×10^-7 mol·L^-1. 该传感器具有良好的抗干扰能力、较高的重现性和稳定性.     

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.     

基于硫堇/碳纳米管修饰电极的新型过氧化氢电化学传感器

基于碳纳米管(CNTs)和硫堇(Th)的协同效应,将辣根过氧化物酶(HRP)通过戊二醛(GA)交联作用固定在硫堇(Th)/CNTs修饰电极上,构造了一种新型酶电极(HRP/GA-Th/CNTs/GC)。CNTs静电吸附正电荷的Th,而Th不仅可以促进电极和酶的氧化还原活性中心之间的电子传递,而且能使CNTs氨基(—NH2)功能化,从而利于HRP的固定。基于HRP/GA-Th/CNTs/GC电极的过氧化氢传感器具有较好的传感性能,且检出限低(0.3μmol.L-1)、响应时间短(5 s内)、抗干扰能力强。     

Novel Nonenzymatic Hydrogen Peroxide Sensor Based on Ag/Cu2O Nanocomposites

The nanocomposites of Ag nanoparticles supported on Cu₂O were prepared and used for fabricating a novel nonenzymatic H₂O₂ sensor. The morphology and composition of the nanocomposites were characterized using the scanning electron microscope (SEM), transmission electron microscope (TEM), energy‐dispersive X‐ray spectrum (EDX) and X‐ray diffraction spectrum (XRD). The electrochemical investigations indicate that the sensor possesses an excellent performance toward H₂O₂. The linear range is estimated to be from 2.0 μM to 13.0 mM with a sensitivity of 88.9 μA mM^?1 cm^?2, a response time of 3 s and a low detection limit of 0.7 μM at a signal‐to‐noise ratio of 3. Additionally, the sensor exhibits good anti‐interference.     

基于聚酰胺-胺功能化碳纳米管负载钯纳米粒子的过氧化氢传感器

采用电化学法将钯纳米粒子(PdNPs)沉积在第四代聚酰胺-胺树状大分子(G4.0 PAMAM)功能化碳纳米管(MWCNTs)复合材料(G4.0-MWCNTs)修饰的玻碳电极表面,构建了一种新型过氧化氢(H2O2)传感器。采用场发射扫描电镜、循环伏安法和电化学阻抗谱对修饰电极进行表征,结果表明,大量高分散的PdNPs沉积在G4.0-MWCNTs修饰的电极上,修饰电极对H2 O2还原具有优异的电催化性能。在优化条件下,H2 O2浓度在1.0×10-9~1.0×10-3 mol/L范围内与电流响应呈线性关系,检出限为3×10-10 mol/L (S/N=3),测定血清实样加标回收率在96.7％~103.1％之间。     

Amperometric Biosensor for Hydrogen Peroxide Based on Myoglobin Doped Multiwalled Carbon Nanotube Enhanced Grafted Collagen Matrix

Abstract

A reagentless H₂O₂ sensor based on the direct electron transfer of myoglobin (Mb) doped in multiwalled carbon nanotubes enhanced grafted collagen matrix is proposed. The formal potential of the immobilized Mb was ?0.358 V with a surface coverage of 4.0×10^?10 mol cm^?2. The electrode process was surface‐controlled with an electron transfer rate constant of 9.7 s^?1. The proposed biosensor displayed an excellent electrocatalytic response to the reduction of H₂O₂ with a linear range from 0.6 to 39.0 µM. Owing to the good biocompatibility and high enzyme loading of the matrix the biosensor exhibited acceptable stability and reproducibility.     

A Non‐Enzymatic Hydrogen Peroxide Sensor Based on Gold Nanoparticles/Carbon Nanotube/Self‐Doped Polyaniline Hollow Spheres

In this study, a novel non‐enzymatic hydrogen peroxide (H₂O₂) sensor was fabricated based on gold nanoparticles/carbon nanotube/self‐doped polyaniline (AuNPs/CNTs/SPAN) hollow spheres modified glassy carbon electrode (GCE). SPAN was in‐site polymerized on the surface of SiO₂ template, then AuNPs and CNTs were decorated by electrostatic absorption via poly(diallyldimethylammonium chloride). After the SiO₂ cores were removed, hollow AuNPs/CNTs/SPAN spheres were obtained and characterized by transmission electron microscopy (TEM), field‐emission scanning electron microscopy (FESEM) and Fourier transform infrared spectroscopy (FTIR). The electrochemical catalytic performance of the hollow AuNPs/CNTs/SPAN/GCE for H₂O₂ detection was evaluated by cyclic voltammetry (CV) and chronoamperometry. Using chronoamperometric method at a constant potential of ?0.1 V (vs. SCE), the H₂O₂ sensor displays two linear ranges: one from 5 µM to 0.225 mM with a sensitivity of 499.82 µA mM^?1 cm^?2; another from 0.225 mM to 8.825 mM with a sensitivity of 152.29 µA mM^?1 cm^?2. The detection limit was estimated as 0.4 µM (signal‐to‐noise ratio of 3). The hollow AuNPs/CNTs/SPAN/GCE also demonstrated excellent stability and selectivity against interferences from other electroactive species. The sensor was further applied to determine H₂O₂ in disinfectant real samples.     

A Novel Hydrogen Peroxide Biosensor Based on Adsorption of Horseradish Peroxidase onto a Nanobiomaterial Composite Modified Glassy Carbon Electrode

In this work, a novel hydrogen peroxide biosensor derived from maize tassel (MT) and multiwalled carbon nanotube (MWCNT) composite was used to adsorb horseradish peroxidase (HRP) onto the surface of a glassy carbon electrode through electrostatic interactions. The morphology and structure of the products were characterized by SEM, FTIR and UV‐visible spectroscopy. The electrochemical and electrocatalytic performance of the HRP/MT‐MWCNT/GCE was studied using voltammetric and amperometric methods. The amperometric response of the biosensor varied linearly with concentration of H₂O₂ from 9 µM to 1 mM with detection limit of 4.0 µM (S/N=3). Furthermore, the biosensor exhibited good reproducibility and stability.     

A New Electrochemical Biosensor for Determination of Hydrogen Peroxide in Food Based on Well‐Dispersive Gold Nanoparticles on Graphene Oxide

Herein, we describe a new method for the detection of hydrogen peroxide (H₂O₂) in food by using an electrochemical biosensor. Initially, ultrafine gold nanoparticles dispersed on graphene oxide (AuNP‐GO) were synthesized by the redox reaction between AuCl₄^? and GO, and thionine‐catalase conjugates were then assembled onto the AuNP‐GO surface on a glassy carbon electrode. With the aid of the AuNP‐GO, the as‐prepared biosensor exhibited good electrocatalytic efficiency toward the reduction of H₂O₂ in pH 5.8 acetic acid buffer. Under optimal conditions, the dynamic responses of the biosensor toward H₂O₂ were achieved in the range from 0.1 µM to 2.3 mM, and the detection limit (LOD) was 0.01 µM at 3s_B. The Michaelis–Menten constant was measured to be 0.98 mM. In addition, the repeatability, reproducibility, selectivity and stability of the biosensor were investigated and evaluated in detail. Finally, the method was applied for sensing H₂O₂ in spiked or naturally contaminated samples including sterilized milk, apple juices, watermelon juice, coconut milk, and mango juice, receiving good correspondence with the results from the permanganate titration method. The disposable biosensor could offer a great potential for rapid, cost‐effective and on‐field analysis of H₂O₂ in foodstuff.     

Electrochemical Determination of Hydrogen Peroxide and Glucose by Titanium(IV) Oxide Nanotube Arrays

Titanium(IV) oxide nanotube arrays (TiO₂) prepared by electrochemical oxidation were used as a sensor for the catalytic reduction of hydrogen peroxide. The effects of pH, applied voltage, interferences, and linear dynamic range were characterized. The electrode showed rapid response and a linear dynamic range from 5.0 micromolar to 12.0 millimolar in phosphate buffer at pH 6.5 at a working voltage of ?0.8 volt. The maximum sensitivity was 474 milliamperes per molar per square centimeter with good reproducibility and reusability. The electrode was also employed for the electrochemical determination of glucose without a mediator by the immobilization of glucose oxidase on the electroactive surface. The resulting biosensor exhibited good activity and rapid response toward glucose and allowed the determination of glucose from 20 micromolar to 1 millimolar and 1–10 millimolar.     

Enhanced Electrocatalysis for the Reduction of Hydrogen Peroxide at New Multiwall Carbon Nanotube Grafted Polydiphenylamine Modified Electrode

A new modified electrode having multiwall carbon nanotube (MWNT) grafted with polydiphenylamine (PDPA) as electrocatalytic layer is fabricated. FESEM image of the modified electrode shows a different morphology indicating the grafting of PDPA over MWNT. This morphology is in quite contrast from the conventional bilayer MWNT/conducting polymer modified electrode. The multiwall carbon nanotube grafted polydiphenylamine (MWNT‐g‐PDPA‐ME) shows excellent electrocatalytic activity towards the reduction of hydrogen peroxide. The combined presence of MWNT and PDPA as a single unit provides better sensitivity than the bilayer configuration (MWNT/PDPA‐ME). This modified electrode shows accelerated electron transfer at the interface with minimized surface fouling and surface renewability. The advantages of MWNT‐g‐PDPA‐ME over the bilayer electrode are demonstrated with chronoamperometric studies. The amperometric response to H₂O₂ obtained at ?300 mV (vs. SCE) is rapid and highly sensitive as evident from the higher (2.83×10^?3 cm³ mol^?1 s^?1) rate constant for the diffusion reduction process.     

Co2SnO4/Carbon Nanotubes Composites: A Novel Approach for Electrochemical Sensing of Hydrogen Peroxide

For the first time Co₂SnO₄ (CTO)/Carbon nanotubes (CNT) composites were prepared and used to modify glassy carbon electrodes for the amperometric determination of hydrogen peroxide. The catalytic activity of composites towards the oxidation of hydrogen peroxide was dependent on the quantity of CNT present in the composite and to the pH of the medium. The pure cobalt stannate phase with a ratio of 3 : 1 (CTO:CNT) exhibited the best catalytic activity towards hydrogen peroxide oxidation at low potentials (0.200 and 0.500 V). A linear relationship between current and hydrogen peroxide concentration was obtained with a sensitivity of 95 and 258 μA mM⁻¹ and a detection limit of 0.130 and 0.08 μM respectively.     

Gold Nanoparticles Electrodeposited on Ordered Mesoporous Carbon as an Enhanced Material for Nonenzymatic Hydrogen Peroxide Sensor

A facile and controllable electrodeposition method was developed to directly attach gold nanoparticles (GNPs) on ordered mesoporous carbon (OMC). The GNPs on OMC substrate were characterized by scanning electron microscopy (SEM), X‐ray diffraction (XRD) and X‐ray photoelectron spectrometer (XPS), respectively. A nonenzymatic hydrogen peroxide (H₂O₂) sensor was fabricated on GNPs‐OMC/GCE. The sensor demonstrated a fast amperometric response (2.5 s), a wide linear range toward H₂O₂ concentrations between 2.0×10^?6 and 3.92×10^?3 M (R=0.999), and a low detection limit of 0.49 µM (S/N=3). Moreover, it exhibited good reproducibility and long‐term stability. The excellent electrocatalytical activity might be attributed to the synergistic effect of OMC and GNPs.     

基于Hemin/多壁碳纳米管纳米复合物构建的过氧化氢生物传感器的研究

利用卟啉(Hemin)具有模拟酶的功能,与多壁碳纳米管(MWCNTs)构建了一种新型的过氧化氢(H2O2)生物传感器。首先,利用Hemin与MWCNTs之间的π-π键作用,在超声分散下制备Hemin/MWCNTs纳米复合物;采用滴涂技术并在nafion的作用下将其固载在电极表面,制得该H2O2生物传感器(nafion/Hemin/MWCNTs/GCE)。采用紫外-可见分光光度法(UV-Vis)对合成的纳米复合物进行了分析;采用扫描电镜(SEM)对电极的表面形貌进行了表征;采用循环伏安法和计时电流法考察了该修饰电极的电化学行为;并对传感器的行为进行了详细的研究。在最优条件下,此修饰电极对H2O2具有明显的催化作用,电流与H2O2的浓度在6.0×10-7~1.8×10-3 mol/L范围内呈现良好的线性关系,检出限达2.0×10-7 mol/L。此传感器制作简单,具有较高的灵敏度和良好的稳定性及重现性。     

一种基于碳纳米管的安培型过氧化氢生物传感器

利用硫堇(th ion ine,Th i)作为介体结合多壁碳纳米管(MWNTs)、壳聚糖(ch itosan,CH IT)、辣根过氧化酶(HRP)的混合包埋物制作过氧化氢(H2O2)生物传感器。研究结果表明所得传感器对H2O2具有明显的增敏效应,线性范围为0.03~5.5 mmol/L,相关系数为0.9995;检出限为19μmol/L(S/N=3),具有良好的稳定性及工作寿命。     

Development of Nonenzymatic Hydrogen Peroxide Sensor Based on Successive Pd‐Ag Electrodeposited Nanoparticles on Glassy Carbon Electrode

A novel strategy to fabricate hydrogen peroxide (H₂O₂) sensor was developed by electrodepositing palladium? silver nanoparticles (NPs) on a glassy carbon electrode. The morphology of the modified electrode was characterized by Scanning electron microscopy (SEM). The result of electrochemical experiments showed that such constructed sensor had a favorable catalytic ability, high sensitivity, excellent selectivity towards reduction of hydrogen peroxide (H₂O₂). The response to H₂O₂ is linear in the range between 0.30 μM to 2.50 mM, and the detection limit is 0.1 μM (at an S/N of 3).     

Electrocatalytic Sensor for Hydrogen Peroxide Based on Immobilized Benzoquinone

An amperometric chemosensor for the detection of hydrogen peroxide is reported. The sensor is based on 1,4-benzoquinone immobilized on the gold electrode using self-assembled monolayer of short chain symmetrical dithiol as an anchor layer. Sensor analysis was performed by cyclic voltammetry at the potential range from −0.6 V till +0.9 V as well as in the anodic or cathodic potential ranges only. The results indicate oxidative electrochemical decomposition of hydrogen peroxide at the potential of ∼+0.4 V leading to the formation of oxygen while at cathodic potentials a reduction of the formed oxygen as well as of the hydrogen peroxide occur. A decrease in the oxidation potential of hydrogen peroxide on the gold electrode coated by self-assembled monolayer with 1,4-benzoquinone in comparison with that measured on the electrodes coated by the same self-assembled monolayer without 1,4-benzoquinone, indicates electrocatalytic effect of this moiety on oxidative decomposition of hydrogen peroxide. Analytical evaluation of the sensor performance was done in the voltammetric as well as in the chronoamperometric mode. The sensor exhibited linear response over the concentration range till 2.5 mM with a limit of detection ∼4 μM.