Electrochemical Detection of Three Monohydroxylated Polycyclic Aromatic Hydrocarbons Using Electroreduced Graphene Oxide Modified Screen‐printed Electrode

An electrochemical sensor for detection of three monohydroxylated polycyclic aromatic hydrocarbons (OH?PAHs) was fabricated by electrochemical reduction of graphene oxide (E‐rGO) on screen‐printed electrode (SPE). The E‐rGO film presents typical wrinkled structure with porous and cavity‐like nanostructure, providing large surface area, effective π‐electron system and high electrical conductivity. The developed E‐rGO/SPE sensor exhibits outstanding sensing performance for the target OH?PAHs, 2‐hydroxynaphthalene, 3‐hydroxyphenanthrene, and 1‐hydroxypyrene, within a linear range varying from 50–800 nM, 50–1150 nM, and 100–1000 nM, and with a limit of detection (LOD) of 10.1 nM, 15.3 nM, and 20.4 nM (S/N=3), respectively. The electrochemical sensor possesses excellent stability, acceptable reproducibility, and good anti‐interference ability. Additionally, the proposed sensor can be applied to the analysis of OH?PAHs in the urine samples with recoveries of 98.1–105.9 %.     

Prussian Blue/Reduced Graphene Oxide Composite for the Amperometric Determination of Dopamine and Hydrogen Peroxide

Prussian blue has significant application for the construction of electrochemical biosensors. In this work, Prussian blue-reduced graphene oxide modified glass carbon electrodes were successfully fabricated using electrochemical deposition. The high surface area of graphene oxide enhanced the deposition of Prussian blue and the resulting electrocatalytic activity. Infrared spectroscopy and scanning electron microscopy showed that the relatively porous Prussian blue was on the surface of reduced graphene oxide. Cyclic voltammetry showed that Prussian blue-coated reduced graphene oxide composite films improved electron transfer compared to Prussian blue films. The Prussian blue-reduced graphene oxide composite film provided higher response for the reduction of hydrogen peroxide and the oxidation of dopamine compared with the Prussian blue film due to synergistic effects between the reduced graphene oxide and Prussian blue particles. The sensitivity of the electrode was 0.1617 µA µM^?1 cm^?2. The linear dynamic range extended from 0.5 µM to 0.7 mM dopamine with a limit of detection equal to 125 nM. This work provided a versatile strategy for the design and construction of sensitive amperometric sensors with robust electrocatalytic behavior.     

Free‐standing Graphene/Poly(methylene blue)/AgNPs Composite Paper for Electrochemical Sensing of NADH

Highly flexible graphene/poly(methylene blue)/AgNPs composite paper was successfully prepared for amperometric biosensing of NADH. For this purpose, a dispersion including graphene oxide (GO), methylene blue (MB) and silver nanoparticles (AgNPs) was prepared and GO/MB/AgNPs paper was acquired by vacuum‐filtration of this dispersion through a suitable membrane. After peeling it off from membrane, it was transformed to rGO/MB/AgNPs paper by performing reduction with hydriodic acid. In a three‐electrode cell, which is containing 0.1 M phosphate buffer solution (pH: 9.0), rGO/MB/AgNPs paper was used as working electrode and rGO/poly(MB)/AgNPs composite paper was generated by surface‐confined electropolymerization of MB using successive cyclic voltammetry approach in a suitable potential window. Characterization of this composite paper was carried out by using scanning electron microscopy, scanning tunneling microscopy, X‐ray photoelectron spectroscopy, powder X‐ray diffraction spectroscopy, Raman spectroscopy, four‐point probe conductivity measurement and cyclic voltammetry techniques. Flexible rGO/poly(MB)/AgNPs composite paper has demonstrated high sensitivity, wide linear range and low detection limit for amperometric quantification of NADH.     

Prussian Blue Nanoparticles Self Assembling on Electrochemically Reduced Graphene Oxide Modified GC Electrode for Sensitive Hydrogen Peroxide Detection

A facile, fast, and convenient route was suggested for the fabrication of Prussian blue nano particles (PBNPs) assembled on reduced graphene oxide (RGO) modified glassy carbon electrode (PBNPs|RGO|GCE). RGO was electrodeposited on the surface of GCE and the prepared RGO|GCE was immersed into a ferric‐hexacyanoferrate(III) solution and PBNPs were assembled on the RGO|GCE for a certain period of time. The PBNPs film thickness can be easily controlled by adjusting the assembling duration. The developed PBNPs|RGO|GCE was successfully used for determining hydrogen peroxide, with a linear response over the concentration range 0.5‐400 μM, a good accuracy and precision, detection limit 0.44 μM, and sensitivity 1168 mA M^?1 cm^?2.     

One-pot green synthesis of Prussian blue nanocubes decorated reduced graphene oxide using mushroom extract for efficient 4-nitrophenol reduction

One-pot green approach to the synthesis of Prussian blue nanocubes/reduced graphene oxide (PBNCs/RGO) nanocomposite had been attempted. It was based on the extract of mushroom with K₃[Fe(CN)₆] and graphene oxide (GO) as precursors, where the reduction of GO and the deposition of PBNCs occurred simultaneously. The obtained nanocomposite was characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray diffraction (XRD), Raman spectroscopy and electrochemical techniques. With the introduction of β-cyclodextrin (β-CD), the β-CD/PBNCs/RGO system showed linear behavior in the range from 0.01 to 700 μM for 4-nitrophenol with a low detection limit of 2.34 nM (S/N = 3).     

Prussian Blue Modified Submicron Structured Gold Electrodes for Amperometric Hydrogen Peroxide Sensing

In this work, we present a simple and effective approach for fabricating sub‐micron structured gold (SM−Au) electrodes by chemically etching the magnetron co‐sputtered gold film in KI solution for certain time. Such electrodes with a large surface area to volume ratio were used as the matrix for electrochemical deposition of Prussian blue (PB) to develop an electrochemical hydrogen peroxide sensor. Experimental characterization using scanning electron microscope and atomic force microscope shows that the thickness of PB layer on SM−Au electrode is around 140 nm, and is composited with cubic PB nanocrystals. The electrochemical performance of the designed sensor, studied using cyclic voltammograms and chronoamperometry methods, suggests that the sensor based on SM−Au/PB electrode presents the direct electron transfer of PB particle towards SM−Au film, and exhibits fast response, wide linearity, low detection limit and high stability. Under the optimized conditions, the sensitivity of the developed sensor for the detection of H₂O₂ reaches the value of 512 mA cm⁻² M⁻¹ with a linear range from 1 μM to 4.5 mM.     

Electroactive Prussian Blue Encapsulated Iron Oxide Nanostructures for Mediator‐Free Cholesterol Estimation

Iron oxide nanoparticles of size ～10 nm have been encapsulated into four nanometer thick shells of Prussian blue and were then electrophoretically deposited onto an indium tin oxide substrate. The immobilization of cholesterol oxidase has been done onto the nanostructured film to investigate the kinetic parameters and biosensing characteristics. The fabricated bioelectrode exhibits an electron transfer coefficient and a charge transfer rate constant of 0.45 and 45.15 s^?1, respectively. Direct electron transfer properties of the nanostructured film result in 3^rd generation cholesterol biosensor. The bioelectrode exhibits high sensitivity (2.15 mAM^?1 cm^?2), a low K_m^app value (0.07 mM), good stability and high selectivity towards cholesterol.     

A New Amperometric Hydrazine Sensor Based on Prussian Blue/Single‐walled Carbon Nanotube Nanocomposites

A slow reaction process has been successfully used to synthesize Prussian blue/single‐walled carbon nanotubes (PB/SWNTs) nanocomposites. Electrochemical and surface characterization by cyclic voltammetry (CV), scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV‐vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD) confirmed the presence of PB nanocrystallites on SWNTs. PB/SWNTs modified glassy carbon electrode (GCE) exhibits efficient electron transfer ability and high electrochemical response towards hydrazine. The fabricated hydrazine sensor showed a wide linear range of 2.0×10^?6–6.0×10^?3 M with a response time less than 4 s and a detection limit of 0.5 μM. PB/SWNTs modified electrochemical sensors are promising candidates for cost‐effective in the hydrazine assays.     

Self‐Assembling of Hybrid Prussian Blue Units in Cinder Matrix: Characterization and Electrocatalysis

Industrial waste cinder (CFe*) has been utilized as a stable anchoring matrix for self‐assembling of Fe(CN)₆^3? as hybrid Prussian blue units (PB, *Fe³⁺Fe^II(CN)₆) on a screen‐printed carbon electrode (SPE) for efficient catalytic applications. The waste cinder was found to be a composite of calcium and iron silicates similar to glass matrix by X‐ray photoelectron spectroscopic (XPS) study. The hybrid PB formations were confirmed by both FT‐IR and electrochemical methods. Most importantly, the free iron (Fe*) ion bound to the non‐bridging oxygen terminals of the silicates was found to play a key role in the PB formation. The self‐assembled PB hybrid on the cinder‐modified screen‐printed electrodes (designated as PBCFe*‐SPE) improved linear detection range and sensitivity for H₂O₂ mediated oxidation than those obtained at a classical PB‐SPE in 0.1 M, pH 2 KCl/HCl base electrolyte at 0.0 V (vs. Ag/AgCl) by amperometric batch analysis.     

普鲁士蓝膜修饰电极的电化学阻抗谱

测量了应用电化学方法制备的不同厚度的普鲁士蓝膜修饰电极的循环伏安行为与电化学阻抗谱.由所得到的循环伏安图讨论了普鲁士蓝修饰膜的氧化还原过程,并对相关的Nyquist图进行了解析,提出了相应的等效电路.在此基础上计算出较薄膜中普鲁士蓝/普鲁士白电化学反应的表观速率常数和表观扩散系数,讨论了膜厚度对电荷扩散的影响.当膜相对较薄时,电极过程主要由动力学过程控制;当膜达到一定厚度时,电荷在膜中的扩散速率受到限制,电极过程由动力学过程和电荷扩散过程共同控制,证实了文献报导的普鲁士蓝膜修饰电极为多层空间分布电荷传递模型.     

Au‐TiO2/Graphene Nanocomposite Film for Electrochemical Sensing of Hydrogen Peroxide and NADH

We describe a simple method for preparing Au‐TiO₂/graphene (GR) nanocomposite by deposition of Au nanoparticles (NPs) on TiO₂/GR substrates. The as‐prepared Au‐TiO₂/GR was characterized by X‐ray diffraction (XRD) and transmission electron microscopy (TEM). The presence of Au NPs on TiO₂/GR surface remarkably improves the electrocatalytic activity towards the oxidation of hydrogen peroxide (H₂O₂) and β‐nicotinamide adenine dinucleotide (NADH). The Au‐TiO₂/GR modified glassy carbon (GC) electrode exhibits good amperometric response to H₂O₂ and NADH, with linear range from 10 to 200 µM and 10 to 240 µM, and detection limit of 0.7 and 0.2 µM, respectively.     

Functionalization of Single‐Walled Carbon Nanotubes with Cubic Prussian Blue and Its Application for Amperometric Sensing

In this work, we synthesized electroactive cubic Prussian blue (PB) modified single‐walled carbon nanotubes (SWNTs) nanocomposites using the mixture solution of ferric‐(III) chloride and potassium ferricyanide under ambient conditions. The successful fabrication of the PB‐SWNTs nanocomposites was confirmed by scanning electron microscopy (SEM), transmission electron microscopy (TEM), UV‐vis absorption spectroscopy, Fourier transform infrared (FTIR) spectroscopy, and cyclic voltammetry (CV). PB nanocrystallites are observed to be finely attached on the SWNTs sidewalls in which the SWNTs not only act as a carrier of PB nanocrystallites but also as Fe(III)‐reducer. The electrochemical properties of PB‐SWNTs nanocomposites were also investigated. Using the electrodeposition technique, a thin film of PB‐SWNTs/chitosan nanocomposites was prepared onto glassy carbon electrode (GCE) for the construction of a H₂O₂ sensor. PB‐SWNTs/chitosan nanocomposites film shows enhanced electrocatalytic activity towards the reduction of H₂O₂ and the amperometric responses show a linear dependence on the concentration of H₂O₂ in a range of 0.5–27.5 mM and a low detection limit of 10 nM at the signal‐to‐noise ratio of 3. The time required to reach the 95% steady state response was less than 2 s. CV studies demonstrate that the modified electrode has outstanding stability. In addition, a glucose biosensor is further developed through the simple one‐step electrodeposition method. The observed wide concentration range, high stability and high reproducibility of the PB‐SWNTs/chitosan nanocomposites film make them promising for the reliable and durable detection of H₂O₂ and glucose.     

Prussian Blue‐Modified Titanate Nanotubes: A Novel Nanostructured Catalyst for Electrochemical Reduction of Hydrogen Peroxide

Prussian blue (PB) modified titanate nanotubes (PB‐TiNT) have been synthesized by the reaction of Fe²⁺‐modified TiNT with hexacyanoferrate(III) ions. The rate constant for heterogeneous catalytic reaction between PB‐TiNT and H₂O₂ was found to be k=2×10⁴ dm³ mol^?1 s^?1, which is an order of magnitude higher than the values of k reported for conventionally prepared, electrochemically deposited PB films. On the PB‐TiNT modified electrode with subnanomolar surface concentration of PB (Γ(PB)=2.8×10^?11 mol/cm²), a stable, reproducible and linear response towards H₂O₂ was obtained in the concentration range 0.02–4 mM, with the sensitivity of 0.10 AM^?1 cm^?2 at ?150 mV.     

Bimetallic CuCo Derived from Prussian Blue Analogue for Nonenzymatic Glucose Sensing

Bimetallic CuCo composites are prepared by calcinating copper hexacyanocobaltate precursor in N₂ atmosphere. The CuCo modified electrodes are fabricated for nonenzymatic glucose sensing in the alkaline electrolyte. The glucose can be directly electro-oxidized on the surface of the electrode catalyst mediated by the redox couples of Cu and Co. The optimal glucose sensor exhibits a high sensitivity (567 μA ⋅ mM⁻¹ ⋅ cm⁻²) in the range up to 825 μM with a detection limit of 3 μM and acceptable selectivity. The sensor can also be applied in serum samples. This work provides a facile and easily-scalable synthesis method of electrocatalysts for nonenzymatic glucose sensors.     

Fabrication of Non‐enzymatic Electrochemical Glucose Sensor Based on Pd−Mn Alloy Nanoparticles Supported on Reduced Graphene Oxide

Mixed metals alloy nanoparticles supported on carbon nanomaterial are the most attractive candidates for the fabrication of non‐enzymatic electrochemical sensor with enhanced electrochemical performance. In this study, palladium‐manganese alloy nanoparticles supported on reduced graphene oxide (Pd?Mn/rGO) are prepared by a simple reduction protocol. Further, a novel enzyme‐free glucose sensing platform is established based on Pd?Mn/rGO. The successful fabrication of Pd?Mn alloy nanoparticles and their attachment at rGO are thoroughly characterized by various microscopic and spectroscopic techniques such as XRD, Raman, TEM and XPS. The electrochemical activity and sensing features of designed material towards glucose detection are explored by amperometric measurments in 0.1 M NaOH at the working voltage of ?0.1 V. Thanks to the newly designed Pd?Mn/rGO nanohybrid for their superior electrorochemical activity towards glucose comprising the admirable sensing features in terms of targeted selectivity, senstivity, two linear parts and good stability. The enhanced electrochemical efficacy of Pd?Mn/rGO electrocatalyst may be credited to the abundant elecrocatalytic active sites formed during the Pd?Mn alloying and the electron transport ability of rGO that augment the electron shuttling phenomenon between the electrode material and targeted analyte.     

Use of Screen‐printed Electrodes Modified by Prussian Blue and Analogues in Sensing of Cysteine

The utilisation of screen‐printing technology allows for a mass scalable approach for the production of electrochemical screen‐printed electrodes (SPEs) and the presence of a redox mediator can add new possibilities to the electrochemical properties of the SPEs. Among the materials used as redox mediators, cyanidoferrates polymers can be used for electro‐oxidation of cysteine. In this work, two monomers, namely, [Fe(CN)₆]⁴⁻ and [Fe(CN)₅NH₃]³⁻ were used to produce Prussian blue (PB) and Prussian blue‐Ammine (PB‐Ammine), respectively. In addition, two modification methods were compared, firstly via a drop‐casting and secondly by the incorporation of these materials into a printable ink. The SPE modified by PB‐Ammine (drop‐casting) exhibits the highest electroactive area, however the highest heterogeneous rate constant was found with the SPE modified by PB‐Ammine that was incorporated into the ink. The highest value of the constant of electro‐oxidation of cysteine and lowest limit of detection was also observed in the SPE modified by PB incorporated into the ink. These studies suggest that the electrocatalytic properties of SPE modified by PB and PB‐Ammine are dependent upon the availability of Fe³⁺ catalytic sites and the increased kinetics of the chemical reaction between the catalytic sites and the analyte.     

Enhanced Electrochemical Water Oxidation Activity by Structural Engineered Prussian Blue Analogue/rGO Heterostructure

Prussian blue analogue (PBA), with a three-dimensional open skeleton and abundant unsaturated surface coordination atoms, attracts extensive research interest in electrochemical energy-related fields due to facile preparation, low cost, and adjustable components. However, it remains a challenge to directly employ PBA as an electrocatalyst for water splitting owing to their poor charge transport ability and electrochemical stability. Herein, the PBA/rGO heterostructure is constructed based on structural engineering. Graphene not only improves the charge transfer efficiency of the compound material but also provides confined growth sites for PBA. Furthermore, the charge transfer interaction between the heterostructure interfaces facilitates the electrocatalytic oxygen evolution reaction of the composite, which is confirmed by the results of the electrochemical measurements. The overpotential of the PBA/rGO material is only 331.5 mV at a current density of 30 mA cm⁻² in 1.0 M KOH electrolyte with a small Tafel slope of 57.9 mV dec⁻¹, and the compound material exhibits high durability lasting for 40 h.     

An Amperometric Hydrogen Peroxide Biosensor Based on a Hemoglobin‐Immobilized Dopamine‐Oxidation Polymer/Prussian Blue/Au Electrode

A novel method to immobilize hemoglobin (Hb) in a polymer grown from dopamine (DA) oxidation was proposed. The growth of the polymeric films during DA oxidation at the Prussian blue (PB) modified Au electrode in weak alkaline phosphate buffer (pH 9.18) and the immobilization of Hb into the polymeric films during their growth were traced by the electrochemical quartz crystal impedance analysis (EQCIA) method. A hydrogen peroxide (H₂O₂) biosensor was thus constructed, and effects of experimental parameters on the sensor performance, including the applied potential, solution pH and electroactive interferents, were examined. At an optimal potential of ?0.25 V vs. SCE, the current response of the biosensor in the selected phosphate buffer (pH 5.29) was linear with the concentration of H₂O₂ from 0.01 to 4.5 mM, with a lower limit of detection of 0.5 μM (S/N=3), short response time (within 10 s) and good anti‐interferent ability. The Michaelis constant (K_m^app) was estimated to be 3.80 mM. Compared with the separate film of PB or Hb, the composite film of Hb and PB exhibited a higher catalytic activity toward the reduction of H₂O₂, as a result of the additive effect of the chemical and biological catalyses.     

二氧化锆/石墨烯复合材料对亚硝酸盐的电化学传感研究

制备了一种二氧化锆/还原氧化石墨烯(ZrO2NPs/rGO)复合材料修饰电极的亚硝酸盐电化学传感器,并成功用于亚硝酸盐的检测.采用循环伏安法和电流-时间曲线考察了修饰电极的电化学行为.实验结果表明,ZrO2NPs/rGO复合材料修饰电极对亚硝酸盐具有良好的电流响应.在最优实验条件下,电流-时间曲线中的电流响应信号与亚硝酸盐浓度在3.0×10Symbolm@@_7～1.0×10Symbolm@@_6 mol/L和1.0×10Symbolm@@_6～6.0×10Symbolm@@_6 mol/L的范围内呈良好的线性关系,检测限为1.0×10Symbolm@@_7 mol/L(S/N 3).该传感器灵敏性高、稳定性和重现性好.使用此传感器检测实际样品香肠中的亚硝酸盐的回收率为93.7％～110.4％,相对标准偏差为1.6％～2.1％.     

Electrocatalysis and Amperometric Detection of the Reduced Form of Nicotinamide Adenine Dinucleotide at Toluidine Blue/Zinc Oxide Coated Electrodes

Thin toluidine blue (TBO) and zinc oxide (ZnO) hybrid films have been grown on glassy carbon electrode (GCE) and indium tin oxide coated (SnO₂) glass electrodes by using cyclic voltammetry (CV). Scanning electron microscopy (SEM) images revealed spherical and beads‐like shape of highly oriented TBO/ZnO hybrid films. Energy dispersive spectrometry (EDS) results declared that the films composed mainly of Zn and O. Moreover, TBO/ZnO hybrid films modified electrode is electrochemically active, dye molecules were not easily leached out from the ZnO matrix and the hybrid films can be considered for potential applications as sensor for amperometric determination of reduced nicotinamide adenine dinucleotide (NADH) at 0.0 V. A linear correlation between electrocatalytic current and NADH concentration was found to be in the range between 25 μM and 100 μM in phosphate buffer. In addition, we observed that dopamine, ascorbic acid and uric acid are not interference in amperometric detection of NADH in this proposed method. In addition, TBO/ZnO hybrid film modified electrode was highly stable and its response to the NADH also remained relentless.