电沉积普鲁士蓝/壳聚糖修饰金电极的电化学研究

应用控制电位电解法在金电极上进行了普鲁士蓝(PB)/壳聚糖(CS)修饰膜的电沉积。在pH2、溶液组成为2.5 mmol/L FeCl3 2.5 mmol/L K3[Fe(CN)6] 0.01%CS 0.01 mol/L HCl和0.1 mol/L KCl的溶液中,于0.4 V(vs.SCE)电沉积300 s,获得性能理想的沉积膜。对修饰膜进行了红外和显微表征,结果表明,PB和CS同时沉积在电极上,且膜结构较纯PB沉积膜粗糙,修饰量大,具有更强的空间结构性。研究了PB/CS/金修饰电极(PB/CS/Au/CME)的电化学行为,该电极在中性(pH7.0~8.0)条件下性能比纯PB修饰膜更稳定,具有良好的电化学活性和对H2O2的电催化性能。氧化峰电流与H2O2浓度在1×10-6~5×10-3mol/L范围内呈良好线性关系,为研制基于酶催化反应的电化学生物传感器奠定了良好基础。     

基于普鲁士蓝/二氧化钛纳米管修饰碳糊电极的电流传感器检测偏二甲肼的研究

以TiO_2纳米管(TNTs)作为普鲁士蓝(PB)的载体,制备了PB/TNTs修饰碳糊电极(PB/TNTs/CPE),考察了偏二甲肼(UDMH)在该电极上的电化学行为,评估PB/TNTs/CPE测定UDMH的可靠性。结果表明,PB可以作为促进UDMH氧化的催化剂,利用TNTs作为PB的载体,可以提高电子的转移效率和速率。通过电流测定法得出测定UDMH的线性范围为0.3~100mg·L~(-1),检测限为2.6×10~(-5) g·L~(-1)。相比PB修饰的碳糊电极,本文基于PB/TNTs修饰碳糊电极所制备的电流传感器具有更高的灵敏度。     

普鲁士蓝膜电化学行为的EQCM研究

应用循环伏安法于铂电极上电化学沉积PB膜,并由电化学石英晶体微天平技术(EQCM)原位测量了PB膜电沉积过程的频率响应.研究表明,沉积液中添加邻菲咯啉对PB膜结构有影响.有邻菲咯啉参与沉积的PB Pt/QCM电极对H2O2的电催化还原性能优于不含邻菲咯啉沉积液制备的PB Pt/QCM电极.     

电化学掺铜(Ⅱ)类普鲁士蓝膜修饰电极的制备及其对亚硝酸根的测定

研究在普鲁士蓝(PB)修饰膜中,利用电化学方法掺杂Cu2+制备的掺Cu2+类普鲁士蓝(Cu-PB)修饰膜.通过循环伏安和交流阻抗实验,考察了制备的Cu-PB修饰膜的电化学性质和对NO-2的响应特性,并与PB修饰膜进行了比较.研究表明,掺Cu2+后不仅改变了PB膜的内部结构,其电化学性能也发生了明显变化,PB修饰膜对NO-2无电催化作用,而Cu-PB修饰膜对亚硝酸根具有明显的电催化作用.在pH=5.85的PBS缓冲溶液中,NO-2的浓度在1.0×10-2～5.0×10-5 mol/L范围内与还原峰电流呈良好的线性关系(r=0 9983); 检出限(3S/N)为1.0 μmol/L.本法用于实际样品的测定,回收率为97.5%～104%,结果令人满意.     

L-半胱氨酸/普鲁士蓝复合修饰玻碳电极的制备及电化学性能

通过电聚合方法和脉冲沉积技术将普鲁士蓝(PB)与L-半胱氨酸(L-Cys)修饰在玻碳电极(GCE)表面,制得复合膜化学修饰电极(L-Cys/PB/GCE/CME),利用循环伏安法和计时安培法研究了对苯二酚在L-Cys/PB/GCE/CME上的电化学特征。结果表明,在0.1 mol/L PBS(pH 7.0)缓冲溶液中,L-Cys/PB/GCE/CME对对苯二酚的电化学氧化具有明显的催化作用,氧化峰电流相对于在裸玻碳电极上增加了5倍。在最佳实验条件下,对苯二酚浓度在0.18~120μmol/L范围内,修饰电极的电流响应与对苯二酚浓度呈线性关系,其相关系数为0.9962,检出限(S/N=3)为0.065μmol/L。本研究制备的对苯二酚传感器具有较好的重复性、重现性、选择性与稳定性,用于实际水样中对苯二酚的测定,结果满意。     

分步电沉积普鲁士蓝、纳米铜复合膜修饰玻碳电极测定芦丁

采用分步电沉积方法,依次将普鲁士蓝膜(PB)和纳米铜(CuNPs)电沉积在玻碳电极(GCE)表面,制备了相应的修饰电极(CuNPs/PB/GCE)。考察了实验条件,并采用循环伏安(CV)法和差分脉冲伏安(DPV)法研究了芦丁在CuNPs/PB/GCE上的电化学行为,求解了相关的电化学参数。最佳条件下,采用DPV法,芦丁的还原峰电流与其浓度在1.0×10-8~1.0×10-4 mol/L范围内呈现良好的线性关系,其检出限(S/N=3)为2.8×10-9 mol/L。结果表明,电极表面PB和CuNPs的存在有效提高了芦丁的电化学响应。该修饰电极的选择性和重现性好,可以应用于水样中芦丁的检测。     

铂/普鲁士蓝复合纳米线的合成及电化学传感应用

利用多孔聚碳酸酯膜,采用两步模板电沉积法制备了铂/普鲁士蓝(Pt/PB)复合纳米线。将Pt/PB复合纳米线固定在玻碳(GC)电极上,构建过氧化氢电化学传感器。实验结果表明,Pt/PB复合纳米线对过氧化氢的还原有良好的电催化作用。在电位为-0.1V时,响应电流信号与过氧化氢浓度呈良好的线性关系,线性范围为6.1×10-4～1.8×10-2 mol/L,检出限(S/N=3)为5.0×10-7 mol/L。该修饰电极具有响应速率快、稳定性高、使用寿命长等优点,同时还具有一定的抗干扰能力。     

Co(OH)2/Ni(OH)2复合电极材料制备及其超级电容性质

以Co(NO_3)_2·6H_2O和Ni(NO_3)_2·6H_2O为钴源和镍源,采用溶剂热法一步合成了Co(OH)_2/Ni(OH)_2复合材料,通过煅烧该复合材料可得到NiCo_2O_4。采用XRD、SEM、BET等对材料进行了表征,结果表明,Co(OH)_2/Ni(OH)_2复合材料是薄片组成的花状形貌,比表面积为37. 48m~2/g。电化学性能测试表明,Co(OH)_2/Ni(OH)_2复合材料比NiCo_2O_4具有更高的比电容值和容量保持率。在0. 5A/g的电流密度下,复合材料比电容值可达到1097. 8F/g,而NiCo_2O_4比电容值仅为86. 1F/g。因此,与煅烧后的NiCo_2O_4材料相比,Co(OH)_2/Ni(OH)_2复合材料具有更加优良的电化学性能,这为高性能超级电容器材料的制备提供了一个新思路。     

自旋交叉和长程磁有序共存的非均相复合材料

采用一种简单的室温沉淀转化方法,有效制备了同时具有自旋交叉和长程磁有序性能的异质结构复合材料FeTrz@PB,其由[Fe(Htrz)₂(trz)]BF₄(Htrz=1H-1,2,4-三氮唑)和普鲁士蓝KFe^Ⅲ[Fe^Ⅱ(CN)₆](PB)构成。通过扫描电子显微镜、透射电子显微镜、粉末X射线衍射、FTIR、X射线光电子能谱、能量色散X射线分析、热重分析和磁性研究,对这些异质结构复合材料的可控生长过程进行了充分表征。复合材料中,PB颗粒的大小和FeTrz@PB的外观可以通过控制反应时间来进行有效调节。随着反应时间的增加,FeTrz@PB复合材料中PB相的比例逐渐增加。值得注意的是,磁性研究发现,这类材料具有室温以上自旋交叉(362～392 K)和低温下长程磁有序(约5.6 K)的共存。高自旋(HS)组分和场冷/零场冷的强度随着反应时间的增加而逐渐增加,而自旋交叉热滞回线的高度逐渐减小。     

Ag/CuS/rGO复合材料的制备及对亚硝酸盐的电化学传感性能研究

以溶剂热法制备Cu3(BTC)2为前驱体,通过两步转化得到Ag/CuS/rGO复合材料,构制了电化学传感器,研究了其对NO2^-离子的电催化行为,建立了测定NO2^-离子的电化学分析方法。Ag/CuS/rGO复合材料对NO2^-离子展现了良好的电催化性能,检测线性范围为1~50μmol/L和50~550μmol/L,检出限为0.04μmol/L(S/N=3)。该传感器具有制作简单、选择性好和检出限低的特点,拓展了金属有机框架材料(MOFs)在电化学领域的应用。     

High-Sensitive Glucose Biosensor Based on Ionic Liquid Doped Polyaniline/Prussian Blue Composite Film

The Prussian blue/ionic liquid-polyaniline/multiwall carbon nanotubes (PB/IL-PANI/MWNTs) composite film was fabricated by using cyclic voltammetry. The ion liquid acting as a lubricating agent, could enhance the electron delocalization degree and reduce the struc-tural defects of the polyaniline. The surface morphology of the composite film revealed that the PB nanoparticles have smaller size than that in pure PB film. Due to the introduction of ion liquid, the PB/IL-PANI/MWNTs composite film showed wonderful synergistic effect which can remarkably enhance sensitivity, expand linear range and broaden acidic adapt-ability for hydrogen peroxide detection. The composite film demonstrated good stability in neutral solution contrast to pure PB film, with a linear range from 2.5 μmol/L to 0.5 mmol/Land a high sensitivity of 736.8 μA·(mmol/L)^-1·cm^-2 for H₂O₂ detection. Based on the com-posite film, an amperometric glucose biosensor was then fabricated by immobilizing glucose oxidase. Under the optimal conditions, the biosensor also exhibits excellent response to glucose with the linear range from 12.5 μmol/L to 1.75 mmol/L and a high sensitivity of 94.79 μA (mmol/L)^-1·cm^-2 for H₂O₂. The detection limit was estimated 1.1 μmol/L. The resulting biosensor was applied to detect the blood sugar in human serum samples without any pretreatment, and the results were comparatively in agreement with the clinical assay.     

A novel Prussian blue‐magnetite composite synthesized by self‐template method and its application in reduction of hydrogen peroxide

A novel Prussian blue (PB)‐Fe₃O₄ composite has been prepared for the first time by self‐template method using PB as the precursor. According to this method, Fe₃O₄ nanoparticles distributed uniformly on the surface of PB cube. The feed ratio of sodium acetate to PB has been proved to be a key factor for magnetic properties and electro‐catalysis properties of the composite. Under the experimental conditions, the saturation magnetization value (Ms) of PB‐Fe₃O₄–2 composite was 22 emug^?1, while the Ms value of other samples reduced. The composites also showed a good peroxidase‐like activity for the oxidation of substrate 3,3,5,5‐tetramethylbenzidine (TMB) in the presence of H₂O₂. The catalytic reduction of hydrogen peroxide capacity was PB‐Fe₃O₄–1> PB‐Fe₃O₄–2> PB‐Fe₃O₄–3> PB‐Fe₃O₄–0, which confirmed the Fe(II) centres in PB surface and Fe₃O₄ nanoparticles had synergistic effect on catalytic reduction of hydrogen peroxide.     

Layer-by-layer assembled multilayer of graphene/Prussian blue toward simultaneous electrochemical and SPR detection of H2O2

A new type of chemically converted graphene sheets, cationic polyelectrolyte-functionalized ionic liquid decorated graphene sheets (PFIL-GS) composite, was synthesized and characterized by Ultraviolet-visible (UV-vis) absorption, Fourier transform infrared, and Raman spectroscopy. It was found that the presence of PFIL enabled the formation of a very stable aqueous dispersion due to the electrostatic repulsion between PFIL modified graphene sheets. With respect to the excellent dispersibility of this material, we have fabricated a novel PFIL-GS/Prussian blue (PB) nanocomposite multilayer film via classic layer-by-layer (LBL) assembly. The assembly process was confirmed by UV-vis spectroscopy and surface plasmon resonance (SPR) spectroscopy, which showed linear responses to the numbers of the deposited PFIL-GS/PB bilayers. Moreover, the as-prepared composite films were used to detect hydrogen peroxide (H₂O₂) by electrochemical surface plasmon resonance (EC-SPR) spectroscopy. This real time EC-SPR technique can provide simultaneous monitoring of both optical SPR signal and electrochemical current responses upon injecting H₂O₂ into the reaction cell. The experimental results revealed that both the electrochemical and SPR signal exhibited splendid linear relationship to the concentration of the injected H₂O₂, and the detection limit could be up to 1 μM.     

Functionalization of graphene with Prussian blue and its application for amperometric sensing of H2O2

As a two-dimensional carbon material with high surface area and conductivity, graphene shows great promise for designing composite nanomaterials to achieve high-performance electrochemical devices. In this work, we prepared graphene-based nanocomposite material by electrochemically depositing Prussian blue (PB) nanoparticles on the surface of graphene. Fourier transform infrared spectra, SEM, and cyclic voltammetry were used to characterize the successful immobilization of PB. Compared with PB films and graphene sheets, the PB–graphene composite films showed the largest current response to the reduction of H₂O₂, probably due to the synergistic effects between graphene sheets and PB nanoparticles. Therefore, a fast and highly sensitive amperometric sensor for H₂O₂ was obtained with a detection sensitivity of 1.6 μA μM^?1 H₂O₂ per cm² and a linear response range of 50～5,000 μM. The detection limit of H₂O₂ was 20 nM at a signal-to-noise ratio of 3. These obtained results are much better than those reported for carbon nanotubes-based amperometric sensors.     

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).     

Synergetic effect of Prussian blue film with gold nanoparticle graphite–wax composite electrode for the enzyme-free ultrasensitive hydrogen peroxide sensor

Enzyme-free amperometric ultrasensitive determination of hydrogen peroxide (H₂O₂) was investigated using a Prussian blue (PB) film-modified gold nanoparticles (AuNPs) graphite–wax composite electrode. A stable PB film was obtained on graphite surface through 2-aminoethanethiol (AET)-capped AuNPs by a simple approach. Field emission scanning electron microscope studies results in formation of PB nanoparticle in the size range of 60–80 nm. Surface modification of PB film on AET–AuNPs–GW composite electrode was confirmed by Fourier transform infrared attenuated total reflection (FTIR-ATR) spectroscopy studies. Highly sensitive determination of H₂O₂ at a peak potential of ?0.10 V (vs. SCE) in 0.1 M KCl PBS, pH?=?7.0) at a scan rate of 20 mVs^?1 with a sensitivity of 23.58 μA/mM was observed with the modified electrode using cyclic voltammetry. The synergetic effect of PB film with AuNPs has resulted in a linear range of 0.05 to 7,800 μM with a detection limit of 0.015 μM for H₂O₂ detection with the present electrode. Chronoamperometric studies recorded for the successive additions of H₂O₂ with the modified electrode showed an excellent linearity (R ²?=?0.9932) in the range of 4.8?×?10^?8 to 7.4?×?10^?8 M with a limit of detection of 1.4?×?10^?8 M. Selective determination of H₂O₂ in presence of various interferents was successfully demonstrated. Human urine samples and stain remover solutions were also investigated for H₂O₂ content.     

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.     

Electrochromic properties of Prussian blue–polypyrrole composite films in dependence on parameters of synthetic procedure

Composite materials of Prussian blue–polypyrrole (PB/PPy) on the surface of indium tin oxide (ITO)-coated glasses were obtained via one-step chemical (redox) and one-stage electrochemical procedures in mixed solution of iron (III), hexacyanoferrate (III), and pyrrole with various concentration ratios of components in nitrate supporting electrolyte. Electrochemical stability of composite films depends on the amount of Py in synthetic solution, whereas color contrast coefficient values depend on the type of synthetic procedure. PB/PPy film electrochromic response (tested by spectroelectrochemical potentiodynamic measurements) was compared with response of both pure PB and pure PPy films. It was shown that degradation of composite films occurs due to PB component instability in Prussian white form. The highest value of color contrast coefficient and great electrochemical stability were revealed for composite films obtained via redox-synthesis procedure from solution with 0.1 mM [Fe³⁺ + Fe(CN)₆ ^3?] and 1.0 mM Ру (PB/PPy-Ch-1:1:10 system).     

Electrochemical Fabrication of Prussian Blue Nanocube‐decorated Electroreduced Graphene Oxide for Amperometric Sensing of NADH

In this study, Prussian blue (PB) film on the electroreduced graphene oxide (ERGO)‐modified Au electrode surface (ERGO/PB) is easily prepared by means of cyclic voltammetric technique in the mixture of K₃Fe(CN)₆ and FeCl₃. Its electrochemical behaviors for NADH biosensor are studied. The structural and morphological characters of modified electrode material are analyzed with using of XPS, XRD, Raman, EDS, and SEM techniques. ERGO/PB hybrid nanocomposite for NADH biosensor is exhibited to the higher catalytic effect (linear range from 1.0 to 100 μM, detection limit of 0.23 μM at S/N=3) compared to naked Au, ERGO‐modified Au, and PB‐modified Au electrodes. In addition to, ERGO/PB electrode was used to voltammetric and amperometric detection of H₂O₂. ERGO/PB electrodes also showed the same behavior as the NADH sensor. This ERGO/PB‐modified electrode supplied a simple, new, and low‐cost route for amperometric sensing of both NADH and H₂O₂.     

Electrochemically deposited thiophene-based polymers as protective agents for Prussian Blue thin films

A composite material based on overlapped layers of electrochemically synthesized Prussian Blue (PB) and terthiophene-derived polymer is described, aiming at enhancing the stability of the hexacyanoferrate thanks to the protective action of the polymer. Two bilayer configurations and deposition methods (for the polymer component) were tested. The morphology and electrochemical behavior in organic solvent and in aqueous solutions containing different supporting electrolytes were carried out. The best performances of electrodes modified with films of the composite material as to increased stability of PB were achieved with the potentiostatically deposited polymer covering the PB layer, in acetate buffer at pH 5.5. As for potential cycling stress, the anodic and cathodic peak currents due to PB were not decreased after 20 cycles. Conversely, PB alone displayed the anodic peak currents relevant to PB/Prussian White (PW) and PB/Berlin Green (BG) systems decreased by about 30 %. The stability to local pH increase was assessed by cyclic voltammetry after electrochemical reduction of H₂O₂. For example, the anodic peak currents were decreasing by 15 % and 5 % for the two PB redox systems, while for PB alone the same currents decreased by 35 % and 10 %. The response sensitivity to hydrogen peroxide was improved by 54 %, with respect to PB alone, as evaluated by chronoamperometry.