酶功能化聚多巴胺包覆纳米普鲁士蓝的制备及电化学分析应用

在纳米金表面原位沉积普鲁士蓝,然后在核壳结构纳米金-普鲁士蓝的表面包覆一层易氧化聚合的多巴胺保护膜,利用多巴胺聚合表面残留的大量氨基和羟基进一步将纳米铂粒子修饰于聚多巴胺膜表面制得普鲁士蓝-聚多巴胺-纳米铂多层纳米复合材料。将此复合材料修饰于金电极表面,协同使用辣根过氧化物酶用于H_2O_2浓度的检测。结果表明:聚多巴胺的引入有效增加了普鲁士蓝的稳定性,增大了纳米铂的负载量以及辣根过氧化物酶的生物活性;由于普鲁士蓝、纳米铂和辣根过氧化物酶的多重信号放大作用,酶功能化纳米复合材料修饰电极对H_2O_2表现出良好的电还原活性。优化条件下,对H_2O_2的检测范围为2.0×10~(-7)~1.0×10~(-3)mol·L~(-1),检出限(S/N=3)为1.2×10~(-7)mol·L~(-1)。     

普鲁士蓝/多壁碳纳米管修饰电极测定维生素C

利用电化学方法在多壁碳纳米管修饰的玻碳电极表面聚合一层普鲁士蓝,制备普鲁士蓝/多壁碳纳米管修饰玻碳电极,运用循环伏安法研究了维生素C(vc)在该修饰电极上的电化学行为.该修饰电极对Vc显示出快速的电化学响应和较好的电催化活性,在pH为4.0的磷酸盐溶液中,Ve浓度与其氧化峰电流在8.0×10-4～1.0×10-2 mol/L范围内呈现良好的线性关系,相关系数为0.9993,检测限为6.4×10-5mol/L.该电极具有较好的稳定性和重现性.     

银离子交换的沸石修饰电极的循环伏安新特性

银离子交换沸石Y修饰电极(Ag⁺-沸石Y)的循环伏安(CV)行为, 不同于溶液中的银离子在固体银电极表面上的CV行为. Ag⁺-沸石电极中银离子还原电位明显受沸石体内银簇影响. 依据Ag⁺-沸石修饰电极在含有能够与银离子形成难溶盐的电解质中的CV行为, 本文发现了沸石对溶液中阴离子具有尺寸选择效应, 并解释了银离子交换沸石修饰电极的循环伏安反应特性.     

磁性普鲁士蓝纳米颗粒的合成及其化学修饰电极的制作

利用FeSO₄与FeCl₃合成了超细磁性Fe₃O₄纳米颗粒, 并进一步利用该纳米颗粒与铁氰酸钾在酸性溶液(pH～2)中的化学反应成功制备了一种新型的磁性普鲁士蓝纳米颗粒; 研究了该磁性颗粒的磁学性能, 通过磁力将其修饰于固体石蜡碳糊电极表面制成了化学修饰电极, 考察了该电极对过氧化氢的电催化还原及对水合肼的电催化氧化特性. 该化学修饰电极可对过氧化氢和水合肼进行测定, 线性范围分别为过氧化氢2×10^－6～5×10^－3 mol/L, 水合肼7.2×10^－7～3.6×10^－4 mol/L. 利用磁性普鲁士蓝纳米颗粒制得的修饰电极具有催化性能高、稳定性好、表面易更新等优点.     

量子点传感器测定水中微量银离子

选择铋试剂Ⅱ作为硫化镉(cds)量子点的修饰剂,合成了表面修饰的量子点,利用其有效官能团与银离子作用,导致修饰的量子点的荧光增强作用,建立了测定银离子的方法,开发了新型的银离子的传感器。结果表明,对水中银离子测定的线性范围为0.01~5.0μmol.L-1,相关系数为0.999 3,检测限达到1.6 nmol.L-1,对实际水样的分析获得了较满意的结果。     

基于聚苯胺-普鲁士蓝/普鲁士蓝复合膜的过氧化氢电化学传感器的制备及表征

利用聚苯胺和普鲁士蓝的协同作用,构建了聚苯胺-普鲁士蓝/普鲁士蓝复合膜的H2O2电化学传感器.聚苯胺的带正电骨架和带负电的普鲁士蓝粒子相互吸引,且聚苯胺提供了很多氧化还原位点,有利于普鲁士蓝粒子的进一步均匀生长,使制备的传感器具备优异的电催化性能.采用扫描电镜和电化学方法对修饰电极进行了表征.在最佳实验条件下,该修饰电极不仅表面具有致密均匀的结构,而且具备在弱碱性条件下良好的电化学操作稳定性,为搭建以H2O2传感为基础的新型传感器提供了一个新的思路.     

基于PB-TNTs复合材料的偏二甲肼电流传感器研究

在偏二甲肼(UDMH)的氧化中使用普鲁士蓝(DB)作为合适的电子转移调节剂,利用Ti O2纳米管特殊的物理和化学性质,以Ti O2纳米管为普鲁士蓝载体,将制备的PB-Ti O2纳米管复合材料修饰玻碳电极,以玻碳电极作为工作电极,可以很好的应用在UDMH的电催化氧化上。通过SEM观察复合材料的外表特征,利用循环伏安技术,观察PB-TNTs/GCE的电化学行为和UDM H在工作电极上的电化学响应,评估PB-T NT s/GCE对UDM H溶液浓度测定的可靠性。结果表明,PB作为促进UDMH氧化的催化剂,Ti O2作为普鲁士蓝的载体,分析检测UDMH溶液时修饰玻碳电极将展现良好的稳定性,利用电流测定法得出线性范围为0.2×10-3~60×10-3g/L,检测限为2.4×10-5g/L。     

化学修饰电极的研究—Ⅸ.普鲁士蓝修饰电极的制备和性能

本文用电化学方法在Pt基体上制备出更稳定的普鲁士蓝修饰电极,可经历0.6—1.1V(Vs.SCE)之间连续一千周以上电位扫描;提出了普鲁士蓝薄膜电化学氧化还原时电子转移的多层模型;系统地研究了电极制备条件、薄膜厚度及溶液pH值对电极伏安行为的影响。     

电化学制备普鲁士蓝-石墨烯复合物及对过氧化氢电催化性能研究

通过电化学方法制备了普鲁士蓝-石墨烯复合物,利用扫描电子显微镜(SEM)技术表征了石墨烯及石墨烯复合物的形貌结构特征。选取H2O2作为探针分子,采用电化学技术考察了普鲁士蓝-石墨烯复合物对的电催化性能。复合物修饰电极对H2O2具有良好的电催化还原活性,增强的催化活性可能与石墨烯与普鲁士蓝纳米颗粒之间的协同效应有关。复合物电极材料能够实现对H2O2的快速、灵敏检测,有望用作检测H2O2的传感平台。     

普鲁士蓝/氧化锆复合材料的电化学行为及对H2O2的电催化

通过一步电沉积技术制备了普鲁士蓝/氧化锆修饰玻碳电极。采用电化学阻抗技术表征修饰电极。采用循环伏安法研究了pH值和扫描速率对该修饰电极的电化学行为的影响。结果表明:普鲁士蓝的峰电流与其扫描速率的一次方在一定范围内呈良好的线性关系。此外,该修饰电极在含有KCl(1.0mol/L)的磷酸盐缓冲溶液(0.1mol/L,pH=7.0)中,对H2O2具有明显的电催化作用,在无酶检测H2O2领域具有潜在的应用价值。     

Electrochemical and electrocatalytic stability of Prussian blue/Berlin green redox transformation in Prussian blue-polypyrrole composite films

Redox transformation of Prussian blue to Berlin green (PB/BG) in Prussian blue-polypyrrole (PB-PPy) composites synthesized via original one-step method has been studied. It was shown that the nature of anion and composition of background electrolyte play an important role for both the stability and the shape of electrochemical response of composite film during redox transfer of Prussian blue to Berlin green. Nitric acid, phosphoric acid, malic acid and citric acid 0.05 N (eq/L) solutions and the same acids partially neutralized with 0.01 N KOH were used as electrolyte to study the role of potassium ions presence in solution. The most stable electrochemical response of PB/BG redox transfer was obtained for the nitrate anions containing solutions in the presence of potassium ions. Nevertheless, the stability of the electrochemical transformation PB/BG in composite films in other media is enough to detect the sulphite ions content in wine samples via electrocatalytic reaction at the potentials of PB/BG redox transformation.

     

A Simple and Sensitive Method for the Amperometric Detection of Trace Chromium(VI) Based on Prussian Blue Modified Glassy Carbon Electrode

A simple and sensitive method for the amperometric detection of trace amount of chromium(VI) using a Prussian blue modified glassy carbon electrode (PB/GCE) is described here. The Everitts salt/Prussian blue redox couple of the PB film was found to mediate the Cr(VI) reduction, and the mechanism of electrochemical reaction was investigated. The effects of PB film thickness, applied potential and electrolyte solution on the current response of Cr(VI) reduction were thoroughly studied. Under the optimized conditions, the PB/GCE provided a wide linear range for Cr(VI) analysis from 0.5 to 200 ppb with excellent sensitivity (15±0.2 nA/ppb) and low detection limit (0.15 ppb). In addition, the modified electrode showed excellent stability, reproducibility and good resistance to other metal ions and surfactants. Finally, the proposed method was applied to detect trace Cr(VI) in wastewater with satisfactory results. The great advantages of the method were characterized by the simplicity, ease of preparation, stability, short analysis time and cost‐efficiency.     

An Electrochemical Study of Prussian Blue Microcrystalines Mixed in PEO_400 Polymer Electrolyte by Solid-state Voltammetry

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Electrochemical properties of (Co,Fe)CN,cobaltous Prussian blue analogue

Journal of Solid State Electrochemistry - A Prussian blue analogue (Co,Fe)CN with Fe and Co ions linked by CN– ions was synthesized; the synthesis was aimed at obtaining cobalt...     

Facile Synthesis of Prussian Blue Derivate‐Modified Mesoporous Material via Photoinitiated Thiol–Ene Click Reaction for Cesium Adsorption

A novel strategy to synthesize a functional mesoporous material for efficient removal of cesium is reported. Specifically, Prussian blue derivate‐modified SBA‐15 (SBA‐15@FC) was prepared by photoinitiated thiol–ene reaction between thiol‐modified SBA‐15 and pentacyano(4‐vinyl pyridine)ferrate complex. The effects of weight percentage of the Prussian blue derivate, pH, adsorbent dose, co‐existing ions, and initial concentration were evaluated on the adsorption of cesium ions. The adsorption kinetically follows a pseudo‐second‐order model and reaches equilibrium within 2 h with a high adsorption capacity of about 13.90 mg Cs g^?1, which indicates that SBA‐15@FC is a promising adsorbent to effectively remove cesium from aqueous solutions.     

Light-powered cell for detection of glucose with the naked eye

A concept for light-powered visual detection of glucose is developed. The detection mechanism is based on pairing a photo-active anode with an electrochromic counter electrode. The photoelectrochemical reaction changes the oxidation state of the analyte, leading to a change in the color of the electrochromic material, which makes visual detection possible. All of the electrical charge required to change the color of the electrochromic material is supplied by the photoelectrochemical reaction powered by visible light, so no conventional energy source is required. The proposed system consists of hematite modified with nickel hydroxide (Ni(OH)₂) as the photoanode, and Prussian blue deposited on a fluorine-doped tin oxide electrode as the electrochromic cathode. Under illumination, photo-oxidation of glucose at the photoanode is followed by reduction of Prussian blue to Prussian white at the cathode. The presence of glucose can therefore be detected visually as decolorization of Prussian blue occurs.     

Potentiodynamic deposition of Prussian blue from a solution containing single component of ferricyanide and its mechanism investigation

Potentiodynamic techniques were used for the direct electrodeposition of Prussian blue nano-clusters from an acidic solution of ferricyanide. Electrochemical, EQCM, IR, AFM, and UV/vis measurements were carried out to characterize deposited nano-sized Prussian blue and to explore the formation mechanism. Results showed that ferricyanide could partially dissociate to free ferric and cyanide ions. The driving force of this dissociation is the formation of PB and the evolution of HCN. The optimal potential window for the potentiodynamic formation of PB from an acidic solution (pH 1.6) is between –0.5 V and 0.4 V. In addition, the influence of surface adsorption of CN^- ions on the formation of PB was discussed.Dedicated to Professor W. Vielstich on the occasion of his 80th birthday.     

普鲁士蓝纳米修饰电极的制备及表征

采用激光加热拉伸的方法制备铂纳米电极,并通过交流电刻蚀的方法制备纳米孔电极,在这两种电极上可通过电化学方法原位合成单颗普鲁士蓝微晶. 结果表明,普鲁士蓝微晶在纳米微孔电极上的机械附着强度增强. 这种方法可用于制备纳米修饰电极或研究功能微晶体材料的电化学性质.     

Stability Improvement of Prussian Blue by a Protective Cellulose Acetate Membrane for Hydrogen Peroxide Sensing in Neutral Media

The cellulose acetate covered Prussian blue modified glassy carbon electrode (GCE/PB/CA) was fabricated as a novel hydrogen peroxide sensor. It was shown by scanning electron microscope (SEM) and atomic force microscope (AFM) that Prussian blue was covered and protected by cellulose acetate perfectly. The modified electrode showed a good electrocatalytic activity for H₂O₂ reduction in neutral aqueous solution. H₂O₂ was detected amperometrically in 0.05 mol/L phosphate buffer solutions (pH 7.0, containing 0.1 mol/L KCl as supporting electrolyte) at an applied potential of ?0.2 V (vs. SCE). The response current was proportional to the concentration of H₂O₂ in the range of 1.0×10^?5 mol/L to 2.5×10^?4 mol/L with the detection limit of 2.2×10^?6 mol/L at a signal to noise ratio 3.     

NaxMyFe（CN）6（M=Fe,Co,Ni）:一类新颖的钠离子电池正极材料

应用化学沉淀法合成了3种普鲁士蓝类化合物NaxMyFe(CN)6(M=Fe,Co,Ni),并研究了以此类化合物作钠离子电池正极材料的可行性.XRD和SEM分析表明,合成的3种目标产物均具有典型的立方晶型结构,粒子尺寸为20～50 nm.循环伏安扫描和恒电流充放电测试表明,这类化合物均能实现可逆的钠离子嵌入-脱嵌反应,但不同的金属表现出不同的电化学性质.如M为Fe或Co,材料中的Fe(CN)64+和Fe2+/Co2+离子这两个电化学活性中心都能参与氧化还原反应,NaFeFe(CN)6和Na2CoFe(CN)6的首周可逆容量分别为113和120mAh.g-1,且循环性能比较稳定.由于这类结构中Ni离子不能参与氧化还原反应,Na2NiFe(CN)6的可逆容量仅为64 mAh.g-1,但循环性能非常优异.本工作的初步结果证明了普鲁士蓝类化合物具有良好的钠离子脱嵌能力,有望成为一类价格低廉、环境友好的钠离子电池正极材料.