Carbonate‐Melt Oxidized Iridium Wire for pH Sensing

A new approach to the preparation of an iridium oxide film for pH sensing is demonstrated. A thick, uniform and dense ceramic oxide layer was grown on the surface of an iridium wire by oxidizing the wire in a molten alkali metal carbonate at high temperature. The alkali metal ion from the carbonate melt was incorporated into the oxide, resulting in a highly stable oxide compound. After treated in acid solution, the oxide layer became hydrated. SEM, XRD, TGA and element analysis were carried out to characterize the oxide film, and a possible formula of the oxide was computed as Li_0.86IrO_2.34(OH)_0.76?0.39H₂O. The electrode made with this new type of oxide film exhibited good pH sensitivity and stability, even in strong acid/base solutions, or in strong corrosive solution such as hydrofluoric acid. Furthermore, the electrode showed excellent long‐term stability over the test period of two and a half years. In addition, individual electrodes prepared from the same batch exhibited remarkable agreement with respect to potential/pH slopes and apparent standard electrode potentials. The performance of the electrodes depends on the properties of the oxide film, such as composition, hydration state and oxidation state.     

丝网印刷纳米金属氧化物型固态pH电极的研制

近年来对非玻璃型 p H电极的开发一直是化学传感器研究领域中的活跃课题之一 ,其中又以氧化物型的 p H电极倍受关注 [1～ 5 ] .与玻璃电极相比 ,氧化物型的固体 p H电极可呈现出如下的优势 :成本低、响应快、机械强度高 ,且可应用于多种玻璃电极不能适宜的测试环境如高温、强腐蚀或有强制对流等体系 .然而迄今为止 ,已研究过的氧化物种类 (包括 Ir O2 ,Ru O2 ,Pt O2 等 )极为有限 ,且价格较昂贵 .本工作以纳米级的几种过渡金属氧化物 (氧化锰、氧化钴、氧化铅、氧化钛 )为敏感材料 ,利用丝网印刷技术制备了各种氧化物电极 ,对电极的 p H…     

基于氮化钛的全固态碱性pH电极的研制

p H值是溶液化学中重要的检测指标 .在工业、农业、生物、医学及环境保护等各个领域都有着广泛应用 .目前 ,多采用玻璃 p H电极进行 p H值的测量 .然而 ,玻璃 p H电极也存在一定的不足 ,玻璃敏感膜阻抗高达 1 0 10 Ω,容易造成电磁干扰 ;玻璃 p H电极极易破碎 ,难以适用于强搅拌的工业过程体系 ;氢氟酸能强烈地浸蚀玻璃膜 .因此 ,玻璃 p H电极不能长时间地用于含氟腐蚀体系 p H的测量 ;另外 ,玻璃 p H电极在强碱性溶液测量时会产生“钠差”.因此 ,多年来对非玻璃型 p H电极的研究一直是化学传感器研究领域中的活跃课题之一 .目前常见的…     

Glass Electrode Measurements in Deuterium Oxide

Abstract

When hydrogen selective glass electrodes are transferred between acid solutions in ordinary water and deuterium oxide their potentials drift systematically by 1–2 mV over several hours, and hence electrodes standardised in H₂O cannot be readily used for the precise measurement of deuterium ion activity a_D+ in D₂O.     

复合型扫描微pH电极及其在局部腐蚀中的应用

研制了一种新型的微米级复合型扫描pH探针.该探针具有体积小、响应速度快、稳定性好和制作方便等优点，能很好地满足微区pH快速测定的要求.应用复合型扫描微pH电极技术研究了Al/Cu合金在0.01 mol•L－1 NaCl溶液中开路状态下局部腐蚀发生的早期过程.     

聚苯胺修饰碳纤维针型复合微pH传感器

由电聚合法用聚苯胺修饰碳纤维电极作为ＰＨ敏感电极。把Ｋ３Ｆｅ（ＣＮ）６／Ｋ４Ｆｅ（ＣＮ）６体系填入医用注射针头内成为参比电极。把经聚苯胺修饰的碳纤维电极安置入该针型参比电极内构成复合针型微ｐＨ传感器。在ＰＨ ２～１２范围内，该传感器呈现超Ｎｅｒｎｓｔ响应，斜率为－７８ ｍＶ／ｐＨ；响应时间<１ｍｉｎ。该传感器成功地应用于在体ｐＨ测定以及水果内微区ｐＨ测定。     

In-situ pH Measurement at the Electrode/Solution Interface

ElectrochemicaldepositionoffunctionalceramiccoatingshasrecentlyattTactedconsiderableattention'-3becauseofavarietyofadvantagesofthemethodofthecoatingfabrication,suchasalowprocesstemPeratUre,theabilitytodepositonporousorcomplexshaPesofsubstrae,thesimPlecontrolofdepositthickness.Themechanismofelectrodepositionforfunctionalceramicsontothesubstr8tehasnotbeenfiJllyclarifiedatpresent.ltwasgenerallygUessed"'thattheelectrochemicalreactionsontheelectrodesurfacemaycauseapHchangeatthecathode/solutionint…     

Development of low-cost metal oxide pH electrodes based on the polymeric precursor method

In this work, the polymeric precursor method was used to prepare low-cost solid-state sensors for pH determination based on iridium oxide as the main pH sensitive material. The iridium content was reduced with addition of TiO₂, forming the binary system IrO_x–TiO₂, whose electroanalytical properties were evaluated in comparison with a commercial glass pH electrode. The minimum iridium content which gave suitable results was 30 mol%, and the electrode presented Nernstian and fast response in the pH range from 1 to 13, with no hysteresis effect observed. Besides, the electrode showed high selectivity in the presence of alkali ions as Li⁺, Na⁺ or K⁺. The amount of iridium in the prepared electrodes was very small (<0.1 mg), supporting the efficiency of this method on the simple preparation of functional low-cost pH electrodes.     

8-羟基喹啉-5-磺酸修饰电极pH传感器的制备及应用

制备了8-羟基喹啉-5-磺酸(HQS)修饰铂丝电极pH传感器,对其pH响应范围,斜率,线性相关系数,响应时间等进行了考察.将该电极用于表面修饰氨基纳米二氧化硅的测定,取得了满意结果.     

Flow Injection Potentiometric Determination of Coke Acidity and Acetic Acid Content in Vinegar Using an Antimony Electrode

Abstract

A flow injection potentiometric procedure is proposed for the determination of acidity of several samples using an antimony/ antimony oxide electrode. The ΔE/pH curve in phosphate buffer solutions in the pH range from 1.58 to 12.00 showed a linear sub-Nernstian behavior with an operational slope S =-42.1mV/pH_c and a conditional standard potential of 264.8mV. This flow potentiometric electrode responds linearly to low acidity variations of dilute acetic acid solutions from 3.16 to 100mM with a slope of 30.1mV/dec and analytical frequency of 23 results/h. Good reproducibility and an average standard deviation of ±0.5% was obtained. The application of this sensor for the determination of coke acidity and acetic acid in vinegar is reported.     

用于检测暂态pH值变化的电量型铂电极

本文报道用铂制作的电量型pH传感器,其原理是铂电极表面上氧化物在形成单分子氧化物覆盖前的覆盖度与溶液pH值之间存在一定的关系,pH值的改变会导致铂表面氧化物覆盖度的改变,并以一定的电量变化为表现形式。在碱性溶液中,该传感器对pH值变化的响应呈线性变化规律,且响应时间小于100ms,精度小于0.2个pH值。该pH传感器可检测反应过程中pH值的暂态变化,适用于研究电极反应或有中间体生成的反应的机理。该传感器的有效性在用扫描电化学显微镜（SECM）探针-基底伏安模式研究氢氧化镍的充放电的过程中得到验证。     

基于碳纳米管修饰电极/鸟嘌呤电化学体系的固体电位型pH传感器

根据鸟嘌呤在短单壁碳纳米管修饰玻碳电极(S-SWCNT/GCE)上发生的电催化氧化特性,及其氧化电位对支持电解质溶液的pH值具有灵敏的响应,制备了以鸟嘌呤为指示剂的固体电位型pH传感器。在优化各种影响因素后,其电位在pH2.0~12.0范围内具有线性响应,回归方程为Epa(V)=-0.0497pH 0.8931。该传感器制备简单,使用方便,响应时间<20 s。在pH响应范围内待测液中离子强度对测定没有影响。酸碱滴定终点具有明显的突跃。对Na 、K 和Ca2 的选择性系数小。已成功地应用于实际样品的测定。     

Graphene Oxide‐Modified Electrode Coated with in‐situ Antimony Film for the Simultaneous Determination of Heavy Metals by Sequential Injection‐Anodic Stripping Voltammetry

The proposed chemically modified electrode was graphene oxide that was synthesized via Hummer's method followed by reduction of antimony film by in‐situ electrodeposition. The experimental process could be concluded in three main steps: preparation of antimony film, reduction of analyte ions on the electrode surface and stripping step under the conditions of square wave anodic stripping voltammetry (SWASV). A simple and rapid approach was developed for the determination of heavy metals simultaneously based on a sequential injection (SI), an automated flow‐based system, coupled with voltammetric method using antimony‐graphene oxide modified screen‐printed carbon electrode (SbF‐GO‐SPCE). The effects of main parameters involved with graphene oxide, antimony and measurement parameters were also investigated. Using SI‐SWASV under the optimal conditions, the proposed electrode platform has exhibited linear range from 0.1 to 1.5 M. Calculated limits of detection were 0.054, 0.026, 0.060, and 0.066 μM for Cd(II), Pb(II), Cu(II) and Hg(II), respectively. In addition, the optimized method has been successfully applied to determine heavy metals in real water samples with acceptable accuracy of 94.29 – 113.42 % recovery.     

Ex Situ Prepared Antimony Film Electrode for Electrochemical Stripping Measurement of Heavy Metal Ions

The antimony film electrode (SbFE) was prepared ex situ for anodic and adsorptive stripping voltammetric measurement of selected heavy metal ions. The electrode revealed good linearity for Cd(II) and Pb(II) in a nondeaerated solution of 0.01 M HCl in the examined concentration range from 25 to 80 μg L^?1 with limits of detection of 1.1 μg L^?1 for Cd(II) and 0.3 μg L^?1 for Pb(II) and an excellent reproducibility. The preplated SbFE was also preliminary tested for measuring low levels of Ni(II) using adsorptive stripping voltammetry exhibiting good linearity and sensitivity in combination with only a 30 s deposition step.     

Fabrication and Use of Dual‐function Iridium Oxide Coated Gold SECM Tips. An Application to pH Monitoring above a Copper Electrode Surface during Nitrate Reduction.

The fabrication of a gold microelectrode modified with iridium oxide film (IrO_x) and its use as tip with a dual function in SECM experiments is reported. The defective structure of the coating onto the microelectrode surface was used as strategy to combine the advantages of both amperometric (for current‐distance determination) and potentiometric (for pH sensing) SECM operation modes. Approach curves, using oxygen and hexaammineruthenium(III) as redox mediators, were obtained without significant loss of the performance and reproducibility of the potentiometric pH response. This allowed the precise positioning of the proposed tip above a substrate in SECM experiments and, subsequently, to monitor pH at the substrate surface. The IrO_x modified microelectrode was applied successfully in SECM experiments involving the local proton consumption during the nitrate reduction at a copper cathode surface.     

全固态复合Ir/IrOx-pH传感器的研制及应用

报道了一种用于直接测定固体、半固体及糊状物表面和内部pH的新型全固态复合pH传感器,建立了原位无破损pH测定的新方法。详细地探索了pH传感器的制备工艺、性能、测试条件和干扰物的影响。pH传感器线性范围1.0~13.0,响应斜率56±1.0 mV/pH,温度系数-0.782 mV/℃,与pH玻璃电极结果对照,△pH≤0.1。该pH传感器的实际应用结果令人满意。     

Reduced Graphene Oxide Impregnated Antimony Nanoparticle Sensor for Electroanalysis of Platinum Group Metals

A very sensitive electrochemical sensor based on a reduced graphene oxide film impregnated with antimony nanoparticles was prepared and applied to the electroanalysis of platinum group metal ions of Pd(II), Pt(II) and Rh(III). The electrochemical behavior of platinum group metals at the modified electrode was studied by adsorptive differential pulse cathodic stripping voltammetry in the presence of dimethylglyoxime as chelating agent. Several operational parameters were optimised to enhance the electroanalytical performance of the modified glassy carbon electrode sensor. The results showed sharp stripping peaks and a relatively constant peak potential with a good linear behaviour in the examined concentration range from 40 to 400 pg L^?1 for all metal ions investigated. The detection limit was found to be 0.45, 0.49 and 0.49 pg L^?1 (S/N=3) for Pd(II), Pt(II) and Rh(III), respectively. The developed electrochemical sensor also exhibited good precision with a relative standard deviation of 4.2 %, 2.55 % and 2.67 % for 5 successive measurements for Pd(II), Pt(II) and Rh(III), respectively. The proposed nanostructure showed good sensitivity and stability, which has promising potential applications in electrochemical sensors.     

Construction and Evaluation of a Gold Tubular Electrode for Flow Analysis: Application to Speciation of Antimony in Water Samples

A tubular gold electrode (TGE) is described for the first time by summarizing the important aspects of its construction and evaluation. Applicability of the TGE is evaluated in the speciation of Sb(III) and Sb(V) using anodic stripping voltammetry in a single flow manifold. Studies with surface active interferences and metallic cations were performed. The proposed conditions for antimony determination showed good tolerance towards cationic, anionic and nonionic surface active substances. A linear response for antimony was obtained for solutions containing significant amounts of several metallic cations. Linear calibration curves for Sb(III) were obtained in the range 1–10 ppb with a detection limit of 0.19 ppb (CV=2.91%, n=5, [Sb(III)]=5 ppb). For Sb(V), linear calibration curves were in the range 1–15 ppb with a detection limit of 0.32 ppb (CV=1.41%, n=5, [Sb(V)]=5 ppb). The figures of merit achieved sustain for the good applicability of the proposed method as it allows the determination of antimony at levels below maximum values permitted in consuming waters. Results of antimony concentration determined in water samples were validated against the ICP‐MS reference procedure or compared with reference water samples.     

一种新的适合低pH范围的中性载体PVC膜电极的研究

设计并合成了Ｎ－十八烷基水杨醛亚胺（ＯＤＳＡＩ）,Ｎ－十八烷基苯甲醛亚胺（ＯＤＢＡＩ）两种新的亚胺化合物,并以此为中性载体,制成了ＰＶＣ膜ＰＨ电极。此电极在ＰＨ０．６－８．５的范围内,对氢离子呈现很的能斯响应,电极斜率为５２ｍＶ／ｐＨ。     

低碳醇氧化电极表面pH值的测量及应用

研究了Ir/IrO₂微平面电极在低碳醇氧化电极表面的pH-E_ocp（pH-开路电位)关系,测量了几种低碳醇在电化学氧化过程中距离电极表面50 μm以内的不同距离处的pH值,对不同低碳醇电化学氧化产生的酸强度进行了比较与分析;Ir/IrO₂微平面电极的pH-E_ocp关系曲线与“醇-羧酸”体系种类有关;乙二醇在电化学氧化过程中产生的pH值最低,甲醇次之,乙醇产生的pH值最高,在500 nm处的稳态pH值分别为0.191、1.13和2.99。通过向电解液中加入NaF,考察了生成的H⁺和F^-结合对金属钛选择性微区刻蚀作用,在乙二醇为前驱体的体系中微孔刻蚀加工速率约为30 nm/min。