Enhanced Sensitive Electrochemical Sensor for Simultaneous Catechol and Hydroquinone Detection by Using Ultrasmall Ternary Pt-based Nanomaterial

The simple and effective method for the novel synthesis of Pt-based nanoparticle was presented with high efficiency. The sensitive catalyst for the simultaneous detection of catechol and hydroquinone was prepared by depositing ternary metal complex on fluorine-doped tin-oxide (FTO). The composition and morphology of nanomaterials were characterized by TEM, HRTEM, XRD, XPS, and EDS (energy dispersive spectroscopy). The size of the Pt-based nanomaterial was about 5±1 nm. The electrochemical performance of the modified catalyst was studied by CV, DPV, and EIS. The modified PtNiCu@FTO catalyst possessed good electro-oxidation activity for hydroquinone and catechol and used for simultaneous detection of catechol and hydroquinone at scan rate of 20 mV s⁻¹ (vs. Ag/AgCl). Detection responses were found in the ranges of 5–2900 μM for hydroquinone and 5–3000 μM for catechol. The detection limits (LOD) for HQ and CC were observed as 0.35 and 0.29 μM, respectively. The sensitivity of HQ and CC were 1515.55 and 1485 μA mM⁻¹ cm⁻², respectively. The prepared nanomaterial were effectively applied for the determination of CC and HQ in real samples.     

金电极上苯二酚异构体的电化学性质及同时测定

采用循环伏安法研究了邻苯二酚(CAT)、间苯二酚（RE）和对苯二酚(HQ)在0.5 mol/L硫酸水溶液中的电化学行为,循环伏安法和差分脉冲伏安法研究了CAT、RE 和HQ共存体系的伏安行为。 实验结果表明,在pH=0的硫酸水溶液中,扫描速率为10 mV/s,循环伏安法扫描电位在0～1.2 V（vs.Ag/Cl）时,分离效果明显。 本文采用差分脉冲伏安法,测定了CAT、RE和HQ的混合物,检出限依次为3.9×10-6、3.9×10-6和7.8×10-6 mol/L。 将该方法用于合成样品测定,其精密度和准确度均满足分析要求。     

Simultaneous Determination of Hydroquinone and Catechol by Differential Alternative Pulses Voltammetry

The second order voltammetric technique of high resolution, Differential Alternative Pulses Voltammetry (DAPV), was applied for the simultaneous determination of hydroquinone (HQ) and catechol (CC) on bare spectroscopic graphite electrode. Well resolved anodic and cathodic peaks situated on both sides of the zero line were obtained, while the differential pulse voltammograms were overlapped. The linear concentration range for HQ and CC quantification by DAPV was extended up to 20 μmol L⁻¹ for both the isomers. The sensitivity of the determination was found to be 6.00 μA L μmol⁻¹ and 3.61 μA L μmol⁻¹, while the limit of detection reached was 0.2 μmol L⁻¹ and 0.5 μmol L⁻¹ for HQ and CC, respectively. No interference was observed from the commonly coexisting organic species such as resorcinol, phenol and p‐benzoquinone. The great resolution power of DAPV permitted obtaining excellent results without any electrode modification and any mathematical data processing.     

聚苯胺-石墨烯修饰玻碳电极同时测定邻苯二酚和对苯二酚

本文制备了聚苯胺-石墨烯修饰玻碳电极,并用循环伏安(CV)法和微分脉冲伏安(DPV)法研究了邻苯二酚(CC)和对苯二酚(HQ)在该修饰电极上的电化学行为。实验结果表明,相对于裸玻碳电极,HQ和CC在聚苯胺-石墨烯修饰电极上的氧化峰电流显著提高,氧化峰电位相差104.8mV,实现了CC和HQ的选择性测定。DPV法同时测定二酚时,HQ和CC分别在1.0×10-6~8.0×10-4 mol/L浓度范围内与其峰电流呈良好的线性关系,相关系数R分别为0.998、0.997,检出限(S/N=3)分别为1.0×10-7、8.0×10-8mol/L。将该方法用于模拟水样分析,回收率为95.3%~103.5%。     

Simultaneous Electrochemical Determination of Hydroquinone and Catechol at MWNTs and Cobalt(II) Tetrakisphenylporphyrin Modified Electrode

A multi-wall carbon nanotubes (MWNTs) and cobalt(II) tetrakisphenylporphyrin (Co(II)TPP) modified glassy carbon electrode (MWNTs/Co(II)TPP/GCE) has been prepared. It can be used for individual or simultaneous determination of hydroquinone (HQ) and catechol (CC). The anodic peaks of HQ and CC can be separated well. Owing to the unique properties of MWNTs and special synergistic effect of MWNTs and Co(II)TPP, the modified electrode exhibited a remarkable and stable current response for CC and HQ. The linear ranges for CC and HQ were 1.0–450.0 µmol L^?1 and 0.8–400.0 µmol L^?1 with detection limits of 0.8 µmol L^?1 and 0.5 µmol L^?1, respectively. Furthermore, Co(II)TPP, MWNTs, and Co(II)TPP/MWNTs composite were also used to construct modified electrodes and the electrochemical performances were studied.     

Sensitive Electrochemical Determination of Catechol with a Graphene Modified Carbon Ionic Liquid Electrode

In this paper a graphene (GR) modified carbon ionic liquid electrode (CILE) was fabricated and used as the voltammetric sensor for the sensitive detection of catechol. Due to the specific physicochemical characteristics of GR such as high surface area, excellent conductivity and good electrochemical properties, the modified electrode exhibits rapid response and strong catalytic activity with high stability toward the electrochemical oxidation of catechol. A pair of well‐defined redox peaks appeared with the anodic and the cathodic peak potential located at 225 mV and 133 mV (vs.SCE) in pH 6.5 phosphate buffer solution, respectively. Electrochemical behaviors of catechol on the GR modified CILE were carefully investigated and the electrochemical parameters were calculated with the results of the electrode reaction standard rate constant (k_s) as 1.24 s^?1, the charge transfer coefficient (α) as 0.4 and the electron transfer number (n) as 2. Under the selected conditions the differential pulse voltammetric peak current increased linearly with the catechol concentrations in the range from 1.0 × 10^‐7 to 7.0 × 10^?4mol L‐1 with the detection limit as 3.0 × 10^?8mol L‐1 (3σ). The proposed method was further applied to the synthetic waste water samples determination with satisfactory results     

Electrochemical Sensing Platform Based on Lotus Stem-derived Porous Carbon for the Simultaneous Determination of Hydroquinone,Catechol and Nitrite

A simple and highly selective electrochemical sensor based on carbonized lotus stem (CLS) was developed for the simultaneous determination of hydroquinone (HQ), catechol (CC), and nitrite (NT) by using cyclic voltammetry (CV) and amperometry (AMP) methods. The CLS was characterized by the methods including field emission scanning electron microscopy (FE-SEM), Raman spectrum, FT-IR spectrum and X-ray diffraction (XRD). Brunauer-Emmett-Teller (BET) method was used to evaluate the pore structure and surface area of CLS. The oxidation peaks for HQ (116.2 mV), CC (220.1 mV), and NT (818.9 mV) were well separated under optimized conditions, which improved their simultaneous determination. The CLS modified electrode showed a good linear range between 1.0×10 ⁻⁶ to 7.0×10 ⁻⁴ M for HQ, and the detection limit was calculated as 0.15 μM. For CC the linear relationship was 1.0×10 ⁻⁶ to 3.0×10 ⁻³ M with the detection limit of 0.11 μM. For NT the linear relationship was 5.0×10 ⁻⁷ to 4.0×10 ⁻³ M with the detection limit of 0.09 μM. The results indicated that the intrinsic structure of natural biomass can be expected to design porous carbon for electrochemical sensors.     

卡尔曼滤波紫外光度法同时测定邻、间、对苯二酚

研究了苯二酚三种分异构体水溶液的紫外吸收光谱，在ＰＨ３．６的缓冲溶液中，邻、间、对苯二酚的紫我吸收峰分别为２７５ｎｍ，２７３ｎｍ和２８８ｎｍ三者重叠严重。选取在２４０ｎｍ－２９０ｎｍ范围内，每隔１ｎｍ测量一次吸光值截５１个点，采用卡尔曼滤波进行处理，可以获得较满意的结果，对１０个不同比例组成 标准混合液进行测定，邻、间、对苯二酚三者的平均回收率分别为９７．４％，１０１、７％和９８．０％，标准偏差分     

碳纳米管修饰电极同时测定邻苯二酚和对苯二酚

用十二烷基磺酸钠(SDS)分散碳纳米管(CNTs),通过层层组装(LBL)聚二甲基二烯丙基氯化铵(PDDA)和CNTs构筑PDDA/CNTs多层膜电极.利用紫外-可见光谱法对PDDA/CNTs多层膜的组装过程进行监测,用循环伏安法(CV)和差分脉冲伏安法(DPV)研究了邻苯二酚和对苯二酚同时存在时PDDA/CNTs多层膜电极上的电化学行为.结果表明,碳纳米管修饰电极对邻苯二酚和对苯二酚有较好的电催化活性和电分离作用,邻苯二酚和对苯二酚无需经过分离即可同时被检出.在修饰电极上的线性范围如下:邻苯二酚为2.0×10-6~1.4×10-4mol/L,线性相关系数R=0.9991;对苯二酚为2.0×10-6~1.4×10-4mol/L,线性相关系数R=0.9987.     

Simultaneous Determination of Catechol and Hydroquinone on Nano-Co/L-Cysteine Modified Glassy Carbon Electrode

In this study, a novel and highly sensitive electrochemical method for simultaneous determination of catechol (CC) and hydroquinone (HQ) was developed, which worked at GCE modified with Nano cobalt (Nano-Co) by electrodeposition and L-Cysteine by electrochemical polymerization. The Nano-Co/L-Cysteine GCE was investigated by cyclic voltammetry (CV), SEM and EIS. The excellent conditions have been selected including supporting electrolyte, pH, accumulation time and scan rate. The calibration curves of were obtained that the linear regression equation was I=0.0734c+6×10⁻⁶ in the range of 5.8 μM to 103 μM (R²=0.9942) for CC and the linear regression equation was I=0.0566c+5×10⁻⁶ in the range of 5.8 μM to 100 μM (R²=0.9967) for HQ. The obtained detection limits of CC and HQ both were 6×10⁻⁷ M. The modified electrode was successfully applied to the simultaneous determination of CC and HQ in water samples.     

卡尔曼滤波紫外光度法同时测定邻、间、对苯二酚

研究了苯二酚三种同分异构体水溶液的紫外吸收光谱，在ｐＨ３．６的缓冲溶液中，邻、间、对苯二酚的紫外吸收峰分别为２７５ｎｍ、２７３ｎｍ和２８８ｎｍ，三者重叠严重。选取在２４０ｕｍ～２９０ｎｍ范围内，每隔１ｎｍ测量一次吸光值共５１个点，采用卡尔曼滤波进行处理。可以获得较满意的结果。对１０个不同比例组成的标准混合液进行测定，邻、间、对苯二酚三者的平均回收率分别为９７．４％，１０１．７％和９８．０％，标准偏差分别为１．７２％，３．８６％和２．０４％。对模拟试样中加入标准的回收率均在９６．０％～１０３．０％之间。     

Simultaneous Determination of Hydroquinone and Catechol at an Activated Glassy Carbon Electrode

A selective and very simple electrochemical method, based on anodization of a glassy carbon electrode (GCE), was developed for the simultaneous detection of hydroquinone (HQ) and catechol (CT). It was found that the activated GCE showed an excellent catalytic behavior and enhanced reversibility towards the oxidation of both HQ and CT. The redox responses from the mixture of HQ and CT were easily resolved at an activated GCE. The detection limits for HQ and CT were calculated to be 0.16 and 0.11 μM, respectively. The activated GCE was successfully examined for real sample analysis with tap water and it showed a stable and reliable recovery data.     

聚谷氨酸修饰电极同时检测对苯二酚和邻苯二酚

以谷氨酸单体为初始试剂,利用电化学聚合方法制备得到聚谷氨酸修饰电极.考察了电化学聚合条件(电位、扫速及扫描圈数)对修饰电极的影响,运用电化学方法对所制备的修饰电极进行了表征.此修饰电极对对苯二酚和邻苯二酚的电化学氧化还原显示出很高的催化能力,显著降低了二者的氧化电位,改善了二者的电化学可逆性,同时增强了二者的氧化还原峰...     

Simultaneous Determination of Hydroquinone and Catechol at a Glassy Carbon Electrode Modified with Multiwall Carbon Nanotubes

A simply and high selectively electrochemical method for simultaneous determination of hydroquinone and catechol has been developed at a glassy carbon electrode modified with multiwall carbon nanotubes (MWNT). It was found that the oxidation peak separation of hydroquinone and catechol and the oxidation currents of hydroquinone and catechol greatly increase at MWNT modified electrode in 0.20 M acetate buffer solution (pH 4.5). The oxidation peaks of hydroquinone and catechol merge into a large peak of 302 mV (vs. Ag/AgCl, 3 M NaCl) at bare glassy carbon electrode. The two corresponding well‐defined oxidation peaks of hydroquinone in the presence of catechol at MWNT modified electrode occur at 264 mV and 162 mV, respectively. Under the optimized condition, the oxidation peak current of hydroquinone is linear over a range from 1.0×10^?6 M to 1.0×10^?4 M hydroquinone in the presence of 1.0×10^?4 M catechol with the detection limit of 7.5×10^?7 M and the oxidation peak current of catechol is linear over a range from 6.0×10^?7 M to 1.0×10^?4 M catechol in the presence of 1.0×10^?4 M hydroquinone with the detection limit of 2.0×10^?7 M. The proposed method has been applied to simultaneous determination of hydroquinone and catechol in a water sample with simplicity and high selectivity.     

金纳米粒子-过氧化聚吡咯-碳纳米管复合膜修饰电极同时测定对苯二酚和邻苯二酚

将多壁碳纳米管(MWCNTs)滴涂于复合陶瓷碳电极(CCE)表面,采用电化学方法在碳纳米管表面逐层沉积过氧化聚吡咯(OPPy)和金纳米粒子(AuNPs),制得金纳米粒子-过氧化聚吡咯-多壁碳纳米管复合膜修饰电极(AuNPs-OPPy-MWCNTs/CCE).采用扫描电镜和电化学方法对修饰电极进行了表征.在0.10 mol/LPBS (pH 7.0)缓冲溶液中研究了对苯二酚(HQ)和邻苯二酚(CC)在修饰电极上的电化学行为.结果表明,修饰电极对HQ和CC的电极过程具有良好的电化学响应和区分效应.基于此建立了一阶导数伏安法同时测定HQ和CC的方法,HQ和CC的线性范围均为2.0×10-7～ 1.0×10-4 mol/L,检出限分别为6.0×10-8 mol/L和8.0×10-8 mol/L(S/N=3).模拟水样中的加标回收率分别为96.2％～99.8％ (HQ)和96.0％～100.0％,表明本方法具有良好的实用性.     

聚L-半胱氨酸/多壁碳纳米管复合修饰电极同时测定邻苯二酚和对苯二酚

将羧基化多壁碳纳米管分散在L-半胱氨酸溶液中并滴涂在玻碳电极表面.将上述电极在pH 6.9的B-R缓冲溶液中,于-1.0～2.5 V的电位范围内进行电聚合,制备了聚L-半胱氨酸/多壁碳纳米管复合修饰电极(Pol-L-Cys/MWCNTs/GCE).研究发现,邻苯二酚和对苯二酚在聚L-半胱氨酸/多壁碳纳米管复合修饰电极上分别出现了一对氧化还原峰,且两者的氧化峰电位差达101 mV,提出了用微分脉冲伏安法同时测定邻苯二酚和对苯二酚的方法.氧化峰电流与邻苯二酚和对苯二酚的浓度在1.0×10-5～1.0×10-3mol·L-1呈线性关系,检出限(3S/N)均达1.0×10-5mol·L-1.修饰电极用于模拟样品中邻苯二酚和对苯二酚的测定,回收率在82.0%～107.0%之间.     

Cysteamine Capped Silver Nanoparticles and Single‐walled Carbon Nanotubes Composite Coated on Glassy Carbon Electrode for Simultaneous Analysis of Hydroquinone and Catechol

A stable complex of silver nanoparticles (Ag NPs) capped by cysteamine (Cst) together with single‐walled carbon nanotube (CNTs) was used to modify a glassy carbon electrode (GCE) for simultaneous detection of hydroquinone (HQ) and catechol (CT). The resulting electrode (AgCst‐CNTs/GCE) showed excellent electrocatalysis and reversibility towards this electroactive pair. The peak separations of their oxidation‐reduction peaks decreased significantly, compared with those of the unmodified GCE. The signal responses of the AgCst‐CNTs/GCE were 5‐fold higher while its peak potential separation remained unchanged (ca. 130 mV), compared to the CNTs‐modified GCE. The oxidation peak currents obtained for HQ and CT exhibited linearly from submicromolar to hundred micromolar concentrations without any cross‐interference. The modified electrode possessed a very large active surface area with a detection limit (S/N=3) of 10 and 40 nM for HQ and CT, respectively. The sensor was demonstrated for the analysis of river water and topical cream as evinced by high accuracy and reproducibility.     

磷钼钒杂多酸-聚邻苯二胺修饰碳糊电极示差脉冲溶出伏安法测定对苯二酚和邻苯二酚

在由磷钼钒杂多酸和邻苯二胺组成的支持电解质中,以0.100V.s-1扫速在碳糊电极上,于0.800～-0.800V范围内循环扫描20周后,制得磷钼钒杂多酸-聚邻苯二胺修饰碳糊电极。循环伏安法研究发现:对苯二酚(HQ)和邻苯二酚(CC)在该修饰电极上均出现了一对氧化还原峰;示差脉冲溶出伏安法研究发现:HQ和CC分别在0.140V和0.288V处出现二次微分溶出峰,两峰电位差为0.148V。HQ和CC的线性范围均为1.50×10-7～7.50×10-4 mol.L-1,检出限(3S/N)均为6.80×10-8 mol.L-1。据此提出了示差脉冲溶出伏安法测定模拟水样中HQ和CC,测得回收率在94.0%～106.0%之间。     

Simultaneous Electrochemical Determination of Hydroquinone and Bisphenol A using a Carbon Paste Electrode Modified with Silver Nanoparticles

In this paper, a rapid and sensitive modified electrode for the simultaneous determination of hydroquinone (HQ) and bisphenol A (BPA) is proposed. The simultaneous determination of these two compounds is extremely important since they can coexist in the same sample and are very harmful to plants, animals and the environment in general. A carbon paste electrode (CPE) was modified with silver nanoparticles (nAg) and polyvinylpyrrolidone (PVP). The PVP was used as a reducing and stabilizing agent of nAg from silver nitrate in aqueous media. The nAg‐PVP composite obtained was characterized by transmission electron microscopy and UV‐vis spectroscopy. The electrochemical behavior of HQ and BPA at the nAg‐PVP/CPE was investigated in 0.1 mol L⁻¹ B−R buffer (pH 6.0) using cyclic voltammetry (CV) and square wave voltammetry (SWV). The results indicate that the electrochemical responses are improved significantly with the use of the modified electrode. The calibration curves obtained by SWV, under the optimized conditions, showed linear ranges of 0.09–2.00 μmol L⁻¹ for HQ (limit of detection 0.088 μmol L⁻¹) and 0.04–1.00 μmol L⁻¹ for BPA (limit of detection 0.025 μmol L⁻¹). The modified electrode was successfully applied in the analysis of water samples and the results were comparable to those obtained using UV‐vis spectroscopy.     

Rational Design of Highly Efficient One-pot Synthesis of Ternary PtNiCo/FTO Nanocatalyst for Hydroquinone and Catechol Sensing

In this work, we present a simple and efficient method for preparation of widely dispersed PtNiCo nanocatalyst on FTO without the use of any heavy complex structure. The proposed nanocatalyst enhances the chemical interaction of PtNiCo/FTO and increases its catalytic activity, which was used for electrochemical sensing of catechol and hydroquinone. The surface morphology was characterized by TEM, HRTEM, and XRD. The size of the PtNiCo/FTO octahedrons nanocatalyst was about 0.35–4 nm. Gradual increase of concentration exhibited linearity in oxidation peak response up to 1100 μM with a low detection limit of 0.79 μM for HQ and 1.05 μM for CC. The sensitivity is 1035 μAmM⁻¹ cm⁻² for catechol and 1197 μAmM⁻¹ cm⁻² for hydroquinone. The prepared nanomaterial/sensor applied to real water samples with good reproducibility (98–99 %).