基于纳米二氧化锆与铂微粒复合修饰玻碳电极的甲醛传感器研究

采用循环伏安法在玻碳电极表面依次电沉积纳米二氧化锆和铂微粒,制备了一种检测甲醛的新型电化学传感器。用电镜扫描对该修饰电极表面进行了表征,循环伏安法和线性扫描伏安法研究了甲醛在该修饰电极上的电催化氧化作用,优化了实验参数。结果表明,该修饰电极对甲醛有很好的电催化氧化作用,在0.1 mol/L H2SO4溶液中,甲醛的氧化峰电流与其浓度在1.0×10-6~5.0×10-3mol/L范围内呈良好线性关系,回归方程为Ip(μA)=79.95+2.005×105c(mol/L),相关系数r=0.999 3,检出限为5.0×10-7mol/L。     

碳纸负载碳酸氢镍纳米颗粒的无酶葡萄糖电化学传感器

通过一步水热法在碳纸上原位生长碳酸氢镍纳米颗粒,利用粉末X射线衍射和扫描电子显微镜对材料的结构及形貌进行表征,发现碳纸上负载纯相Ni （HCO₃）₂时具有较多的催化活性位点,利于葡萄糖的催化氧化反应进行。循环伏安法和时间-电流响应曲线表明该电极的检测限为0.98 μmol·L^-1,线性范围为2.95~1.02 mmol·L^-1,灵敏度为935 μA·L·mmol^-1·cm^-2,同时具有优异的选择性及稳定性。此外,该传感器能够实现对乳制品中葡萄糖的快速检测。这些结果表明,过渡金属和导电基底的协同作用会增强复合材料整体的导电性能和催化性能。     

Mesoporous Nickel Electrode for the Detection of Alcohol

Mesoporous nickel electrodes have been shown to be excellent amperometric sensors for alcohol detection over a wide‐range of concentrations. At a higher electrolyte concentrations (NaOH, 4 M), the electrodes exhibited a remarkably higher sensitivity (1072.7 μA mM^?1 cm^?2) than conventional nickel based electrodes, within an alcohol concentration range 0.5–3 M. Additionally, electrodeposited Ni electrodes formed with Brij 56 as a template, have significantly higher roughness than similar electrodes made without template. Higher roughness factors correlated with higher sensitivities for alcohol sensing, but needed longer times to remove the template from the Ni film.     

A Novel Sensitive Electrochemical Sensor Based on Nickel Chloride Solution Modified Glassy Carbon Electrode for Curcumin Determination

In this research, the high conductivity of nickel chloride solution as well as the ability of nickel ions in establishing particular bonds with curcumin was benefited to fabricate a new electrochemical sensor based on nickel chloride solution modified glassy carbon electrode (NiCl₂/GCE) for detection and measurement of curcumin in human blood serum. Atomic force microscope (AFM), cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS) methods indicated that using nickel chloride solution for the modification of the glassy carbon electrode (GCE) surface had a significant effect on improvement of the electrode performance. Differential pulse voltammetry (DPV) was used for quantitative measurement of curcumin, which exhibited the linear response of NiCl₂/GCE toward curcumin within the concentration range of 10–600 μM and provided the detection limit of 0.109 μM for curcumin in human blood serum.     

刚果红功能化水溶性碳纳米管膜电极的制备及在电化学传感器中的应用

基于刚果红(CR)表面修饰多壁碳纳米管(MWNTs)在干燥时所具有的良好成膜性能,在玻碳电极表面制备了一种水溶性MWNTs(MWNTs-CR)膜,用扫描电镜(SEM)、傅立叶红外光谱(FTIR)和交流阻抗谱(ElS)对其进行了表征.结果表明,MWNTs-CR能在电极表面形成一层致密、均匀含有大量纳米级微孔的纳米结构薄膜.和裸玻碳电极相比,MWNTs-CR膜修饰电极能极大的增强雌酮和羟甲香豆素的电化学响应.在体系中加入表面活性剂后,其电化学响应能得到进一步的提高.羟甲香豆素的浓度在8.0×10-8～4.0×10-6 mol/L范围内,其氧化峰电流与浓度呈现出良好的线性关系.在开路条件下富300 s后,HMC的检出限为2.0×10-8 mol/L.实验证明水溶性MWNTs膜是构建碳纳米管电化学传感器的理想材料.     

Electroless Nickel Plating and Electroplating on FBG Temperature Sensor

Metal-coated fiber Bragg grating（FBG）temperature sensors were prepared via electroless nickel（EN）plating and tin electroplating methods on the surface of normal bare FBG.The surface morphologies of the metal-coated layers were observed under a metallographic microscope.The effects of pretreatment sequence,pH value of EN plating solution and current density of electroplating on the performance of the metal-coated layers were analyzed.Meanwhile, the Bragg wavelength shift induced by temperature was monitored by an optical spectrum analyzer.Sensitivity of the metal-coated FBG（MFBG）sensor was almost two times that of normal bare FBG sensor.The measuring temperature of the MFBG sensor could be up to 280℃,which was much better than that of conventional FBG sensor.     

Ni电极电化学流通池检测四环素类药品的研究

比较Au、GC和Ni电极对四环素的电化学响应,讨论了纯Ni电极对四环素的电催化氧化特性,提出以纯Ni为工作电极的电化学流通池,优化结构,建立了测定四环素类抗生素的电化学流通池安培检测法.该方法对四环素、土霉素和强力霉素都有较高的响应灵敏度,线性范围0.1～15mg/L.最低检出限分别为35、45和43μg/L.用此方法可以直接测定四环素类药品的含量.     

甲醛电化学传感器多孔气体扩散电极不同催化层结构与响应性能研究

多孔气体扩散电极的制备是制备甲醛电化学传感器的关键所在, 其中催化层的结构直接影响到传感器的响应性能. 通过柠檬酸三钠还原法合成了纳米金-活性炭、纳米金-碳纳米管催化剂, 制备了甲醛电化学传感器多孔气体扩散电极, 并对电极进行SEM(扫描电子显微镜)物理表征. 在甲醛气体浓度为0.24和0.63 mg/m³时, 电极C具有较好的响应, 在0.1到0.84 mg/m³浓度范围内, 线性方程为y＝10.515x＋4.4049 (R²＝0.9917), 响应时间约80 s. 分析了不同催化剂的气体扩散电极结构与甲醛响应性的关系, 为研制开发性能优良的甲醛电化学传感器奠定了基础.     

An Electrochemical Sensor Based on Nitrogen‐doped Carbon Nanofiber for Bisphenol A Determination

In this paper, bisphenol A was determined by electrochemical method at a nitrogen‐doped carbon nanofiber modified carbon paste electrode (NCNF/CPE) with high sensitivity and good selectivity. NCNF was obtained by a simple electrospinning followed by carbonization procedure, in which polyacrylonitrile (PAN) as precursor and nitrogen doping was realized by re‐utilizing the tail gas that produced in the thermal pretreatment process. Good reproducibility and high stability were obtained for BPA detection at NCNF modified CPE. Current response plotted with BPA concentration was linear in the range of 0.1–60 μM with LOD of 0.05 μM. The proposed electrochemical sensor was employed for BPA determination with satisfactory recoveries for real water samples, indicating the practical applicability of NCNF/CPE.     

Modified Natural Rubber as a Simple Chemical Sensor with Smartphone Detection for Formaldehyde Content in a Seafood Sample

A new biodegradable platform-based sensor for formaldehyde assay is proposed. Natural rubber latex was modified to polylactic acid–chloroacetated natural rubber polymer blend sheets. The polymer blend sheet was grafted using a water-based system with amine monomers as a platform, with a spot exhibiting positive polarity for immobilizing with anionic dye (Acid Red 27). The sensor was exposed to formaldehyde. The color intensity of the dye on the sensor spot would decrease. Using a smartphone with image processing (via ImageJ program), the color intensity change (∆B) could be followed. A linear calibration, ∆B intensity = 0.365 [FA] + 6.988, R² = 0.997, was obtained for 10–150 mM FA with LOD and LOQ at 3 and 10 mM, respectively (linear regression method). The precision was lower than 20% RSD. Application to real seafood samples was demonstrated. The ready-to-use sensor with the proposed method was cost-effective, was portable for on-site analysis, and demonstrated green chemical analysis.     

基于聚苯胺-镍酞菁多孔渗透薄膜的氨气传感器

利用磺化镍酞菁(NiTSPc)对苯胺(PANI)聚合的催化作用,通过简单的电聚合方法在叉指金电极(IAE)表面合成了PANI/NiTSPc多孔渗透膜.利用扫描电子显微镜(SEM)、原子力显微镜(AFM)、能量色散图谱(EDS)和拉曼光谱对PANI/NiTSPc多孔膜进行表征.在室温下,采用基于PANI/NiTSPc多孔膜制备的传感器对不同浓度(3.8~1900 mg/m~3)的NH_3进行了检测.结果表明,对于76 mg/m~3的NH_3,传感器的灵敏度为2.75,响应时间为10 s,且该传感器具有恢复时间短、重复性及稳定性良好等优点.所制备的PANI/NiTSPc薄膜传感器在NH3检测及电子鼻的应用中具有巨大潜力.     

DNA-纳米金修饰玻碳电极用于水中甲醛的测定

利用纳米金的生物共容性和高电荷传递性能在玻碳电极表面构建纳米粒子生物活性界面,研究了DNA在其界面上对甲醛的电催化作用.通过电化学沉积方法制备了DNA-纳米金修饰的玻碳电极,并对该电极进行了形貌表征,发现平均直径为100 nm的多面体纳米金均匀分布在电极表面.利用微分脉冲伏安法和安培法对甲醛进行了检测,优化了实验参数.结果表明:该修饰电极实现了对甲醛的灵敏测定,线性范围为1×10-5 ～1×10-3 mol/L,检出限为1.0 μmol/L.该电极表现出较好的稳定性,对实际水样的测定回收率为95% ～103%.     

Nickel and Tungsten Bimetallic Nanoparticles Modified Pencil Graphite Electrode: A High-performance Electrochemical Sensor for Detection of Endocrine Disruptor Bisphenol A

In this work, an economically viable, very low cost, indigenous, ubiquitously available electrochemical sensor based on bimetallic nickel and tungsten nanoparticles modified pencil graphite electrode (NiNP-WNP@PGE) was fabricated for the sensitive and selective detection of bisphenol A (BPA). The NiNP-WNP@PGE sensor was prepared by a facile electrochemical one step co-deposition method. The prepared nanocomposite was morphologically characterized by scanning electron microscopy (SEM), energy dispersive X-ray (EDX), X-ray diffraction (XRD), electrochemically by cyclic voltammetry (CV), and electrochemical impedance spectroscopy (EIS). The proposed sensor displayed high electrocatalytic activity towards electro-oxidation of BPA with one irreversible peak. The fabricated sensor displayed a wide detection window between 0.025 μM and 250 μM with a limit of detection of 0.012 μM. PGE sensor was successfully engaged for the detection of BPA in bottled water, biological, and baby glass samples.     

呋喃妥因分子印迹电化学传感器的制备及应用

以甲基丙烯酸为功能单体,呋喃妥因为模板分子,马来松香丙烯酸乙二醇酯(EGMRA)为交联剂,在玻碳电极表面制备了呋喃妥因分子印迹膜。采用循环伏安(CV)法、差分脉冲伏安(DPV)法及交流阻抗(EIS)法对印迹膜进行表征。实验表明,DPV法测定的氧化峰电流与呋喃妥因浓度在8.0×10-8~5.0×10-6 mol/L范围内呈良好的线性关系(R=0.9939),检出限为6.5×10-8 mol/L。该传感器用于呋喃妥因肠溶片的测定,其回收率为96.6%~101.6%。     

On the Existence and Role of Formaldehyde During Aqueous Electrochemical Reduction of Carbon Monoxide to Methanol by Cobalt Phthalocyanine

A long-time challenge in aqueous CO₂ electrochemical reduction is to catalyze the formation of products beyond carbon monoxide with selectivity. Formaldehyde is the simplest of these products and one of the most relevant due to its broad use in the industry. Paradoxically it is one of the less reported product. Such scarcity may be in part explained by difficult identification and quantification using conventional chromatography or proton nuclear magnetic resonance techniques. Likewise, indirect detection methods are usually not compatible with labelled studies for asserting product origin. Recently, the possible production of formaldehyde during electrochemical reduction of carbon monoxide to methanol at cobalt phthalocyanine molecular catalyst in basic media has been the object of contradictory reports. By applying an analytical procedure based on proton NMR along with labelled studies, we provide definitive evidence for HCHO formation. We have further identified the possible scenarios for methanol formation through formaldehyde and revealed that the formation of the intermediate and its subsequent reduction are taking place at the same single active site. These studies open a new perspective to improve selectivity toward formaldehyde formation and to develop a subsequent chemistry based on reacting it with nucleophiles.     

单壁碳纳米管-氨基二茂铁复合物修饰玻碳电极对对硝基苯酚的电化学检测

本研究用氨基二茂铁(Aminoferrocene,AFc)经重氮化反应后修饰单壁碳纳米管(SWNTs),制备SWNTs-AFc复合物,并以该复合物修饰玻碳电极(GCE),通过循环伏安法(CV)和差分脉冲伏安法(DPV)等电化学方法检测对硝基苯酚(p-NP)。结果表明,与裸玻碳电极相比,SWNTs-AFc/GCE对p-NP响应的还原过电位显著减小,峰电流大大增强,p-NP的检测线性范围为1~850μmol/L(R2=0.997),检测限为1μmol/L。该方法电流响应快、灵敏度高、检测限低,具有良好的应用前景。     

基于分子印迹电聚合膜的双酚A电化学传感器

以双酚A为模板分子,邻氨基苯硫酚为单体,采用自组装和电聚合方法,在电极表面制备了对双酚A有选择性的分子印迹聚合物膜.通过循环伏安法研究传感器对双酚A的响应特性.结果表明: 在6.0×10-7～5.5×10-5 mol/L浓度范围内峰电流值与浓度呈良好线性关系(r=0.991);检出限2.0×10-7 mol/L; 相对标准偏差<5%(n=9),达到稳定电流所用时间约2 min.此传感器具有良好的选择性、重现性及稳定性.通过交流阻抗技术和计时电流法表征了电极表面膜的电化学性质.将传感器初步用于实际样品的分析,获得了较满意的结果.     

Electrochemical Sensor Based on Multi‐walled Carbon Nanotube/Gold Nanoparticle Modified Glassy Carbon Electrode for Detection of Estradiol in Environmental Samples

We report a rapid and simple method for sensing estradiol by electro‐oxidation on a multi‐walled carbon nanotube (MWCNT) and gold nanoparticle (AuNP) modified glassy carbon electrode (GCE). Compared with a bare GCE, AuNP/GCE and MWCNT/GCE, the composite modified GCE shows an enhanced response to estradiol in 0.1 M phosphate buffer solution. Experimental parameters, including pH and accumulation time for estradiol determination were optimised at AuNP/MWCNT/GCE. A pH of 7.0 was found to be optimum pH with an accumulation time of 5 minutes. Estradiol was determined by linear sweep voltammetry over a dynamic range up to 20 %mol L^?1 and the limit of detection was estimated to be 7.0×10^?8 mol L^?1. The sensor was successfully applied to estradiol determination in tap water and waste water.     

Disposable Electrochemical Sensor for Food Colorants Detection by Reduced Graphene Oxide and Methionine Film Modified Screen Printed Carbon Electrode

A facile synthesis of reduced graphene oxide (rGO) and methionine film modified screen printed carbon electrode (rGO-methionine/SPCE) was proposed as a disposable sensor for determination of food colorants including amaranth, tartrazine, sunset yellow, and carminic acid. The fabrication process can be achieved in only 2 steps including drop-casting of rGO and electropolymerization of poly(L-methionine) film on SPCE. Surface morphology of modified electrode was studied by scanning electron microscopy (SEM). This work showed a successfully developed novel disposable sensor for detection of all 4 dyes as food colorants. The electrochemical behavior of all 4 food colorants were investigated on modified electrodes. The rGO-methionine/SPCE significantly enhanced catalytic activity of all 4 dyes. The pH value and accumulation time were optimized to obtain optimal condition of each colorant. Differential pulse voltammetry (DPV) was used for determination, and two linear detection ranges were observed for each dye. Linear detection ranges were found from 1 to 10 and 10 to 100 µM for amaranth, 1 to 10 and 10 to 85 µM for tartrazine, 1 to 10 and 10 to 50 µM for sunset yellow, and 1 to 20 and 20 to 60 µM for carminic acid. The limit of detection (LOD) was calculated at 57, 41, 48, and 36 nM for amaranth, tartrazine, sunset yellow, and carminic acid, respectively. In addition, the modified sensor also demonstrated high tolerance to interference substances, good repeatability, and high performance for real sample analysis.