PVP-GR/GCE电化学检测塑料制品中双酚A的研究

针对塑料制品中双酚A(BPA)检测问题,制备了聚乙烯吡咯烷酮-石墨烯复合膜修饰玻碳电极(PVP-GR/GCE)并建立了BPA的电化学检测方法。通过扫描电子显微镜对PVP-GR的形貌进行了表征;以循环伏安法分别对GCE、PVP/GCE、GR/GCE以及PVP-GR/GCE进行了电化学表征;采用二阶导数线性扫描伏安法研究了PVP-GR/GCE对BPA的电化学性能;对检测条件进行了优化,并在最佳检测条件下对该电化学检测方法的线性范围、检测限、重现性、再现性、稳定性、选择性以及样品加标回收率进行了研究。实验结果表明:PVP-GR仍具有GR的特有性能,且其在水溶液中的分散性优于GR;K3[Fe(CN)6]在PVP-GR/GCE上的氧化峰电流最大,即PVP的引入改善了GR的水溶性,使PVP-GR/GCE的电化学性能增强;BPA在PVPGR/GCE的电化学响应较裸GCE明显增强;在最佳检测条件下,BPA的氧化峰电流与其浓度在0.01~0.40μmol/L和0.40~60.00μmol/L范围内呈良好的线性关系,检测限为8.0 nmol/L(信噪比为3),且该方法具有良好的选择性、灵敏度、重现性和稳定性,并成功被用于塑料制品中BPA的检测,回收率为97.3%~105.2%。     

脉冲电流法制备聚苯胺/纳米银复合膜

以高导电率的Ag作为添加材料 ,首次采用换向脉冲电流法使PANI和Ag发生共沉积 ,制成PANI/Ag复合电极。并用循环伏安研究了复合电极在硝酸溶液中的电化学性能及沉积过程中电化学参数对膜层电化学性能的影响。当Ag 浓度为 0 0 1mol/L ,苯胺浓度为 0 3mol/L ,沉积平均电流密度为 3～ 4mA/cm2 ,且脉冲阳极峰电流和阴极峰电流比值适当时可获得电化学性能最为优异的膜层。     

基于电沉积技术构建聚苯胺/海藻酸膜及电化学性能研究

基于电沉积技术的方法在电极表面构建聚苯胺(PANI)/海藻酸膜,直接构建PANI/海藻酸修饰电极,结合了海藻酸的阳极电沉积和苯胺的电化学聚合,具有条件温和以及后处理简便的特点。PANI/海藻酸膜呈现出与PANI类似的深绿色,其不仅可以稳定的存在于电极表面,而且还可以从电极表面取下来作为独立的膜材料。X射线衍射、红外光谱以及扫描电镜的测试结果均表明利用电沉积技术在电极表面制备得到了PANI/海藻酸膜。电化学性能分析结果表明,与PANI修饰电极相比,PANI/海藻酸修饰电极的电荷转移电阻更小,具备更高的电化学电容、更好的电荷储存能力和循环稳定性。     

基于碲膜置换制备粗糙金电极的无酶葡萄糖 电化学传感器

高粗糙度薄层贵金属纳米结构的界面组装对研制高性能的电化学传感器具有重要意义。以玻碳电极(GCE)上电沉积锯齿状形貌的半导体碲(Te)膜为模板,再将其与HAuCl_4进行原电池置换反应,制备了条棒状的粗糙Au薄膜修饰电极(AuTe-R/GCE)。在碱性环境中采用循环伏安法研究了AuTe-R/GCE对葡萄糖的电催化氧化性能,并藉此构建了无酶葡萄糖电化学传感器。结果表明,与普通的镀金GCE(Aucon/GCE)和裸Au电极相比,AuTe-R/GCE对葡萄糖的电催化氧化活性更高;在最优条件下,采用恒电位计时安培法检测了葡萄糖浓度,AuTe-R/GCE对葡萄糖的线性检测范围(LDR)为0.01～2.00 mmol·L~(-1),灵敏度为3.8 mA·mmol~(-1)·cm~(-2),检测下限(LOD)为55 nmol·L~(-1);且该无酶葡萄糖电化学传感器抗干扰能力强,稳定性好。以半导体碲膜制备特定形貌与高粗糙度薄层纳米Au的方法具有简便、快捷和低成本等优点,有望在高活性纳米电催化剂的界面组装及其电化学性能研究中被广泛应用。     

Ag/PANI纳米复合材料的超声合成及对酪氨酸的电催化研究

以苯胺、硝酸银为原料,在氮气氛围保护且不加氧化剂的稀硝酸溶液中,超声辐射合成Ag/PANI纳米复合材料。利用XRD、FT-IR、FESEM、EDS分别对产物的结构和形貌进行表征,并对Ag/PANI纳米复合材料修饰玻碳电极在电化学中对酪氨酸的电催化氧化情况进行研究。结果表明,Ag纳米粒子聚集体直径为(50±1)nm,均匀分布在PANI基体中,Ag/PANI纳米复合材料修饰电极对酪氨酸有较高的电催化活性。     

银/聚苯胺纳米复合材料的制备及电化学性能

采用苯胺为分散剂合成纳米银胶溶液,并在此基础上引发苯胺的原位复合,制备出银/聚苯胺(Ag/PANI)纳米复合材料。通过傅里叶变换红外光谱仪、X射线衍射分析仪、扫描电镜、透射电镜和电化学分析仪对产物进行了分析与检测。研究结果表明,Ag/PANI纳米复合材料中形成了聚苯胺在外、银纳米粒子在内的包覆结构,纳米复合粒子为类球形状形貌。引入纳米银粒子后,制备的Ag/PANI纳米复合材料的电化学活性和比容量较PANI有了很大提高。Ag/PANI纳米复合材料的腐蚀电流密度为72.1μA/cm2,比PANI的腐蚀电流密度106μA/cm2降低了33.9μA/cm2,纳米复合材料防腐性能得到显著提高。     

碳纳米管/聚苯胺化学修饰电极的制备及其对抗坏血酸的检测

通过恒电压沉积法将纳米金属镍沉积于石墨电极表面, 经化学气相沉积法在石墨电极表面原位生长出碳纳米管(CNTs), 通过电化学聚合法在CNTs表面原位聚合聚苯胺, 从而获得化学修饰电极。采用扫描电子显微镜对所得电极形貌结构进行表征, 并研究CNTs与PNAI复合电极对抗坏血酸(AA)的检测效果。研究结果表明: 制备的CNTs都能均匀地生长在石墨电极表面, 纳米中空管状结构都保持完好; PANI均匀地包覆在CNTs管壁上, 复合材料呈现出典型的三维网状结构。所制备的CNTs/PANI修饰电极对AA具有良好的电化学响应, 其中管径较小CNTs的修饰电极对AA的电化学响应更强: 具有更宽的检测范围和更低的检出限。其检测线性范围为1.0×10^-6~4.5×10^-4 mol/L, 检出限为1.0×10^-7 mol/L (S/N = 3)。且具有良好的稳定性、重复性和可靠性。     

一步法合成具有优异循环性能的聚苯胺纳米线/自支撑石墨烯复合材料

研究采用一步电化学剥离和电沉积法,在含Na₂SO₄、HCl与苯胺(An)单体的混合溶液中,以柔性石墨纸为原料,利用电场条件下电解液离子定向迁移和苯胺单体的电聚合制备聚苯胺纳米线/自支撑石墨烯(PANI/SGr)复合材料。更具活性的新生SGr与PANI结合,显著提高了PANI/SGr复合材料的稳定性。PANI呈纳米线状均匀分布在SGr上,形成的三维网络结构所呈现出的孔隙促进了电解液离子扩散到复合材料的内部结构中。将PANI/SGr复合材料作为超级电容器电极材料进行电化学测试,2 mV·s?1的扫速下获得的比电容为453 F·g?1。在0.5~10 A·g?1的电流密度范围内,PANI/SGr复合材料倍率性能达73.1%。在1 A·g?1的电流密度下PANI/SGr复合材料经10000次充放电之后的循环稳定性仍高达87.3%。这表明PANI/SGr复合材料具有良好的电容性能和优异的循环稳定性,有望作为超级电容器电极材料。      

涂覆热分解与电化学聚合法制备聚苯胺/RuO2复合电极材料

通过涂覆热分解法并结合电化学聚合法制备得到聚苯胺(PANI)/RuO₂电极材料。使用涂覆热分解法于260℃热处理3 h制备RuO₂薄膜, 通过电化学聚合法将PANI粒子沉积在RuO₂薄膜上, 并在80℃加热12 h。采用XRD分析PANI/RuO₂复合物晶相, 采用SEM观察PANI/RuO₂复合电极材料的形貌变化。利用循环伏安及恒流充放电测试了该复合电极的电化学性能。结果表明, PANI沉积时间为25 min, 该PANI/RuO₂复合电极的最大电容量为9.72 F, 比电容为452 F·g^-1, 充放电曲线体现了较低的电压降、等效串联电阻及良好的充放电性能。经1000次循环伏安后, 其比电容损失约为11%。     

纤维素纳米纤丝-还原氧化石墨烯/聚苯胺气凝胶柔性电极复合材料的制备与性能

利用高长径比的纤维素纳米纤丝（CNF）与片层结构的氧化石墨烯（GO）形成的CNF-GO复合水凝胶经抗坏血酸还原制备出CNF-还原氧化石墨烯（rGO）复合水凝胶材料。通过冷冻干燥法得到CNF-rGO复合气凝胶,并进一步通过苯胺单体在CNF-rGO复合气凝胶的孔道内原位聚合制备出CNF-rGO/聚苯胺（PANI）气凝胶柔性电极复合材料。研究了不同苯胺、CNF和GO的质量比对CNF-rGO/PANI气凝胶柔性电极复合材料的结构形貌和电化学性能的影响。结果表明,苯胺原位聚合后所得CNF-rGO/PANI复合气凝胶仍具有紧密的三维多孔网络结构。与rGO/PANI气凝胶电极复合材料相比,CNF-rGO/PANI气凝胶电极复合材料具有更理想的电容行为。当CNF与GO质量比为60∶40,PANI添加量为0.1 mol时,CNF-rGO/PANI气凝胶电极复合材料比电容可达85.9 Fg-1,且其电化学性能几乎不受弯曲程度的影响,展现出了良好的柔韧性和电化学性能。      

基于Pd/Fe3O4/rGO纳米复合材料的H2O2无酶传感器

环境监测、食品工业、临床、制药等领域对过氧化氢(H_2O_2)的快速、准确检测有极大的需求,而电化学检测方法由于灵敏度高、响应快、检测限低等特点被认为是最理想的H_2O_2检测方法.本文利用电化学沉积的方法将Pd纳米颗粒沉积到四氧化三铁/石墨烯(Fe_3O_4/rGO)纳米复合材料修饰的玻碳电极表面,形成基于新型磁性纳米复合材料的H_2O_2无酶传感器;并采用循环伏安和计时安培电流等方法对修饰电极的电化学性能进行了表征.结果表明:制备的Pd/Fe_3O_4/r GO/GCE对H_2O_2的催化还原显示出较好的电催化活性,Pd纳米颗粒和Fe_3O_4/rGO在催化H_2O_2还原的过程中表现出了良好的协同作用.测定H_2O_2的线性范围为0.05~1 m M和1~2.6 m M两段,最低检测限达到3.918μM(S/N=3).并且该传感器具有较高的灵敏度和较好的重现性和抗干扰性,具有一定的实际应用价值.     

A selective and sensitive electrochemical determination of catechol based on reduced graphene oxide decorated β-cyclodextrin nanosheet modified glassy carbon electrode

In the present work, we have demonstrated the fabrication of catechol (CC) biosensor based on reduced graphene oxide (rGO) decorated β-cyclodextrin (β-CD) nanosheet immobilized using nafion (Nf) on modified GCE (glassy carbon electrode). The rGO/β-CD nanocomposite is synthesized through sonochemical approach and characterized by spectral (UV–visible, FT-IR, and Raman), analytical techniques (XRD, SEM, SAED, mapping analysis, HR-TEM and EDX) and electrochemical studies. The rGO/β-CD/Nf modified GCE exhibit a prominent electrocatalytic activity towards selective and sensitive determination of CC than other modified electrodes. Besides, the electrochemical sensor was revealed an excellent current response for the determination of CC with wide linear ranges (0.1–0.7 µM), high sensitivity (19.1 µA µM^-1cm²) and very low detection limit (LOD) 0.0012 µM. The excellent reproducibility, selectivity, stability, and sensitivity results are achieved for the determination of CC.     

Synthesis,characterization, and voltammetric hydrogen peroxide sensing on novel monometallic (Ag,Co/MWCNT) and bimetallic (AgCo/MWCNT) alloy nanoparticles

Multiwall carbon nanotube supported (MWCNT) Ag, Co, and Ag-Co alloy nanocatalysts were synthesized at varying metal loadings by borohydride reduction methods without stabilizers to obtain enhanced hydrogen peroxide sensitivity. The resulting materials were characterized employing Scanning electron microscopy (SEM), Energy dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD). For electrochemical measurements carried out cyclic voltammetry (CV) and differential pulse voltammetry (DPV), glassy carbon electrode (GCE) was modified with Ag/MWCNT, Co/MWCNT, and Ag-Co/MWCNT alloy nanoparticles. Ag-Co/MWCNT/GCE exhibited the highest performance toward electrochemical oxidation of H₂O₂ in 0.1 M phosphate buffered solution (PBS). Furthermore, the sensitivity and the limit of detection values for Ag-Co/MWCNT/GCE were obtained as 57.14 µA cm^?2 mM^?1and 0.74 µM, respectively. However, the sensitivity values for Ag/MWCNT/GCE, and Co/MWCNT/GCE are 41.66 and 13.88 µA cm^?2 mM^?1, respectively. The LOD values were predicted as 1.84 µM for Ag/MWCNT/GCE and 3.3 µM for Co/MWCNT/GCE.

In addition, the interference experiment indicated that the Ag-Co/MWCNT alloy nanoparticles have good selectivity toward H₂O₂.     

A reduced graphene oxide based electrochemical biosensor for tyrosine detection

In this paper, a 'green' and safe hydrothermal method has been used to reduce graphene oxide and produce hemin modified graphene nanosheet (HGN) based electrochemical biosensors for the determination of l-tyrosine levels. The as-fabricated HGN biosensors were characterized by UV-visible absorption spectra, fluorescence spectra, Fourier transform infrared spectroscopy (FTIR) spectra and thermogravimetric analysis (TGA). The experimental results indicated that hemin was successfully immobilized on the reduced graphene oxide nanosheet (rGO) through π-π interaction. TEM images and EDX results further confirmed the attachment of hemin on the rGO nanosheet. Cyclic voltammetry tests were carried out for the bare glass carbon electrode (GCE), the rGO electrode (rGO/GCE), and the hemin-rGO electrode (HGN/GCE). The HGN/GCE based biosensor exhibits a tyrosine detection linear range from 5?×?10(-7)?M to 2?×?10(-5)?M with a detection limitation of 7.5?×?10(-8)?M at a signal-to-noise ratio of 3. The sensitivity of this biosensor is 133 times higher than that of the bare GCE. In comparison with other works, electroactive biosensors are easily fabricated, easily controlled and cost-effective. Moreover, the hemin-rGO based biosensors demonstrate higher stability, a broader detection linear range and better detection sensitivity. Study of the oxidation scheme reveals that the rGO enhances the electron transfer between the electrode and the hemin, and the existence of hemin groups effectively electrocatalyzes the oxidation of tyrosine. This study contributes to a widespread clinical application of nanomaterial based biosensor devices with a broader detection linear range, improved stability, enhanced sensitivity and reduced costs.     

Fabrication of TiO2 nanoparticles/surfactant polymer complex film on glassy carbon electrode and its application to sensing trace dopamine

A novel method for the fabrication of a TiO₂/Nafion nano-film on glassy carbon electrode (NTGCE) is described. In the presence of dispersant, TiO₂ nanoparticles were dispersed into water to give a homogeneous and stable suspension. After the solvent evaporation, a porous and uniform TiO₂ nano-film was obtained on the GCE surface. Further coated with Nafion, the complex film possesses remarkable stability in aqueous solution. This nano-film was characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The prepared electrode showed excellent electrocatalytic behavior of dopamine and high concentration of ascorbic acid does not interfere with the dopamine detection. Based on this, an electrochemical method is developed for the determination of dopamine with simplicity and high sensitivity.     

Scaly Graphene Oxide/Graphite Fiber Hybrid Electrodes for DNA Biosensors

The demand for a highly sensitive and stable DNA biosensor that can be used for implantable or on‐time monitoring is constantly increasing. In this work, for the first time graphene oxide (GO) sheets are synthesized in situ at the surface of graphite fibers to yield scaly GO/graphite fiber hybrid electrodes. The partially peeled GO sheets, directly connected with the graphite fibers, not only provide a large number of binding sites for single‐stranded DNA, but also favor high electron transfer rates from GO to the graphite fibers. Cyclic voltammetry (CV) confirms that the scaly GO/graphite fiber hybrid electrode has excellent electrochemical activity. As a working electrode in an electrochemical impedance DNA biosensor, the fiber hybrid electrode exhibits high selectivity, sensitivity, and stability. Due to its simplicity, low cost, high stability, small size, and unique microfiber morphology, the scaly GO/graphite fiber hybrid electrode is an excellent candidate for an implantable biosensor. The method developed here could have a profound impact on the design of GO‐based biosensors for DNA detection.     

Direct determination of oxalic acid by a bare platinum electrode contrasting a platinum nanoparticles-modified glassy carbon electrode

A bare platinum disk electrode without further decoration was directly used to determine oxalic acid (OA), showing good linear ranges of 0.57–104.01 μM and 104.01–228.75 μM with a low detection limit of 0.38 μM (S/N = 3). In contrast, platinum nanoparticles (PtNPs) dispersed on a glassy carbon electrode were successfully achieved by an one-step electrochemical deposition method, possessing relatively wider linear detection ranges of 1.14–342.80 μM and 342.80–548.92 μM for OA with a lower detection limit of 0.28 μM (S/N = 3). Both the proposed electrochemical sensors exhibit great reproducibility, stability and selectivity. In particular, they have been applied to the determination of OA in real spinach samples, showing excellent analytical performance.     

2D-titanium carbide (MXene) based selective electrochemical sensor for simultaneous detection of ascorbic acid,dopamine and uric acid

Two-dimensional (2D) titanium carbide (MXene) nanosheets exhibited excellent conductivity,flexibility,high volumetric capacity,hydrophilic surface,thermal stability,etc.So,it has been exploited in various applications.Herein,we report synthesis of mixed phase 2D MXene as a catalytic material for simultaneous detection of important biomolecules such as ascorbic acid (AA),dopamine (DA) and uric acid (UA),Crystalline structure,surface morphology and elemental composition of mixed phase titanium carbide (Ti-C-Tx) MXene (Tx =-F,-OH,or-O) nanosheets were confirmed by X-ray diffraction (XRD),Raman spectroscopy,high-resolution transmission electron microscopy (HR-TEM),high-resolution scanning electron microscopy (HR-SEM) and Energy-dispersive X-ray spectroscopy (EDS) mapping analysis.Furthermore,Ti-C-Tx modified glassy carbon electrode (GCE) was prepared and its electrochemical properties are studied by cyclic voltammetry (CV) and differential pulse voltammetry (DPV).It was found that Ti-C-Tx modified GCE (Ti-C-Tx/GCE) showed excellent electrocatalytic activity and separated oxidation peaks of important biomolecules such as AA (at 0.01 V),DA (at 0.21 V) and UA (at 0.33 V).Also,Ti-C-Tx/GCE sensor is enabled their simultaneous detection in physiological pH from 100 to 1000 μM for AA,0.5-50 μM for DA and 0.5-4 μM & 100-1500 μM for UA.The limit ofdetection's (LOD) was estimated as 4.6 μM,0.06 μM and 0.075 μM for AA,DA and UA,respectively.Moreover,real sample analysis indicated that spiked AA,DA and UA can be determined accurately by Ti-C-Tx/GCE with the recovery ratio in the range between 100.5％-103％ in human urine samples.The proposed Ti-C-Tx modified electrode exhibited good stability,selectivity and reproducibility as an electrochemical sensor for the detection ofAA,DA and UA molecules.