自组装时间和高温处理对Au/BDD电极表面形貌的影响及电化学性能分析

应用静电力自组装的方法在掺硼金刚石薄膜(BDD)电极表面制备了纳米Au颗粒的单层膜,通过高温加热使纳米Au颗粒牢固修饰在BDD薄膜表面。采用SEM和XPS对其表面形貌进行了表征,纳米Au颗粒在BDD薄膜表面分散均匀,且不存在团聚现象。采用循环伏安法和电化学阻抗谱对其电化学性能进行了研究,并对多巴胺进行了检测。结果表明:修饰后的BDD电极界面间电子转移速率显著提高,且对多巴胺表现出良好的电催化性;氧化峰电位由0.52V减小为0.3V,且氧化峰电流为BDD电极的1.9倍,检测限为3.0×10-6 mol/L,且在多巴胺和尿酸的混合溶液中有很强的选择性,为生物分子的检测提供了新方法。     

超薄金修饰的钯电极用于乙醇安培传感研究

超薄贵金属膜具有独特的结构和功能,创新其制备方法,拓展其电 化学应用具有重要意义。通过在镀 Pd 的玻碳电极（GCE）上电沉积欠导电 Se 超薄膜并作为模板,再与 HAuCl 4 进行原电池置换反应,制备了超薄 Au 膜修饰的镀 Pd 电极（Au Se /Pd/GCE）,并在碱性条件下采用循环伏安法研究 了 Au Se /Pd/GCE 对乙醇的电催化氧化性能影响,并构建了乙醇安培传感器。 研究表明,与裸 Pd 电极相比,Au Se /Pd/GCE 对乙醇的电催化氧化活性更高; 在最优条件下,修饰电极对乙醇的线性检测范围为 0.025~10.000 mmol·L -1,灵敏度为 0.94 (mA·cm -2)/(mmol·L-1),优于多数已报道的方法。此种以欠导电物质均匀电沉积薄膜为模板,采用原电池置换反应制备超薄贵金属膜的新 方法有望在纳米电催化剂的制备及电催化与电分析研究中广泛应用。     

基于[C_(10)-mim~+]Br~-固定HRP于Au/石墨烯复合材料电极表面的新型H_2O_2酶生物传感器

利用长链离子液体特殊的性质,用其固定HRP于Au/graphene电极表面(Nafion/HRP/[C10-mim+]Br-/Au/Gr/GCE)组装成H2O2传感器。用透射电镜来表征Au/氧化石墨烯的形貌,金纳米颗粒很均匀的分散在石墨烯表面,并不存在团聚现像。电化学技术检测Nafion/HRP/[C10-mim+]Br-/Au/Gr修饰电极对H2O2的响应情况,显示修饰电极对H2O2有很好的响应,在H2O2浓度2.0×10-6~1.2×10-3 mol/L的范围内,还原电流与浓度存在线性关系(R=0.997),检测限为3.0×10-7 mol/L;另外传感器具有很好的稳定性和选择性,为生物分子的检测提供新方法。     

功能化石墨烯多层膜载金催化剂的制备及其对肼的电催化氧化

以聚二甲基二烯丙基氯化铵功能化石墨烯(PDDA-GNs)和磷钼酸功能化石墨烯(PMo₁₂-GNs)为原料,利用层层自组装法制备了功能化石墨烯多层膜({PDDA-GNs/PMo₁₂-GNs}),以此多层膜为载体,通过恒电位电沉积法制备功能化石墨烯多层膜载金催化剂(Au/{PDDA-GNs/PMo₁₂-GNs}_n)。采用XRD、XPS和SEM等表征Au/{PDDA-GNs/PMo₁₂-GNs}_n催化剂的组成、结构和形貌。结果表明:实验成功制备了Au/{PDDA-GNs/PMo₁₂-GNs}_n催化剂,且多层膜载体改善了Au粒子的分散性。利用循环伏安(CV)、计时电流(It)和交流阻抗(EIS)等评价催化剂对肼氧化的电催化性能。结果表明,Au/{PDDA-GNs/PMo₁₂-GNs}_n催化剂使肼氧化的电催化活性和稳定性得到很大提高。与Au/玻碳电极(GCE)相比,Au/{PDDA-GNs/PMo₁₂-GNs}_n催化肼氧化反应的峰电流密度从0.46 mA/cm2提高到0.87 mA/cm2,600 s时的稳态电流密度是Au/GCE的2.5倍。      

铁氰化铈/还原石墨烯纳米材料的制备及其对水合肼的电化学检测

通过电沉积的方法,在玻碳电极表面上沉积铁氰化铈/石墨烯(Ce HCF/RGO)纳米复合材料。用扫描电子显微镜(SEM)对其形貌进行表征,发现其粒径大小均一。用循环伏安法(CV)研究水合肼在不同电极的电化学行为。结果表明,与RGO修饰电极(RGO/GCE)和铁氰化铈修饰电极(Ce HCF/GCE)相比,铁氰化铈/石墨烯复合物修饰电极对水合肼具有更好的电催化氧化性能。在一定条件下,它对水合肼响应的线性范围为2.87×10~(-7)~8.56×10~(-4)mol/L,检出限为8.5×10~(-8)mol/L。可用于水合肼的电化学传感检测。     

纳米态电极催化材料Au-Pt/半胱氨酸/Au电极的制备及性能研究

利用自组装技术制备了纳米态Au-Pt/半胱氨酸/Au电极,TEM、ED、XPS等研究表明双金属纳米粒子为Au合金,粒子的平均粒径＜10nm;通过组装时间可以控制双金属纳米颗粒组装的数量.对组装电极的电化学性能进行了测试,通过SEM对其表面结构进行了表征.结果表明,利用自组装方法可以制备纳米态Au-Pt/半胱氨酸/Au电极,该电极具有良好的电催化性能.     

基于Pt-Pb纳米花的无酶葡萄糖传感器性能研究

利用超声恒电流沉积法在金电极表面制备了Pt-Pb纳米花,并将其用于构建无酶葡萄糖传感器,采用阻抗谱、循环伏安和差分脉冲伏安法研究了其电化学性能。SEM结果表明,当沉积电流为10mA时,电极表面形成Pt-Pb纳米花结构。电化学测试结果表明,该电极对葡萄糖具有很好的电催化性能,在含有氯离子的溶液中不会失活。Pt-Pb纳米花电极构建的无酶传感器对葡萄糖的线性响应范围为0.5×10-3～22×10-3 mol/L,灵敏度为3.68mA·cm-2·(mol/L)-1,检测限为24×10-6 mol/L。此外,传感器具有良好的选择性、重复性和稳定性。     

CuO-NSG的制备及其在非酶葡萄糖传感器中的应用

采用氮和硫共掺杂石墨烯(NSG)作为固定CuO纳米颗粒的新型载体材料,并将获得的CuO-NSG作为电催化葡萄糖氧化(EGO)的催化剂应用于非酶葡萄糖传感器,解决EGO催化剂的稀缺性和高成本性。结果表明,NSG赋予CuO-NSG大的表面积,且NSG和CuO之间存在强界面耦合。由于NSG的显著效果和NSG与CuO的协同效应,CuO-NSG显示出比CuO和CuO-还原氧化石墨烯(RGO)更高的EGO活性。基于CuO-NSG的传感器显示出优异的葡萄糖感测性能,表现出1722μA·mmol·L~(-1)·cm~(-2)的高灵敏度和0.07μmmol·L~(-1)的低检测限及在实际样品分析中的选择性、再现性、稳定性和可行性的良好检测性能。     

石墨烯支持Pt纳米粒子修饰电极的制备及电催化活性研究

采用一步电化学法制备了石墨烯支持Pt纳米粒子修饰电极(Nano-Pt/ERGO/GCE),利用交流阻抗研究了电极的性能以及该修饰电极的电催化活性。结果表明,采用循环伏安法制备石墨烯支持Pt纳米粒子,具有制备方法简单且纳米粒子粒径可控等优点。与单独的Pt纳米粒子修饰电极相比,Nano-Pt/ERGO/GCE电极表面Pt粒子分布更均匀,对甲醇的氧化具有极强的电催化活性。研究成果在甲醇燃料电池的研发中具有潜在的应用价值。     

Au-Pt纳米颗粒/石墨烯-纤维素微纤维复合电极的制备与电化学性能

石墨烯和金属纳米是优异的导电纳米材料,为构建具有高效活性表面积的电化学传感界面,以玻碳电极作为导电基底,采用滴涂法结合一步电沉积成功制备了Au-Pt纳米颗粒/还原氧化石墨烯-纤维素微纤维(Au-Pt NPs/RGO-CMF)复合材料。SEM、原子力显微镜(AFM)、EDS和拉曼光谱分析表明,Au-Pt纳米颗粒均匀分布在RGO-CMF的薄层上,同时实现了氧化石墨烯(GO)还原为RGO。以铁氰化钾作为氧化还原探针对界面的电化学性质进行研究,在优化的实验条件下(循环伏安法电沉积:电位为?1.2~0 V,周期为20,电解质pH值为6,滴涂GO-CMF体积为8 μL),得到Au-Pt NPs/RGO-CMF复合材料的高效活性表面积(3.54 cm2)远远优于裸玻碳电极(1.52 cm2)。表明构建界面具有高的电催化活性,为传感器的进一步应用提供理论支持。      

Enhanced oxidation of diclofenac sodium at a nano-structured electrochemical sensing film constructed by multi-wall carbon nanotubes–surfactant composite

A multi-walled carbon nanotubes (MWNTs)–dihexadecyl hydrogen phosphate (DHP) film-coated glassy carbon electrode (GCE) was fabricated, and the voltammetric determination method of diclofenac sodium was investigated on this modified electrode by using different kinds of electrochemical techniques. The results showed that this nano-structured film electrode exhibits excellent enhancement effects on the electrochemical oxidation of diclofenac sodium. The oxidation peak current of diclofenac sodium at this film-modified electrode increased significantly compared with that at a bare glassy carbon electrode. Based on the experiment outcomes a possible mechanism was proposed and discussed. The proposed method was demonstrated by using diclofenac sodium tablets and the result was satisfying.     

Investigation of the electrochemical and electrocatalytic behavior of single-wall carbon nanotube film on a glassy carbon electrode

The electrochemical behavior of a film of single-wall carbon nanotubes (SWNTs) functionalized with carboxylic acid groups was studied extensively on a glassy carbon (GC) electrode. One stable couple corresponding to the redox of the carboxylic acid group, which was supported by XPS and IR experiments, was observed. The electrode process involved four electrons, while the rate-determining step was a one-electron reduction. The SWNT film-modified electrode showed favorable electrocatalytic behavior toward the oxidation of biomolecules such as dopamine, epinephrine, and ascorbic acid.     

Determination of pentachlorophenol at carbon nanotubes modified electrode incorporated with beta-cyclodextrin

A facile and reliable electrochemical technique at beta-cyclodextrin incorporated carbon nanotubes modified glassy carbon electrode (beta-CD/CNTs/GCE) was proposed for determination of pentachlorophenol (PCP). The electrochemical behavior of PCP at the beta-CD/CNTs/GCE was investigated by cyclic voltammetry and linear sweep voltammetry. The beta-CD/CNTs/GCE showed good analytical performance characteristics in electrocatalytic oxidation of PCP, compared with the simple carbon nanotube modified electrode (CNTs/GCE) and bare glassy carbon electrode (GCE). After accumulation for 5 min on beta-CD/CNTs/GCE, the peak current increased linearly with the concentration of PCP in the range from 8.0 x 10(-7) to 1.04 x 10(-5) mol/L. The detection limit was 4.0 x 10(-8) mol/L at 3 sigma level. The proposed electrode presented good repeatability for the determination of PCP in artificial wastewater, and the recovery was 97%-103%. This modified electrode combined the advantages of carbon nanotubes and supramolecular cyclodextrin, leading to new capabilities for electrochemical detection of PCP.     

Simultaneous determination of serotonin and dopamine at the PEDOP/MWCNTs-Pd nanoparticle modified glassy carbon electrode

Electrochemical determination of dopamine (DA) and serotonin (5-HT) have been studied at a modified glassy carbon electrode (GCE) in 0.1 M phosphate buffer solution (PBS) using cyclic voltammetry (CV) and differential pulse voltammetry (DPV) at pH 7.4, all over the interfering biomolecule ascorbic acid (AA). The GCE was modified by palladium-functionalized, multi-walled carbon nanotubes (MWCNTs-Pd) with electrochemical deposition of poly 3,4-ethylenedioxy pyrrole (PEDOP), denoted as PEDOP/MWCNTs-Pd/GCE, and investigated by SEM and EIS experiments. The highly electrocatalytic activity of the modified electrode toward 5-HT and DA was demonstrated from the sensitive and well-separated voltammetric experiment. The oxidation peaks found were 0.165 and 0.355 mV for DA and 5-HT, respectively. The composite film shows a significant accumulation effects on two species, as well as the mutual interference among the analytes. This biosensor was best in response compared to other modified electrodes made in the same lab. The lowest detection limits were found to be 5.0 x 10(-9) and 1.0 x 10(-8) for 5-HT and DA, respectively. The respective linear ranges were determined as 1.0 x 10(-7) to 2.0 x 10(-4) and 1.0 x 10(-7) to 2.0 x 10(-4) for 5-HT and DA.     

Direct electrochemical determination of ascorbic acid by a cobalt(II) tetra-neopentyloxy phthalocyanine-multi-walled carbon nanotubes glassy carbon electrode

A cobalt(II) tetra-neopentyloxy phthalocyanine-multi-walled carbon nanotubes (CoTNPPc–MWNTs) composite was synthesized and characterized by UV–Vis spectra and transmission electron microscopy. The CoTNPPc–MWNTs glassy carbon electrode (CoTNPPc–MWNTs/GCE) was prepared by drop coating. The electrocatalytic performance of the chemically modified electrode was investigated for oxidation of ascorbic acid (AA). It was found that in phosphate buffer solution at pH = 6.60, the chemically modified electrode exhibited excellent electrocatalytic activity toward the oxidation of AA. The oxidation peak current increased linearly with the concentration of AA in the range of 10 μM–1.6 mM within the detection limit of 5 μM and low response time of 4 s.     

Electrochemical behavior of gold nanoparticles modified nitrogen incorporated tetrahedral amorphous carbon and its application in glucose sensing

Gold nanoparticles (NPs) with 10-50 nm in diameter were synthesized on nitrogen incorporated tetrahedral amorphous carbon (ta-C:N) thin film electrode by electrodeposition. The deposition and nucleation processes of Au on ta-C:N surface were investigated by cyclic voltammetry and chronoamperometry. The morphology of Au NPs was characterized by scanned electron microscopy. The electrochemical properties of Au NPs modified ta-C:N (ta-C:N/Au) electrode and its ability to sense glucose were investigated by voltammetric and amperometric measurements. The potentiostatic current-time transients showed a progressive nucleation process and diffusion growth of Au on the surface of ta-C:N film according to the Scharifker-Hills model. The Au NPs acted as microelectrodes improved the electron transfer and electrocatalytic oxidation of glucose on ta-C:N electrode. The ta-C:N/Au electrode exhibited fast current response, a linear detection range of glucose from 0.5 to 25 mM and a detection limit of 120 microM, which hinted its potential application as a glucose biosensor.     

Fabrication of multi-wall carbon nanotube film on glassy carbon electrode surface and the determination of tyrosine

A novel chemically modified electrode has been prepared on the basis of the attachment of multi-wall carbon nanotubes (MWNT) onto the surface of a glassy carbon electrode (GCE) in the presence of a hydrophobic surfactant, dihexadecyl phosphate (DHP). This MWNT film was characterized by transmission electron microscopy images (TEM) and scanning electron microscopy (SEM). The electrochemical behavior of tyrosine at the MWNT film coated GCE was examined and it is found that this MWNT-modified GCE greatly enhances the oxidation peak current of tyrosine. Effects of some important factors, including pH, scan rate and amount of modifier, on the oxidation process of tyrosine were investigated. When the signal to noise ratio (SNR) is 3, the detection limit is 1 x 10(-7) M. The low relative standard deviations of the detection of tyrosine in human morning urine (3.3%) and white wine (5.2%) suggest a good reproducibility of the modified electrode.     

Synthesis, characterization and application in electrocatalysis of polyaniline/Au composite nanotubes

Polyaniline (PANI) nanotubes were successfully synthesized using the hydrothermal method via an in situ polymerization. In the process, a fibrillar complex of FeCl(3) and methyl orange (MO), acting as the reactive self-degraded templates, directed the growth of PANI on its surface and promoted the assembly into nanotubular structures. By introducing PANI nanotubes into Au colloid, Au nanoparticles (NPs) could be decorated onto the PANI nanotube surface through the electrostatic effect. The morphology of the nanotubes and the number of decorated Au NPs could be controlled effectively by adjusting the experimental conditions. The resulting products were characterized by transmission electron microscopy (TEM), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR). In addition, the electrocatalytic activity of the composites towards the oxidation of NADH (nicotinamide adenine dinucleotide) was studied by immobilizing PANI/Au composites on the surface of a glassy carbon electrode (GCE).