自组装普鲁士蓝膜修饰电极的制备及表征

通过静电自组装技术在Pt电极表面组装了不同层数的普鲁士蓝（PB）膜,得到了PB修饰的Pt电极。分别利用扫描电镜（SEM）和紫外-可见分光光度计（UV-Vis）表征膜的形貌及光学特性,并且采用循环伏安法（CV）测量膜修饰的Pt电极的循环伏安特性。结果表明：通过自组装技术可以制备出可控厚度的纳米尺度的PB膜修饰电极,膜的紫外吸收峰强度与组装层数符合线性关系,膜的组成同时含有可溶和不溶性PB,且循环伏安法所得到的峰电流正比于扫描速度的平方根以及PB的本体浓度,修饰电极具有好的电化学性能,可用于生物传感器。     

Scrap cast iron and copper‐modified cast iron for reductive degradation of 2,4‐dinitrotoluene

BACKGROUND: Little attention has been paid to the use of large‐sized scrap cast iron for reduction of refractory organic pollutants at neutral pH and in the presence of dissolved oxygen (DO). RESULTS: Scrap cast iron and copper‐modified cast iron with fresh surfaces have a high reactivity towards the reduction of 2,4‐dinitrotoluene (2,4‐DNT). The extent of conversion reached around 80% and 97% respectively, though it gradually decreased with repeated reactions to relatively stable values of 63% and 72%, and recovered once the reacted filings were cleaned by dilute acid. After 50 days reaction, no dissolved copper appeared in the copper‐modified cast iron process. The mass loss of copper due to physical detachment reached 1.1% of the total coated copper within the initial 20 reaction days, and only 0.3% appeared in the next 30 days. 2,4‐DNT oxidizes scrap cast iron to generate mainly FeFe₂O₄ with DO, however, it oxidizes scrap copper‐modified cast iron to generate mainly γ‐FeO(OH) and α‐FeO(OH). CONCLUSION: Both samples of cast iron were successfully applied in the treatment of neutral wastewater containing 2,4‐DNT with high reactivity and good repeatable efficiency. Electrode reaction rate was enhanced by the deposited copper, which has strong chemical and physical stability. Copyright © 2011 Society of Chemical Industry     

碳纳米管修饰电极的研究进展

化学修饰电极如今在电化学和电分析化学中应用极为广泛。综述了碳纳米管的结构和性能,介绍了碳纳米管修饰电极的制备及应用。     

H2O2 determination at iron-rich clay modified electrodes

The electrochemical properties of natural or synthetic ferruginous clays, nontronite, montmorillonite and saponite, were studied by cyclic voltammetry and impedancemetry. Clay modified electrodes were then tested for the reduction of hydrogen peroxide under different conditions: in acidic medium without redox mediator, in phosphate buffer solutions (pH 7 or 8) with a redox cation (methyl viologen, MV²⁺) or a biomolecule (hemoglobin, Hb) absorbed within the clay coating. In all cases, the presence of iron species in the octahedral lattice of the clays enhanced the electrocatalytic reduction currents of H₂O₂. The sensitivities of H₂O₂ calibration curves were 0.23, 54 and 132 mA/M cm² for Nont, MV²⁺-Nont and Hb-Nont modified electrodes, respectively.     

Electrocatalytic reduction of dioxygen at glassy carbon electrodes modified with polypyrrole/anthraquinonedisulphonate composite film in various pH solutions

Functionalized polypyrrole (PPy) film with anthraquinonedisulphonate (AQDS) incorporated as dopant was prepared by anodic polymerization of pyrrole (Py) at a glassy carbon electrode from aqueous solution. The electrochemical behavior of AQDS in PPy matrix and the electrocatalytic reduction of dioxygen on the resulting composite film were investigated in various pH solutions. The formal potential of AQDS and the reduction potential of dioxygen both exhibit pH dependence. In all pH solutions employed, the electrocatalytic reduction of dioxygen at the PPy/AQDS composite film establishes a pathway of irreversible two-electron reduction to form hydrogen peroxide. The pH 6.0 buffer solution is a more suitable medium for the reduction of dioxygen, where the PPy/AQDS composite film showed a more efficient electrocatalytic performance. It was found that AQDS is an effective mediator for the reduction of dioxygen and the reduced AQ is responsible for the enhanced catalytic activity. The catalytic current is under mixed kinetic-diffusion control. The number of electrons transferred and kinetic parameters of dioxygen reduction were determined using cyclic voltammetry, rotating disk voltammetry and Tafel polarization technique.     

载铂聚苯胺/聚砜复合膜修饰电极对甲醇的电催化氧化行为研究

采用循环伏安法制备聚苯胺(PAN)/聚砜(PSF)复合膜修饰电极,在其上电沉积铂粒子,制得载铂聚苯胺/聚砜复合膜修饰电极,用循环伏安法和交流阻抗法研究它对甲醇的电催化氧化行为。复合膜的化学组分用FTIR进行表征,复合膜内层载铂后的表面形态用SEM进行表征。结果表明,复合膜的内层(与工作电极接触的一面)是聚苯胺,外层(与溶液接触的一面)是聚砜,铂粒子在复合膜内层的多孔聚苯胺上均匀沉积,从而使载铂聚苯胺/聚砜复合膜修饰电极对甲醇有好的电催化氧化性能。     

Molecular-level design of binary self-assembled monolayers on polycrystalline gold electrodes

In this study, we followed up, by measuring the reductive desorption patterns, the time-dependent growth of the self-assembled monolayer (SAM) of a thiol compound (typically cysteine) formed on polycrystalline Au (poly-Au) electrode. Cysteine molecules appeared to adsorb preferentially and consecutively at the Au(1 1 0), Au(1 0 0) and then at the Au(1 1 1) surface domains of the poly-Au. A 95% surface coverage of cysteine (Γ_cysteine) was attained after 5 s, 120 s and more than 300 s for the Au(1 1 0), Au(1 0 0) and Au(1 1 1) domains, respectively, of the poly-Au electrode. The electrochemical reduction of molecular oxygen (O₂) in O₂-saturated 0.5 M KOH was utilized as a probing reaction for the extent of the compactness of the SAM. A binary SAM of two thiols (cysteine and cystamine) has been successfully designed over the poly-Au electrode at which a precise positioning of cysteine was achieved, i.e., cysteine was attached to the Au(1 1 1) domains, while cystamine to the Au(1 0 0) and Au(1 1 0) domains. SEM images for the electrodeposited Ag over the cysteine sub-SAM/Au electrode gave a possible mapping of the Au(1 1 1) domains of the poly-Au electrode.     

Effect of microstructure on the electrochemical behavior of Pt/YSZ electrodes

Two types of O₂,Pt/YSZ electrode preparation (Pt/YSZ cermet and sputtered platinum film) have been characterized by SEM and by cyclic voltammetry and chronoamperometry at 450 °C in 20 kPa oxygen. Cyclic voltammetry on the cermet and on the as-sputtered non-porous film electrode evidenced the characteristics of the PtO _x /Pt couple. The corresponding redox reaction occurs at the metal/electrolyte interface and it manifests itself by an anodic wave and one of more cathodic peaks in the voltammogram. Heat treatment of the sputtered electrode at 700 °C in oxygen atmosphere resulted in a porous structure by coalescence of the film. Cyclic voltammetry of the porous film electrode featured the characteristics of the O₂/O²⁻ couple, i.e. the redox reaction of gaseous oxygen occurring at the tpb. Chronoamperometry at anodic potentials showed similar features for both electrode preparations: an initial inhibition, a current peak and a slow activation, the latter being related to the phenomenon of electrochemical promotion of catalysis.     

Electrochemical behavior of folic acid at calixarene based chemically modified electrodes and its determination by adsorptive stripping voltammetry

Voltammetric behavior of folic acid at plain carbon paste electrode and electrode modified with calixarenes has been studied. Two peaks for irreversible oxidation were observed. Out of the three calixarenes chosen for modification of the electrodes, p-tert-butyl-calix[6]arene modified electrode (CME-6) was found to have better sensitivity for folic acid. Chronocoulometric and differential pulse voltammetric studies reveal that folic acid can assemble at CME-6 to form a monolayer whose electron transfer rate is 0.00273 s⁻¹ with 2-electron/2-proton transfer for the peak at +0.71 V against SCE. An adsorption equilibrium constant of 5 × 10³ l/mol for maximum surface coverage of 2.89 × 10⁻¹⁰ mol/cm² was obtained. The current is found to be rectilinear with concentration by differential pulse voltammetry. However, linearity in the lower range of concentration 8.79 × 10⁻¹² M to 1.93 × 10⁻⁹ M with correlation coefficient of 0.9920 was achieved by adsorptive stripping voltammetry. The limit of detection obtained was found to be 1.24 × 10⁻¹² M. This method was used for the determination of folic acid in a variety of samples, viz. serum, asparagus, spinach, oranges and multivitamin preparations.     

Synthesis and properties of polymer film modified electrodes to detect metal ions

In order to obtain modified polymeric electrodes, polymers were synthesized that are insoluble in water but soluble in common organic solvents and contain different functional groups that are able to coordinate metal ions from low concentrations. Poly(acrylic acid‐co‐styrene), poly(acrylamide‐co‐4‐vinyl pyridine), and poly(styrene‐co‐4‐vinyl pyridine) were synthesized by radical polymerization. The copolymers were characterized by FTIR, ¹H‐NMR, ¹³C‐NMR, scanning electron microscopy, and thermal analysis. The molecular weight and molecular weight distribution were determined by size exclusion chromatography. These complexing polymers were used in the preparation by spin coating of complexing chemically modified electrodes. The polymer film modified electrodes were then tested for the detection of metal ions using the chemical preconcentration and anodic stripping technique. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1192–1197, 2005     

Ionic liquid modified Pt/C electrocatalysts for cathode application in proton exchange membrane fuel cells

The modification of Pt/C catalyst by using ionic liquids to improve their catalyst activities has been reported by many researchers, but their practical behavior in operating fuel cells is still unknown. In this work, we study the ionic liquid modified Pt/C nanoparticle catalysts within cathodes for proton exchange membrane fuel cells. The influence of the ionic liquid amount, adsorption times and dispersing solvents are investigated. The experiment results show the best performance enhancement is achieved through two-time surface modification with 2 wt-% ionic liquid solution. The mechanisms are explored with the attribution to the high oxygen solubility in the ionic liquid enabling an improved oxygen diffusion in micropores and to good hydrophobicity facilitating water expelling from the active sites in fuel cell operation.     

Impedance study of the charge transport at poly-o-phenylenediamine film electrodes

The measured low-frequency capacitance of the polymer film was proportional to the film thickness and showed a maximum at the formal potential of the polymer. We analyzed the relation between the capacitance and potential by taking into account the contribution of an interaction between electroactive sites. The Warburg coefficient and the width of a linear 45 ° region in an impedance diagram showed each their minima near the formal potential. These impedance data were interpreted in terms of the diffusion-migration transport of both electron and anion through the film. The results of the impedance analysis suggested that electron transport was ensured by interchain electron hopping. From the combinations of the measured kinetic parameters, we inferred that one of the two charge carriers moved much faster than the other. The obtained diffusion coefficient showed a maximum in the vicinity of a voltammetric current peak; this corresponded with the potential dependence of a coupled diffusion coefficient expected in the extreme case of electron-transport control.     

On the adsorption and kinetics of phase transients of adenosine at the different carbon electrodes modified with a mercury layer

Optical roughness of a pyrolytic graphite electrode with basal (PGEb) and edge orientation (PGEe), a glassy carbon electrode (GCE), and the same electrodes modified with mercury (MFE) was studied by an optical diffractive element (DOE) based sensor. Electrochemical characterisation of these electrodes used was performed by cyclic voltammetry (CV) and capacitance measurements (C-E curves and electrochemical impedance spectroscopy, EIS). The kinetics of phase transients of adenosine adsorbed on PGEb, and GCE modified with mercury layer of different thicknesses (thickness was changed from 0.02 to 2 μm) was studied by chronoamperometry (j-t curves) and capacitance measurements (C-E curves). In acidic (pH 5) solution adenosine forms two different two-dimensional (2D) physisorbed condensed layers on the MFE. The first of these (region I) is located at more positive potential; the centre of this adlayer is situated around −0.4 V. The second 2D physisorbed film (region III) is formed at more negative potentials; the centre of the region III is around −1.3 V. The 2D condensed films (adlayer I and III) of adenosine still exist on the PGEb substrate modified by 0.02 μm thick mercury layer. Adlayers III and I of adenosine exist on the GCE modified with mercury layer down to 0.02 and 0.2 μm, respectively. The kinetics of phase transients of the adenosine films taking place by a potential jump from dilute adsorption region (state II and IV) to the 2D physisorbed film (region I and III) at the PGEb and GCE substrates modified with mercury (Hg-PGEb and Hg-GCE) were studied, respectively. During both of the phase transients of IV→III and II→III of adenosine a polynucleation and growth process on both the Hg-PGEb and Hg-GCE was detected. The phase transients of II→I are characterised by an exponential decay of the current without the current maximum (the adsorption process took place only). It was observed that the phase transients of IV→III are the fastest at the HMDE and gradually slow down on 2 μm Hg-GCE and 2 μm Hg-PGEb, respectively.     

卟吩铁大环配合物FeTFPP修饰电极对氧的催化还原

采用循环伏安法研究了卟吩铁大环配合物FeTFPP在H2SO4溶液中对氧的催化还原,讨论了Nafion膜修饰电极上FeTFPP对电极催化活性和稳定性的影响;测定了FeTFPP在电极表面的异相电子转移反应速率常数为4.34×10-5cm/s,扩散系数为4.43×10-6cm/s。     

Effect of cerium oxide nanoparticles coating on the electrodes of benthic microbial fuel cell

Benthic microbial fuel cell is a power source for low-power devices. For enhancement of power, Cerium oxide (CeO₂) nanoparticles (NPs) were coated on anode and cathode electrodes and compared separately. CeO₂ NPs were synthesized by hydrothermal method and characterized by Dynamic light scattering. Polyvinylidene fluoride and graphite powder were used as a conductive matrix for binding CeO₂ NPs. Coated electrodes were characterized by physical and electrochemical analysis. Maximum power densities generated by CeO₂ coated cathode and anode were 60 and 43 mW/m³ respectively; whereas conductive matrix only produced 14 mW/m³. Results demonstrated that CeO₂ at cathode performed better than at anode. NPs show their effectiveness as an oxygen reduction reaction catalyst in the sea water.     

Characterization and electrochemical studies of Nafion/nano-TiO2 film modified electrodes

A nano-TiO₂ film from stable aqueous dispersion has been modified on a glassy carbon electrode (GCE), and was characterized by scanning electron microscopy (SEM) and surface-enhanced Raman spectroscopy (SERS). This nanostructured film exhibits an ability to improve the electron-transfer rate between electrode and dopamine (DA), and electrocatalyze the redox of DA. The electrocatalytical behavior of DA was examined by cyclic voltammetry (CV). Combined with Nafion, the bilayer-modified electrode (N/T/GCE) gives a sensitive voltammetric response of DA regardless of excess ascorbic acid (AA). Electrochemical impedance spectroscopy (EIS) at a fixed potential was performed at variously treated GCEs. The mechanism of the electrode reaction of DA at N/T/GCE and the equivalent circuits of different GCEs have been proposed.     

Electrocatalytic oxidation of hydroxylamine by (RuPc)2 graphite modified electrode

Electrocatalytic oxidation of hydroxylamine on dinuclear ruthenium phthalocyanine (RuPc)₂ modified electrode is studied using cyclic voltammetry (CV) and rotating disc electrode (RDE) techniques. A two-electron oxidation of hydroxylamine to N₂O is observed in the pH range of 9–13. A suitable mechanism is proposed by analyzing the rate equation and the Tafel slope.     

Electrocatalytic properties of NDGA and NDGA/FAD hybrid film modified electrodes for NADH/NAD redox reaction

The fabrication of monolayers composed of nordihydroguaiaretic acid (NDGA), and hybrid films composed of NDGA-flavin adenine dinucleotide (FAD) adsorbed films was performed in neutral aqueous solutions to produce electrochemically active thin films exhibiting one and two redox couples, respectively. An electrochemical quartz crystal microbalance and cyclic voltammetry were used to study the in situ growth of the NDGA and hybrid NDGA/FAD film monolayers. The NDGA modified film electrocatalytically oxidized NADH, ascorbic acid, dopamine, and N₂H₄ in neutral aqueous solutions. Well-separated voltammetric peaks were observed for dopamine and uric acid mixtures, and also for ascorbic acid and uric acid mixtures using the NDGA/GC modified electrode. When transferred to various aqueous buffered solutions, the two redox couples of the NDGA/FAD hybrid film and their formal potentials were observed to be pH-dependent. The electrocatalytic oxidation and reduction of NADH and NAD⁺ by a NDGA/FAD hybrid film in neutral aqueous solutions was carried out, and the electrocatalytic oxidation of NADH was performed using a NDGA/FAD hybrid film.     

Electro-oxidation of hydrazine on electrodes modified with vitamin B12

In this paper we report a kinetic study of the electro-oxidation of hydrazine catalyzed by vitamin B₁₂ pre-adsorbed on an ordinary pyrolytic graphite electrode. Kinetic parameters were determined by linear sweep voltammetry and rotating-disk electrode polarization curves. The order of the reaction is 1 in OH⁻ ions and Tafel plots give slopes of 80 mV/decade. A possible redox-catalysis mechanistic scheme is proposed.