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.     

Electrocatalytic reduction of dioxygen at a modified glassy carbon electrode based on Nafion-dispersed single-walled carbon nanotubes and cobalt–porphyrin with palladium nanoparticles in acidic media

Cathodic dioxygen (O₂) reduction was performed at a modified glassy carbon electrode (GCE) by single-walled carbon nanotubes (SWCNT)/Nafion^® (NF) film with cobalt (II) tetra (2-amino-phenyl) porphyrin (CoTAPP) and palladium (Pd) nanoparticles incorporated and employed as doping agents. Both the electrochemical behavior of SWCNT with a P(CoTAPP)–Pd nanoparticle matrix and the electrocatalytic reduction of O₂ were investigated using transmission electron microscopy (TEM), cyclic voltammetry (CV) and rotating ring-disk electrode (RRDE) techniques in 0.1 mol l⁻¹ H₂SO₄ aqueous solutions. The electrocatalytic reduction of O₂ at the SWCNT/NF/P(CoTAPP)–Pd composite film established a pathway of four-electron transfer reductions into H₂O. Hydrodynamic voltammetry revealed that the modified electrode was catalyzed effectively by the four-electron transferred reduction of dioxygen into H₂O with minimal generation of H₂O₂. The SWCNT/NF/P(CoTAPP)–Pd composite film showed a highly efficient electrocatalytic performance. P(CoTAPP)–Pd was an effective mediator for the reduction of dioxygen and was responsible for the enhanced catalytic activity.     

Electrochemical reduction of oxygen on thin-film Pt electrodes in acid solutions

The electrochemical reduction of oxygen on thin-film platinum electrodes in 0.1 M HClO₄ and 0.05 M H₂SO₄ solutions has been investigated using the rotating disk electrode (RDE) method. Thin films of Pt (0.25-20 nm thick) were prepared by vacuum evaporation onto glassy carbon substrate. The surface morphology of Pt films was examined by transmission electron microscopy (TEM). The specific activity of O₂ reduction was higher in HClO₄ and decreased with decreasing film thickness. In H₂SO₄, the specific activity was lower and appeared to be independent of the Pt loading. The values of Tafel slopes close to −120 mV dec⁻¹ in high current density range and −60 mV dec⁻¹ in low current density range were obtained for all electrodes in both solutions, indicating that the mechanism of O₂ reduction is the same for thin-film electrodes as for bulk Pt. The number of electrons transferred per O₂ molecule was close to four for all thin Pt films studied.     

Pt/Pd alloy nanoparticles composed of bimetallic nanobowls: Synthesis, characterization and electrocatalytic activities

Bowl-like nanostructures of Pt/Pd bimetallic nanocrystals are prepared by employing Ag nanoparticles as a template and completely removing the residual Ag after the displacement. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) observations display that the thin walls of Pt/Pd nanobowls are composed of nanoparticles. X-ray diffraction (XRD) pattern demonstrates that Pt and Pd form the alloy in the nanobowls. The crystal structures of the nanobowls consist of [1 1 1], [2 0 0], [2 2 0] surfaces as revealed by both high-resolution TEM (HRTEM) and XRD results. The Pt/Pd nanobowls exhibit significant high electrocatalytic activities toward the methanol oxidation and oxygen reduction compared with the Pt/Pd nanospheres and Pt nanobowls.     

Oxygen reduction activity of Pt and Pt-Mn-Co electrocatalysts sputtered on nano-structured thin film support

We report on extensive measurements of oxygen reduction activity of Pt and Pt-Co-Mn electrocatalysts using the rotating ring-disk electrode (RRDE) method. The electrocatalysts were prepared by sputtering from Pt or Pt, Co and Mn targets onto 3M's nano-structured thin film support (NSTF) structures. The area specific activity of Pt/NSTF, measured in 0.1 M HClO₄ and at room temperature, is similar to that of bulk Pt. The area specific measurements show a 20 mV reduction in the Pt-Co-Mn/NSTF overpotential compared to Pt/NSTF. The corresponding kinetic gain in the area specific activity of the ternary alloy is about a factor of two. This ORR enhancement factor observed in the ternary Pt-Co-Mn/NSTF by RRDE measurements is similar to the results obtained in 50 cm² H₂/air fuel cells.     

Optimization of deposition parameters of thin films composed of Pt nanoparticles

The optimization of a number of film deposition variables was carried out for thin Pt films formed from a sol (generated by the reduction of hexachloroplatinic acid (CPA) by sodium ethoxide) containing Pt nanoparticles and a partially reduced Pt(II) species (NaPtCl₃(C₂H₄)). Increasing the film drying temperature leads to the thermal decomposition of this species, generating another Pt(II) crystalline species, as well as additional Pt. It also leads to improved inter-particle and particle-substrate contact of the 2 nm Pt nanoparticles, thereby increasing the Pt film charge density up to 200 °C drying temperature. Above this temperature, particle sintering occurs (8 nm diameter when dried to 400 °C), consistent with an observed loss in film charge. Increasing the withdrawal rate of the substrate from the sol leads to a thicker Pt film, while maintaining a constant Pt particle size. By changing the substrate from Au sputter-coated glass to carbon paper (CP), the Pt loading was increased; however, the effective usage of Pt was lower than anticipated, possibly related to the pooling of the liquid sol within the CP structure, resulting in poor nanoparticle dispersion.     

Vertically aligned carbon nanotube film electrodes for bioelectrocatalytic dioxygen reduction

We have prepared vertically aligned carbon nanotube (VACNT) film electrodes for bioelectrocatalytic dioxygen reduction. The electrodes were prepared by a CNT-transfer technique attaching the as-grown VACNTs to an ITO electrode with a conductive CNT/epoxy glue. The VACNTs greatly enhance the active electrode area as shown by the substantial current increase of the slow electroreduction of hydrogen peroxide as well as the increase of the efficiency of the oxidation and reduction of the water-insoluble redox probe t-butylferrocene. Several methods for immobilisation of the multicopper enzyme laccase, both with and without mediator, were evaluated. Very high non-mediated catalytic dioxygen reduction current was measured using VACNTs functionalised with 1-pyrenesulfonic acid. The VACNT electrodes were successfully applied as cathode in a zinc–oxygen battery, reaching a power density of 275 μW cm⁻² at 1.5 V with pyrene-functionalised VACNTs and 115 μW cm⁻² at 0.9 V with syringaldazine as a mediator in oxygen saturated buffer.     

Platinum-alloy nanostructured thin film catalysts for the oxygen reduction reaction

In an effort to study advanced catalytic materials for the oxygen reduction reaction (ORR), a number of metallic alloy nanostructured thin film (NSTF) catalysts have been characterized by rotating disk electrode (RDE). Optimal loadings for the ORR and activity enhancement compared to conventional carbon supported nanoparticles (Pt/C) were established. The most efficient catalyst was found to be PtNi alloy with 55 wt% of Pt. The enhancement in specific activity is more than one order of magnitude, while the improvement factor in mass activity is 2.5 compared to Pt/C. Further lowering of the platinum to nickel ratio in NSTF catalysts did not lead to increased mass activity values.     

Electrocatalytic reduction of oxygen at glassy carbon electrode modified by polypyrrole/anthraquinones composite film in various pH media

The electrocatalytic reduction of dioxygen by one mono and four dihydroxy derivatives of 9,10-anthraquinone (AQ) incorporated in polypyrrole (PPy) matrix on glassy carbon electrode has been investigated. The electrochemical behaviour of the modified electrodes was examined in various pH media and both the formal potential of anthraquinones and reduction potential of dioxygen exhibited pH dependence. AQ and PPy composite film showed excellent electrocatalytic performance for the reduction of O₂ to H₂O₂. pH 6.0 was chosen as the most suitable medium to study the electrocatalysis by comparing the peak potential of oxygen reduction and enhancement in peak current for oxygen reduction. The diffusion coefficient values of AQ at the modified electrodes and the number of electrons involved in AQ reduction were evaluated by chronoamperometric and chronocoulometric techniques, respectively. In addition, hydrodynamic voltammetric studies showed the involvement of two electrons in O₂ reduction. The mass specific activity of AQ used, the diffusion coefficient of oxygen and the heterogeneous rate constants for the oxygen reduction at the surface of modified electrodes were also determined by rotating disk voltammetry.     

An antibacterial submicron fiber mat with in situ synthesized silver nanoparticles

This work presents an alternative approach for fabricating electrospun submicron highly hydrophilic fiber mats loaded with silver nanoparticles. These fiber mats show a high efficient antibacterial behavior, very attractive for applications like wound healing and skin regeneration processes. The fabrication method is divided in two steps. First, poly(acrylic acid) (PAA) and β‐cyclodextrin (β‐CD) submicron fibers were electrospun and further stabilized using a thermal treatment, yielding stable hydrogel‐like fibers with diameters ranging from 100 nm up to several microns. In the second step, silver ions were loaded into the fibers and then reduced to silver nanoparticles in‐situ. The electrospinning parameters were adjusted to achieve the desired properties of the fiber mat (density, size) and afterwards, the characteristics of the silver nanoparticles (amount, size, aggregation) were tuned by controlling the silver ion loading mechanism. Highly biocide surfaces were achieved showing more than 99.99% of killing efficiency. The two‐step process improves the reproducibility and tunability of the fiber mats. To our knowledge, this is the first time that stable hydrogel fibers with a highly biocide behavior have been fabricated using electrospinning. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Hydrophilic carbon nanoparticle-laccase thin film electrode for mediatorless dioxygen reduction: SECM activity mapping and application in zinc-dioxygen battery

Laccase from Cerrena unicolor was adsorbed on hydrophilic carbon nanoparticles (diameter = ca. 7.8 nm) modified with phenyl sulfonate groups and immobilized on an ITO electrode surface in a sol-gel processed silicate film. As shown by scanning electron and atomic force microscopies, the nanoparticles are evenly distributed on the electrode surface forming small aggregates of tens of nanometers in size. The mediator-free electrode exhibits significant and pH-dependent electrocatalytic activity towards dioxygen reduction. The maximum catalytic current density (95 μA cm⁻²) is obtained at pH 4.8 corresponding to maximum activity of the enzyme. Under these conditions dioxygen electroreduction commences at 0.575 V vs. Ag|AgCl_sat, a value close to the formal potential of the T1 redox centre of the laccase. The scanning electrochemical microscopy images obtained in redox competition mode exploiting mediatorless electrocatalysis show that the laccase is evenly distributed in the composite film. The obtained electrode was applied as biocathode in a zinc-dioxygen battery operating in 0.1 M McIlvaine buffer (pH 4.8). It provides 1.48 V at open circuit and a maximum power density 17.4 μW cm⁻² at 0.7 V.     

Enhancing the temperature coefficient of resistance of Pt thin film resistance-temperature-detector by short-time annealing

In this work, we report the influence of annealing time on the electrical properties of Pt thin film resistance-temperature-detectors (RTD) with Ti adhesion layers. It is found that the temperature coefficient of resistance (TCR) of the Pt thin film RTD strongly depends on the air annealing time. Increasing the annealing durations from 1, 3, 10 to 60 min at 900 °C, the TCR tends to rise up firstly, and then drops down. A maximum TCR of 3.2 × 10⁻³/°C at 25 °C is achieved in the RTD annealed for 3 min, which is larger than most of other reported values. It is believed that the annealing time of 3 min may be sufficient to enlarge the grain size and to reduce the lattice defects, giving rise to the maximum TCR by decreasing the resistance at 25 °C. On the contrary, prolonging the annealing duration causes the interdiffusion and oxidation Ti significantly, which has been clearly evidenced by the depth analyses of X-ray photoelectron spectroscopy. Such interdiffusion and oxidation of Ti reduces the TCR by increasing the resistance.     

In situ impedance study of the Y-Ni thin film under electrochemical hydrogenation

A thin film of yttrium Y (150 nm) protected by a 6 nm coating of nickel Ni on a glass substrate was completely hydrogenated in a 1 M NaOH electrolyte at a constant negative current until the transparent Y tri-hydride phase was achieved and hydrogen gas evolution from the electrode began. A series of impedance measurements were performed in situ during the electrochemical experiment to study the properties of the system as dependent on hydrogenation degree and time of relaxation. The equivalent electrical circuit (EEC) simulations were performed with a Randles-like scheme R₀[R₁CPE₁], where R₀ is the thin film electrode resistance, R₁ the charge transfer resistance and CPE₁ is the capacitive constant phase element. The behavior of all the components of the EEC undergoes a clear transition when the hydrogenation degree of the electrode is approximated to its maximum value (H to Y ratio 2.7) and electrochemical process changes from hydrogen uptake to hydrogen evolution.     

Electrochemical synthesis of WO3/PANI composite for electrocatalytic reduction of iodate

Composite film of polyaniline (PANI) and tungsten oxide (WO₃) was electrodeposited by cyclic voltammetric technique from a solution of aniline and tungstic acid. The obtained WO₃/PANI film displayed a significant enhancement of electrocatalytic activity for iodate reduction and a better stability than that of pure WO₃ and PANI films. Result of amperometric experiment revealed a good linear relationship with concentration of IO₃⁻ from 20 to 500 μM, with a high sensitivity of 0.54 μA/μM and a detection limit of 2.7 μM for the determination of iodate. This composite film was also successfully applied in determination of iodate in commercial table salt.     

In situ synthesis of highly dispersed VO2(M) nanoparticles on glass surface for energy efficient smart windows

Thermochromic VO₂-based smart windows are considered as a highly promising building envelope to reduce building energy consumption. However, the inherent unsatisfactory optical performance hindered its practical applications and nanocomposite films are testified to be the most promising strategy addressing this issue, while uniformly dispersing nanoparticles is often a challenge. Herein, a facile in situ method was proposed to directly fabricate highly dispersed VO₂ nanoparticles (HD-VN) on a glass surface from the VOC₂O₄·xH₂O aqueous solution to achieve the high-optical performance VO₂ film (HD-VN film). The forming mechanism of HD-VN was fully elucidated and HD-VN was generated via the sintering process from the irregular VO₂ particles derived from the decomposition of polyvinyl pyrrolidone (PVP). The HD-VN film showed excellent luminous transmittance (T_lum) of 72.5% and solar energy modulation efficiency (ΔT_sol) of 10.1%, the former was attributed to the reduced refractive index which led to a reduced reflectance of HD-VN film, and the latter was ascribed to the localized surface plasmon resonance (LSPR) behavior of the HD-VN. The simple and cost-efficient synthesis strategy would promote the application of VO₂ film in energy-efficient glazing, and also shed light on the structures’ design applied to the field of optics, catalysts, and sensors.     

Modification of Pt nanoparticles with polyoxometallate monolayers: Competition between activation and blocking of reactive sites for the electrocatalytic oxygen reduction

Surfaces of bulk platinum and unsupported (Vulcan-free) Pt nanoparticles, that are modified and stabilized with such Keggin type heteropolyacids of molybdenum and tungsten as H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀, have been characterized using cyclic voltammetry, FTIR (by reflectance), as well as transmission and scanning electron microscopies. The presence of the polyoxometallate monolayer on platinum results in the partial suppression of the interfacial formation of PtOH/PtO oxides. Both molybdates and tungstates seem to interact with Pt surface via their corner oxygen atoms. The existence of spacious, largely hydrated, polyoxometallate monolayers on platinum does not block access of reactant (oxygen) to the catalytic Pt sites. The electrocatalytic properties of H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀ modified Pt nanoparticles towards reduction of oxygen in acid medium have been examined and compared using rotating ring-disk voltammetry. Reactivity of Pt-free H₃PMo₁₂O₄₀ and H₃PW₁₂O₄₀ with respect to reduction of hydrogen peroxide has also been considered. Our results clearly show that modification of Pt nanoparticles with PW₁₂ (but not with PMo₁₂) results in the enhancement of the electrocatalytic reduction of oxygen.     

原位还原制备滤纸载纳米银粒子复合材料及其催化特性

基于绿色化学的角度,直接以滤纸(FP)为基底材料,在碱性条件下无需外加还原剂和稳定剂,原位还原得到负载纳米银(AgNPs)的AgNPs/FP复合材料。通过扫描电子显微镜(SEM)、X射线电子能谱仪(EDS)、热重分析仪(TGA)和紫外-可见(UV-vis)分光光度计等对复合材料的形貌、组成和催化性能进行表征。研究结果表明,Ag⁺被还原为AgNPs后致密又均匀地负载于滤纸表面上,所制得的AgNPs/FP复合材料中纳米银呈球形、尺寸均一且团聚较少。AgNPs/FP复合材料对对硝基苯酚(4-NP)的还原具有较好的催化活性,且易于回收再利用。     

Finely dispersed Pt nanoparticles in conducting poly(o-anisidine) nanofibrillar matrix as electrocatalytic material

A new approach based on stepwise oxidation of o-anisidine is explored for generating nanoporous films of poly(o-anisidine), POA and loading of Pt nanoparticles that are subsequently used for electrocatalysis of methanol oxidation are presented and compared with bulk Pt. POA film can easily be prepared by stepwise electro-oxidation procedure with very high porosity consisting of nanofibrillar structure using without templates. Controlled sizes of Pt nanoparticles were entrapped into POA matrix by a two-step process in which first PtCl₆²⁻ ions are sorbed into the pores of polymer matrix followed by electroreduction at −0.55 V in a 0.5 M H₂SO₄ solution. Loading of Pt nanoparticles (10-200 μg/cm²) onto POA matrix were accomplished by varying the concentration (2-10 mM) of the sorbate, i.e., H₂PtCl₆. The sizes of the Pt nanoparticles were determined from TEM analysis and Pt particles were found to be in the range of 10-20 nm. The crystallite phase of Pt particles in POA was examined from XRD pattern. AFM image further supports Pt particles embedded in POA matrix.     

Fabrication of conducting polymer-gold nanoparticles film on electrodes using monolayer protected gold nanoparticles and its electrocatalytic application

We wish to report a simple and new strategy for the fabrication of gold nanoparticles-conducting polymer film on glassy carbon (GC) and indium tin oxide (ITO) surfaces using 5-amino-2-mercapto-1,3,4-thiadiazole capped gold nanoparticles (AMT-AuNPs) in 0.01 M H₂SO₄ by electropolymerization. The presence of amine groups on the surface of the AuNPs was responsible for the deposition of the AMT-AuNPs film on the electrode surface. The atomic force microscopy (AFM) studies reveal that the fabricated p-AMT-AuNPs film showed homogeneously distributed AuNPs with a spherical shape of ∼8 nm diameter. The XPS spectrum shows the binding energies at 83.8 and 87.5 eV in the Au 4f region corresponding to 4f_7/2 and 4f_5/2, respectively. The position and difference between these two peaks (3.7 eV) exactly match the value reported for Au⁰. The N1s XPS showed three binding energies at 396.7, 399.6 and 403.3 eV, corresponding to the NH, –NH– and –N⁺H–, respectively, confirming that the electropolymerization proceeded through the oxidation of –NH₂ groups present on the periphery of the AMT-AuNPs. The application of the present p-AMT-AuNPs modified electrode was demonstrated by studying the electro reduction of oxygen at pH 7.2. The p-AMT-AuNPs film enhanced the oxygen reduction current more than three times than that of p-AMT film prepared under identical conditions.