Studies of the morphology, composition and reactivity of osmium nanodeposits on platinum single crystal electrodes

In the present work, the morphology and composition of osmium deposits formed in submonolayer amount on Pt(1 0 0) and Pt(1 1 1) single crystal surfaces either by spontaneous deposition or by electrolysis at 50 mV in different deposition times (t_dep), were studied. The cyclic voltammetric curves for Pt(1 0 0)/Os and Pt(1 1 1)/Os were recorded in the potential range where the oxidation of deposited osmium species occurs, which suggests that the chemical composition of the deposits is a mixture of metallic Os and OsO₂. The ratio of each species deposited depends directly on the deposition potential, as well as the surface structure characteristics. The composition of the modified platinum single crystal surfaces has also been estimated by X-ray photoelectron spectroscopy (XPS), whose results agree with those obtained by CV, about the amount of osmium oxide on Pt(1 1 1) to be higher than on Pt(1 0 0). This feature of the Pt(1 1 1)/Os becomes its surface more active for ethanol oxidation at lower potentials than that observed for Pt(1 0 0)/Os, although at high potentials the high presence of OsO₂ is prejudicial to the catalytic activity of the electrode. The Pt-Os surfaces were also explored by use of the scanning tunneling microscopy (STM) technique in order to image the features of osmium deposits on platinum, after a short and a long deposition time. It was found, by using spontaneous deposition procedure, that the dimensions of osmium deposits islands do not grow with the increase of degree of coverage of osmium on the surface, as well as they keep the monoatomic thickness.     

Scanning electrochemical microscopy for studying electrocatalysis on shape-controlled gold nanoparticles and nanorods

The electrocatalytic activity for the oxygen reduction reaction (ORR) of different shape-controlled gold nanoparticles (NPs) and nanorods has been studied by scanning electrochemical microscopy (SECM). TEM images and lead underpotential deposition (UPD) voltammetric profiles were used to physically and electrochemically characterize all gold particles studied here, providing information on the shape and surface structure of the different NPs and nanorods. The SECM results demonstrate that cubic gold NPs are the most active towards ORR in 0.1 M NaOH, followed by the spherical gold NPs and, finally, by the short gold nanorods. These results are in agreement with previous studies using conventional electrochemical techniques with gold NPs and single crystal electrodes, since they established that higher ratio of (1 0 0) domains provide higher catalytic activity for ORR.     

Imaging of DNA microarray with scanning electrochemical microscopy

DNA duplex regions of a spot on a DNA microarray were successfully visualized by scanning electrochemical microscopy (SECM) coupled with ferrocenylnaphthalene diimide as an electrochemically active DNA hybrid indicator. Correlation of a normalized steady-state current with the normalized tip-substrate distance suggested that the tip current was generated by direct contact of the DNA duplex layer on the DNA spot bound to this ferrocenylnaphthalene diimide with the tip (not meaning the direct physical touching of the surface). Single nucleotide polymorphisms (SNPs) of Arg or Pro type of cancer suppression gene p53 were detected by using this system.     

Visualization of local degradation processes in coated metals by means of scanning electrochemical microscopy in the redox competition mode

Herein, the redox competition mode of scanning electrochemical microscopy (RC-SECM) has been applied to in situ monitor the local reactivity arising from a circular holiday operated in a painted metal. The metal-coating system consisted of a carbon steel substrate coated with an epoxy-polyamine polymeric film containing glass flakes as pigment. The present work demonstrates the possibility to use RC-SECM for investigation of the corrosion reactions occurring when protective coatings are applied on a metal surface without the addition of a redox mediator to the experimental system. Oxygen reduction was employed to monitor the reactive metal-polymer system, though the onset of a redox competition for this redox species between the SECM tip and the bare metal inside the holiday could be found in certain conditions. Whether attack predominated inside the holiday or the system became non-reactive depended on the composition of the test electrolyte, with borate ions acting as corrosion inhibitor.     

Fabrication of gold and platinum single crystal ultramicroelectrodes

Recent work in this laboratory involving the fabrication of single crystal ultramicroelectrodes (SCUMES) of gold and platinum is summarized in this paper. The method for growing the gold and platinum single crystals of micron dimensions is discussed in detail and the technique for incorporating these crystals into ultramicroelectrodes is described. The electrochemical response of these ultramicroelectrodes is shown with cyclic voltammograms recorded in selected electrolytes. The atomic force microscopy (AFM) images of the platinum and gold crystals, which were used to make the ultramicroelectrodes, are also presented.     

Visualization of local electrocatalytic activity of metalloporphyrins towards oxygen reduction by means of redox competition scanning electrochemical microscopy (RC-SECM)

The redox competition mode of scanning electrochemical microscopy (RC-SECM) has been utilized to visualize the local electrocatalytic activity of metalloporphyrin spots towards oxygen reduction in 0.1 M phosphate buffer as electrolyte solution. The metalloporphyrin spots were obtained by electrochemically induced deposition using a droplet cell. Tetratolyl porphyrins (TTPs) of Mn, Fe and Co have been investigated, with that containing Mn as central metal atom showing highest catalytic activity. The multiple stable oxidation states of Mn were seen as a key factor in the influence of the metal ion on the catalytic activity. From the RC-SECM results, it is shown that oxygen reduction at a manganese TTP (MnTTP) modified electrode surface yielded the least amount of H₂O₂ when compared to iron TTP (FeTTP) and cobalt TTP (CoTTP). As further confirmed by means of rotating disc electrode (RDE) measurements this was attributed to the high activity of MnTTP for H₂O₂ reduction.     

Electrocatalytic activity mapping of model fuel cell catalyst films using scanning electrochemical microscopy

Scanning electrochemical microscopy has been employed to spatially map the electrocatalytic activity of model proton exchange membrane fuel cell (PEMFC) catalyst films towards the hydrogen oxidation reaction (the PEMFC anode reaction). The catalyst films were composed of platinum-loaded carbon nanoparticles, similar to those typically used in PEMFCs. The electrochemical characterisation was correlated with a detailed physical characterisation using dynamic light scattering, transmission electron microscopy and field-emission scanning electron microscopy. The nanoparticles were found to be reasonably mono-dispersed, with a tendency to agglomerate into porous bead-type structures when spun-cast. The number of carbon nanoparticles with little or no platinum was surprisingly higher than would be expected based on the platinum-carbon mass ratio. Furthermore, the platinum-rich carbon particles tended to agglomerate and the clusters formed were non-uniformly distributed. This morphology was reflected in a high degree of heterogeneity in the film activity towards the hydrogen oxidation reaction.     

Studying the localized deposition of Ag nanoparticles on self-assembled monolayers by scanning electrochemical microscopy (SECM)

The local deposition of Ag nanoparticles (NPs) on ω-mercaptoalkanoic acid, HS(CH₂)_nCO₂H, (n = 2, 10) self-assembled monolayers (SAMs) by scanning electrochemical microscopy (SECM) is reported. We found that the presence of a SAM had a pronounced effect on Ag deposition. Experiments were conducted by applying different potentials to an Au(1 1 1) substrate either in the presence of a constant concentration of Ag⁺ ions in solution (bulk deposition) or by generating a flux of Ag⁺ from an Ag microelectrode that was positioned close to the Au(1 1 1) substrate (SECM deposition). SECM was used for generating a controlled flux of silver ions by anodic dissolution of an Ag microelectrode close to the SAMs modified Au(1 1 1). We found that the shape of the NPs was affected by the length of the carbon-chain of the SAM. Tetrahedral NPs were obtained on bare Au(1 1 1) surfaces while rod like and cubic Ag NPs were deposited onto 3-mercaptopropanoic acid (MPA) and 11-mercaptoundecanoic acid (MUA) SAMs, respectively. The size and shape of the deposited NPs were influenced by the deposition potential.We conclude that the shape and distribution of locally deposited Ag NPs on Au(1 1 1) can be controlled by modification of the substrate with a SAM and through controlling the Ag⁺ flux generated by SECM.     

Generation of platinum microstructures on non-conducting surfaces by means of the scanning electrochemical microscope (SECM)

The scanning electrochemical microscope (SECM) was used to form platinum microstructures. For this purpose, a thin layer of platinum dichloride was deposited as precursor on different substrates by evaporating it in high vacuum. For the reduction of this precursor the SECM provided methyl viologen radical cations locally as reducing agent. The mechanism of the reduction is discussed.     

Recent advances in platinum monolayer electrocatalysts for oxygen reduction reaction: Scale-up synthesis, structure and activity of Pt shells on Pd cores

We have established a scale-up synthesis method to produce gram-quantities of Pt monolayer electrocatalysts. The core-shell structure of the Pt/Pd/C electrocatalyst has been verified using the HAADF-STEM Z-contrast images, STEM/EELS, and STEM/EDS line profile analysis. The atomic structure of this electrocatalyst and formation of a Pt monolayer on Pd nanoparticle surfaces were examined using in situ EXAFS. The Pt mass activity of the Pt/Pd/C electrocatalyst for ORR is considerably higher than that of commercial Pt/C electrocatalysts. The results with Pt monolayer electrocatalysts may significantly impact science of electrocatalysis and fuel-cell technology, as they have demonstrated an exceptionally effective way of using Pt that can resolve problems of other approaches, including electrocatalysts’ inadequate activity and high Pt content.     

Electrooxidation of methanol and 2-propanol mixtures at platinum single crystal electrodes

In the present work the electrooxidation of methanol, 2-propanol and different mixtures of both alcohols has been studied on the three platinum basal planes in three different electrolytes (H₂SO₄, HClO₄ and NaOH). The results indicate that, like in the case of both individual alcohols, the electrooxidation of the mixture is a structure sensitive reaction and that Pt(1 1 1) leads to higher current densities for some mixture compositions as compared to what could be expected from the contribution of the individual compounds. The effect of the methanol concentration in the mixture points out that 2-propanol is the main reacting fuel at the Pt(1 1 1) surface. Interestingly, the addition of methanol clearly has a positive effect on 2-propanol oxidation. For a specific mixture composition, while results from cyclic voltammetry indicate a modest twofold increase in current density, chronoamperometric results after 10 min experiment show a nearly 200 times higher current density. IR experiments have been performed to gain information about the enhancement mechanism. Nevertheless, we have found that both methanol and 2-propanol seem to follow the same mechanism as they follow in the absence of the other alcohol, and therefore the enhancement could be probably related to a competitive adsorption for the active surface sites.     

Evidence for high performances of low Pt loading electrodes based on capped platinum electrocatalyst and carbon nanotubes in fuel cell devices

Recently we reported the preparation and electrochemical behaviour of porous electrodes based on the controlled combination of carbon nanotubes and capped platinum nanoparticles towards oxygen reduction. Due to the organic crown of the nanoparticles, the electrodes exhibited low hydrogen underpotential deposition (H upd) electroactive surface areas but significant activity towards oxygen reduction was recorded down to very low platinum loadings of few μg/cm². While the presence of organic stabilizing material, at the surface of the electrocatalyst synthesized by wet chemistry, may be considered as a potential drawback in fuel cell community, we present in this paper results showing that our capped electrocatalyst associated with carbon nanotubes can be used without any pre-treatment and exhibit high performances in fuel cell devices, in spite of low platinum loadings. Beyond the practical interest of such capped nanoparticles in fuel cell technology demonstrated here, fundamental question related to the high performances of the capped electrocatalyst are still opened and are currently under investigation.     

Characterization of coating systems by scanning electrochemical microscopy: Surface topology and blistering

Operation of the scanning electrochemical microscope used in feedback mode over a coated metal allows changes in the state of the coating surface to be monitored during immersion in aqueous electrolytes. This paper reports changes in the coating induced by specific anions in the electrolyte in situ during immersion. Significant surface roughening is observed for immersion times shorter than 1 day when the electrolyte contains chloride ions. This effect is also observed when the oxygen dissolved in the electrolytic phase is employed as redox mediator for SECM imaging. The coated system exposed to chloride-free electrolytes containing sulphate or nitrate maintains a featureless topography within the same time scale. The observed features are due to the nucleation and growth of blisters at the metal/coating interface induced by chloride ions in the environment. The implication is that ionic migration occurs simultaneously with the absorption of water by the coating already from the beginning of exposure to the aqueous environment. The unique role of chloride ions compared with sulphate or nitrate ions towards coating performance has been established at a very early stage following immersion of the sample.     

Visualisation of the local electrochemical activity of thermal sprayed anti-corrosion coatings using scanning electrochemical microscopy

Scanning electrochemical microscopy was used to study the electrochemical activity of anti-corrosion coatings formed from Inconel 625, a Ni-Cr-Mo alloy commonly used in engineering applications. The coatings were formed using a high velocity oxygen fuel thermal spraying technique. Upon spraying the alloy onto mild steel substrates, clear splat boundaries were formed at the interface between adjacent droplets as they cooled on the substrate surface. Scanning electrochemical microscopy in the feedback mode, employing ferrocenemethanol as redox mediator, was used to study the local electrochemical activity of samples of the wrought alloy, the sintered alloy and the thermal sprayed coating. The wrought and sintered materials showed responses typical of that expected for a purely insulating material. However, SECM approach curve data showed that the electrochemical activity of the thermal sprayed material was higher than that of the bulk alloy. Local variations in the coating's electrochemical activity were then visualised using SECM imaging, which appear to be related to the splat boundaries formed during the thermal spray process.     

Photoelectrochemical kinetics of Eosin Y-sensitized zinc oxide films investigated by scanning electrochemical microscopy under illumination with different LED

The overall efficiency of the light-induced charge separation in dye-sensitized solar cells depends on the kinetic competition between back electron transfer and dye regeneration processes by a redox electrolyte. In a previous study, the reduction of the intermittently formed photo-oxidized dye molecules by iodide ions in the electrolyte phase was investigated using the feedback mode of a scanning electrochemical microscope (SECM) and a quantitative model had been derived. Here we provide a more thorough experimental verification of this model by variation of the excitation wavelength, light intensities and mediator concentrations. Nanoporous ZnO/Eosin Y films prepared by self-assembly were used as model electrodes and were used with an iodide/triiodide electrolyte. The experimentally found effective rate constants could be related to the rate constant for the reaction of the dissolved donor with photo-oxidized Eosin Y bound to ZnO and the absorption spectrum of the dye and confirmed the assumption made in the derivation of the model. For the regeneration process of Eosin Y, a rate constant of k_ox with different light emitting diodes and light intensities is determined.     

The use of scanning electrochemical microscopy for the characterisation of patinas on copper alloys

The scanning electrochemical microscopy (SECM) was employed in the feedback mode for the visualisation of the local changes of morphology and reactivity, occurring on the surface of a quaternary copper-based alloy, due to exposure to environment. First, samples artificially aged by exposure to leaching acid rain were tested. The layer of corrosion products (“patina”) was investigated by performing SECM scans and approach curves, and the information provided by this electrochemical technique was compared with SEM–EDX–Raman characterisation. Successively, to highlight the early stages of localised corrosion processes, in situ examination of the surface exposed to an acidic environment was performed. The results show that SECM is a powerful characterisation tool of the deterioration process and is able to map the precursor sites of corrosion on the bronze surface.     

Uses of scanning electrochemical microscopy for the characterization of thin inhibitor films on reactive metals: The protection of copper surfaces by benzotriazole

Scanning electrochemical microscopy (SECM) was used to study the film formation of benzotriazole towards corrosion of copper. SECM was operated in the feedback mode by using ferrocene-methanol as redox mediator, and the sample was left unbiased at all times to freely attain its open circuit potential in the test environment. Following exposure to aggressive electrolytes the anticorrosion abilities of the layers were characterized by image analysis and by an electrochemical method derived from the experimental approach curves. Changes in the shape of the approach curves were clearly observed during the inhibitor film formation process. They showed the transition from an active conducting behaviour towards ferrocinium reoxidation typical of unprotected copper, to a surface exhibiting insulating characteristics when the metal was covered by a surface film containing the inhibitor. This supports that SECM is a practical technique in the investigation of corrosion inhibitor performance. However, a consistent tendency for the characterization of inhibitor film formation using SECM measurements in the positive feedback mode for the copper-benzotriazole system was only found if the experiments were conducted when the inhibitor molecule was not present in the test solution. That is, inhibitor molecules were found to interact not only with the copper surface during the monitoring process, but with the SECM tip as well, this effect being significantly enhanced when chloride ions were present in the electrolyte. Finally, a procedure to image the chemical activity of copper surfaces partially covered with the inhibitor film with SECM is proposed.     

Controlled growth and shape formation of platinum nanoparticles and their electrochemical properties

Cubic Pt nanoparticles were prepared from a solution of K₂PtCl₄ containing sodium polyacrylate as a capping reagent. The effects of the Pt/polymer molar ratio, the average molecular weight (M_w) of the polymer, and reaction temperature on the shape and size were investigated. When the polymer of M_w = 5100 was added at a molar ratio of Pt/polymer = 1/12, cubic platinum nanoparticles of an average size of 10.3 nm were predominantly formed (ca. 50% in number) at 25 °C. The electron diffraction pattern of the cubic nanoparticles revealed that they are single crystals with Pt {1 0 0} faces on the surface.The cubic nanoparticles were electrochemically active, and showed strong features of Pt {1 0 0} faces on cyclic voltammogram under argon atmosphere. After repeated potential cycling in the range 0.05-1.4 V, the features of Pt {1 0 0} were gradually lost, and changed to those of polycrystalline Pt. Rotating ring disk electrode measurements in O₂-saturated H₂SO₄ solution revealed that the cubic nanoparticles had a high catalytic activity for oxygen reduction reaction (ORR). After polycrystallization by repeated potential cycling, the activity for ORR and hydrogen peroxide formation decreased slightly, which were attributed to the surface structural change from Pt {1 0 0} to polycrystalline.     

Platinum monolayer electrocatalysts for oxygen reduction

We have synthesized a new class of electrocatalysts for the oxygen reduction reaction, consisting of a monolayer of Pt or mixed monolayer of Pt and another late transition metal (Au, Pd, Ir, Ru, Rh, Re or Os) deposited on a Pd(1 1 1) single crystal or on carbon-supported Pd nanoparticles. Several of these electrocatalysts exhibited very high activity, amounting to 20-fold increase in a Pt mass activity, compared with conventional all-Pt electrocatalysts. Their superior activity reflects a low OH coverage on Pt, caused by the lateral repulsion between the OH adsorbed on Pt and the OH or O adsorbed on neighboring, other than Pt, late transition metal atoms. The origin of this effect was identified through a combination of experimental and theoretical methods, employing electrochemical techniques, X-ray absorption spectroscopy, and periodic, self-consistent density functional theory calculations. This new class of electrocatalysts promises to alleviate some major problems of existing fuel cell technology by simultaneously decreasing materials cost and enhancing performance.     

Micropatterning of active enzyme with a high-resolution by scanning electrochemical microscopy coupled with a nanometer-sized carbon fiber disk tip

We developed a new method for fabrication of nanometer-sized carbon fiber disk electrodes and applied them to micropattern active horseradish peroxidase (HRP) with a high-resolution by scanning electrochemical microscopy (SECM). In order to pattern active HRP, except for active HRP micropatterns predesigned other regions on a HRP-immobilized substrate was deactivated by a reactive species generated at the electrode as the tip of SECM held at 1.7 V through oxidation of Br⁻ in 0.20 mol/L phosphate buffer (PB) containing 2.5 × 10⁻² mol/L KBr and 2.0 × 10⁻³ mol/L BQ (pH 7.0). The micropatterns of active HRP were characterized using the feedback mode of SECM in PB containing 2.0 × 10⁻³ mol/L BQ and 2.0 × 10⁻³ mol/L H₂O₂, when the tip potential was held at −0.2 V.