Elena R. Savinova

Influence of particle agglomeration on the catalytic activity of carbon-supported Pt nanoparticles in CO monolayer oxidation

Fuel cell electrocatalysts usually feature high noble metal contents, and these favour particle agglomeration. In this paper a variety of synthetic approaches (wet chemical deposition, electrodeposition and electrodeposition on chemically preformed Pt nuclei) is employed to shed light on the influence of nanoparticle agglomeration on their electrocatalytic properties. Pt loading on model glassy carbon (GC) support is increased systematically from 1.8 to 10.6 μg Pt cm−2 and changes in the catalyst structure are followed by transmission electron microscopy. At low metal loadings (≤5.4 μg Pt cm−2) isolated single crystalline Pt nanoparticles are formed on the support surface by wet chemical deposition from H2PtCl4 precursor. An increase in the metal loading results, first, in a systematic increase of the average diameter of isolated Pt nanoparticles and, second, in coalescence of nanoparticles and formation of particle agglomerates. This behaviour is in line with the previous observations on carbon-supported noble metal fuel cell electrocatalysts. The catalytic activity of Pt/GC electrodes is tested in CO monolayer oxidation. In agreement with the previous studies (F. Maillard, M. Eikerling, O. V. Cherstiouk, S. Schreier, E. Savinova and U. Stimming, Faraday Discuss., 2004, 125, 357), we find that the reaction is strongly size sensitive, exhibiting an increase of the reaction overpotential as the particle size decreases below ca. 3 nm. At larger particle sizes the dependence levels off, the catalytic activity of particles with diameters above 3 nm approaching that of polycrystalline Pt. Meanwhile, Pt agglomerates show remarkably enhanced catalytic activity in comparison to either isolated Pt nanopraticles or polycrystalline Pt foil, catalysing CO monolayer oxidation at ca. 90 mV lower overpotential. Enhanced catalytic activity of Pt agglomerates is ascribed to high concentration of surface defects. CO stripping voltammograms from Pt/GC electrodes, comprising Pt agglomerates along with isolated single crystalline Pt nanoparticles from 2 to 6 nm size, feature double voltammetric peaks, the more negative corresponding to CO oxidation on Pt agglomerates, while the more positive to CO oxidation on isolated Pt nanoparticles. It is shown that CO stripping voltammetry provides a fingerprint of the particle size distribution and the extent of particle agglomeration in carbon-supported Pt catalysts.

Model approach to evaluate particle size effects in electrocatalysis: Preparation and properties of Pt nanoparticles supported on GC and HOPG

Although metal nanoparticles are widely used in electrocatalysis, in particular for the preparation of the electrodes for fuel cells, it is still not fully understood how the size of a metal phase affects its electrochemical reactivity. In this paper, we demonstrate a possible approach to design model electrodes for studying size effects in electrocatalysis. A simple chemical deposition procedure is introduced, which allows reproducible preparation of 1.5/3.0 nm Pt nanoparticles anchored to the surface of glassy carbon (GC) or highly oriented pyrolytic graphite (HOPG). Pt nanoparticles supported on GC are stable versus potential variation and can be used for studying size effects. They are examined in electrochemical reactions relevant to low temperature fuel cells: electrooxidation of adsorbed CO and methanol. It is demonstrated that reactivity of Pt nanoparticles in these reactions is considerably decreased in comparison to bulk polycrystalline Pt.

The structure analysis of the active centers of Ru-containing electrocatalysts for the oxygen reduction. An in situ EXAFS study

Abstract A family of novel catalysts for oxygen electroreduction is presented, based on nanostructured Ru x X y chalcogenide compounds (X=S, Se, Te). EXAFS data suggest that the catalysts have a core of ruthenium atoms, which has triangular co-ordination and a direct metalmetal bond. Depending on the chalcogen, the Ru-cluster consists of two or three metal layers of different size and mutual co-ordination with chalcogen atoms co-ordinated to the periphery of the cluster. Variation of the chalcogen type affects the size of the Ru-cluster and the strength of its interaction with the chalcogen. This influences the interaction of Ru-clusters with oxygen and thus their activity in the reduction of molecular oxygen.

CO monolayer oxidation at Pt nanoparticles supported on glassy carbon electrodes

CO monolayer oxidation on glassy carbon supported 1–2 nm Pt nanoparticles is studied using potential sweep and potential step methods. The CO stripping peak on the nanoparticles is significantly shifted to positive potentials vs. the corresponding feature at bulk polycrystalline Pt. Current transients at nanoparticulate electrodes are highly asymmetric with a steep rise, maximum at θCO≈0.8–0.9, and a slow decay following t−1/2. The experimental results are compared to the theoretical models of adsorbed CO oxidation described in the literature. A tentative model is suggested to account for the experimental observations, which comprises spatially confined formation of oxygen containing species at active sites, and slow diffusion of CO molecules to the active sites, where they are oxidized. The upper limit of the CO surface diffusion coefficient at Pt nanoparticles is estimated as approximately 4×10−15 cm2 s−1.

On the influence of the metal loading on the structure of carbon-supported PtRu catalysts and their electrocatalytic activities in CO and methanol electrooxidation

PtRu (1:1) catalysts supported on low surface area carbon of the Sibunit family (S(BET) = 72 m(2) g(-1)) with a metal percentage ranging from 5 to 60% are prepared and tested in a CO monolayer and for methanol oxidation in H(2)SO(4) electrolyte. At low metal percentage small (<2 nm) alloy nanoparticles, uniformly distributed on the carbon surface, are formed. As the amount of metal per unit surface area of carbon increases, particles start coalescing and form first quasi two-dimensional, and then three-dimensional metal nanostructures. This results in a strong enhancement of specific catalytic activity in methanol oxidation and a decrease of the overpotential for CO monolayer oxidation. It is suggested that intergrain boundaries connecting crystalline domains in nanostructured PtRu catalysts produced at high metal-on-carbon loadings provide active sites for electrocatalytic processes.

One step synthesis of niobium doped titania nanotube arrays to form (N,Nb) co-doped TiO2 with high visible light photoelectrochemical activity

The chemical modification of aligned titanium dioxide nanotube (TiO2-NT) arrays provides new doping possibilities to improve their photoelectrochemical activity under visible light. Niobium doped TiO2-NTs containing up to 15% of Nb in the near-surface region are prepared by a flexible single step procedure using a fluoroniobate complex simultaneously acting as a source of the doping element and fluoride anions required for nanotube formation. This negatively charged complex allows an efficient insertion of Nb in the forming TiO2-NT structure during the anodization process. These nanotube arrays are further modified with nitrogen to achieve (Nb,N) co-doped nanotubes with noticeable visible light photoelectrochemical activity.

Electrocatalytic oxygen reduction reaction on perovskite oxides: series versus direct pathway.

The mechanism of the oxygen reduction reaction (ORR) on LaCoO(3) and La(0.8)Sr(0.2)MnO(3) perovskite oxides is studied in 1 M NaOH by using the rotating ring disc electrode (RRDE) method. By combining experimental studies with kinetic modeling, it was demonstrated that on perovskite, as well as on perovskite/carbon electrodes, the ORR follows a series pathway through the intermediate formation of hydrogen peroxide. The escape of this intermediate from the electrode strongly depends on: 1) The loading of perovskite; high loadings lead to an overall 4 e(-) oxygen reduction due to efficient hydrogen peroxide re-adsorption on the active sites and its further reduction. 2) The addition of carbon to the catalytic layer, which affects both the utilization of the perovskite surface and the production of hydrogen peroxide. 3) The type of oxide; La(0.8)Sr(0.2)MnO(3) displays higher (compared to LaCoO(3)) activity in the reduction of oxygen to hydrogen peroxide and in the reduction/oxidation of the latter.

Improvement of the Performance of a Direct Methanol Fuel Cell Using a Pulse Technique

A pulse method is suggested for the improvement of the performance of a direct methanol fuel cell operated with PtRu anode and Pt cathode. The pulse method can be realized either in a potentiostatic or in a galvanostatic mode. In the galvanostatic regime of low current densities it allows for a temporary hoist of the cell voltage by up to 150 mV. It is suggested that by periodically applying a pulse to the fuel cell, the anode potential is shifted to positive values at which the otherwise high CO ads coverage on the PtRu anode is decreased by oxidation. After the pulse, the methanol oxidation rate is enhanced until the previous CO ads coverage is re-established and a new pulse is then applied. Differential electrochemical mass spectroscopy data reveal that an appreciable voltage gain can be obtained at a reduction of only ca. 10-15% of the Co ads saturation coverage.

Uncovering the Stabilization Mechanism in Bimetallic Ruthenium-Iridium Anodes for Proton Exchange Membrane Electrolyzers.

Proton exchange membrane (PEM) electrolyzers are attracting an increasing attention as a promising technology for the renewable electricity storage. In this work, near ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) is applied for in situ monitoring of the surface state of membrane electrode assemblies with RuO2 and bimetallic Ir0.7Ru0.3O2 anodes during water splitting. We demonstrate that Ir protects Ru from the formation of an unstable hydrous Ru(IV) oxide thereby rendering bimetallic Ru-Ir oxide electrodes with higher corrosion resistance. We further show that the water splitting occurs through a surface Ru(VIII) intermediate, and, contrary to common opinion, the presence of Ir does not hinder its formation.

Platinum group metal-free NiMo hydrogen oxidation catalysts: high performance and durability in alkaline exchange membrane fuel cells

We introduce a new platinum group metal-free (PGM-free) hydrogen oxidation electrocatalyst with superior performance in anodes of alkaline exchange membrane fuel cells (AEMFCs). A carbon-supported bimetallic nickel–molybdenum catalyst was synthesized by thermal reduction of transition metal precursors on the surface of a carbon support (KetjenBlack 600J). The mass-weighted activity of 4.5 A gMe−1 determined in a liquid electrolyte 0.1 M NaOH using a rotating disk electrode (RDE) technique is comparable to the value reported for Pd/C with a comparable particle size under similar conditions. This NiMo/KB catalyst was integrated in a membrane electrode assembly (MEA) using an alkaline exchange membrane and ionomer. Single AEMFC tests performed in a H2/O2 configuration resulted in a record power density output of 120 mW cm−2 at 0.5 V, the MEA was found to be durable under the conditions of potential hold of 0.7 V for 115 h. For the first time, operando X-ray computed tomography (CT) experiments were performed demonstrating liquid water formation at the PGM-free anode during cell operation, and in situ ambient pressure X-ray photoelectron spectroscopy (APXPS) and X-ray absorption spectroscopy (APXAS) were used to study the role of molybdenum in hydrogen adsorption.