Tailoring of highly porous SnO2 and SnO2-Pd thin films

Abstract Tin oxide is a material that attracts attention due to variety of technological applications. The main parameters that influence its properties are morphology, crystalline structure and stoichiometry. Researchers try to develop nanostructured thin films with tunable parameters that would conform its technological applications. Herein, we report on the preparation and characterization of highly porous SnO2 and Pd-doped SnO2 thin films. These films were deposited in the form of nanorods with controllable geometry. Such morphology was achieved by utilizing glancing angle deposition (GLAD) with assisted magnetron sputtering. This arrangement allowed preparation of slanted pillars, zig-…

In-situ electrochemical atomic force microscopy study of aging of magnetron sputtered Pt-Co nanoalloy thin films during accelerated degradation test

Abstract A Pt-Co nanoalloy thin film catalyst was prepared by using simultaneous magnetron sputtering of Pt and Co. The catalyst was characterized during accelerated degradation test using in-situ electrochemical atomic force microscopy complemented with ex-situ techniques such as energy dispersive X-ray spectroscopy, X-ray photoelectron spectroscopy and synchrotron radiation photoelectron spectroscopy. The combined results gave the full step-by-step picture of the catalyst behavior during the aging test.

Electronic exchanges between adsorbed Ni atoms and TiO2(110) surface evidenced by resonant photoemission

Abstract Nickel was deposited on stoichiometric TiO2(1 1 0) surface in the 0.02–2.1 equivalent monolayer (eqML) range and analyzed by means of photoemission and resonant photoemission. In the case of very low coverage (lower than 0.1 eqML), deposited nickel reacts with the surface through an electronic transfer from nickel atoms towards titanium ions. This exchange caused the filling of unoccupied Ti3d states leading to the increase of a peak in the TiO2 band gap. These states can be better characterized through resonant photoemission experiments at the Ti 3p → 3d absorption edge: for very low coverage, these states in the TiO2 band gap have resonant behavior of Ti3d electrons rather than N…

Platinum-doped CeO2 thin film catalysts prepared by magnetron sputtering.

The interaction of Pt with CeO(2) layers was investigated by using photoelectron spectroscopy. The 30 nm thick Pt doped CeO(2) layers were deposited simultaneously by rf-magnetron sputtering on a Si(001) substrate, multiwall carbon nanotubes (CNTs) supported by a carbon diffusion layer of a polymer membrane fuel cell and on CNTs grown on the silicon wafer by the CVD technique. The synchrotron radiation X-ray photoelectron spectra showed the formation of cerium oxide with completely ionized Pt(2+,4+) species, and with the Pt(2+)/Pt(4+) ratio strongly dependent on the substrate. The TEM and XRD study showed the Pt(2+)/Pt(4+) ratio is dependent on the film structure.

Maximum Noble-Metal Efficiency in Catalytic Materials: Atomically Dispersed Surface Platinum

International audience; Platinum is the most versatile element in catalysis, but it is rare and its high price limits large-scale applications, for example in fuel-cell technology. Still, conventional catalysts use only a small fraction of the Pt content, that is, those atoms located at the catalyst's surface. To maximize the noble-metal efficiency, the precious metal should be atomically dispersed and exclusively located within the outermost surface layer of the material. Such atomically dispersed Pt surface species can indeed be prepared with exceptionally high stability. Using DFT calculations we identify a specific structural element, a ceria ``nanopocket'', which binds Pt2+ so strongly…

Growth of nano-porous Pt-doped cerium oxide thin films on glassy carbon substrate

Abstract Glassy carbon (GC) substrates were treated by the oxygen plasma over several periods of time. Scanning electron microscopy (SEM), transmission electron microscopy (TEM) and atomic force microscopy (AFM) study showed the dramatic influence of oxygen plasma on the morphology of glassy carbon. The treatment leads to the formation of nanostructured surface, which consists of well separated rod-like nanostructures oriented perpendicularly to the substrate surface. The surface roughness was found to increase with increasing treatment time. By using magnetron co-sputtering of platinum and cerium oxide we can prepare oxide layers continuously doped with Pt atoms during the growth. This tec…

Preparation of magnetron sputtered thin cerium oxide films with a large surface on silicon substrates using carbonaceous interlayers.

The study focuses on preparation of thin cerium oxide films with a porous structure prepared by rf magnetron sputtering on a silicon wafer substrate using amorphous carbon (a-C) and nitrogenated amorphous carbon films (CNx) as an interlayer. We show that the structure and morphology of the deposited layers depend on the oxygen concentration in working gas used for cerium oxide deposition. Considerable erosion of the carbonaceous interlayer accompanied by the formation of highly porous carbon/cerium oxide bilayer systems is reported. Etching of the carbon interlayer with oxygen species occurring simultaneously with cerium oxide film growth is considered to be the driving force for this effec…

Back Cover: Maximum Noble-Metal Efficiency in Catalytic Materials: Atomically Dispersed Surface Platinum (Angew. Chem. Int. Ed. 39/2014)

An epitaxial hexagonal tungsten bronze as precursor for WO3 nanorods on mica.

International audience; Tungsten oxide nanorods are grown at atmospheric pressure and low temperature (360 1C), by sublimation of WO3 and condensation on mica substrates. The nanorods are characterized by atomic force microscopy, high-resolution electron microscopy, energy-dispersive X-ray spectroscopy and high energy electron diffraction. The experimental results evidence the formation of a hexagonal tungsten bronze at the nanorod–substrate interface. The epitaxial relationships of the nanorods on mica are determined and the role of epitaxial orientation of the interfacial bronze in the nanorod growth and morphology are discussed.

High efficiency of Pt2+ - CeO2 novel thin film catalyst as anode for proton exchange membrane fuel cells

Abstract The elevated price of Pt limits the large-scale implementation of commercial proton exchange membrane fuel cells, which effectively convert chemical energy into electricity. In order to increase the cost-efficiency in proton-exchange membrane fuel cells, we have designed a family of novel anode catalysts consisting of thin films of ceria with low Pt loadings sputtered on a nanostructured carbon support. Remarkably, only such small amounts of Pt are necessary for achieving power density values comparable to the reference commercial catalysts, which results in excellent specific activities of our samples. By combining photoelectron spectroscopy and catalytic performance analysis, we …

Pt–CeO thin film catalysts for PEMFC

Abstract Platinum is the mostly used element in catalysts for fuel cell technology, but its high price limits large-scale applications. Platinum doped cerium oxide represents an alternative solution due to very low loading, typically few micrograms per 1 cm2, at the proton exchange membrane fuel cell (PEMFC) anode. High efficiency is achieved by using magnetron sputtering deposition of cerium oxide and Pt of 30 nm thick nanoporous films on large surface carbon nanoparticle substrates. Thin film techniques permits to grow the catalyst film characterized by highly dispersed platinum, mostly in ionic Pt2+ state. Such dispersed Pt species show high activity and stability. These new materials ma…

Rücktitelbild: Auf dem Weg zu größtmöglicher Effizienz bei der katalytischen Nutzung von Edelmetallen: atomar dispergiertes Oberflächen-Platin (Angew. Chem. 39/2014)

Electrochemically shape-controlled transformation of magnetron sputtered platinum films into platinum nanostructures enclosed by high-index facets

Abstract A new method based on transformation of magnetron sputtered platinum thin films into platinum nanostructures enclosed by high-index facets, using electrochemical potential cycling in a twin working electrode system is reported. The controllable formation of various Pt nanostructures, described in this paper, indicates that this method can be used to control a selective growth of high purity Pt nanostructures with specific shapes (facets or edges). The method opens up new possibilities for electrochemical preparation of nanostructured Pt catalysts at high yield.

Oxide-based nanomaterials for fuel cell catalysis:the interplay between supported single Pt atoms and particles

The concept of single atom catalysis offers maximum noble metal efficiency for the development of low-cost catalytic materials. Among possible applications are catalytic materials for proton exchange membrane fuel cells. In the present review, recent efforts towards the fabrication of single atom catalysts on nanostructured ceria and their reactivity are discussed in the prospect of their employment as anode catalysts. The remarkable performance and the durability of the ceria-based anode catalysts with ultra-low Pt loading result from the interplay between two states associated with supported atomically dispersed Pt and sub-nanometer Pt particles. The occurrence of these two states is a co…

Growth and composition of nanostructured and nanoporous cerium oxide thin films on a graphite foil.

The morphology and composition of CeOx films prepared by r.f. magnetron sputtering on a graphite foil have been investigated mainly by using microscopy methods. This study presents the formation of nanocrystalline layers with porous structure due to the modification of a carbon support and the formation of cerium carbide crystallites as a result of the deposition process. Chemical analyses of the layers with different thicknesses performed by energy dispersive X-ray spectroscopy, electron energy loss spectroscopy and X-ray photoelectron spectroscopy have pointed to the reduction of the cerium oxide layers. In the deposited layers, cerium was present in mixed Ce(3+) and Ce(4+) valence. Ce(3+…

Deposition of Pt and Sn doped CeOx layers on silicon substrate

Abstract Radio Frequency Magnetron Sputtering is used to elaborate CeO x layers doped with platinum and/or tin on a SiO 2 /Si substrate. Morphology, chemical composition and crystallographic structures were investigated by Transmission Electron Microscopy. The presence of nanoparticles of mainly ceria and metallic platinum is exhibited.

Proton exchange membrane fuel cell made of magnetron sputtered Pt–CeO and Pt–Co thin film catalysts

Abstract Preparation of catalysts for proton exchange membrane fuel cells (PEMFCs) is of growing interest during last years. The magnetron sputtering technique is a promising method of catalyst preparation because it permits to synthesize catalysts in a fast and relatively less expensive way, however control of specific surface and durability of such catalysts still remains the main concern. We tested a single cell PEMFC catalyzed by using exclusively thin film approach by combining state-of-the art Pt-doped cerium oxide anode and a new Pt–Co alloy cathode. We have shown that beside very high mass activity of the catalysts relative to the membrane electrode assembly the catalyst nanoporous …

Structural and Chemical Characterization of Cerium Oxide Thin Layers Grown on Silicon Substrate

In this study, we report transmission electron microscopy and electron energy loss spectroscopy study of cerium oxide thin layers deposited on silicon substrate. Transmission electron microscopy experiments have revealed the flat morphology of the deposited layers. In addition, studies of high resolution images have indicated the presence of mainly ceria crystallized nanoparticles. Energy electron loss spectroscopy measurements were also performed in scanning mode to study the evolution of the cerium valence. In addition to Ce4+ inside the layer, the presence of amorphous cerium silicate with valence +3 is pointed out at the vicinity of the substrate.

Refractory metal reactivity towards oxide surface : W/TiO2(1 1 0) case.

International audience; Reactivity of deposited tungsten towards TiO2(1 1 0) surface was studied using synchrotron radiation photoemission spectroscopy (both core levels, valence band and resonant photoemission) on Materials Science Beamline at ELETTRA. W depositions carried out at room temperature on TiO2(1 1 0) surface give rise to an interfacial reaction which leads to a metastable situation due to kinetic limitations. Annealing induces chemical changes which are function of the initial coverage; for fractional coverage, annealing induces completion of oxidation of deposit whereas reduction to metallic tungsten occurs for highest coverage. These results demonstrate that interaction of W …

Auf dem Weg zu größtmöglicher Effizienz bei der katalytischen Nutzung von Edelmetallen: atomar dispergiertes Oberflächen-Platin

Platin ist das am vielseitigsten eingesetzte Element in der Katalyse. Allerdings begrenzt der hohe Preis des Edelmetalls die Verwendung in vielen Bereichen, z. B. in Katalysatormaterialien fur Brennstoffzellen. Trotzdem nutzen konventionelle Katalysatoren oftmals nur einen Bruchteil ihres Pt-Gehaltes, namlich diejenigen Atome, die sich auf der Oberflache des Katalysators befinden. Eine effizientere Edelmetallnutzung setzt somit eine hohere, bevorzugt atomare Dispersion der Pt-Atome auf der Oberflache voraus. Tatsachlich ist es moglich, solche atomar dispergierten Pt-Spezies mit sehr hoher Stabilitat auf einer Katalysatoroberflache herzustellen. Mithilfe von DFT-Rechnungen identifizieren wir…