Pt-doped CeO x thin film electrocatalysts have recently been shown to exhibit high activity and stability at the anode of proton exchange membrane fuel cells (PEM-FC). To identify the role of the Pt dopant and the origin of the high stability of Pt–CeO x films, we applied electrochemical in situ IR spectroscopy on Pt–CeO x model thin film catalysts during methanol (1 M methanol) oxidation. The model catalysts were prepared by magnetron cosputtering of Pt (9–21 atom %) and CeO2 onto clean and carbon-coated Au supports. All samples were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray photoelectron spectroscopy (XPS) before and after reaction. At pH 1 (0.1 M HClO4) the Pt–CeO x dissolves partially during potential cycling, whereas the films are largely stable at pH 6 (0.1 M phosphate buffer). Electrochemical IR spectroscopy of the adsorbed CO shows that metallic Pt is formed on all Pt–CeO x samples during methanol oxidation. In comparison to Pt(111), Pt aggregates on Pt–CeO x show a CO on-top signal, which is red shifted by at least 25 cm–1 and suppression of the bridging CO signals. Whereas the Pt particles on Pt–CeO x films with high Pt concentration (>20 atom %) undergo rapid sintering during the potential cycling, small metallic Pt aggregates are stable under the same conditions on films with low Pt concentration (<15 atom % Pt). By means of density functional theory (DFT) calculations we analyzed the spectral shifts of adsorbed CO as a function of nanoparticle size both on free and ceria-supported Pt particles. Comparison with the experiment suggests the formation of “subnano”-particles, i.e., particles with up to 30 atoms (<1 nm particle diameter), which do not expose regular (111) facet sites. At sufficiently low Pt loading, these subnano-Pt particles are efficiently stabilized by the interaction with the ceria support under conditions of the dynamically changing electrode potential.

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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 effect resulting in the formation of nanostructured cerium oxide films with large surface. In this regard, results of oxygen plasma treatment of a-C and CNx films are presented. Gradual material erosion with increasing duration of plasma impact accompanied by modification of the surface roughness is reported for both types of films. The CNx films were found to be much less resistant to oxygen etching than the a-C film.

Summary An ultra‐low‐platinum catalyst based on finely dispersed platinum (Pt) deposited on a highly porous complex microporous layer was investigated as a candidate of durable anode catalyst for hydrogen oxidation reaction (HOR) in proton exchange membrane fuel cells. Etching of teflonated and nitridized base carbon substrate in oxygen plasma and simultaneous deposition of cerium oxide were applied to increase active surface area and electrochemical activity of the platinum nanocatalyst. Ultra‐low loadings of Pt (between 0.85 and 8.5 μg cm−2) deposited by magnetron sputtering on this substrate were assembled with Nafion 212 membrane and commercially available Pt/C cathodes (300‐400 μg cm−2 Pt). Such membrane electrode assembly (MEA) with extremely low Pt content at anode can deliver high output power densities, reaching 0.95 W cm−2 or 0.65 W cm−2 with only 1.7 μg cm−2 of Pt, using H2 as fuel and pure O2 or air as an oxidant, respectively. Although electrocatalysts with highly dispersed active metals are known to often suffer from irreversible degradation, the above MEAs proved to be very stable when the cell was subjected to a durability test under heavy duty conditions of on/off cycling. The system with lower Pt content is more prone to water flooding which can, however, be eliminated by maintaining better control over the fuel humidity. Average decay of the cell voltage less than 50 μV h−1 was obtained in the cycling regime, while excellent stability <10 μV h−1 is achievable under the static load of 0.4 A cm−2.

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