Systematic increase of electrocatalytic turnover at nanoporous platinum surfaces prepared by atomic layer deposition

We establish a procedure for the fabrication of electrocatalytically active, nanoporous surfaces coated with Pt and exhibiting a high geometric area. Firstly, the mechanism of the surface reactions between platinum(II) acetylacetonate and ozone is investigated by piezoelectric microbalance measurements. The data reveal that ozone oxidizes the metallic Pt surface to an extent which can exceed one monolayer depending on the reaction conditions. Proper reaction parameters yield a self-limited growth in atomic layer deposition (ALD) mode. Secondly, the ALD procedure is applied to porous anodic oxide substrates. The morphology and the crystal structure of the deposits are characterized. The ALD coating results in a continuous layer of Pt nanocrystallites along deep pore walls (aspect ratio 70). Thirdly, the Pt/TiO2 surfaces are shown to be electrochemically active in both acidic and alkaline media, in a way that qualitatively conforms to literature precedents based on Pt. Finally, we apply the anodization and ALD procedure to commercial Ti felts and demonstrate systematically how the electrochemical current density is increased by the large specific surface area and by the presence of the catalyst. Thereby, the catalyst loading, as well as its efficient utilization, can be optimized accurately. The preparative approach demonstrated here can be generalized and applied to the various electrocatalytic reactions of energy conversion devices.