Abstract
Atomic-scale control in the formation of Pd thin films is being developed using electrochemical atomic layer deposition (E-ALD) via surface limited redox replacement (SLRR). Pd has unique hydrogen storage properties. To study hydrogen storage capacity, hydrogen charging and discharging kinetics and its catalytic properties at the nanoscale will require films with well-defined thickness and structure. SLRR is the use of underpotential deposition (UPD) to form a sacrificial atomic layer of a less noble metal, such as Cu or Pb, and to exchange it at open circuit potential (OCP) for a more noble metal (Pd) via galvanic displacement. The deposits were grown using an automated electrochemical flow cell system which allowed sequential variation of solutions and potentials. Electron probe microanalysis (EPMA) revealed excess growth at the flow cell ingress, suggesting that the SLRR mechanism involved electron transfer from substrate to Pd2+ ions, rather than direct electron exchange from sacrificial metal atom(s) to Pd2+ ions. Ethylenediaminetetraacetic acid (EDTA) was used to slow the galvanic displacement by complexing the Pd2+, in an attempt to form more uniform Pd deposits. The resulting films were more homogeneous and displayed the expected Pd voltammetry in H2SO4. The charge for UPD remained constant from cycle to cycle, indicating no roughening of the surface. Ways of optimizing complexing agent properties, as well as the flow cell design and deposition parameters are discussed.
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Acknowledgment is made of the support of the National Science Foundation, Division of Materials Science, as well as Sandia National Laboratories, a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.
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Sheridan, L.B., Czerwiniski, J., Jayaraju, N. et al. Electrochemical Atomic Layer Deposition (E-ALD) of Palladium Nanofilms by Surface Limited Redox Replacement (SLRR), with EDTA Complexation. Electrocatalysis 3, 96–107 (2012). https://doi.org/10.1007/s12678-012-0080-7
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DOI: https://doi.org/10.1007/s12678-012-0080-7