Supportless, Bismuth-Modified Palladium Nanotubes with Improved Activity and Stability for Formic Acid Oxidation

Robert W. Atkinson, Samuel St. John, Ondrej Dyck, Kinga A. Unocic, Raymond R. Unocic, Colten S. Burke, Joshua W. Cisco, Cynthia A. Rice, Thomas A. Zawodzinski, Alexander B. Papandrew

Research output: Contribution to journalArticlepeer-review

37 Scopus citations

Abstract

Palladium nanotubes (PdNTs) were synthesized by templated vapor deposition and investigated for formic acid electrooxidation. Annealed PdNTs are 2.4 times more active (2.19 mA/cm2) than commercial carbon-supported palladium (0.91 mA/cm2) at 0.3 V vs RHE. Bismuth modification improved nanotube performance over 4 times (3.75 mA/cm2) vs Pd/C and nearly 2 times vs unmodified PdNTs. A surface Bi coverage of 80% results in optimal site-specific activity by drastically reducing surface-poisoning CO generation during formic acid electrooxidation. The Bi-modified PdNTs are exceptionally stable, maintaining 2 times the area-normalized current density as Pd/C after 24 h at 0.2 V vs RHE. We attribute the enhanced activity and stability of the nanotube catalysts to the presence of highly coordinated surfaces, mimicking a flat polycrystal while retaining high surface area geometry.

Original languageEnglish
Pages (from-to)5154-5163
Number of pages10
JournalACS Catalysis
Volume5
Issue number9
DOIs
StatePublished - Jul 22 2015

Funding

FundersFunder number
National Science FoundationEPS-1004083

    Keywords

    • anodic alumina
    • bismuth adatom
    • chemical vapor deposition
    • formic acid oxidation
    • palladium nanotube
    • templated synthesis

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