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

doi:10.1021/acscatal.5b01239

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

Materials MicroAnalysis

Research output: Contribution to journal › Article › peer-review

39 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 language	English
Pages (from-to)	5154-5163
Number of pages	10
Journal	ACS Catalysis
Volume	5
Issue number	9
DOIs	https://doi.org/10.1021/acscatal.5b01239
State	Published - Jul 22 2015

Keywords

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

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10.1021/acscatal.5b01239

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@article{f7d9ed3d7b6a407a8764b62b0d978334,

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

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.",

keywords = "anodic alumina, bismuth adatom, chemical vapor deposition, formic acid oxidation, palladium nanotube, templated synthesis",

author = "Atkinson, \{Robert W.\} and \{St. John\}, Samuel and Ondrej Dyck and Unocic, \{Kinga A.\} and Unocic, \{Raymond R.\} and Burke, \{Colten S.\} and Cisco, \{Joshua W.\} and Rice, \{Cynthia A.\} and Zawodzinski, \{Thomas A.\} and Papandrew, \{Alexander B.\}",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2015",

month = jul,

day = "22",

doi = "10.1021/acscatal.5b01239",

language = "English",

volume = "5",

pages = "5154--5163",

journal = "ACS Catalysis",

issn = "2155-5435",

publisher = "American Chemical Society",

number = "9",

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TY - JOUR

T1 - Supportless, Bismuth-Modified Palladium Nanotubes with Improved Activity and Stability for Formic Acid Oxidation

AU - Atkinson, Robert W.

AU - St. John, Samuel

AU - Dyck, Ondrej

AU - Unocic, Kinga A.

AU - Unocic, Raymond R.

AU - Burke, Colten S.

AU - Cisco, Joshua W.

AU - Rice, Cynthia A.

AU - Zawodzinski, Thomas A.

AU - Papandrew, Alexander B.

PY - 2015/7/22

Y1 - 2015/7/22

N2 - 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.

AB - 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.

KW - anodic alumina

KW - bismuth adatom

KW - chemical vapor deposition

KW - formic acid oxidation

KW - palladium nanotube

KW - templated synthesis

UR - https://www.scopus.com/pages/publications/84941123639

U2 - 10.1021/acscatal.5b01239

DO - 10.1021/acscatal.5b01239

M3 - Article

AN - SCOPUS:84941123639

SN - 2155-5435

VL - 5

SP - 5154

EP - 5163

JO - ACS Catalysis

JF - ACS Catalysis

IS - 9

ER -

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

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Keywords

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