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",

}

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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