Pd@Pt Core-Shell Concave Decahedra: A Class of Catalysts for the Oxygen Reduction Reaction with Enhanced Activity and Durability

Xue Wang, Madeline Vara, Ming Luo, Hongwen Huang, Aleksey Ruditskiy, Jinho Park, Shixiong Bao, Jingyue Liu, Jane Howe, Miaofang Chi, Zhaoxiong Xie, Younan Xia

Research output: Contribution to journalArticle

163 Citations (Scopus)

Abstract

We report a facile synthesis of multiply twinned Pd@Pt core-shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200°C, naturally generating a core-shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2 Pt) and mass (1.60 A/mgPt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2 Pt and 0.32 A/mgPt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgPt, more than twice that of the pristine Pt/C catalyst.

Original languageEnglish (US)
Pages (from-to)15036-15042
Number of pages7
JournalJournal of the American Chemical Society
Volume137
Issue number47
DOIs
StatePublished - Nov 13 2015

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Seed
Seeds
Durability
Thermodynamic properties
Oxygen
Catalysts
Coatings
Atoms
Adatoms
Surface diffusion
Density (specific gravity)
Catalyst activity
Weights and Measures
Defects

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

Pd@Pt Core-Shell Concave Decahedra : A Class of Catalysts for the Oxygen Reduction Reaction with Enhanced Activity and Durability. / Wang, Xue; Vara, Madeline; Luo, Ming; Huang, Hongwen; Ruditskiy, Aleksey; Park, Jinho; Bao, Shixiong; Liu, Jingyue; Howe, Jane; Chi, Miaofang; Xie, Zhaoxiong; Xia, Younan.

In: Journal of the American Chemical Society, Vol. 137, No. 47, 13.11.2015, p. 15036-15042.

Research output: Contribution to journalArticle

Wang, X, Vara, M, Luo, M, Huang, H, Ruditskiy, A, Park, J, Bao, S, Liu, J, Howe, J, Chi, M, Xie, Z & Xia, Y 2015, 'Pd@Pt Core-Shell Concave Decahedra: A Class of Catalysts for the Oxygen Reduction Reaction with Enhanced Activity and Durability', Journal of the American Chemical Society, vol. 137, no. 47, pp. 15036-15042. https://doi.org/10.1021/jacs.5b10059
Wang, Xue ; Vara, Madeline ; Luo, Ming ; Huang, Hongwen ; Ruditskiy, Aleksey ; Park, Jinho ; Bao, Shixiong ; Liu, Jingyue ; Howe, Jane ; Chi, Miaofang ; Xie, Zhaoxiong ; Xia, Younan. / Pd@Pt Core-Shell Concave Decahedra : A Class of Catalysts for the Oxygen Reduction Reaction with Enhanced Activity and Durability. In: Journal of the American Chemical Society. 2015 ; Vol. 137, No. 47. pp. 15036-15042.
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AU - Huang, Hongwen

AU - Ruditskiy, Aleksey

AU - Park, Jinho

AU - Bao, Shixiong

AU - Liu, Jingyue

AU - Howe, Jane

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AU - Xie, Zhaoxiong

AU - Xia, Younan

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N2 - We report a facile synthesis of multiply twinned Pd@Pt core-shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200°C, naturally generating a core-shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2 Pt) and mass (1.60 A/mgPt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2 Pt and 0.32 A/mgPt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgPt, more than twice that of the pristine Pt/C catalyst.

AB - We report a facile synthesis of multiply twinned Pd@Pt core-shell concave decahedra by controlling the deposition of Pt on preformed Pd decahedral seeds. The Pt atoms are initially deposited on the vertices of a decahedral seed, followed by surface diffusion to other regions along the edges/ridges and then across the faces. Different from the coating of a Pd icosahedral seed, the Pt atoms prefer to stay at the vertices and edges/ridges of a decahedral seed even when the deposition is conducted at 200°C, naturally generating a core-shell structure covered by concave facets. The nonuniformity in the Pt coating can be attributed to the presence of twin boundaries at the vertices, as well as the {100} facets and twin defects along the edges/ridges of a decahedron, effectively trapping the Pt adatoms at these high-energy sites. As compared to a commercial Pt/C catalyst, the Pd@Pt concave decahedra show substantial enhancement in both catalytic activity and durability toward the oxygen reduction reaction (ORR). For the concave decahedra with 29.6% Pt by weight, their specific (1.66 mA/cm2 Pt) and mass (1.60 A/mgPt) ORR activities are enhanced by 4.4 and 6.6 times relative to those of the Pt/C catalyst (0.36 mA/cm2 Pt and 0.32 A/mgPt, respectively). After 10 000 cycles of accelerated durability test, the concave decahedra still exhibit a mass activity of 0.69 A/mgPt, more than twice that of the pristine Pt/C catalyst.

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