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Title: Structural Evolution of Sub-10 nm Octahedral Platinum$$-$$Nickel Bimetallic Nanocrystals

Journal Article · · Nano Letters
ORCiD logo [1];  [1];  [2];  [1];  [1];  [3];  [3];  [3]; ORCiD logo [2]; ORCiD logo [4]
  1. Hong Kong Univ. of Science and Technology, Hong Kong (China)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  3. Kyungpook National Univ., Daegu (Korea, Republic of). Dept. of Chemistry and Green-Nano Materials Research Center
  4. Hong Kong Univ. of Science and Technology, Hong Kong (China); Hong Kong Univ. of Science and Technology, Hong Kong (China). Energy Inst.

Octahedral Pt alloy nanocrystals (NCs) have shown excellent activities as electrocatalysts toward oxygen reduction reaction (ORR). As the activity and stability of NCs are highly dependent on their structure and the elemental distribution, it is of great importance to understand the formation mechanism of octahedral NCs and to rationally synthesize shape-controlled alloy catalysts with optimized ORR activity and stability. However, the factors controlling the structural and compositional evolution during the synthesis have not been well understood yet. Here in this paper, we systematically investigated the structure and composition evolution pathways of Pt–Ni octahedra synthesized with the assistance of W(CO)6 and revealed a unique core–shell structure consisting of a Pt core and a Pt–Ni alloy shell. Below 140 °C, sphere-like pure Pt NCs with the diameter of 3–4 nm first nucleated, followed by the isotropic growth of Pt–Ni alloy on the seeds at temperatures between 170 and 230 °C forming Pt@Pt–Ni core–shell octahedra with {111} facets. Owing to its unique structure, the Pt@Pt–Ni octahedra show an unparalleled stability during potential cycling, that is, no activity drop after 10 000 cycles between 0.6 and 1.0 V. This work proposes the Pt@Pt–Ni octahedra as a high profile electrocatalyst for ORR and reveals the structural and composition evolution pathways of Pt-based bimetallic NCs.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Research Foundation of Korea (NRF); Hong Kong University of Science and Technology
Grant/Contract Number:
SC0012704
OSTI ID:
1362156
Report Number(s):
BNL-113903-2017-JA; KC0403020
Journal Information:
Nano Letters, Vol. 17, Issue 6; ISSN 1530-6984
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 46 works
Citation information provided by
Web of Science

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Cited By (8)

Transformation of carbon-supported Pt–Ni octahedral electrocatalysts into cubes: toward stable electrocatalysis journal January 2018
Icosahedral Pt-Ni Nanocrystalline Electrocatalyst: Growth Mechanism and Oxygen Reduction Activity journal February 2018
Localized surface plasmon enhanced electrocatalytic methanol oxidation of AgPt bimetallic nanoparticles with an ultra-thin shell journal January 2019
Morphological, Structural, and Compositional Evolution of Pt–Ni Octahedral Electrocatalysts with Pt‐Rich Edges and Ni‐Rich Core: Toward the Rational Design of Electrocatalysts for the Oxygen Reduction Reaction journal January 2019
Recent advances in electrocatalysts toward the oxygen reduction reaction: the case of PtNi octahedra journal January 2018
Influence of Metal–Ligand Coordination on the Elemental Growth and Alloying Composition of Pt–Ni Octahedral Nanoparticles for Oxygen Reduction Electrocatalysis journal May 2019
Alloy Nanocatalysts for the Electrochemical Oxygen Reduction (ORR) and the Direct Electrochemical Carbon Dioxide Reduction Reaction (CO 2 RR) journal December 2018
One-step fabrication of bimetallic PtNi mesoporous nanospheres as an efficient catalyst for the oxygen reduction reaction journal January 2018