skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets

Abstract

A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.

Authors:
 [1];  [1];  [2];  [3];  [3];  [1]
  1. Georgia Inst. of Technology, Atlanta, GA (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  3. Univ. of Wisconsin, Madison, WI (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); University of Wisconsin-Madison
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Contributing Org.:
China Scholarship Council; EMSL; CNM at ANL; NERSC; ORNL’s Center for Nanophase Materials Sciences; Arizona State University
OSTI Identifier:
1355818
Alternate Identifier(s):
OSTI ID: 1265782; OSTI ID: 1395998
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231; AC02-06CH11357; FG02-05ER15731
Resource Type:
Published Article
Journal Name:
Science
Additional Journal Information:
Journal Volume: 349; Journal Issue: 6246; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Zhang, Lei, Wang, Xue, Chi, Miaofang, Mavrikakis, Manos, Roling, Luke, and Xia, Younan. Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets. United States: N. p., 2015. Web. doi:10.1126/science.aab0801.
Zhang, Lei, Wang, Xue, Chi, Miaofang, Mavrikakis, Manos, Roling, Luke, & Xia, Younan. Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets. United States. doi:10.1126/science.aab0801.
Zhang, Lei, Wang, Xue, Chi, Miaofang, Mavrikakis, Manos, Roling, Luke, and Xia, Younan. Fri . "Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets". United States. doi:10.1126/science.aab0801.
@article{osti_1355818,
title = {Platinum-Based Nanocages with Subnanometer-Thick Walls and Well-Defined Facets},
author = {Zhang, Lei and Wang, Xue and Chi, Miaofang and Mavrikakis, Manos and Roling, Luke and Xia, Younan},
abstractNote = {A cost-effective catalyst should have a high dispersion of the active atoms, together with a controllable surface structure for the optimization of activity, selectivity, or both. We fabricated nanocages by depositing a few atomic layers of platinum (Pt) as conformal shells on palladium (Pd) nanocrystals with well-defined facets and then etching away the Pd templates. Density functional theory calculations suggest that the etching is initiated via a mechanism that involves the formation of vacancies through the removal of Pd atoms incorporated into the outermost layer during the deposition of Pt. With the use of Pd nanoscale cubes and octahedra as templates, we obtained Pt cubic and octahedral nanocages enclosed by {100} and {111} facets, respectively, which exhibited distinctive catalytic activities toward oxygen reduction.},
doi = {10.1126/science.aab0801},
journal = {Science},
number = 6246,
volume = 349,
place = {United States},
year = {2015},
month = {7}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1126/science.aab0801

Citation Metrics:
Cited by: 237 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Review: Durability and Degradation Issues of PEM Fuel Cell Components
journal, February 2008


Synthesis of Pd-Rh Core-Frame Concave Nanocubes and Their Conversion to Rh Cubic Nanoframes by Selective Etching of the Pd Cores
journal, September 2012

  • Xie, Shuifen; Lu, Ning; Xie, Zhaoxiong
  • Angewandte Chemie International Edition, Vol. 51, Issue 41
  • DOI: 10.1002/anie.201206044

Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces
journal, February 2014


Synthesis of monolayer platinum nanosheets
journal, January 2014

  • Funatsu, A.; Tateishi, H.; Hatakeyama, K.
  • Chem. Commun., Vol. 50, Issue 62
  • DOI: 10.1039/C4CC02527J

Shape-Controlled Synthesis of Surface-Clean Ultrathin Palladium Nanosheets by Simply Mixing a Dinuclear Pd I Carbonyl Chloride Complex with H 2 O
journal, June 2013

  • Li, Huan; Chen, Guangxu; Yang, Huayan
  • Angewandte Chemie International Edition, Vol. 52, Issue 32
  • DOI: 10.1002/anie.201303772

Ultrathin rhodium nanosheets
journal, January 2014

  • Duan, Haohong; Yan, Ning; Yu, Rong
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4093

Platinum Monolayer Fuel Cell Electrocatalysts
journal, November 2007


Highly stable Pt monolayer on PdAu nanoparticle electrocatalysts for the oxygen reduction reaction
journal, January 2012

  • Sasaki, Kotaro; Naohara, Hideo; Choi, YongMan
  • Nature Communications, Vol. 3, Issue 1
  • DOI: 10.1038/ncomms2124

Manipulating the oxygen reduction activity of platinum shells with shape-controlled palladium nanocrystal cores
journal, January 2013

  • Shao, Minhua; He, Guannan; Peles, Amra
  • Chemical Communications, Vol. 49, Issue 79
  • DOI: 10.1039/c3cc43276a

Atomic Layer-by-Layer Deposition of Platinum on Palladium Octahedra for Enhanced Catalysts toward the Oxygen Reduction Reaction
journal, February 2015

  • Park, Jinho; Zhang, Lei; Choi, Sang-Il
  • ACS Nano, Vol. 9, Issue 3
  • DOI: 10.1021/nn506387w

Formation of Hollow Nanocrystals Through the Nanoscale Kirkendall Effect
journal, April 2004


Synthesis of Pd nanocrystals enclosed by {100} facets and with sizes <10 nm for application in CO oxidation
journal, October 2010


On the role of surface diffusion in determining the shape or morphology of noble-metal nanocrystals
journal, April 2013

  • Xia, X.; Xie, S.; Liu, M.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 17
  • DOI: 10.1073/pnas.1222109110

Formation and Analysis of Core–Shell Fine Structures in Pt Bimetallic Nanoparticle Fuel Cell Electrocatalysts
journal, August 2012

  • Heggen, Marc; Oezaslan, Mehtap; Houben, Lothar
  • The Journal of Physical Chemistry C, Vol. 116, Issue 36
  • DOI: 10.1021/jp306426a

Evolution of nanoporosity in dealloying
journal, March 2001

  • Erlebacher, Jonah; Aziz, Michael J.; Karma, Alain
  • Nature, Vol. 410, Issue 6827, p. 450-453
  • DOI: 10.1038/35068529

Interdiffusion study in the Pd–Pt system
journal, March 2013

  • Baheti, Varun A.; Ravi, Raju; Paul, Aloke
  • Journal of Materials Science: Materials in Electronics, Vol. 24, Issue 8
  • DOI: 10.1007/s10854-013-1179-1

Surface science studies of model fuel cell electrocatalysts
journal, April 2002


Synthesis and Oxygen Reduction Activity of Shape-Controlled Pt 3 Ni Nanopolyhedra
journal, February 2010

  • Zhang, Jun; Yang, Hongzhou; Fang, Jiye
  • Nano Letters, Vol. 10, Issue 2
  • DOI: 10.1021/nl903717z

Shape and Composition-Controlled Platinum Alloy Nanocrystals Using Carbon Monoxide as Reducing Agent
journal, February 2011

  • Wu, Jianbo; Gross, Adam; Yang, Hong
  • Nano Letters, Vol. 11, Issue 2
  • DOI: 10.1021/nl104094p

Synthesis and Characterization of 9 nm Pt–Ni Octahedra with a Record High Activity of 3.3 A/mg Pt for the Oxygen Reduction Reaction
journal, June 2013

  • Choi, Sang-Il; Xie, Shuifen; Shao, Minhua
  • Nano Letters, Vol. 13, Issue 7
  • DOI: 10.1021/nl401881z

Compositional segregation in shaped Pt alloy nanoparticles and their structural behaviour during electrocatalysis
journal, June 2013

  • Cui, Chunhua; Gan, Lin; Heggen, Marc
  • Nature Materials, Vol. 12, Issue 8
  • DOI: 10.1038/nmat3668

Element-specific anisotropic growth of shaped platinum alloy nanocrystals
journal, December 2014


Electrochemical surface area measurements of platinum- and palladium-based nanoparticles
journal, June 2013


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Alloy catalysts designed from first principles
journal, October 2004

  • Greeley, Jeff; Mavrikakis, Manos
  • Nature Materials, Vol. 3, Issue 11
  • DOI: 10.1038/nmat1223

Ligand effects in heterogeneous catalysis and electrochemistry
journal, May 2007


Size and Shape Effects of Pd@Pt Core–Shell Nanoparticles: Unique Role of Surface Contraction and Local Structural Flexibility
journal, July 2013

  • An, Wei; Liu, Ping
  • The Journal of Physical Chemistry C, Vol. 117, Issue 31
  • DOI: 10.1021/jp4057785

Origin of the Overpotential for Oxygen Reduction at a Fuel-Cell Cathode
journal, November 2004

  • Nørskov, J. K.; Rossmeisl, J.; Logadottir, A.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 46
  • DOI: 10.1021/jp047349j

    Works referencing / citing this record:

    One-nanometer-thick platinum-based nanowires with controllable surface structures
    journal, May 2019


    Transition-sized Au 92 nanoparticle bridging non-fcc-structured gold nanoclusters and fcc-structured gold nanocrystals
    journal, January 2016

    • Liao, Lingwen; Chen, Jishi; Wang, Chengming
    • Chemical Communications, Vol. 52, Issue 81
    • DOI: 10.1039/c6cc06108g

    Noble Metal Based Alloy Nanoframes: Syntheses and Applications in Fuel Cells
    journal, July 2019