Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory
Abstract
Core–shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core–shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt4L core–shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core–shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determinemore »
- Authors:
-
- Georgia Inst. of Technology, Atlanta, GA (United States)
- Univ. of Wisconsin-Madison, Madison, WI (United States)
- Georgia Inst. of Technology, Atlanta, GA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Univ. of Wisconsin, Madison, WI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- Oak Ridge National Laboratory’s Center for Nanophase Materials Sciences; Center for Nanoscale Materials at Argonne National Laboratory; the Environmental Molecular Sciences Laboratory; the National Energy Research Scientific Computing Center (NERSC); and the UW-Madison Center for High Throughput Computing (CHTC)
- OSTI Identifier:
- 1398267
- Grant/Contract Number:
- FG02-05ER15731
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Nano
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 5; Journal ID: ISSN 1936-0851
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; core−shell nanocrystal; density functional theory; electron microscopy; in situ heating; thermal stability
Citation Formats
Vara, Madeline, Roling, Luke T., Wang, Xue, Elnabawy, Ahmed O., Hood, Zachary D., Chi, Miaofang, Mavrikakis, Manos, and Xia, Younan. Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory. United States: N. p., 2017.
Web. doi:10.1021/acsnano.6b08692.
Vara, Madeline, Roling, Luke T., Wang, Xue, Elnabawy, Ahmed O., Hood, Zachary D., Chi, Miaofang, Mavrikakis, Manos, & Xia, Younan. Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory. United States. https://doi.org/10.1021/acsnano.6b08692
Vara, Madeline, Roling, Luke T., Wang, Xue, Elnabawy, Ahmed O., Hood, Zachary D., Chi, Miaofang, Mavrikakis, Manos, and Xia, Younan. Tue .
"Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory". United States. https://doi.org/10.1021/acsnano.6b08692. https://www.osti.gov/servlets/purl/1398267.
@article{osti_1398267,
title = {Understanding the Thermal Stability of Palladium–Platinum Core–Shell Nanocrystals by In Situ Transmission Electron Microscopy and Density Functional Theory},
author = {Vara, Madeline and Roling, Luke T. and Wang, Xue and Elnabawy, Ahmed O. and Hood, Zachary D. and Chi, Miaofang and Mavrikakis, Manos and Xia, Younan},
abstractNote = {Core–shell nanocrystals offer many advantages for heterogeneous catalysis, including precise control over both the surface structure and composition, as well as reduction in loading for rare and costly metals. Although many catalytic processes are operated at elevated temperatures, the adverse impacts of heating on the shape and structure of core–shell nanocrystals are yet to be understood. In this work, we used ex situ heating experiments to demonstrate that Pd@Pt4L core–shell nanoscale cubes and octahedra are promising for catalytic applications at temperatures up to 400 °C. We also used in situ transmission electron microscopy to monitor the thermal stability of the core–shell nanocrystals in real time. Our results demonstrate a facet dependence for the thermal stability in terms of shape and composition. Specifically, the cubes enclosed by {100} facets readily deform shape at a temperature 300 °C lower than that of the octahedral counterparts enclosed by {111} facets. A reversed trend is observed for composition, as alloying between the Pd core and the Pt shell of an octahedron occurs at a temperature 200 °C lower than that for the cubic counterpart. Density functional theory calculations provide atomic-level explanations for the experimentally observed behaviors, demonstrating that the barriers for edge reconstruction determine the relative ease of shape deformation for cubes compared to octahedra. Furthermore, the opposite trend for alloying of the core–shell structure can be attributed to a higher propensity for subsurface Pt vacancy formation in octahedra than in cubes.},
doi = {10.1021/acsnano.6b08692},
journal = {ACS Nano},
number = 5,
volume = 11,
place = {United States},
year = {Tue May 09 00:00:00 EDT 2017},
month = {Tue May 09 00:00:00 EDT 2017}
}
Web of Science
Works referenced in this record:
Structurally ordered intermetallic platinum–cobalt core–shell nanoparticles with enhanced activity and stability as oxygen reduction electrocatalysts
journal, October 2012
- Wang, Deli; Xin, Huolin L.; Hovden, Robert
- Nature Materials, Vol. 12, Issue 1, p. 81-87
Highly Crystalline Multimetallic Nanoframes with Three-Dimensional Electrocatalytic Surfaces
journal, February 2014
- Chen, C.; Kang, Y.; Huo, Z.
- Science, Vol. 343, Issue 6177
Pt-Based Core–Shell Catalyst Architectures for Oxygen Fuel Cell Electrodes
journal, September 2013
- Oezaslan, Mehtap; Hasché, Frédéric; Strasser, Peter
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 19
Straightforward synthesis of bimetallic Co/Pt nanoparticles in ionic liquid: atomic rearrangement driven by reduction–sulfidation processes and Fischer–Tropsch catalysis
journal, January 2014
- Silva, Dagoberto O.; Luza, Leandro; Gual, Aitor
- Nanoscale, Vol. 6, Issue 15
Role of Strain and Ligand Effects in the Modification of the Electronic and Chemical Properties of Bimetallic Surfaces
journal, October 2004
- Kitchin, J. R.; Nørskov, J. K.; Barteau, M. A.
- Physical Review Letters, Vol. 93, Issue 15
Review of Pt-Based Bimetallic Catalysis: From Model Surfaces to Supported Catalysts
journal, August 2012
- Yu, Weiting; Porosoff, Marc D.; Chen, Jingguang G.
- Chemical Reviews, Vol. 112, Issue 11, p. 5780-5817
Platinum Monolayer on Nonnoble Metal−Noble Metal Core−Shell Nanoparticle Electrocatalysts for O2 Reduction
journal, December 2005
- Zhang, J.; Lima, F. H. B.; Shao, M. H.
- The Journal of Physical Chemistry B, Vol. 109, Issue 48, p. 22701-22704
Catalytic Activity of Pt/TaB 2 (0001) for the Oxygen Reduction Reaction
journal, March 2013
- Toyoda, Eishiro; Jinnouchi, Ryosuke; Ohsuna, Tetsu
- Angewandte Chemie International Edition, Vol. 52, Issue 15
Atomic Layer-by-Layer Deposition of Pt on Pd Nanocubes for Catalysts with Enhanced Activity and Durability toward Oxygen Reduction
journal, May 2014
- Xie, Shuifen; Choi, Sang-Il; Lu, Ning
- Nano Letters, Vol. 14, Issue 6
Oxygen Reduction Reaction on Pt and Pt Bimetallic Surfaces: A Selective Review
journal, July 2001
- Marković, N. M.; Schmidt, T. J.; Stamenković, V.
- Fuel Cells, Vol. 1, Issue 2
Gold and platinum catalysis—a convenient tool for generating molecular complexity
journal, January 2009
- Fürstner, Alois
- Chemical Society Reviews, Vol. 38, Issue 11
Unsteady-state operation of supported platinum catalysts for high conversion of methane
journal, May 2016
- Fouladvand, Sheedeh; Skoglundh, Magnus; Carlsson, Per-Anders
- Chemical Engineering Journal, Vol. 292
Thermally stable Pt/mesoporous silica core–shell nanocatalysts for high-temperature reactions
journal, November 2008
- Joo, Sang Hoon; Park, Jeong Young; Tsung, Chia-Kuang
- Nature Materials, Vol. 8, Issue 2
Shape-Controlled Synthesis of Metal Nanostructures: The Case of Palladium
journal, September 2007
- Xiong, Y.; Xia, Y.
- Advanced Materials, Vol. 19, Issue 20
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
Pd@Pt Core–Shell Concave Decahedra: A Class of Catalysts for the Oxygen Reduction Reaction with Enhanced Activity and Durability
journal, November 2015
- Wang, Xue; Vara, Madeline; Luo, Ming
- Journal of the American Chemical Society, Vol. 137, Issue 47
Kinetically Stabilized Pd@Pt Core–Shell Octahedral Nanoparticles with Thin Pt Layers for Enhanced Catalytic Hydrogenation Performance
journal, January 2015
- Zhang, Peipei; Hu, Yibo; Li, Baihai
- ACS Catalysis, Vol. 5, Issue 2
Palladium–platinum core-shell icosahedra with substantially enhanced activity and durability towards oxygen reduction
journal, July 2015
- Wang, Xue; Choi, Sang-Il; Roling, Luke T.
- Nature Communications, Vol. 6, Issue 1
Enhanced shape stability of Pd–Rh core–frame nanocubes at elevated temperature: in situ heating transmission electron microscopy
journal, January 2013
- Lu, Ning; Wang, Jinguo; Xie, Shuifen
- Chemical Communications, Vol. 49, Issue 100
Surface faceting and elemental diffusion behaviour at atomic scale for alloy nanoparticles during in situ annealing
journal, November 2015
- Chi, Miaofang; Wang, Chao; Lei, Yinkai
- Nature Communications, Vol. 6, Issue 1
Coalescence in the Thermal Annealing of Nanoparticles: An in Situ STEM Study of the Growth Mechanisms of Ordered Pt–Fe Nanoparticles in a KCl Matrix
journal, February 2013
- Chen, Hao; Yu, Yingchao; Xin, Huolin L.
- Chemistry of Materials, Vol. 25, Issue 8
Thermal Stability of Core–Shell Nanoparticles: A Combined in Situ Study by XPS and TEM
journal, October 2015
- Bonifacio, Cecile S.; Carenco, Sophie; Wu, Cheng Hao
- Chemistry of Materials, Vol. 27, Issue 20
Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets
journal, July 2015
- Zhang, L.; Roling, L. T.; Wang, X.
- Science, Vol. 349, Issue 6246
Diffusion path for an Al adatom on Al(001)
journal, August 1990
- Feibelman, Peter J.
- Physical Review Letters, Vol. 65, Issue 6
Synthesis of Pd nanocrystals enclosed by {100} facets and with sizes <10 nm for application in CO oxidation
journal, October 2010
- Jin, Mingshang; Liu, Hongyang; Zhang, Hui
- Nano Research, Vol. 4, Issue 1
Palladium nanocrystals enclosed by {100} and {111} facets in controlled proportions and their catalytic activities for formic acid oxidation
journal, January 2012
- Jin, Mingshang; Zhang, Hui; Xie, Zhaoxiong
- Energy Environ. Sci., Vol. 5, Issue 4
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996
- Kresse, G.; Furthmüller, J.
- Physical Review B, Vol. 54, Issue 16, p. 11169-11186
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996
- Kresse, G.; Furthmüller, J.
- Computational Materials Science, Vol. 6, Issue 1, p. 15-50
Projector augmented-wave method
journal, December 1994
- Blöchl, P. E.
- Physical Review B, Vol. 50, Issue 24, p. 17953-17979
From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999
- Kresse, G.; Joubert, D.
- Physical Review B, Vol. 59, Issue 3, p. 1758-1775
Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992
- Perdew, John P.; Wang, Yue
- Physical Review B, Vol. 45, Issue 23, p. 13244-13249
Special points for Brillouin-zone integrations
journal, June 1976
- Monkhorst, Hendrik J.; Pack, James D.
- Physical Review B, Vol. 13, Issue 12, p. 5188-5192
Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992
- Neugebauer, Jörg; Scheffler, Matthias
- Physical Review B, Vol. 46, Issue 24
A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000
- Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
- The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
CRC Handbook of Chemistry and Physics
book, June 2016
- Haynes, W. M.; Lide, David R.; Bruno, Thomas J.
- CRC press
Works referencing / citing this record:
In Situ Transmission Electron Microscopy Study of Nanocrystal Formation for Electrocatalysis
journal, October 2019
- Shi, Fenglei; Li, Fan; Ma, Yanling
- ChemNanoMat, Vol. 5, Issue 12
Reversible loss of core–shell structure for Ni–Au bimetallic nanoparticles during CO2 hydrogenation
journal, March 2020
- Zhang, Xiaoben; Han, Shaobo; Zhu, Beien
- Nature Catalysis, Vol. 3, Issue 4
Toward affordable and sustainable use of precious metals in catalysis and nanomedicine
journal, November 2018
- Xia, Younan; Zhao, Ming; Wang, Xue
- MRS Bulletin, Vol. 43, Issue 11
Shape‐Controlled Synthesis of Colloidal Metal Nanocrystals by Replicating the Surface Atomic Structure on the Seed
journal, April 2018
- Gilroy, Kyle D.; Yang, Xuan; Xie, Shuifen
- Advanced Materials, Vol. 30, Issue 25
Magnetically Hollow Pt Nanocages with Ultrathin Walls as a Highly Integrated Nanoreactor for Catalytic Transfer Hydrogenation Reaction
journal, February 2019
- Ai, Yongjian; Hu, Zenan; Liu, Lei
- Advanced Science, Vol. 6, Issue 7
Surface and interface design for heterogeneous catalysis
journal, January 2019
- Huang, Weixin; Li, Wei-Xue
- Physical Chemistry Chemical Physics, Vol. 21, Issue 2
Surface faceting and compositional evolution of Pd@Au core–shell nanocrystals during in situ annealing
journal, January 2019
- Wu, Zhemin; Tang, Min; Li, Xiaoyan
- Physical Chemistry Chemical Physics, Vol. 21, Issue 6
Magnetically Hollow Pt Nanocages with Ultrathin Walls as a Highly Integrated Nanoreactor for Catalytic Transfer Hydrogenation Reaction
journal, February 2019
- Ai, Yongjian; Hu, Zenan; Liu, Lei
- Advanced Science, Vol. 6, Issue 7
Interface-mediated Kirkendall effect and nanoscale void migration in bimetallic nanoparticles during interdiffusion
journal, June 2019
- Chee, See Wee; Wong, Zicong Marvin; Baraissov, Zhaslan
- Nature Communications, Vol. 10, Issue 1