Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution

Sanchez, Sergio I.; Small, Matthew W.; Zuo, Jian-min; Nuzzo, Ralph G.

doi:10.1021/ja9020952

Title: Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution

Abstract

We describe the results of a study at atomic resolution of the structures exhibited by polymer-capped monometallic and bimetallic Pt and Pd nanoclusters—models for nanoscale material electrocatalysts—as carried out using an aberration-corrected scanning transmission electron microscope (STEM). The coupling of sub-nanometer resolution with Z-contrast measurements provides unprecedented insights into the atomic structures and relative elemental speciation of Pt and Pd within these clusters. The work further defines the nature of deeply quenched states that prevent facile conversions of core–shell motifs to equilibrium alloys and the nature of nonidealities such as twinning (icosahedral cores) and atomic segregation that these structures can embed. The nature of the facet structure present in these model systems is revealed by theory directed modeling in which experimental intensity profiles obtained in Z-contrast measurements at atomic resolution are compared to simulated intensity profiles using theoretically predicted cluster geometries. These comparisons show close correspondences between experiment and model and highlight striking structural complexities in these systems that are compositionally sensitive and subject to amplification by subsequent cluster growth processes. Here, the work demonstrates an empowering competency in nanomaterials research for STEM measurements carried out using aberration corrected microscopes, approaches that hold considerable promise for characterizing the structure ofmore »« less

Authors:

Sanchez, Sergio I. ^[1]; Small, Matthew W. ^[1]; Zuo, Jian-min ^[1]; Nuzzo, Ralph G. ^[1]

Univ. of Illinois at Urbana-Champaign, IL (United States)

Publication Date:: Thu May 28 00:00:00 EDT 2009

Research Org.:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division

OSTI Identifier:: 1876401

Grant/Contract Number:: FG02-07ER46471; FG02-03ER15476; FG02-01ER45923; FG02-07ER46453

Resource Type:: Accepted Manuscript

Journal Name:: Journal of the American Chemical Society

Additional Journal Information:: Journal Volume: 131; Journal Issue: 24; Journal ID: ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cluster chemistry; Metal nanoparticles; Nanoparticles; Palladium; Platinum

Citation Formats


                    Sanchez, Sergio I., Small, Matthew W., Zuo, Jian-min, and Nuzzo, Ralph G. Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution.  United States: N. p., 2009. 
Web.  doi:10.1021/ja9020952.

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                    Sanchez, Sergio I., Small, Matthew W., Zuo, Jian-min, & Nuzzo, Ralph G. Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution.  United States.  https://doi.org/10.1021/ja9020952

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                    Sanchez, Sergio I., Small, Matthew W., Zuo, Jian-min, and Nuzzo, Ralph G. Thu .  
"Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution".  United States.  https://doi.org/10.1021/ja9020952.  https://www.osti.gov/servlets/purl/1876401.

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@article{osti_1876401,

  title        = {Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution},

  author       = {Sanchez, Sergio I. and Small, Matthew W. and Zuo, Jian-min and Nuzzo, Ralph G.},

  abstractNote = {We describe the results of a study at atomic resolution of the structures exhibited by polymer-capped monometallic and bimetallic Pt and Pd nanoclusters—models for nanoscale material electrocatalysts—as carried out using an aberration-corrected scanning transmission electron microscope (STEM). The coupling of sub-nanometer resolution with Z-contrast measurements provides unprecedented insights into the atomic structures and relative elemental speciation of Pt and Pd within these clusters. The work further defines the nature of deeply quenched states that prevent facile conversions of core–shell motifs to equilibrium alloys and the nature of nonidealities such as twinning (icosahedral cores) and atomic segregation that these structures can embed. The nature of the facet structure present in these model systems is revealed by theory directed modeling in which experimental intensity profiles obtained in Z-contrast measurements at atomic resolution are compared to simulated intensity profiles using theoretically predicted cluster geometries. These comparisons show close correspondences between experiment and model and highlight striking structural complexities in these systems that are compositionally sensitive and subject to amplification by subsequent cluster growth processes. Here, the work demonstrates an empowering competency in nanomaterials research for STEM measurements carried out using aberration corrected microscopes, approaches that hold considerable promise for characterizing the structure of these and other important catalytic materials systems at the atomic scale.},

  doi          = {10.1021/ja9020952},

  journal      = {Journal of the American Chemical Society},

  number       = 24,

  volume       = 131,

  place        = {United States},

  year         = {Thu May 28 00:00:00 EDT 2009},

  month        = {Thu May 28 00:00:00 EDT 2009}

}

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Similar Records

Title: Structural Characterization of Pt–Pd and Pd–Pt Core–Shell Nanoclusters at Atomic Resolution

Abstract

Citation Formats

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Size Effects of PVP−Pd Nanoparticles on the Catalytic Suzuki Reactions in Aqueous Solution journal, June 2002

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Preparation of Pd−Pt Bimetallic Colloids with Controllable Core/Shell Structures journal, July 1997

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Kinetically Controlled Growth and Shape Formation Mechanism of Platinum Nanoparticles journal, April 1998

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Periodicity and Atomic Ordering in Nanosized Particles of Crystals journal, May 2008

Direct Sub-Angstrom Imaging of a Crystal Lattice journal, September 2004

Three-dimensional atomic-scale structure of size-selected gold nanoclusters journal, December 2007

Sub-ångstrom resolution using aberration corrected electron optics journal, August 2002

VMD: Visual molecular dynamics journal, February 1996

The Structure of Surfaces book, January 1985

Catalytic Materials by Design journal, October 1998

Electrochemical Behavior of Gold-Silver Alloy Nanoparticles journal, May 2016

Continuous syntheses of Pd@Pt and Cu@Ag core–shell nanoparticles using microwave-assisted core particle formation coupled with galvanic metal displacement journal, January 2014

The Electrochemical Characterization of Single Core-Shell Nanoparticles journal, November 2015

Size and Shape of Nanoclusters: Single-Shot Imaging Approach journal, May 2012

Wet-Chemical Synthesis of Pd-Au Core-Shell Nanoparticles (8 nm): From Nanostructure to Biological Properties journal, May 2018

Core@shell bimetallic nanoparticle synthesis via anion coordination journal, April 2011

Recent developments and applications of electron microscopy to heterogeneous catalysis journal, January 2012

Self-assembly of Pt nanocrystals into three-dimensional superlattices results in enhanced electrocatalytic performance for methanol oxidation journal, January 2019

Atomic Surface Segregation and Structural Characterization of PdPt Bimetallic Nanoparticles journal, October 2018

Size and Shape of Nanoclusters: Single-Shot Imaging Approach journal, May 2012

Atomic Surface Segregation and Structural Characterization of PdPt Bimetallic Nanoparticles journal, October 2018

STEM-based mass spectroscopy of supported Re clusters
journal, June 1997

Size Effects of PVP−Pd Nanoparticles on the Catalytic Suzuki Reactions in Aqueous Solution
journal, June 2002

Atomic-resolution chemical analysis using a scanning transmission electron microscope
journal, November 1993

Preparation of Pd−Pt Bimetallic Colloids with Controllable Core/Shell Structures
journal, July 1997

Morphological Control of Catalytically Active Platinum Nanocrystals
journal, November 2006

Formation of monodispersed ultrafine platinum particles and their electrophoretic deposition on electrodes
journal, January 1997

Design and Preparation of Highly Active Pt−Pd/C Catalyst for the Oxygen Reduction Reaction
journal, April 2007

The Nature of the Metal-Metal Bond in Bimetallic Surfaces
journal, August 1992

A New Catalytically Active Colloidal Platinum Nanocatalyst: The Multiarmed Nanostar Single Crystal
journal, April 2008

Transmission Electron Microscopy
book, January 1996

A Water-Based Synthesis of Octahedral, Decahedral, and Icosahedral Pd Nanocrystals
journal, December 2007

Electron microscopy image enhanced
journal, April 1998

Kinetically Controlled Growth and Shape Formation Mechanism of Platinum Nanoparticles
journal, April 1998

Effect of Substrate Strain on Adsorption
journal, May 1998

Breaking the spherical and chromatic aberration barrier in transmission electron microscopy
journal, February 2005

The surface energy of metals
journal, August 1998

Size Effects in the Catalytic Activity of Unsupported Metallic Nanoparticles
journal, January 2003

High resolution TEM studies on palladium nanoparticles
journal, September 2001

Structural Characterization of Carbon-Supported Platinum−Ruthenium Nanoparticles from the Molecular Cluster Precursor PtRu ₅ C(CO) ₁₆
journal, August 1997

Carbon Support Effects on Bimetallic Pt−Ru Nanoparticles Formed from Molecular Precursors
journal, February 1999

The Molecular Origins of Selectivity in Methanol Decomposition on Pd Nanoparticles
journal, January 2002

The Impact of Geometric and Surface Electronic Properties of Pt-Catalysts on the Particle Size Effect in Electrocatalysis
journal, August 2005

Modeling Electron Diffraction and Imaging in Microscopes with Aberration Correctors for Quantitative Materials Structural Analysis
journal, August 2008

Depth sectioning of aligned crystals with the aberration-corrected scanning transmission electron microscope
journal, March 2006

Nanoparticles: Strained and Stiff
journal, July 2004

Sub-ångström-resolution diffractive imaging of single nanocrystals
journal, December 2008

Carbon-Supported Pseudo-Core–Shell Pd–Pt Nanoparticles for ORR with and without Methanol
journal, January 2008

Atomic-Scale Structure of Nanocrystals by High-Energy X-ray Diffraction and Atomic Pair Distribution Function Analysis: Study of Fe _x Pd _100- _x ( x = 0, 26, 28, 48) Nanoparticles
journal, January 2007

Shape-controlled synthesis of platinum nanocrystals for catalytic and electrocatalytic applications
journal, February 2009

Platinum Nanoparticle Shape Effects on Benzene Hydrogenation Selectivity
journal, October 2007

Preparation of TiO2-supported Au nanoparticle catalysts from a Au13 cluster precursor: Ligand removal using ozone exposure versus a rapid thermal treatment
journal, October 2006

Enhanced Activity for Oxygen Reduction Reaction on “Pt ₃ Co” Nanoparticles: Direct Evidence of Percolated and Sandwich-Segregation Structures
journal, October 2008

The Size-Dependent Structural Phase Behaviors of Supported Bimetallic (Pt−Ru) Nanoparticles
journal, February 2003

Interactions of adsorbates with locally strained substrate lattices
journal, June 2001

The effects of surface defects in a catalysis model
journal, October 2002

When Gold Is Not Noble: Catalysis by Nanoparticles
journal, April 2003

Preface
book, January 2000

Synthesis, surface studies, composition and structural characterization of CdSe, core/shell and biologically active nanocrystals
journal, April 2007

Supported Gold Nanoparticles from Quantum Dot to Mesoscopic Size Scale: Effect of Electronic and Structural Properties on Catalytic Hydrogenation of Conjugated Functional Groups
journal, November 2000

Pt Nanocrystals: Shape Control and Langmuir−Blodgett Monolayer Formation
journal, January 2005

Periodicity and Atomic Ordering in Nanosized Particles of Crystals
journal, May 2008

Direct Sub-Angstrom Imaging of a Crystal Lattice
journal, September 2004

Three-dimensional atomic-scale structure of size-selected gold nanoclusters
journal, December 2007

Sub-ångstrom resolution using aberration corrected electron optics
journal, August 2002

VMD: Visual molecular dynamics
journal, February 1996

The Structure of Surfaces
book, January 1985

Catalytic Materials by Design
journal, October 1998

Electrochemical Behavior of Gold-Silver Alloy Nanoparticles
journal, May 2016

Continuous syntheses of Pd@Pt and Cu@Ag core–shell nanoparticles using microwave-assisted core particle formation coupled with galvanic metal displacement
journal, January 2014

The Electrochemical Characterization of Single Core-Shell Nanoparticles
journal, November 2015

Size and Shape of Nanoclusters: Single-Shot Imaging Approach
journal, May 2012

Wet-Chemical Synthesis of Pd-Au Core-Shell Nanoparticles (8 nm): From Nanostructure to Biological Properties
journal, May 2018

Core@shell bimetallic nanoparticle synthesis via anion coordination
journal, April 2011

Recent developments and applications of electron microscopy to heterogeneous catalysis
journal, January 2012

Self-assembly of Pt nanocrystals into three-dimensional superlattices results in enhanced electrocatalytic performance for methanol oxidation
journal, January 2019

Atomic Surface Segregation and Structural Characterization of PdPt Bimetallic Nanoparticles
journal, October 2018

Size and Shape of Nanoclusters: Single-Shot Imaging Approach
journal, May 2012

Atomic Surface Segregation and Structural Characterization of PdPt Bimetallic Nanoparticles
journal, October 2018