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

Title: Kinetics, energetics, and size dependence of the transformation from Pt to ordered PtSn intermetallic nanoparticles

Abstract

The outstanding catalytic activity and chemical selectivity of intermetallic compounds make them excellent candidates for heterogeneous catalysis. However, the kinetics of their formation at the nanoscale is poorly understood or characterized, and precise control of their size, shape and composition during synthesis remains challenging. Here, using well-defined Pt nanoparticles (5 nm and 14 nm) encapsulated in mesoporous silica, we study the transformation kinetics from monometallic Pt to intermetallic PtSn at different temperatures by a series of time-evolution X-ray diffraction studies. Observations indicate an initial transformation stage mediated by Pt surface-controlled intermixing kinetics, followed by a second stage with distinct transformation kinetics corresponding to a Ginstling–Brounstein (G–B) type bulk diffusion mode. Moreover, the activation barrier for both surface intermixing and diffusion stages is obtained through the development of appropriate kinetic models for the analysis of experimental data. Our density-functional-theory (DFT) calculations provide further insights into the atomistic-level processes and associated energetics underlying surface-controlled intermixing.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1];  [3]; ORCiD logo [1]; ORCiD logo [1];  [4]; ORCiD logo [5]; ORCiD logo [6]
  1. Department of Chemistry, Iowa State University, Ames, USA
  2. Department of Physics and Astronomy, Iowa State University, Ames, USA
  3. Department of Chemistry, Iowa State University, Ames, USA, Department of Chemistry
  4. Department of Chemistry, Boston College, Chestnut Hill, USA
  5. Department of Physics and Astronomy, Iowa State University, Ames, USA, Division of Chemical and Biological Sciences
  6. Department of Chemistry, Iowa State University, Ames, USA, Division of Chemical and Biological Sciences
Publication Date:
Research Org.:
Ames Lab., Ames, IA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1498573
Alternate Identifier(s):
OSTI ID: 1509483; OSTI ID: 1542948
Report Number(s):
IS-J-9927
Journal ID: ISSN 2040-3364; NANOHL
Grant/Contract Number:  
AC02-05CH11231; AC02-07CH11358; DNI-55170; 1507223; ACI-1548562
Resource Type:
Published Article
Journal Name:
Nanoscale
Additional Journal Information:
Journal Name: Nanoscale Journal Volume: 11 Journal Issue: 12; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Chen, Minda, Han, Yong, Goh, Tian Wei, Sun, Rong, Maligal-Ganesh, Raghu V., Pei, Yuchen, Tsung, Chia-Kuang, Evans, James W., and Huang, Wenyu. Kinetics, energetics, and size dependence of the transformation from Pt to ordered PtSn intermetallic nanoparticles. United Kingdom: N. p., 2019. Web. doi:10.1039/C8NR10067E.
Chen, Minda, Han, Yong, Goh, Tian Wei, Sun, Rong, Maligal-Ganesh, Raghu V., Pei, Yuchen, Tsung, Chia-Kuang, Evans, James W., & Huang, Wenyu. Kinetics, energetics, and size dependence of the transformation from Pt to ordered PtSn intermetallic nanoparticles. United Kingdom. doi:https://doi.org/10.1039/C8NR10067E
Chen, Minda, Han, Yong, Goh, Tian Wei, Sun, Rong, Maligal-Ganesh, Raghu V., Pei, Yuchen, Tsung, Chia-Kuang, Evans, James W., and Huang, Wenyu. Thu . "Kinetics, energetics, and size dependence of the transformation from Pt to ordered PtSn intermetallic nanoparticles". United Kingdom. doi:https://doi.org/10.1039/C8NR10067E.
@article{osti_1498573,
title = {Kinetics, energetics, and size dependence of the transformation from Pt to ordered PtSn intermetallic nanoparticles},
author = {Chen, Minda and Han, Yong and Goh, Tian Wei and Sun, Rong and Maligal-Ganesh, Raghu V. and Pei, Yuchen and Tsung, Chia-Kuang and Evans, James W. and Huang, Wenyu},
abstractNote = {The outstanding catalytic activity and chemical selectivity of intermetallic compounds make them excellent candidates for heterogeneous catalysis. However, the kinetics of their formation at the nanoscale is poorly understood or characterized, and precise control of their size, shape and composition during synthesis remains challenging. Here, using well-defined Pt nanoparticles (5 nm and 14 nm) encapsulated in mesoporous silica, we study the transformation kinetics from monometallic Pt to intermetallic PtSn at different temperatures by a series of time-evolution X-ray diffraction studies. Observations indicate an initial transformation stage mediated by Pt surface-controlled intermixing kinetics, followed by a second stage with distinct transformation kinetics corresponding to a Ginstling–Brounstein (G–B) type bulk diffusion mode. Moreover, the activation barrier for both surface intermixing and diffusion stages is obtained through the development of appropriate kinetic models for the analysis of experimental data. Our density-functional-theory (DFT) calculations provide further insights into the atomistic-level processes and associated energetics underlying surface-controlled intermixing.},
doi = {10.1039/C8NR10067E},
journal = {Nanoscale},
number = 12,
volume = 11,
place = {United Kingdom},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: https://doi.org/10.1039/C8NR10067E

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Figures / Tables:

Figure 1 Figure 1: TEM images of (A) 14 and (B) 5 nm Pt@mSiO2.

Save / Share:

Works referenced in this record:

Tiny seeds make a big difference
journal, September 2007


An inorganic capping strategy for the seeded growth of versatile bimetallic nanostructures
journal, January 2015

  • Pei, Yuchen; Maligal-Ganesh, Raghu V.; Xiao, Chaoxian
  • Nanoscale, Vol. 7, Issue 40
  • DOI: 10.1039/C5NR04614A

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Toward rational nanoparticle synthesis: predicting surface intermixing in bimetallic alloy nanocatalysts
journal, January 2017


Superconductivity in the quaternary intermetallic compounds LnNi2B2C
journal, January 1994

  • Cava, R. J.; Takagi, H.; Zandbergen, H. W.
  • Nature, Vol. 367, Issue 6460
  • DOI: 10.1038/367252a0

Diffusion-Limited Aggregation and Two-Fluid Displacements in Porous Media
journal, April 1984


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
  • DOI: 10.1038/nmat2329

Real-Time Ab Initio KMC Simulation of the Self-Assembly and Sintering of Bimetallic Epitaxial Nanoclusters: Au + Ag on Ag(100)
journal, June 2014

  • Han, Yong; Liu, Da-Jiang; Evans, James W.
  • Nano Letters, Vol. 14, Issue 8
  • DOI: 10.1021/nl5017128

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


Formation and Characterization of PdZn Alloy: A Very Selective Catalyst for Alkyne Semihydrogenation
journal, April 2011

  • Tew, Min Wei; Emerich, Herman; van Bokhoven, Jeroen A.
  • The Journal of Physical Chemistry C, Vol. 115, Issue 17
  • DOI: 10.1021/jp1103164

A comparison of hydrogen diffusivities in Pd and CuPd alloys using density functional theory
journal, November 2003


Dehydroisomerization of butane into isobutene on Pt–Sn intermetallic compounds supported on H-SAPO-11
journal, July 2006


From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999


Progress of hydrogen storage alloys for Ni-MH rechargeable power batteries in electric vehicles: A review
journal, October 2017


Solid-State Kinetic Models:  Basics and Mathematical Fundamentals
journal, September 2006

  • Khawam, Ammar; Flanagan, Douglas R.
  • The Journal of Physical Chemistry B, Vol. 110, Issue 35
  • DOI: 10.1021/jp062746a

A review of the properties of Nb 3 Sn and their variation with A15 composition, morphology and strain state
journal, June 2006


Intermetallic Nanocrystals: Syntheses and Catalytic Applications
journal, February 2017

  • Yan, Yucong; Du, Jingshan S.; Gilroy, Kyle D.
  • Advanced Materials, Vol. 29, Issue 14
  • DOI: 10.1002/adma.201605997

In situ quantitative single-molecule study of dynamic catalytic processes in nanoconfinement
journal, January 2018


Isolated Single-Atom Pd Sites in Intermetallic Nanostructures: High Catalytic Selectivity for Semihydrogenation of Alkynes
journal, May 2017

  • Feng, Quanchen; Zhao, Shu; Wang, Yu
  • Journal of the American Chemical Society, Vol. 139, Issue 21
  • DOI: 10.1021/jacs.7b01471

Ab initiomolecular dynamics for liquid metals
journal, January 1993


Atomic Layer Deposition Route To Tailor Nanoalloys of Noble and Non-noble Metals
journal, September 2016

  • Ramachandran, Ranjith K.; Dendooven, Jolien; Filez, Matthias
  • ACS Nano, Vol. 10, Issue 9
  • DOI: 10.1021/acsnano.6b04464

Bimetallic nanostructures with magnetic and noble metals and their physicochemical applications
journal, April 2013

  • Duan, Sibin; Wang, Rongming
  • Progress in Natural Science: Materials International, Vol. 23, Issue 2
  • DOI: 10.1016/j.pnsc.2013.02.001

Selective PdZn Alloy Formation in the Reduction of Pd/ZnO Catalysts
journal, June 1998

  • Iwasa, Nobuhiro; Ogawa, Noriaki; Masuda, Satoshi
  • Bulletin of the Chemical Society of Japan, Vol. 71, Issue 6
  • DOI: 10.1246/bcsj.71.1451

Analysis of a diffusion-limited island growth mechanism for chemisorption and epitaxy
journal, September 1989


Ab Initio Thermodynamics and Kinetics for Coalescence of Two-Dimensional Nanoislands and Nanopits on Metal (100) Surfaces
journal, September 2016

  • Han, Yong; Stoldt, Conrad R.; Thiel, Patricia A.
  • The Journal of Physical Chemistry C, Vol. 120, Issue 38
  • DOI: 10.1021/acs.jpcc.6b07328

Grain boundary diffusion and growth of intermetallic layers: Nb 3 Sn
journal, September 1974

  • Farrell, H. H.; Gilmer, G. H.; Suenaga, M.
  • Journal of Applied Physics, Vol. 45, Issue 9
  • DOI: 10.1063/1.1663907

An energy functional for surfaces
journal, August 2001

  • Mattsson, Ann E.; Kohn, Walter
  • The Journal of Chemical Physics, Vol. 115, Issue 8
  • DOI: 10.1063/1.1396649

Palladium-tin catalysts for the direct synthesis of H2O2 with high selectivity
journal, February 2016


Induction of coherent magnetization switching in a few atomic layers of FeCo using voltage pulses
journal, November 2011

  • Shiota, Yoichi; Nozaki, Takayuki; Bonell, Frédéric
  • Nature Materials, Vol. 11, Issue 1
  • DOI: 10.1038/nmat3172

Intermetallic NaAu 2 as a Heterogeneous Catalyst for Low-Temperature CO Oxidation
journal, June 2013

  • Xiao, Chaoxian; Wang, Lin-Lin; Maligal-Ganesh, Raghu V.
  • Journal of the American Chemical Society, Vol. 135, Issue 26
  • DOI: 10.1021/ja403175c

FeCo/graphitic-shell nanocrystals as advanced magnetic-resonance-imaging and near-infrared agents
journal, November 2006

  • Seo, Won Seok; Lee, Jin Hyung; Sun, Xiaoming
  • Nature Materials, Vol. 5, Issue 12
  • DOI: 10.1038/nmat1775

Converting nanocrystalline metals into alloys and intermetallic compounds for applications in catalysis
journal, January 2008

  • Bauer, J. Chris; Chen, Xiaole; Liu, Qingsheng
  • J. Mater. Chem., Vol. 18, Issue 3
  • DOI: 10.1039/B712035D

Understanding the selectivity of methanol steam reforming on the (1 1 1) surfaces of NiZn, PdZn and PtZn: Insights from DFT
journal, October 2015


The formation of surfaces by diffusion limited annihilation
journal, August 1986

  • Meakin, Paul; Deutch, J. M.
  • The Journal of Chemical Physics, Vol. 85, Issue 4
  • DOI: 10.1063/1.451129

A Ship-in-a-Bottle Strategy To Synthesize Encapsulated Intermetallic Nanoparticle Catalysts: Exemplified for Furfural Hydrogenation
journal, February 2016


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


Theory for intermetallic phase growth between cu and liquid Sn-Pb solder based on grain boundary diffusion control
journal, November 1998

  • Schaefer, Matt; Fournelle, Raymond A.; Liang, Jin
  • Journal of Electronic Materials, Vol. 27, Issue 11
  • DOI: 10.1007/s11664-998-0066-7

Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


High temperature transformations of the Au7Cu5Al4 shape-memory alloy
journal, February 2011


PtSn Intermetallic, Core-Shell, and Alloy Nanoparticles as CO-Tolerant Electrocatalysts for H 2 Oxidation
journal, April 2010

  • Liu, Zhufang; Jackson, Greg S.; Eichhorn, Bryan W.
  • Angewandte Chemie International Edition, Vol. 49, Issue 18
  • DOI: 10.1002/anie.200907019

Size-Dependent Disorder–Order Transformation in the Synthesis of Monodisperse Intermetallic PdCu Nanocatalysts
journal, May 2016


Silica-Encapsulated Pt-Sn Intermetallic Nanoparticles: A Robust Catalytic Platform for Parahydrogen-Induced Polarization of Gases and Liquids
journal, March 2017

  • Zhao, Evan W.; Maligal-Ganesh, Raghu; Xiao, Chaoxian
  • Angewandte Chemie, Vol. 129, Issue 14
  • DOI: 10.1002/ange.201701314

Ultrasmall Dispersible Crystalline Nickel Oxide Nanoparticles as High-Performance Catalysts for Electrochemical Water Splitting
journal, March 2014

  • Fominykh, Ksenia; Feckl, Johann M.; Sicklinger, Johannes
  • Advanced Functional Materials, Vol. 24, Issue 21
  • DOI: 10.1002/adfm.201303600

The Solvent Matters: Kinetic versus Thermodynamic Shape Control in the Polyol Synthesis of Rhodium Nanoparticles
journal, September 2011

  • Biacchi, Adam J.; Schaak, Raymond E.
  • ACS Nano, Vol. 5, Issue 10
  • DOI: 10.1021/nn2026758

In Situ X-ray Scattering Guides the Synthesis of Uniform PtSn Nanocrystals
journal, May 2018


Enhancement in the elongation, yield strength and magnetic properties of intermetallic FeCo alloy using spark plasma sintering
journal, August 2017

  • Albaaji, Amar J.; Castle, Elinor G.; Reece, Mike J.
  • Journal of Materials Science, Vol. 52, Issue 22
  • DOI: 10.1007/s10853-017-1435-5

Sub-4 nm PtZn Intermetallic Nanoparticles for Enhanced Mass and Specific Activities in Catalytic Electrooxidation Reaction
journal, March 2017

  • Qi, Zhiyuan; Xiao, Chaoxian; Liu, Cong
  • Journal of the American Chemical Society, Vol. 139, Issue 13
  • DOI: 10.1021/jacs.6b12780

Calculating the vacancy formation energy in metals: Pt, Pd, and Mo
journal, December 2002


Platinum-based nanocages with subnanometer-thick walls and well-defined, controllable facets
journal, July 2015


Well-structured bimetallic surface capable of molecular recognition for chemoselective nitroarene hydrogenation
journal, January 2016

  • Furukawa, Shinya; Takahashi, Katsuya; Komatsu, Takayuki
  • Chemical Science, Vol. 7, Issue 7
  • DOI: 10.1039/C6SC00817H

PtSn Intermetallic, Core-Shell, and Alloy Nanoparticles as CO-Tolerant Electrocatalysts for H 2 Oxidation
journal, April 2010

  • Liu, Zhufang; Jackson, Greg S.; Eichhorn, Bryan W.
  • Angewandte Chemie, Vol. 122, Issue 18
  • DOI: 10.1002/ange.200907019

Surface Diffusion
journal, October 1980


    Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.