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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 [1]; ORCiD logo [1];  [2]; ORCiD logo [1]; ORCiD logo [1];  [3]; ORCiD logo [4]; ORCiD logo [4]
  1. Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States); Beijing Normal Univ. (China)
  3. Boston College, Chestnut Hill, MA (United States)
  4. Iowa State Univ., Ames, IA (United States); Ames Lab., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), 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:  
DNI-55170; 1507223; AC02-05CH11231; AC02-07CH11358; ACI-1548562
Resource Type:
Published Article
Journal Name:
Nanoscale
Additional Journal Information:
Journal Volume: 11; Journal Issue: 12; Journal ID: ISSN 2040-3364
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
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 States: 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 States. 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., and Huang, Wenyu. Mon . "Kinetics, energetics, and size dependence of the transformation from Pt to ordered PtSn intermetallic nanoparticles". United States. doi: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 States},
year = {2019},
month = {2}
}

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

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Cited by: 2 works
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Works referenced in this record:

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