Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles

Yu Lei; Haiyan Zhao; Rosa Diaz Rivas; Sungsik Lee; Bin Liu; Junling Lu; Eric Stach; Randall E. Winans; Karena W. Chapman; Jeffrey P. Greeley; Jeffrey T. Miller; Peter J. Chupas; Jeffrey W. Elam

doi:10.1021/ja4126998

Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles

Yu Lei
, Haiyan Zhao
, Rosa Diaz Rivas
, Sungsik Lee
, Bin Liu
, Junling Lu
, Eric Stach
, Randall E. Winans
, Karena W. Chapman
, Jeffrey P. Greeley
, Jeffrey T. Miller
, Peter J. Chupas
, Jeffrey W. Elam

Chemistry

University of Alabama in Huntsville
Argonne National Laboratory
Brookhaven National Laboratory
Kansas State University
Purdue University

Research output: Contribution to journal › Article › peer-review

84 Scopus citations

Abstract

We investigated changes in the Pt-Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1-3 nm) and adsorbate (H₂, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ∼1 nm Pt nanoparticles showed a Pt-Pt bond distance contraction of ∼1.4%. The adsorption of H₂ and CO at room temperature relaxed the Pt-Pt bond distance contraction to a value close to that of bulk fcc Pt. The adsorption of H₂ improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1-3 nm Pt nanoparticles compared to the H₂ adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back-donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system.

Original language	English
Pages (from-to)	9320-9326
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	136
Issue number	26
DOIs	https://doi.org/10.1021/ja4126998
State	Published - Jul 2 2014

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@article{6311434bcd3d43daba8a9bf9b1039dd4,

title = "Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles",

abstract = "We investigated changes in the Pt-Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1-3 nm) and adsorbate (H2, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ∼1 nm Pt nanoparticles showed a Pt-Pt bond distance contraction of ∼1.4\%. The adsorption of H2 and CO at room temperature relaxed the Pt-Pt bond distance contraction to a value close to that of bulk fcc Pt. The adsorption of H2 improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1-3 nm Pt nanoparticles compared to the H2 adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back-donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system.",

author = "Yu Lei and Haiyan Zhao and Rivas, \{Rosa Diaz\} and Sungsik Lee and Bin Liu and Junling Lu and Eric Stach and Winans, \{Randall E.\} and Chapman, \{Karena W.\} and Greeley, \{Jeffrey P.\} and Miller, \{Jeffrey T.\} and Chupas, \{Peter J.\} and Elam, \{Jeffrey W.\}",

year = "2014",

month = jul,

day = "2",

doi = "10.1021/ja4126998",

language = "English",

volume = "136",

pages = "9320--9326",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

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TY - JOUR

T1 - Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles

AU - Lei, Yu

AU - Zhao, Haiyan

AU - Rivas, Rosa Diaz

AU - Lee, Sungsik

AU - Liu, Bin

AU - Lu, Junling

AU - Stach, Eric

AU - Winans, Randall E.

AU - Chapman, Karena W.

AU - Greeley, Jeffrey P.

AU - Miller, Jeffrey T.

AU - Chupas, Peter J.

AU - Elam, Jeffrey W.

PY - 2014/7/2

Y1 - 2014/7/2

N2 - We investigated changes in the Pt-Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1-3 nm) and adsorbate (H2, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ∼1 nm Pt nanoparticles showed a Pt-Pt bond distance contraction of ∼1.4%. The adsorption of H2 and CO at room temperature relaxed the Pt-Pt bond distance contraction to a value close to that of bulk fcc Pt. The adsorption of H2 improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1-3 nm Pt nanoparticles compared to the H2 adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back-donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system.

AB - We investigated changes in the Pt-Pt bond distance, particle size, crystallinity, and coordination of Pt nanoparticles as a function of particle size (1-3 nm) and adsorbate (H2, CO) using synchrotron radiation pair distribution function (PDF) and X-ray absorption spectroscopy (XAS) measurements. The ∼1 nm Pt nanoparticles showed a Pt-Pt bond distance contraction of ∼1.4%. The adsorption of H2 and CO at room temperature relaxed the Pt-Pt bond distance contraction to a value close to that of bulk fcc Pt. The adsorption of H2 improved the crystallinity of the small Pt nanoparticles. However, CO adsorption generated a more disordered fcc structure for the 1-3 nm Pt nanoparticles compared to the H2 adsorption Pt nanoparticles. In situ XANES measurements revealed that this disorder results from the electron back-donation of the Pt nanoparticles to CO, leading to a higher degree of rehybridization of the metal orbitals in the Pt-adsorbate system.

UR - https://www.scopus.com/pages/publications/84903719198

U2 - 10.1021/ja4126998

DO - 10.1021/ja4126998

M3 - Article

AN - SCOPUS:84903719198

SN - 0002-7863

VL - 136

SP - 9320

EP - 9326

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 26

ER -

Adsorbate-induced structural changes in 1-3 nm platinum nanoparticles

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