Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts
Abstract
The surface atomic structure of metallic nanoparticles (NPs) plays a key role in shaping their physicochemical properties and response to external stimuli. Not surprisingly, current research increasingly focuses on exploiting its prime characteristics, including the amount, location, coordination, and electronic configuration of distinct surface atomic species, as tunable parameters for improving the functionality of metallic NPs in practical applications. The effort requires clear understanding of the extent to which changes in each of these characteristics would contribute to achieving the targeted functionality. This, in the first place, requires good knowledge of the actual surface of metallic NPs at atomic level. Through a case study on Au–Pd nanoalloy catalysts of industrial and environmental importance, we demonstrate that the surface atomic structure of metallic NPs can be determined in good detail by resonant high-energy X-ray diffraction (HE-XRD). Furthermore, using our experimental surface structure and CO oxidation activity data, we shed new light on the elusive origin of the remarkable catalytic synergy between surface Au and Pd atoms in the nanoalloys. In particular, we show that it arises from the formation of a specific “skin” on top of the nanoalloys that involves as many unlike, i.e., Au–Pd and Pd–Au, atomic pairs as possiblemore »
- Authors:
-
[1];
- Central Michigan Univ., Mount Pleasant, MI (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- State Univ. of New York at Binghamton, Binghamton, NY (United States)
- Publication Date:
- Research Org.:
- Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1395888
- Grant/Contract Number:
- AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. C
- Additional Journal Information:
- Journal Volume: 121; Journal Issue: 14; Journal ID: ISSN 1932-7447
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Petkov, Valeri, Prasai, Binay, Shastri, Sarvjit, Kim, Jong -Woo, Shan, Shiyao, Kareem, Haval R., Luo, Jin, and Zhong, Chuan -Jian. Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts. United States: N. p., 2017.
Web. doi:10.1021/acs.jpcc.7b00139.
Petkov, Valeri, Prasai, Binay, Shastri, Sarvjit, Kim, Jong -Woo, Shan, Shiyao, Kareem, Haval R., Luo, Jin, & Zhong, Chuan -Jian. Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts. United States. https://doi.org/10.1021/acs.jpcc.7b00139
Petkov, Valeri, Prasai, Binay, Shastri, Sarvjit, Kim, Jong -Woo, Shan, Shiyao, Kareem, Haval R., Luo, Jin, and Zhong, Chuan -Jian. Thu .
"Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts". United States. https://doi.org/10.1021/acs.jpcc.7b00139. https://www.osti.gov/servlets/purl/1395888.
@article{osti_1395888,
title = {Surface Atomic Structure and Functionality of Metallic Nanoparticles: A Case Study of Au–Pd Nanoalloy Catalysts},
author = {Petkov, Valeri and Prasai, Binay and Shastri, Sarvjit and Kim, Jong -Woo and Shan, Shiyao and Kareem, Haval R. and Luo, Jin and Zhong, Chuan -Jian},
abstractNote = {The surface atomic structure of metallic nanoparticles (NPs) plays a key role in shaping their physicochemical properties and response to external stimuli. Not surprisingly, current research increasingly focuses on exploiting its prime characteristics, including the amount, location, coordination, and electronic configuration of distinct surface atomic species, as tunable parameters for improving the functionality of metallic NPs in practical applications. The effort requires clear understanding of the extent to which changes in each of these characteristics would contribute to achieving the targeted functionality. This, in the first place, requires good knowledge of the actual surface of metallic NPs at atomic level. Through a case study on Au–Pd nanoalloy catalysts of industrial and environmental importance, we demonstrate that the surface atomic structure of metallic NPs can be determined in good detail by resonant high-energy X-ray diffraction (HE-XRD). Furthermore, using our experimental surface structure and CO oxidation activity data, we shed new light on the elusive origin of the remarkable catalytic synergy between surface Au and Pd atoms in the nanoalloys. In particular, we show that it arises from the formation of a specific “skin” on top of the nanoalloys that involves as many unlike, i.e., Au–Pd and Pd–Au, atomic pairs as possible given the overall chemical composition of the NPs. Moreover, unlike atoms from the “skin” interact strongly, including both changing their size and electronic structure in inverse proportions. That is, Au atoms shrink and acquire a partial positive charge of 5d-character whereas Pd atoms expand and become somewhat 4d-electron deficient. Accordingly, the reactivity of Au increases whereas Pd atoms become less reactive, as compared to atoms at the surface of pure Au and Pd NPs, respectively. Ultimately, this renders Au–Pd alloy NPs superb catalysts for CO oxidation reaction over a broad range of alloy compositions. Our findings are corroborated by DFT calculations based on a refined version of d-band center theory on the catalytic properties of late transition metals and alloys. Here, we discuss opportunities for improving the accuracy of current theory on surface-controlled properties of metallic NPs through augmenting the theory with surface structure data obtained by resonant XRD.},
doi = {10.1021/acs.jpcc.7b00139},
journal = {Journal of Physical Chemistry. C},
number = 14,
volume = 121,
place = {United States},
year = {Thu Mar 23 00:00:00 EDT 2017},
month = {Thu Mar 23 00:00:00 EDT 2017}
}
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