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Title: Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering

Abstract

We introduce an experimental approach for structural characterization of catalysts for fuel cells combining synchrotron x-ray spectroscopy and total scattering. The approach allows probing catalysts inside operating fuel cells with atomic-level precision (~ 0.02 Å) and element specificity (~ 2–3 at%) in both time (~ 1 min) and space (~ μm) resolved manner. The approach is demonstrated on exemplary Pd-Sn and Pt-Ni-Cu nanoalloy catalysts for the oxygen reduction reaction (ORR) deposited on the cathode of an operating proton exchange membrane fuel cell. In operando x-ray data show that under operating conditions, the catalyst particles can undergo specific structural changes, ranging from sub-Å atomic fluctuations and sharp nanophase transitions to a gradual strain relaxation and growth, which inflict significant losses in their ORR activity. Though triggered electrochemically, the changes are not driven solely by differences in the reduction potential and surface energy of the metallic species constituting the nanoalloys but also by the formation energy of competing nanophases, mismatch between the size of individual atomic species and their ability to interdiffuse fast in search of energetically favorable configurations. Given their complexity, the changes are difficult to predict and so the resulting ORR losses remain difficult to limit. We show that inmore » operando knowledge of the structural evolution of nanoalloy catalysts helps create strategies for improving their activity and stability. In particular, we show that shaping Pd-Sn nanoalloys rich in Pd as cubes reduces the interdiffusion of atoms at their surface and so makes them better catalysts for ORR in fuel cells in comparison to other Pd-Sn nanoalloys. In addition, we demonstrate that the approach introduced here can provide knowledge of other major factors affecting the performance of fuel cells such as operating temperature and the overall catalyst utilization, in particular the evolution of elemental and mass distribution of catalyst particles over the cells’ cathode. Last but not least, we discuss how in operando x-ray spectroscopy and total x-ray scattering can bridge the knowledge gap between the widely used in situ SAXS, EXAFS and monocrystal surface XRD techniques for structural characterization of nanoalloy catalysts explored for energy related applications.« less

Authors:
 [1];  [1];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [2];  [3];  [3]
  1. Central Michigan Univ., Mount Pleasant, MI (United States)
  2. State Univ. of New York (SUNY), Binghamton, NY (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1439859
Alternate Identifier(s):
OSTI ID: 1630158
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Nano Energy
Additional Journal Information:
Journal Volume: 49; Journal Issue: C; Journal ID: ISSN 2211-2855
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE

Citation Formats

Petkov, Valeri, Maswadeh, Yazan, Zhao, Yinguang, Lu, Aolin, Cronk, Hannah, Chang, Fangfang, Shan, Shiyao, Kareem, Haval, Luo, Jin, Zhong, Chuan-Jian, Shastri, Sarvjit, and Kenesei, Peter. Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering. United States: N. p., 2018. Web. doi:10.1016/j.nanoen.2018.04.049.
Petkov, Valeri, Maswadeh, Yazan, Zhao, Yinguang, Lu, Aolin, Cronk, Hannah, Chang, Fangfang, Shan, Shiyao, Kareem, Haval, Luo, Jin, Zhong, Chuan-Jian, Shastri, Sarvjit, & Kenesei, Peter. Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering. United States. https://doi.org/10.1016/j.nanoen.2018.04.049
Petkov, Valeri, Maswadeh, Yazan, Zhao, Yinguang, Lu, Aolin, Cronk, Hannah, Chang, Fangfang, Shan, Shiyao, Kareem, Haval, Luo, Jin, Zhong, Chuan-Jian, Shastri, Sarvjit, and Kenesei, Peter. Wed . "Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering". United States. https://doi.org/10.1016/j.nanoen.2018.04.049. https://www.osti.gov/servlets/purl/1439859.
@article{osti_1439859,
title = {Nanoalloy catalysts inside fuel cells: An atomic-level perspective on the functionality by combined in operando x-ray spectroscopy and total scattering},
author = {Petkov, Valeri and Maswadeh, Yazan and Zhao, Yinguang and Lu, Aolin and Cronk, Hannah and Chang, Fangfang and Shan, Shiyao and Kareem, Haval and Luo, Jin and Zhong, Chuan-Jian and Shastri, Sarvjit and Kenesei, Peter},
abstractNote = {We introduce an experimental approach for structural characterization of catalysts for fuel cells combining synchrotron x-ray spectroscopy and total scattering. The approach allows probing catalysts inside operating fuel cells with atomic-level precision (~ 0.02 Å) and element specificity (~ 2–3 at%) in both time (~ 1 min) and space (~ μm) resolved manner. The approach is demonstrated on exemplary Pd-Sn and Pt-Ni-Cu nanoalloy catalysts for the oxygen reduction reaction (ORR) deposited on the cathode of an operating proton exchange membrane fuel cell. In operando x-ray data show that under operating conditions, the catalyst particles can undergo specific structural changes, ranging from sub-Å atomic fluctuations and sharp nanophase transitions to a gradual strain relaxation and growth, which inflict significant losses in their ORR activity. Though triggered electrochemically, the changes are not driven solely by differences in the reduction potential and surface energy of the metallic species constituting the nanoalloys but also by the formation energy of competing nanophases, mismatch between the size of individual atomic species and their ability to interdiffuse fast in search of energetically favorable configurations. Given their complexity, the changes are difficult to predict and so the resulting ORR losses remain difficult to limit. We show that in operando knowledge of the structural evolution of nanoalloy catalysts helps create strategies for improving their activity and stability. In particular, we show that shaping Pd-Sn nanoalloys rich in Pd as cubes reduces the interdiffusion of atoms at their surface and so makes them better catalysts for ORR in fuel cells in comparison to other Pd-Sn nanoalloys. In addition, we demonstrate that the approach introduced here can provide knowledge of other major factors affecting the performance of fuel cells such as operating temperature and the overall catalyst utilization, in particular the evolution of elemental and mass distribution of catalyst particles over the cells’ cathode. Last but not least, we discuss how in operando x-ray spectroscopy and total x-ray scattering can bridge the knowledge gap between the widely used in situ SAXS, EXAFS and monocrystal surface XRD techniques for structural characterization of nanoalloy catalysts explored for energy related applications.},
doi = {10.1016/j.nanoen.2018.04.049},
journal = {Nano Energy},
number = C,
volume = 49,
place = {United States},
year = {Wed Apr 18 00:00:00 EDT 2018},
month = {Wed Apr 18 00:00:00 EDT 2018}
}

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Cited by: 13 works
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