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  4. Unraveling Thermodynamics, Stability, and Oxygen Evolution Activity of Strontium Ruthenium Perovskite Oxide
 
research article

Unraveling Thermodynamics, Stability, and Oxygen Evolution Activity of Strontium Ruthenium Perovskite Oxide

Kim, Bae-Jung
•
Abbott, Daniel F.
•
Cheng, Xi
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2017
Acs Catalysis

Extensive investigations in understanding the functional mechanisms of metal oxides behind oxygen evolution have been carried out since an electrolyzer has demonstrated promising possibilities as a device to produce hydrogen for electrochemical energy conversion systems. In particular, perovskite oxides are reputable for high activity toward the oxygen evolution reaction (OER). Here, we revisited the list of active perovskite oxides constructed based on theoretical oxygen binding energies of reaction intermediates to the catalyst surface. From this list, Ru-based perovskites, i.e. SrRuO3 and LaRuO3, have been predicted as active perovskites to exhibit a particularly high OER activity. We report on the stability of nanoscaled SrRuO3 perovskite prepared by a simple and scalable flame synthesis method. Attempts to obtain LaRuO3 were made; however, its DFT calculated phase diagram suggests that its perovskite phase is not thermodynamically stable, which supports our experimental results such that only a mixture of different La Ru O phases has been obtained. Nanoscaled SrRuO3 is evaluated for its electrochemical activity with a particular emphasis pointed toward stability in both alkaline and acidic media. Through conjoining electrochemical methods, operando X-ray absorption spectroscopy (XAS), and theoretical calculations, we show that SrRuO3 exhibits trivial activity toward OER that decreases promptly. The loss in activity is rationalized through DFT based computations, which corroboratively suggest the poor chemical stability of both selected perovskites. Regardless of the predicted theoretical OER activity, the intrinsic instability strongly suggests that Sr- and La-based ruthenium oxides are not viable catalysts for OER in aqueous media. This further suggests that their activities are independent of their binding energies between intermediates and catalyst surface but rather closely associated with material dissolution. We highlight that understanding the origin of stability under a real operating environment is absolutely essential for the design of a sustainable electrocatalyst with optimal balance between activity and stability.

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Type
research article
DOI
10.1021/acscatal.6b03171
Web of Science ID

WOS:000401054300018

Author(s)
Kim, Bae-Jung
Abbott, Daniel F.
Cheng, Xi
Fabbri, Emiliana
Nachtegaal, Maarten
Bozza, Francesco
Castelli, Ivano E.
Lebedev, Dmitry
Schaeublin, Robin
Coperet, Christophe
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Date Issued

2017

Publisher

Amer Chemical Soc

Published in
Acs Catalysis
Volume

7

Issue

5

Start page

3245

End page

3256

Subjects

perovskite

•

oxygen evolution reaction

•

strontium

•

lanthanum

•

ruthenium oxide

•

thermodynamic stability

•

Pourbaix diagram

•

X-ray absorption spectroscopy

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
THEOS  
Available on Infoscience
July 10, 2017
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/139133
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