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Title: Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis

Abstract

Understanding the interaction between oxides and water is critical to design many of their functionalities, including the electrocatalysis of molecular oxygen reduction. In this study, we probed the hydroxylation of model (001)-oriented La(1-x)SrxMnO3 (LSMO) perovskite surfaces, where the electronic structure and manganese valence was controlled by five substitution levels of lanthanum with strontium, using ambient pressure X-ray photoelectron spectroscopy in a humid environment. The degree of hydroxyl formation on the oxide surface correlated with the proximity of the valence band center relative to the Fermi level. LSMO perovskites with a valence band center closer to the Fermi level were more reactive toward water, forming more hydroxyl species at a given relative humidity. More hydroxyl species correlate with greater electron-donating character to the surface free energy in wetting, and reduce the activity to catalyze oxygen reduction reaction (ORR) kinetics in basic solution. New strategies to design more active catalysts should include design of electronically conducting oxides with lower valence band centers relative to the Fermi level at ORR-relevant potentials.

Authors:
ORCiD logo; ; ; ; ; ; ; ;  [1]; ORCiD logo [1]; ORCiD logo; ORCiD logo
  1. Advanced Light Source, Lawrence Berkeley National Laboratory, 1 Cyclotron Road, MS6R2100, Berkeley, California 94720, United States
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1414540
Report Number(s):
PNNL-SA-130538
Journal ID: ISSN 0897-4756
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 23
Country of Publication:
United States
Language:
English
Subject:
ambient pressure X-ray photoelectron spectroscopy; electrocatalysis

Citation Formats

Stoerzinger, Kelsey A., Hong, Wesley T., Wang, Xiao Renshaw, Rao, Reshma R., Bengaluru Subramanyam, Srinivas, Li, Changjian, Ariando,, Venkatesan, T., Liu, Qiang, Crumlin, Ethan J., Varanasi, Kripa K., and Shao-Horn, Yang. Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b03399.
Stoerzinger, Kelsey A., Hong, Wesley T., Wang, Xiao Renshaw, Rao, Reshma R., Bengaluru Subramanyam, Srinivas, Li, Changjian, Ariando,, Venkatesan, T., Liu, Qiang, Crumlin, Ethan J., Varanasi, Kripa K., & Shao-Horn, Yang. Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis. United States. doi:10.1021/acs.chemmater.7b03399.
Stoerzinger, Kelsey A., Hong, Wesley T., Wang, Xiao Renshaw, Rao, Reshma R., Bengaluru Subramanyam, Srinivas, Li, Changjian, Ariando,, Venkatesan, T., Liu, Qiang, Crumlin, Ethan J., Varanasi, Kripa K., and Shao-Horn, Yang. Fri . "Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis". United States. doi:10.1021/acs.chemmater.7b03399.
@article{osti_1414540,
title = {Decreasing the Hydroxylation Affinity of La 1–x Sr x MnO 3 Perovskites To Promote Oxygen Reduction Electrocatalysis},
author = {Stoerzinger, Kelsey A. and Hong, Wesley T. and Wang, Xiao Renshaw and Rao, Reshma R. and Bengaluru Subramanyam, Srinivas and Li, Changjian and Ariando, and Venkatesan, T. and Liu, Qiang and Crumlin, Ethan J. and Varanasi, Kripa K. and Shao-Horn, Yang},
abstractNote = {Understanding the interaction between oxides and water is critical to design many of their functionalities, including the electrocatalysis of molecular oxygen reduction. In this study, we probed the hydroxylation of model (001)-oriented La(1-x)SrxMnO3 (LSMO) perovskite surfaces, where the electronic structure and manganese valence was controlled by five substitution levels of lanthanum with strontium, using ambient pressure X-ray photoelectron spectroscopy in a humid environment. The degree of hydroxyl formation on the oxide surface correlated with the proximity of the valence band center relative to the Fermi level. LSMO perovskites with a valence band center closer to the Fermi level were more reactive toward water, forming more hydroxyl species at a given relative humidity. More hydroxyl species correlate with greater electron-donating character to the surface free energy in wetting, and reduce the activity to catalyze oxygen reduction reaction (ORR) kinetics in basic solution. New strategies to design more active catalysts should include design of electronically conducting oxides with lower valence band centers relative to the Fermi level at ORR-relevant potentials.},
doi = {10.1021/acs.chemmater.7b03399},
journal = {Chemistry of Materials},
number = 23,
volume = 29,
place = {United States},
year = {Fri Nov 17 00:00:00 EST 2017},
month = {Fri Nov 17 00:00:00 EST 2017}
}