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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}
}
  • High temperature reaction calorimetry using molten lead borate as solvent has been used to study the thermochemistry of NdMnO{sub 3}, YMnO{sub 3}, La{sub 1{minus}x}Sr{sub x}MnO{sub 3} (with 0 < x < 0.5), and Ln{sub 0.5}Ca{sub 0.5}MnO{sub 3} (with Ln = La, Nd, Y). The enthalpies of formation of these multicomponent oxides from their binary constituents have been calculated from the measured enthalpy of drop solution. The energetic stability of the perovskite depends on the size of the A cation. The enthalpy of formation of YMnO{sub 3} (smallest A cation) is more endothermic than those of NdMnO{sub 3} and LaMnO{sub 3}.more » The energetics of the perovskite also depends on the oxidation state of the B site`s ions. In the La{sub 1{minus}x}Sr{sub x}MnO{sub 3} system, the energetic stability of the structure increases with the Mn{sup 4+}/Mn{sup 3+} ratio. The new values of the enthalpies of oxidations, with reliable standard entropies, were used to plot the phase stability digram of the lanthanum-manganese-oxygen system in the temperature range 300--1,100 K. The LaMnO{sub 3}/MnO phase boundary evaluated in this study agrees with the one published by Atsumi et al. calculated from thermogravimetric and conductivity measurements. 41 refs., 6 figs., 7 tabs.« less
  • No abstract prepared.
  • The dynamic response of La{sub 1{minus}x}Sr{sub x}MnO{sub 3} perovskites has been studied in the low doped regime (x{le}0.14). The frequency dependence of the ac susceptibility gives clear indications in favor of the existence of electronic phase separation not only in the O{sup {double_prime}} phase but also at temperatures between the ferromagnetic transition temperature T{sub C}, and the O{sup {prime}}{endash}O{sup {double_prime}} structural transition occurring at T{sub FI}. The influence of the Jahn{endash}Teller distortion on the magnetic susceptibility is also detected as a drop in the magnetic susceptibility on crossing down the O{endash}O{sup {prime}} structural transition, while a jump occurs at O{supmore » {prime}}{endash}O{sup {double_prime}} transition. A close similarity, both structural and magnetic, between the O and O{sup {double_prime}} phase is strongly suggested by the experimental results. {copyright} 2001 American Institute of Physics.« less
  • The magnetic and transport properties of (La,Gd){sub 1{minus}x}Sr{sub x}MnO{sub 3+{delta}} (x=0.15, 0.2, 0.25, and 0.3) with a fixed tolerance factor t=0.913 are studied. Special attention is paid to the postannealing effects of the compounds. Two magnetic transitions are observed in samples x=0.2 and 0.25 which are single phase in structure according to powder x-ray diffraction. Different effects on the two resulting states are produced by the postannealing. Accompanying the weakening of the state at lower temperature, the magnetic ordering of high-temperature state is enhanced substantially by the introduction of excess oxygen due to annealing the samples in O{sub 2}. Onemore » typical paramagnetic{endash}ferromagnetic transition occurs in samples x=0.15 and 0.3. There is a strong indication that the magnetic states in x=0.15 and 0.3 are, respectively, the developments of the high- and low-temperature states in x=0.2 (or x=0.25). The occurrence of two metal{endash}semiconductor transitions in x=0.15{endash}0.25 and their responses to postannealing suggest magnetic heterogeneity in the compound. By assuming the coexistence of vacancy-rich and vacancy-deficient domains in the compounds, these observations can be understood qualitatively. {copyright} {ital 1997 American Institute of Physics.}« less
  • The experimental study of Double Negative (DNG) state of electromagnetic wave propagating in lanthanum manganite-perovskites doped with strontium La{sub 1-x}Sr{sub x}MnO{sub 3} is provided firstly below individual Curie temperatures (in ferromagnetic metal state (FM) for La{sub 1-x}Sr{sub x}MnO{sub 3}). Various dopant concentrations are considered for ceramic specimens: x = 0.15;  0.225;  0.3;  0.45;  0.6. It is shown that dependence of the DNG-peak intensity on dopant concentration is sharply non-monotone with maximum at the dopant concentrations x = 0.225 – 0.3. This behaviour follows the change of Curie temperature with increase of dopant concentration in such substances. The obtained dependence of DNG peak intensity supportsmore » the opinion concerning the role of disorder in highly doped manganite-perovskite magnetic ceramics under study.« less