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Understanding the Electronic Structure Evolution of Epitaxial LaNi1-xFexO3 Thin Films for Water Oxidation

Journal Article · · Nano Letters
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  1. BATTELLE (PACIFIC NW LAB)
  2. Oregon State University
  3. Chinese Academy of Sciences
  4. OREGON STATE UNIVERSITY
  5. Argonne National Laboratory
  6. Lawrence Berkeley National Laboratory
  7. Beijing Synchrotron Radiation Facility
  8. Lawrence Berkeley National Labratory
+ Show Author Affiliations

Rare earth nickelates including LaNiO3 are promising catalysts for water electrolysis to produce oxygen gas. Recent studies report that Fe substitution for Ni can significantly enhance the oxygen evolution reaction (OER) activity of LaNiO3. However, the role of Fe in increasing activity remains ambiguous, with potential origins both structural and electronic in nature. Here, by utilizing a series of epitaxial LaNi1-xFexO3 thin films synthesized by oxygen-assisted molecular beam epitaxy, we report that Fe substitution tunes the oxidation state of Ni in LaNi1-xFexO3 and a volcano-like OER trend is observed with x = 0.375 being the most active. Spectroscopy and ab initio modeling reveal that the high-valent Fe3+? B-site cationic species strongly increases the transition metal (TM) 3d bandwidth via Ni-O-Fe bridges and enhances the TM 3d-O 2p hybridization, boosting the OER activity. Furthermore, pH-dependent electrochemical measurements suggest that the OER on LaNi1-xFexO3 involves a lattice oxygen-mediated mechanism.

Research Organization:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
DOE Contract Number:
AC05-76RL01830
OSTI ID:
1829602
Report Number(s):
PNNL-SA-163586
Journal Information:
Nano Letters, Vol. 21, Issue 19
Country of Publication:
United States
Language:
English

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Related Subjects

LaNiO3
Fe substitution
charge transfer
lattice oxygen-mediated mechanism
oxygen evolution reaction