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Title: First-principles study of electronic structure and photocatalytic properties of MnNiO 3 as an alkaline oxygen-evolution photocatalyst

Abstract

We present a first-principles study of MnNiO 3, a promising oxygen-evolution photocatalyst. Using density functional theory with the PBE + U functional and the screened hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE), we compute and analyze the ground-state geometry and electronic structure. We find that MnNiO 3 is a ferrimagnetic semiconductor with an indirect band gap, consistent with experimental observations. We also predict that MnNiO3 has promising band edge positions relative to the vacuum, with potential to straddle the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) redox potentials in aqueous solution. A detailed analysis of the band structure and density of states provides a clear explanation for why MnNiO 3 has appropriate electronic properties for OER. Furthermore, comprehensive calculations of its Pourbaix diagram suggest that MnNiO 3 is stable in alkaline solution at potentials relevant for oxygen evolution.

Authors:
 [1];  [2]; ORCiD logo [3];  [3];  [4];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Joint Center for Artificial Photosynthesis; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Environmental Energy Technologies Division
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry; Univ. of California, Berkeley, CA (United States). Dept. of Physics; Kavli Energy NanoSciences Inst., Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1512169
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
ChemComm
Additional Journal Information:
Journal Volume: 51; Journal Issue: 14; Journal ID: ISSN 1359-7345
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English

Citation Formats

Yu, Jie, Yan, Qimin, Chen, Wei, Jain, Anubhav, Neaton, Jeffrey B., and Persson, Kristin A. First-principles study of electronic structure and photocatalytic properties of MnNiO 3 as an alkaline oxygen-evolution photocatalyst. United States: N. p., 2015. Web. doi:10.1039/c4cc08111k.
Yu, Jie, Yan, Qimin, Chen, Wei, Jain, Anubhav, Neaton, Jeffrey B., & Persson, Kristin A. First-principles study of electronic structure and photocatalytic properties of MnNiO 3 as an alkaline oxygen-evolution photocatalyst. United States. doi:10.1039/c4cc08111k.
Yu, Jie, Yan, Qimin, Chen, Wei, Jain, Anubhav, Neaton, Jeffrey B., and Persson, Kristin A. Thu . "First-principles study of electronic structure and photocatalytic properties of MnNiO 3 as an alkaline oxygen-evolution photocatalyst". United States. doi:10.1039/c4cc08111k. https://www.osti.gov/servlets/purl/1512169.
@article{osti_1512169,
title = {First-principles study of electronic structure and photocatalytic properties of MnNiO 3 as an alkaline oxygen-evolution photocatalyst},
author = {Yu, Jie and Yan, Qimin and Chen, Wei and Jain, Anubhav and Neaton, Jeffrey B. and Persson, Kristin A.},
abstractNote = {We present a first-principles study of MnNiO3, a promising oxygen-evolution photocatalyst. Using density functional theory with the PBE + U functional and the screened hybrid functional of Heyd, Scuseria, and Ernzerhof (HSE), we compute and analyze the ground-state geometry and electronic structure. We find that MnNiO3 is a ferrimagnetic semiconductor with an indirect band gap, consistent with experimental observations. We also predict that MnNiO3 has promising band edge positions relative to the vacuum, with potential to straddle the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) redox potentials in aqueous solution. A detailed analysis of the band structure and density of states provides a clear explanation for why MnNiO3 has appropriate electronic properties for OER. Furthermore, comprehensive calculations of its Pourbaix diagram suggest that MnNiO3 is stable in alkaline solution at potentials relevant for oxygen evolution.},
doi = {10.1039/c4cc08111k},
journal = {ChemComm},
number = 14,
volume = 51,
place = {United States},
year = {2015},
month = {1}
}

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