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Title: Resolving atomistic structure and oxygen evolution activity in nickel antimonates

Abstract

The oxygen evolution reaction (OER) requires electrodes that are not only catalytically active, but also stable under harsh electrochemical environments to enable efficient, durable technologies. Our recent report of a stable amorphous Ni0.5Sb0.5Oz OER photoanode established Ni–Sb–O as an important system for computational understanding of both the structural and catalytic behavior of these complex oxides. In the present work we show that NixSb1-xOz with x > 0.33 crystallizes into a previously unknown phase. Guided by experimental X-ray diffraction, here, we use density functional theory calculations to perform a prototype phase search to identify a broad family of stable and metastable mixed rutile and hexagonal-like phases for x = 0.33, 0.50, and 0.66 compositions. For the identified phases, we predict favorable oxygen vacancy formation energies for Ni-rich compositions under the reducing synthesis conditions which match measured Ni K-edge X-ray absorption spectra. The calculated overpotential for the most active site decreases with increasing Ni content, from 0.91 V (x = 0.33) to 0.49 V (x = 0.66), which captures the experimentally observed trend. We find the active site changes from the Ni–O–Sb bridge to a Ni–O–Ni bridge at increasing Ni concentrations, rather than the commonly studied singly under-coordinated sites. Finally, detailed Pourbaixmore » analysis of the identified phases show excellent electrochemical stability, consistent with experimentally measured low metal ion concentrations in the electrolyte of photoelectrochemical cells. Collectively, our consideration of an ensemble of structures enables identification of the most catalytically prolific structural motifs, aiding the understanding of crystalline and amorphous catalysts and elucidating the co-optimization of activity and durability in nickel antimonates.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [2];  [2];  [3];  [4];  [4]; ORCiD logo [2]; ORCiD logo [5]
+ Show Author Affiliations
  1. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis; Stanford Univ., CA (United States)
  2. California Institute of Technology (CalTech), Pasadena, CA (United States)
  3. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  4. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
  5. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). SUNCAT Center for Interface Science and Catalysis
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
2006853
Alternate Identifier(s):
OSTI ID: 1922690
Grant/Contract Number:  
AC02-76SF00515; SC0021266; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Materials Chemistry. A
Additional Journal Information:
Journal Volume: 11; Journal Issue: 10; Journal ID: ISSN 2050-7488
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Rao, Karun K., Zhou, Lan, Lai, Yungchieh, Richter, Matthias H., Li, Xiang, Lu, Yubing, Yano, Junko, Gregoire, John M., and Bajdich, Michal. Resolving atomistic structure and oxygen evolution activity in nickel antimonates. United States: N. p., 2022. Web. doi:10.1039/d2ta08854a.
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Rao, Karun K., Zhou, Lan, Lai, Yungchieh, Richter, Matthias H., Li, Xiang, Lu, Yubing, Yano, Junko, Gregoire, John M., & Bajdich, Michal. Resolving atomistic structure and oxygen evolution activity in nickel antimonates. United States. https://doi.org/10.1039/d2ta08854a
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Rao, Karun K., Zhou, Lan, Lai, Yungchieh, Richter, Matthias H., Li, Xiang, Lu, Yubing, Yano, Junko, Gregoire, John M., and Bajdich, Michal. Thu . "Resolving atomistic structure and oxygen evolution activity in nickel antimonates". United States. https://doi.org/10.1039/d2ta08854a. https://www.osti.gov/servlets/purl/2006853.
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@article{osti_2006853,
title = {Resolving atomistic structure and oxygen evolution activity in nickel antimonates},
author = {Rao, Karun K. and Zhou, Lan and Lai, Yungchieh and Richter, Matthias H. and Li, Xiang and Lu, Yubing and Yano, Junko and Gregoire, John M. and Bajdich, Michal},
abstractNote = {The oxygen evolution reaction (OER) requires electrodes that are not only catalytically active, but also stable under harsh electrochemical environments to enable efficient, durable technologies. Our recent report of a stable amorphous Ni0.5Sb0.5Oz OER photoanode established Ni–Sb–O as an important system for computational understanding of both the structural and catalytic behavior of these complex oxides. In the present work we show that NixSb1-xOz with x > 0.33 crystallizes into a previously unknown phase. Guided by experimental X-ray diffraction, here, we use density functional theory calculations to perform a prototype phase search to identify a broad family of stable and metastable mixed rutile and hexagonal-like phases for x = 0.33, 0.50, and 0.66 compositions. For the identified phases, we predict favorable oxygen vacancy formation energies for Ni-rich compositions under the reducing synthesis conditions which match measured Ni K-edge X-ray absorption spectra. The calculated overpotential for the most active site decreases with increasing Ni content, from 0.91 V (x = 0.33) to 0.49 V (x = 0.66), which captures the experimentally observed trend. We find the active site changes from the Ni–O–Sb bridge to a Ni–O–Ni bridge at increasing Ni concentrations, rather than the commonly studied singly under-coordinated sites. Finally, detailed Pourbaix analysis of the identified phases show excellent electrochemical stability, consistent with experimentally measured low metal ion concentrations in the electrolyte of photoelectrochemical cells. Collectively, our consideration of an ensemble of structures enables identification of the most catalytically prolific structural motifs, aiding the understanding of crystalline and amorphous catalysts and elucidating the co-optimization of activity and durability in nickel antimonates.},
doi = {10.1039/d2ta08854a},
journal = {Journal of Materials Chemistry. A},
number = 10,
volume = 11,
place = {United States},
year = {Thu Dec 29 00:00:00 EST 2022},
month = {Thu Dec 29 00:00:00 EST 2022}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1039/d2ta08854a
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Figures / Tables:

Figure 1 Figure 1: (a) The 2D XRD heatmap constructed from a series of 21 XRD patterns along the composition gradient of the NixSb1-xOz library. This composition library was deposited on SiO2/Si substrate with Ni concentration x from 0.19 to 0.75 and subsequently annealed at 700 °C in air. The three horizontalmore » dashed lines mark compositions of interest of x = 0.33, 0.49, and 0.63, where the latter 2 compositions contain XRD signals that do not correspond to known Ni-Sb-O phases. (b) The XRD patterns of these three compositions are shown with calculated XRD stick patterns from the disordered prototype crystal structures that were identified from the XRD-guided structure search. These structures have space groups of (c) P42/mnm (rutile), (d) Pnnm, and (e) P63/mmc (hexagonal) aligned with the x = 0.33, 0.49 and 0.63 spectra, respectively. In (c), (d), and (e), red circles are oxygen atoms and brown atoms/polyhedra are metal sites. The P42/mnm. phase has metal site occupation of NixSb(1-x), while the proposed Pnnm and P63/mmc prototypes have 50% vacancy on each metal site resulting in Nix/2Sb(1-x)/2 occupations.« less
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