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Rutile alloys in the Mn-Sb-O system stabilize Mn^(+3) to enable oxygen evolution in strong acid

Zhou, Lan and Shinde, Aniketa and Montoya, Joseph H. and Singh, Arunima and Gul, Sheraz and Yano, Junko and Ye, Yifan and Crumlin, Ethan J. and Richter, Matthias H. and Cooper, Jason K. and Stein, Helge S. and Haber, Joel A. and Persson, Kristin A. and Gregoire, John M. (2018) Rutile alloys in the Mn-Sb-O system stabilize Mn^(+3) to enable oxygen evolution in strong acid. ACS Catalysis, 8 (12). pp. 10938-10948. ISSN 2155-5435. doi:10.1021/acscatal.8b02689.

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Electrocatalysis of the oxygen evolution reaction is central to several energy technologies including electrolyzers, solar fuel generators, and air-breathing batteries. Strong acid electrolytes are desirable for many implementations of these technologies, although the deployment of such device designs is often hampered by the lack of non-precious-metal oxygen evolution electrocatalysts, with Ir-based oxides comprising the only known catalysts that exhibit stable activity at low overpotential. During our exploration of the Mn–Sb–O system for precious-metal-free electrocatalysts, we discovered that Mn can be incorporated into the rutile oxide structure at much higher concentrations than previously known, and that these Mn-rich rutile alloys exhibit great catalytic activity with current densities exceeding 50 mA cm^(–2) at 0.58 V overpotential and catalysis onset at 0.3 V overpotential. While this activity does not surpass that of IrO_2, Pourbaix analysis reveals that the Mn–Sb rutile oxide alloys have the same or better thermodynamic stability under operational conditions. By combining combinatorial composition, structure, and activity mapping with synchrotron X-ray absorption measurements and first-principles materials chemistry calculations, we provide a comprehensive understanding of these oxide alloys and identify the critical role of Sb in stabilizing the trivalent Mn octahedra that have been shown to be effective oxygen evolution reaction (OER) catalysts.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Zhou, Lan0000-0002-7052-266X
Shinde, Aniketa0000-0003-2386-3848
Montoya, Joseph H.0000-0001-5760-2860
Singh, Arunima0000-0002-7212-6310
Gul, Sheraz0000-0001-8920-8737
Yano, Junko0000-0001-6308-9071
Crumlin, Ethan J.0000-0003-3132-190X
Richter, Matthias H.0000-0003-0091-2045
Cooper, Jason K.0000-0002-7953-4229
Stein, Helge S.0000-0002-3461-0232
Haber, Joel A.0000-0001-7847-5506
Persson, Kristin A.0000-0003-2495-5509
Gregoire, John M.0000-0002-2863-5265
Alternate Title:Rutile alloys in the Mn-Sb-O system stabilize Mn+3 to enable oxygen evolution in strong acid
Additional Information:© 2018 American Chemical Society. Received: July 10, 2018; Revised: October 5, 2018; Published: October 16, 2018. This study is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy (Award DE-SC0004993). Computational work was additionally supported by the Materials Project Program (Grant KC23MP) through the DOE Office of Basic Energy Sciences, Materials Sciences and Engineering Division, under Contract DE-AC02-05CH11231. Computational resources were provided by the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the DOE under Contract DE-AC02-05CH11231. Part of this work (XAS data collection) was carried out at Stanford Synchrotron Radiation Lightsource, SLAC National Accelerator Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-76SF00515. XAS studies were performed with support of the Office of Science, OBES, Division of Chemical Sciences, Geosciences, and Biosciences (CSGB) of the DOE under Contract DE-AC02-05CH11231 (J. Yano). AP-XPS was carried out at Advanced Light Source, Lawrence Berkeley National Laboratory, supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Contract DE-AC02-05CH11231. We acknowledge support from the Beckman Institute of the California Institute of Technology to the Molecular Materials Research Center that enabled vacuum XPS characterization. The authors declare no competing financial interest.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Department of Energy (DOE)KC23MP
Department of Energy (DOE)DE-AC02-05CH11231
Department of Energy (DOE)DE-AC02-76SF00515
Subject Keywords:oxygen evolution reaction, catalysis, electrochemical stability, metal oxide alloys, combinatorial materials science
Issue or Number:12
Record Number:CaltechAUTHORS:20181017-092736202
Persistent URL:
Official Citation:Rutile Alloys in the Mn–Sb–O System Stabilize Mn3+ To Enable Oxygen Evolution in Strong Acid. Lan Zhou, Aniketa Shinde, Joseph H. Montoya, Arunima Singh, Sheraz Gul, Junko Yano, Yifan Ye, Ethan J. Crumlin, Matthias H. Richter, Jason K. Cooper, Helge S. Stein, Joel A. Haber, Kristin A. Persson, and John M. Gregoire. ACS Catalysis 2018 8 (12), 10938-10948. DOI: 10.1021/acscatal.8b02689
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90304
Deposited By: Tony Diaz
Deposited On:18 Oct 2018 16:47
Last Modified:16 Nov 2021 03:31

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