Rutile Alloys in the Mn–Sb–O System Stabilize Mn3+ To Enable Oxygen Evolution in Strong Acid

Zhou, Lan; Shinde, Aniketa; Montoya, Joseph H.; Singh, Arunima; Gul, Sheraz; Yano, Junko; Ye, Yifan; Crumlin, Ethan J.; Richter, Matthias H.; Cooper, Jason K.; Stein, Helge S.; Haber, Joel A.; Persson, Kristin A.; Gregoire, John M.

doi:10.1021/acscatal.8b02689

Title: Rutile Alloys in the Mn–Sb–O System Stabilize Mn³⁺ To Enable Oxygen Evolution in Strong Acid

Journal Article · 15 October 2018 · ACS Catalysis

DOI: https://doi.org/10.1021/acscatal.8b02689 · OSTI ID:1530318

Zhou, Lan ^[1];

^[1]; Montoya, Joseph H. ^[2]; Singh, Arunima ^[2]; Gul, Sheraz ^[2];

^[2]; Ye, Yifan ^[2];

^[2];

^[1];

^[2]; Stein, Helge S. ^[1];

^[1];

^[3];

^[1]

California Inst. of Technology (CalTech), Pasadena, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)

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 IrO₂, 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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1530318

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 12 Vol. 8; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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