TY - JOUR
T1 - Unraveling Oxygen Evolution on Iron-Doped β-Nickel Oxyhydroxide
T2 - The Key Role of Highly Active Molecular-like Sites
AU - Martirez, John Mark P.
AU - Carter, Emily Ann
N1 - Funding Information:
This article is based upon work supported by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-14-1-0254. E.A.C. would also like to thank the High Performance Computing Modernization Program (HPCMP) of the U.S. Department of Defense and Princeton University's Terascale Infrastructure for Groundbreaking Research in Engineering and Science (TIGRESS) for providing the computational resources.
Funding Information:
This article is based upon work supported by the Air Force Office of Scientific Research under AFOSR Award No. FA9550-14-1-0254. E.A.C. would also like to thank the High Performance Computing Modernization Program (HPCMP) of the U.S. Department of Defense and Princeton University’s Terascale Infrastructure for Groundbreaking Research in Engineering and Science (TIGRESS) for providing the computational resources. We thank Ms. Nari L. Baughman for proofreading the manuscript. The atomic structures are visualized using VESTA.79
PY - 2019/1/9
Y1 - 2019/1/9
N2 - The active site for electrocatalytic water oxidation on the highly active iron(Fe)-doped β-nickel oxyhydroxide (β-NiOOH) electrocatalyst is hotly debated. Here we characterize the oxygen evolution reaction (OER) activity of an unexplored facet of this material with first-principles quantum mechanics. We show that molecular-like 4-fold-lattice-oxygen-coordinated metal sites on the (1211) surface may very well be the key active sites in the electrocatalysis. The predicted OER overpotential (η OER ) for a Fe-centered pathway is reduced by 0.34 V relative to a Ni-centered one, consistent with experiments. We further predict unprecedented, near-quantitative lower bounds for the η OER , of 0.48 and 0.14 V for pure and Fe-doped β-NiOOH(1211), respectively. Our hybrid density functional theory calculations favor a heretofore unpredicted pathway involving an iron(IV)-oxo species, Fe 4+ =O. We posit that an iron(IV)-oxo intermediate that stably forms under a low-coordination environment and the favorable discharge of Ni 3+ to Ni 2+ are key to β-NiOOH's OER activity.
AB - The active site for electrocatalytic water oxidation on the highly active iron(Fe)-doped β-nickel oxyhydroxide (β-NiOOH) electrocatalyst is hotly debated. Here we characterize the oxygen evolution reaction (OER) activity of an unexplored facet of this material with first-principles quantum mechanics. We show that molecular-like 4-fold-lattice-oxygen-coordinated metal sites on the (1211) surface may very well be the key active sites in the electrocatalysis. The predicted OER overpotential (η OER ) for a Fe-centered pathway is reduced by 0.34 V relative to a Ni-centered one, consistent with experiments. We further predict unprecedented, near-quantitative lower bounds for the η OER , of 0.48 and 0.14 V for pure and Fe-doped β-NiOOH(1211), respectively. Our hybrid density functional theory calculations favor a heretofore unpredicted pathway involving an iron(IV)-oxo species, Fe 4+ =O. We posit that an iron(IV)-oxo intermediate that stably forms under a low-coordination environment and the favorable discharge of Ni 3+ to Ni 2+ are key to β-NiOOH's OER activity.
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U2 - 10.1021/jacs.8b12386
DO - 10.1021/jacs.8b12386
M3 - Article
C2 - 30543110
AN - SCOPUS:85059621068
SN - 0002-7863
VL - 141
SP - 693
EP - 705
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 1
ER -