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Published February 14, 2017 | Published + Supplemental Material
Journal Article Open

Influence of iron doping on tetravalent nickel content in catalytic oxygen evolving films

Abstract

Iron doping of nickel oxide films results in enhanced activity for promoting the oxygen evolution reaction (OER). Whereas this enhanced activity has been ascribed to a unique iron site within the nickel oxide matrix, we show here that Fe doping influences the Ni valency. The percent of Fe^(3+) doping promotes the formation of formal Ni^(4+), which in turn directly correlates with an enhanced activity of the catalyst in promoting OER. The role of Fe^(3+) is consistent with its behavior as a superior Lewis acid.

Additional Information

© 2017 National Academy of Sciences. Contributed by Daniel G. Nocera, December 19, 2016 (sent for review July 12, 2016; reviewed by Curtis P. Berlinguette and Shannon W. Boettcher). Published ahead of print January 30, 2017. We are grateful to Adam Graham for assistance with scanning transmission electron microscopy (STEM), Zhongxing Chen for assistance with ICP, and Michael Huynh for helpful discussions. We also acknowledge Tianpin Wu, Lu Ma, and George Sterbinsky for assistance with XAS measurements. This material is based upon work supported under the Solar Photochemistry Program of the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences of the US Department of Energy. R.G.H. is an Enrico Fermi Fellow at Argonne National Laboratory (ANL). D.H. is supported by the Joseph J. Katz Postdoctoral Fellowship at ANL. Work by D.C.B. and F.v.C. was supported by the Science and Technology Center for Integrated Quantum Materials, National Science Foundation (NSF) Grant DMR-1231319. Use of beamline 9BM-B at the Advanced Photon Source at ANL was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract DE-AC02-06CH11357. The Center for Nanoscale Systems at Harvard University is a member of the National Nanotechnology Infrastructure Network, which is supported by the National Science Foundation under ECS-0335765. Author contributions: N.L., D.K.B., R.G.H., D.C.B., L.X.C., and D.G.N. designed research; N.L., D.K.B., R.G.H., D.H., T.J.K., and F.v.C. performed research; N.L., D.K.B., and R.G.H. contributed new reagents/analytic tools; N.L., D.K.B., R.G.H., D.H., and D.G.N. analyzed data; and N.L., D.K.B., R.G.H., and D.G.N. wrote the paper. Reviewers: C.P.B., University of British Columbia; and S.W.B., University of Oregon. The authors declare no conflict of interest. This article contains supporting information online at www.pnas.org/lookup/suppl/doi:10.1073/pnas.1620787114/-/DCSupplemental.

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Supplemental Material - pnas.1620787114.sapp.pdf

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Created:
August 22, 2023
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