Communication
pubs.acs.org/JACS
Reactive Fe-Sites in Ni/Fe (Oxy)hydroxide Are Responsible for
Exceptional Oxygen Electrocatalysis Activity
Michaela Burke Stevens, Christina D. M. Trang, Lisa J. Enman, Jiang Deng, and Shannon W. Boettcher*
Department of Chemistry and Biochemistry, University of Oregon, Eugene, Oregon 97403, United States
*
S Supporting Information
ABSTRACT: Fe is a critical component of record-activity
Ni/Fe (oxy)hydroxide (Ni(Fe)OxHy) oxygen evolution
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reaction (OER) catalysts, yet its precise role remains
unclear. We report evidence for different types of Fe
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species within Ni(Fe)OxHy those that are rapidly
incorporated into the Ni oxyhydroxide from Fe cations
in solution (and that are likely at edges or defects) and are
responsible for the enhanced OER activity, and those
substituting for bulk Ni that modulate the observed Ni
voltammetry. These results suggest that the exceptional
OER activity of Ni(Fe)OxHy does not depend on Fe in the
bulk or on average electrochemical properties of the Ni
cations measured by voltammetry, and instead emphasize
the role of the local structure.
U nderstanding the oxygen evolution half reaction (OER, in
alkaline media: 4OH− → 2H2O + 4e− + O2) is important
for an array of energy-conversion technologies.1,2 Fe-doped Ni-
and Co-based oxide/oxyhydroxide catalysts are among the
most-active OER catalysts in alkaline media.3,4 Fe increases the
intrinsic activity of both Co and Ni (oxy)hydroxides by roughly
30- and 1000-fold, respectively.3,5−8 For electrodeposited Ni or
Co (oxy)hydroxide, Fe can be stabilized in a solid solution (i.e.,
it does not form phase segregated islands) apparently up to
∼25 and ∼50%, respectively.6,9 Further, Klaus et al. have shown
that active Ni(Fe)OOH phases form regardless of catalyst
deposition method.10
Despite the similarity of phases formed under a wide variety
of preparation conditions, there have been many different
mechanistic hypotheses regarding the role that Fe plays in
(oxy)hydroxide OER activity.9,11,12 Li et al. have hypothesized
that increased Ni−O hybridization as a result of the Lewis
acidity of Fe3+ resulted in a more-active material.11 Gorlin et al.
coupled quasi-in-situ X-ray absorption spectroscopy (XAS) and
differential electrochemical mass spectrometry and reported
that Ni remains in a 2+ oxidation state; they observe no
evidence for increased hybridization as a function of Fe.12
Friebel et al. show that the Fe−O bond length in Ni(Fe)OxHy
is different from the Fe−O bond length in FeOxHy and that the
overpotential on this Fe−O site was lower than the
overpotential on the Ni−O sites.9
It is similarly debated what the oxidation state of Ni and Fe
are during catalysis and what role this plays in determining the
OER activity. Friebel et al.9 and Gorlin et al.12 see no change in
the Fe oxidation state (Fe3+) during the OER; however, Ahn
and Bard13 and Chen et al.14 have shown evidence for Fe4+ in
© 2017 American Chemical Society
the films using surface-interrogation scanning electrochemical
microscopy and Mössbauer spectroscopy, respectively. Despite
the large difference in the proposed mechanism or active site
and the Fe/Ni oxidation state, all the materials in the cited
studies are similarly efficient OER catalysts.
The various reports discussed above have all demonstrated
changes in the electrochemical profile, e.g. Ni redox potential,
redox peak size and shape, etc., as a function of Fe
incorporation into the NiOxHy film. Theoretical/computational
studies have also provided insights into the role of Fe.15
However, it remains unclear where the Fe incorporates into the
film to result in highly active Fe−O, Ni−O, or Ni−O−Fe sites.
It is also unclear if the changes in bulk electronic structure, i.e.,
as interrogated by measurements of conductivity, redox peak
position, and average e− per Ni in the redox wave, are directly
responsible for the increased activity or simply a byproduct of
the Fe incorporation unrelated to the enhanced catalytic
activity. Answering these questions is important to develop a
mechanistic picture of OER and a structural picture of probable
active sites.
Here we report the characterization of highly OER-active
Ni(Fe) (oxy)hydroxides that are nearly identical in reduction
potential, conductivity, and electrochemical accessibility to their
Fe-free parent materials (that have low catalytic activity).
Furthermore, we describe two Ni(Fe)OxHy films that have
incorporated Fe differently and have significantly different
electronic/electrochemical properties, while still maintaining
high activity. These results indicate the presence of different
types of active sites within Ni(Fe) (oxy)hydroxides and
emphasize the role of the local geometric structure on activity
as opposed to bulk electrochemical behavior.
An electrolyte permeable (i.e., disordered/porous) Ni(OH)2
film was cathodically deposited from an aqueous Ni(NO3)2
solution onto a conductive substrate (Au or Pt).16 As Ni(OH)2
is cycled, a sharp precatalytic redox feature is visible (Figure
S1). This redox wave is typically associated with the nominal 2+
→ 3+ oxidation of Ni(OH)2 to NiOOH; however, as has been
previously shown, this redox feature typically accounts for
between 1.3 and 1.7 e− per Ni.17,18 The extra 0.3−0.7 e− per Ni
could be due to further oxidation of the Ni3+ to an average
Ni∼3.5+ with possible Ni4+ sites and/or to the oxidation of
oxygen in the lattice (i.e., anion redox).19 Due to the dynamic
changes in oxidation state, hydration level, counterion content
during electrochemical cycling or catalysis, we typically refer to
Received: July 8, 2017
Published: August 8, 2017
11361 DOI: 10.1021/jacs.7b07117
J. Am. Chem. Soc. 2017, 139, 11361−11364
Journal of the American Chemical Society
these (oxy)hydroxide catalysts as MOxHy (where M is the
metal cation).
During the first four voltammetry cycles under Fe-free
conditions the NiOxHy anodic peak potential (Epa) shifts
cathodically 12−15 mV and the anodic peak integrated
intensity decreases by 2−5%. From cycle 5−104 the Epa and
e− per Ni do not change significantly (Figure S1).
When Fe(NO3)3 at 1 mM is spiked into the alkaline solution
(Figure 1), there is an immediate increase in activity shown by
Figure 1. Cyclic voltammetry demonstrating the role of Fe
incorporation into NiOxHy from electrolyte solution. (A) NiOxHy
cycled (10 mV s−1) initially in Fe-free aq. 1 M KOH (red, cycle 1−4)
then moved to a 1 M KOH solution with 1 mM Fe(NO3)3 (cycle 5−
104). The inset depicts a possible schematic of Fe incorporation into a
NiOxHy platelet as a function of cycling in Fe saturated solution. From
the cyclic voltammetry, (B) the percent change in e− per Ni (triangles)
and (C) the change in overpotential (mV) at 1 mA cm−2 (open
circles) and position of Epa (mV) (squares) as a function of cycling
relative to the last cycle in Fe-free conditions. Fe content listed is from
ICP-OES analysis on samples cycled in identical conditions for 2
(orange), 10 (green), 30 (blue), and 100 cycles (violet) after Fe-
spiking. The error bars are based on samples in triplicate with ∼3−5
μg cm−2 loading.
the 130−150 mV decrease in overpotential. This dramatic
change in activity is accompanied by a minimal increase in
electrochemical accessibility to Ni (2−4%, as measured by the
integrated charge in the redox wave) and anodic shift in the Ni
Epa (2−5 mV). During 100 cycles in Fe3+ spiked solution, Epa
shifts a maximum of 30 mV and the peak integration shrinks to
reach 30% less e− per Ni than the Fe-Free NiOxHy. A similar
trend is seen with the cathodic peak size and potential (Epc)
(Figure S2). After electrochemical analysis, the film has 23−
25% Fe as determined by ICP-OES analysis (Table S1).
Despite the large changes in apparent redox wave and peak
potential of the Ni species, there is only a minimal increase in
activity after the initial cycle in the Fe-spiked solution. The
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Communication
overpotential at 1 mA cm−2 decreases only ∼20 mV between
cycles 5 and 100 and >50% of that change occurs in the first 10
cycles after Fe-spiking (Figure 1, cycles 5−15, orange and
green). Electron microscopy shows that the film morphology
does not dramatically change as a function of cycling (Figure
S3).
The inconsistency between observed changes in activity and
electrochemical profile as a function of Fe incorporation
suggests that there is initial Fe incorporation at easily accessible
edge/defect sites, forming Ni−O−Fe species that dramatically
enhance catalysis, but that this has minimal effect on the
majority of the Ni redox species (Figure 1a inset). In fact, this
large effect on the catalysis is evidence that the catalysis is not
particularly influenced by Fe in the NiOxHy bulk (i.e., Fe sitting
on a Ni site fully coordinated by bridging O(H) with other
metal cations) or by the bulk electronic structure. This is
consistent with previous suggestions of active Fe edge sites.20
To probe the effect of incorporating Fe species, the effective
electrical conductivity of Fe-spiked NiOxHy was measured as a
function of applied potential before and after the addition of
Fe(NO3)3 at 1 mM to the initially Fe-free electrolyte. Figure 2
Figure 2. Steady-state effective conductivity of NiOxHy on an
interdigitated array (IDA) electrode as a function of Fe incorporation
from 1 mM Fe(NO3)3 in a 1 M aq. KOH solution. The effective
conductivity was measured before Fe spiking (pre-Fe), immediately
after Fe spiking (1), and after cycling (2−3). The film was held at each
step for 2 min. Cyclic voltammetry is overlaid. There were two cycles
(10 mV s−1) between each steady-state conductivity measurement; the
second of each series is shown.
shows no correlation between conductivity and activity; the
activity increases dramatically with Fe incorporation while there
is only a small decrease in the effective conductivity. The
decrease as a function of cycling is also seen in the Fe-free
NiOxHy (Figure S4).7 As the film is cycled, the onset potential
for conductivity shifts with the shift in Epa indicating a change
in bulk electronic structure. This result is consistent with the
edge and defect sites dominating the catalytic response of the
system while the bulk electronic properties dominate the
electrical transport properties. This result is different from
coelectrodeposited Ni−Fe (oxy)hydroxides where the addition
of Fe increased the conductivity; the difference is likely
explained by a higher degree of crystallinity for the Ni−Fe
relative to the pure Ni oxy(hydroxides) when both are
electrodeposited under similar conditions.7
Small amounts of Fe are also known to induce large OER
activity changes on Au substrates likely due to FeOxHy sites
DOI: 10.1021/jacs.7b07117
J. Am. Chem. Soc. 2017, 139, 11361−11364
Journal of the American Chemical Society
integrated with Au−O surface species.21,22 Fe-spiked control
experiments on blank Au and Pt electrodes (Figure S5)
demonstrate that although the activities of both “bare”
electrodes are significantly impacted by Fe spiking, the majority
of activity enhancement discussed here occurs on the NiOxHy
rather than the substrate. However, fundamentally the Fe-
activated Au−O electrodes may be catalyzing the OER in a
similar fashion to the Fe-activated NiOxHy with both utilizing
surface (in the case of Au−O) or edge (in the case of NiOxHy)
Fe sites for the enhanced activity. It is possible that the
difference in active surface area between the NiOxHy film and
the Au surface is largely responsible for the difference in
overpotential, although efforts to normalize and extract the
intrinsic activity suggest the Fe-activated NiOxHy is the faster
catalyst.22
With continued cycling of NiOxHy in 1 M aq. KOH with 1
mM Fe(NO3)3 (Figure 1) the Epa shifts significantly anodically.
It is known that the reduction potential of nominally Ni2+/3+
shifts anodically with increasing Fe content when deposited as a
mixed (oxy)hydroxide.7,23,24 This shift in reduction potential
has been associated with a bulk change in the electronic
structure of the material and can be used to determine if Fe has
incorporated into the Ni(Fe)OxHy film. Figure 3a and 3b
compare an Fe-free NiOxHy film, a spiked Fe−NiOxHy film
cycled 2 and 100 times, and a codeposited Ni(Fe)OxHy film
with similar Fe content. The OER activity (Figure 3c) is based
on the total-metal turnover frequency (TOFtm) or amount of
O2 produced per metal cation per second.
Figure 3. Cyclic voltammetry (10 mV s−1) of Fe-free NiOxHy film
(red) compared to (A) spiked Ni(Fe)OxHy cycled 2 (orange, 10% Fe)
and (B) 100 (violet, 25% Fe) times in 1 mM Fe(NO3)3 and
codeposited Ni(Fe)OxHy films with similar Fe content (green 8% Fe
and teal 30% Fe, respectively). (C) TOFtm at η = 300 mV based on
total metal content using the average of the forward and reverse sweep
from panel (A). (D) e− per Ni obtained by integration of the oxidation
wave. Metal content and ratios were determined after electrochemical
analyses using ICP-OES. Open and closed symbols are for codeposited
and Fe-spiked samples, respectively. Error bars are based on samples
measured in triplicate.
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Communication
Within 2 cycles in the Fe-spiked base, the NiOxHy film picks
up an average of 11% Fe (the example in Figure 3a has 10% Fe)
and the activity increases by ∼150-fold; however, there is only
an ∼10 mV anodic shift in Epa and ∼2% difference in e− per Ni
in the redox wave. The Epa for the codeposited Ni(Fe)OxHy
sample with similar Fe content (Figure 3a) is ∼26 mV anodic
of the Fe-free NiOxHy wave and has ∼7% more e− per Ni. The
Fe-spiked sample has twice the TOFtm (Figure 3c) than the
codeposited Ni(Fe)OxHy. After 100 voltammetry cycles in the
Fe-spiked solution, the film incorporates ∼25% Fe. Epa is,
however, ∼55 mV cathodic of that observed for a codeposited
Ni(Fe)OxHy film with similar Fe content (Figure 3b). The e−
per Ni is ∼30% smaller for the Fe-spiked sample compared to
the codeposited one. The activity of the two, however, is more
similar than for the lower Fe concentration pair. For the
codeposited 30% Fe sample, the cathodic and anodic peaks are
relatively narrow (and split by Epa − Epc = 80 mV) indicating a
sample that has homogeneously incorporated the Fe into the
bulk of the Ni lattice. This is consistent with the literature in
which ∼25% Fe is soluble in NiOOH.9 In contrast, the 25% Fe-
spiked sample has two distinct reduction and oxidation peaks
yielding broader redox features; this suggests that Fe is
inhomogeneously distributed in the bulk and on the edges of
the NiOxHy in the Fe-spiked sample, thus inhomogeneously
affecting the Ni redox wave position.
The data discussed above demonstrate (1) a Fe−NiOxHy
catalyst nearly identical to its parent NiOxHy in terms of Ni
redox behavior but is ∼100-fold more active and (2) a spiked
Fe-NiOxHy and codeposited Ni(Fe)OxHy that have similar Fe
content and activities, but large differences in e− per Ni, Epa,
and redox wave shape. This supports a view in which FeOxHy
species initially incorporate into NiOxHy from solution at
surface/edge/defect sites, before moving into the bulk of the
NiOxHy nanosheet samples and significantly affecting the Ni
redox behavior. Co-deposited Ni(Fe)OxHy films appear to
incorporate Fe more uniformly during synthesis. These results
indicate that the Ni−Fe activity is more related to the local
active-site environment than the bulk electronic structure and
there are Fe-sites in different local environments (i.e., edge
versus bulk). Future studies should therefore search for
different Fe geometries directly in samples such as these, for
example using EXAFS at the Fe K-edge or infrared
specroscopy.8
In conclusion, upon the introduction of Fe into the NiOxHy
from solution the electronic properties, reduction potential,
redox peak size, peak shape, etc. of the Fe−NiOxHy film change
independently of the OER activity. Fe may initially incorporate
at edges/defects and further incorporate into the “bulk” of the
NiOxHy nanosheets (with Fe also remaining at the edge/defect
sites). The e− per Ni in the redox wave does slightly increase
with Fe addition, but the sample stays active even as the e− per
Ni decreases with continued Fe incorporation in the bulk of the
NiOxHy. The electrical conductivity of Fe−NiOxHy decays with
cycling in Fe-containing solution even as the sample becomes
more active. Finally, the reduction potential (as monitored by
the Epa) does not shift to a potential expected of a codeposited
sample with similar Fe content. These experiments are all
consistent with the view that the “bulk” (oxy)hydroxide
electronic structure is not the main factor influencing OER
activity.
These results may help explain the recent conflicting
hypotheses on the role of Fe in Ni-based OER catalysts. The
deposition method and electrochemical conditioning appear to
DOI: 10.1021/jacs.7b07117
J. Am. Chem. Soc. 2017, 139, 11361−11364
Journal of the American Chemical Society Communication

be directly responsible for the Fe location and local
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bulk sites. This could determine the electrochemical profile of
the material, and even the average oxidation state of the Ni and
Fe sites, but leave the overall activity of the film unaffected.
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AUTHOR INFORMATION
Corresponding Author
*swb@uoregon.edu
ORCID
Shannon W. Boettcher: 0000-0001-8971-9123
Notes
The authors declare no competing financial interest.

■ ACKNOWLEDGMENTS
This work was supported by the National Science Foundation
under Grant CHE-1566348. J.D. acknowledges support from
Zhejiang University and C.D.M.T. from the University of
Oregon Presidential Undergraduate Research Scholarship.

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11364 DOI: 10.1021/jacs.7b07117

J. Am. Chem. Soc. 2017, 139, 11361−11364