pubs.acs.

org/JPCC Article

Raman Spectroscopic Observation of Electrolyte-Dependent

Oxygen Evolution Reaction Intermediates in Nickel-Based
Electrodes
Published as part of The Journal of Physical Chemistry C special issue “Celebrating 50 Years of Surface
Enhanced Spectroscopy”.
Tomohiro Fukushima, Kenko Tsuchimoto, Nobuaki Oyamada, Daiki Sato, Hiro Minamimoto,
and Kei Murakoshi*
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sı Supporting Information

ABSTRACT: Oxygen evolution reaction (OER) is the counterpart in

hydrogen production by water electrolysis. Further challenges have been
required to bypass the energy consumption processes in the OER. It is still
important to unveil the OER intermediates toward effective green hydrogen
production. In this study, we conducted in situ Raman observation of the
OER intermediates over Ni nanohole-array electrodes in the various
electrolyte conditions. Ni nanohole-array electrodes were prepared with
interference exposure methods. Intense Raman peaks were observed from
Ni−OH, Ni-OOH, and active oxygen species as the OER intermediates.
The OER behavior can be classified with the reactants, such as OH− and
H2O. The presented study demonstrates the importance of the electrolyte
for the designing active OER catalysis for the next generation energy society.

■ INTRODUCTION
Hydrogen production by water electrolysis is important for the
activity of water, can be variable in terms of the electrolytes.
Therefore, the understanding of the effect of electrolyte on the
upcoming energy society. Water electrolysis requires efficient OER catalytic activity can be informative for the principle-
electron transfer reactions in both the hydrogen evolution
based design of the next generation catalysts.
reaction (HER) and the oxygen evolution reaction (OER). It is
pointed out that overpotential for the OER is nominally high Here, we utilize nickel-based electrodes for the evaluation of
even for the state-of-the-art electrocatalysts, resulting in the the OER activity. Raman spectroscopy was utilized for the
low efficiency of energy conversion from electricity to H2.1−4 evaluation of the OER activity. First, we prepared the Ni
The multiple reaction intermediates during the OER process nanohole-array electrode by using interference exposure
cause difficulty for the understanding the underlying
mechanism.5−8 The highly sensitive methods such as Raman methods. The electrochemical behavior was evaluated, depend-
spectroscopy9−26 are powerful methods for the evaluation of ing on the electrolyte solution. OER behavior is further
such OER intermediates at electrode surface during the analyzed by machine-learning methods. Furthermore, Raman
electrocatalytic reactions.
spectroscopy was utilized for the evaluation of the OER
Recently, the electrolytes are highlighted to attain the
enhanced OER catalytic ability.17,27−35 Shao-Horn et al. intermediates during the OER processes. We discuss the effect
reported that hydration network at electrode−electrolyte of the electrolyte condition on the OER intermediates and
interface can be modified with the cationic species in alkaline reaction mechanism.
condition.35 Koper et al. reported that active oxygen species
can be even modified with the cationic species in alkaline
condition.14 However, these studies are still limited for the Received: October 4, 2024
alkaline condition, which has been routinely studied in the Revised: October 30, 2024
alkaline hydrogen production method. In particular for the Accepted: October 30, 2024
near-neutral pH conditions, the choice of the electrolyte is Published: November 14, 2024
important for the improvement of the catalytic activity in terms
of the activity29 or even for the stability.36 Local pH, the

© 2024 American Chemical Society https://doi.org/10.1021/acs.jpcc.4c06732

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■ EXPERIMENTS
In-Situ Electrochemical Raman Measurements. Raman
hydrogen electrode (RHE). The electrode potentials were
converted to the scale using following equation, E (RHE) = E
spectra was collected by using the 633 nm laser (1 mW, 10 s) (Ag/AgCl) + 0.197 V + 0.059 (pH) V. The electrochemical
with the Raman microscope, inVia Qontor, Renishaw. In-situ potential was not corrected with the iR compensation.
electrochemical Raman measurements were conducted using Preparation of Ni Nanoholes-Array Electrodes. Inter-
HSV-110, Meiden Hokuto, Japan. The handmade electro- ference exposure method was utilized as the preparation of the
chemical cell was made of PCTFE. Prior to use, the cell was nanostructure in the large area.40,41 First, CAUT-200 was spin-
washed with the sulfuric acid and nitric acid (3:1 in volumetric coated onto the FTO substrate (4000 rpm, 30 s). Photoresist
ratio). The cell was washed with the boiling water three times (TDM-AR80) was also spin-coated (4000 rpm, 30 s). The
to remove the residual small amount of acid. Prior to use the substrate was heated to 135 °C for 20 min. Aquathal was spin-
electrochemical cell was washed with the electrolyte solution. coated (2000 rpm, 30 s). Interference exposure was conducted
Ni nanohole-array electrodes were used as a working electrode. with different incident light angle at 90° (λ = 325 nm, 60 μW,
The Ag/AgCl electrode was used as a reference electrode. The 140 s). The substrate was heated at 135 °C for 90 s. The
Pt black electrode37 was used as a counter electrode to avoid structure was developed by immersion of the substrate in
the contamination of Pt catalyst to investigate the OER from NMD-3 for 90 s. After template development, 40 nm of Ni was
Ni nanohole-array electrode.38,39 The electrodes were deposited by the electron beam (deposition rate = 0.1 nm/s).
assembled in the cell (Figure 1a). The electrode surface of The resist was removed by immersion of the substrate in ST-
120. Figure 1c shows the SEM image of the as-prepared Ni-
nanohole-array electrode. The periodic square lattice can be
formed by the interference exposure methods. The diameter of
the nanoholes were approximately 400 nm. The distance
between each hole is approximately 700 nm.
Machine-Learning Analysis. Reaction kinetics of OER
was analyzed by the machine-learning methods by using the
python program package (version 3.7).48 The machine-
learning was conducted based on the genetic algorithm.49
Machine-learning-based microkinetic analysis was performed
by assuming the following sequential PCET reactions.
M + OH V MOH + e (a)
Figure 1. (a) Schematic cell structure for in situ Raman spectroscopic
experiments under electrochemical potential control. (b) Optical MOH + OH V MO + H 2O + e (b)
image of the Ni nanohole-array electrodes. (c) SEM image of the Ni
nanohole electrodes. MO + OH V MOOH + e (c)

the working electrode was exposed through the hole located at MOOH + OH V M + O2 + H 2O + e (d)
the bottom part of the cell (Φ = 1 cm). The reference
electrode was located within 1 cm from the working electrode Where, catalytic active sites (M) are oxidized to the surface
to avoid the ohmic loss. As described later, the large-area Ni hydroxide species (MOH) (reaction a). MOH can be further
nanohole-array electrode was prepared by interference oxidized to the oxo (MO) (reaction b) and peroxide species
exposure method.28,40−42 The optical image of the nanohole- (MOOH) (reaction c). Finally, the desorption of O2 from the
array electrodes is shown in Figure 1b. A scanning electron catalytic active site regenerates the catalytic active sites
microscope (SEM) image of the Ni nanohole-array electrode is (reaction d). Following equations were calculated by
shown in Figure 1c. supposing the microkinetic analysis on the equations.7,48
Oxygen evolution reaction was conducted in the following
electrolyte condition. pH 13 solution was prepared from 0.3 M
j = nFN
K10k 20cOH
2
exp ( F(E E1)
RT )
NaOH and 0.7 M NaClO4. The pH 11 unbuffered electrolyte
exp( )
F(E E1)
solution was prepared from 0.003 M NaOH and 1 M NaClO4. 1 + K10cOH RT
The pH 11 buffered electrolyte solution was prepared from 2.8 ÅÄÅ (1 É
E2) ÑÑÑÑ
Å )F (E
M NaOH and 1 M H3PO4 electrolyte solution. The pH value expÅÅÅ ÑÑ
ÅÅÅ RT ÑÑÑ
was confirmed by a pH meter (Horiba, F-71S). The local pH Ç Ö (1)
was calculated to be similar for pH 13 and pH 11 buffered ÅÄÅ F(2E E1 E2) ÑÉÑ ÅÄÅÅ (1 )F(E E3) ÑÉÑÑ
solution below 5 mA cm−2 for the OER current density even K10K 20k 30cOH
3
expÅÅÅ ÑÑexpÅÅ
ÑÑÖ ÅÇ ÑÑ
ÑÖ
ÅÇ RT RT
under the effect of naturally occurring convection conditions at j = nFN ÄÅ F(E E ) ÉÑ ÄÅ F(2E E É
E 2) Ñ
Å Ñ Å ÑÑ
c H2O + K10cOH c H2OexpÅÅÅ RT 1 ÑÑÑ + K10K 20cOH 2
expÅÅÅ 1
ÑÑ
the stationary electrode.43−47 Otherwise noted, all of the ÅÇ ÑÖ ÅÇ RT ÑÖ
electrochemical potential was referenced to the reversible (2)

ÄÅ F(3E E E E ) ÉÑ
Å 3 Ñ
expÅÅÅ ÑÑ
0 4
K10K 20K30k4 cOH 1 2
ÑÑÖ
ÅÇ RT
j = nFN ÄÅ F(E E ) ÉÑ ÄÅ F(2E E E ) ÉÑ ÄÅ F(3E É
E3) Ñ
Å Ñ Å Ñ ÅÅ ÑÑ
c H2OexpÅÅÅ RT 1 ÑÑÑ + K1 K 2 cOH expÅÅÅ 2 Ñ E1 E 2
c H2O +K10cOH 0 0 2 1
Ñ
Ñ + K 0 0 0 3
K K c exp ÅÅ ÑÑ
ÅÇ ÑÖ ÅÇ RT ÑÖ 1 2 3 OH
ÅÇ RT ÑÖ (3)

Where ki represents the i-th kinetic parameter, Ki represents

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Figure 2. Linear sweep voltammograms (solid lines) of the Ni nanohole-array electrodes in (a) pH 13 electrolyte, (b) pH 11 buffered electrolyte,
and (c) pH 11 unbuffered electrolyte. Sweep rate was 5 mV s−1. Current densities were obtained from the potentiostatic polarization from
chronoamperometry experiments during the Raman measurements. Open circles were obtained at the initial polarization. Steady state data after
polarization of 20 s are shown as closed circle. (d) Tafel plot of the Ni nanohole-array electrode in (d) pH 13 electrolyte, (e) pH 11 buffered
electrolyte, and (f) pH 11 unbuffered electrolyte. Red and green lines represent fitting for the Tafel plots. Corresponding Tafel slope values are
shown in the Figure.

i-th equilibrium constant, and Ei represents the standard of the PO43− is 21 mM, where the concentration of the OH−
electrochemical potential for the i-th equation. n is the number should be 1 mM in pH11 buffered electrolyte. (see Supporting
of electrons, N is the active site density, C H2O is the Information for the detailed calculations).54
concentration of water, COH is the concentration of hydroxide, In the case with both pH 13 and pH 11 buffered electrolyte,
is the symmetry factor, F is the Faradaic constant, R is the the Ni nanohole-array electrode showed an intensive OER
universal gas constant, T is the absolute temperature. For the from 1.5 and 1.6 V, respectively. On the other hand, linear
simplification of the analyses, the symmetry factors were fixed; sweep voltammogram showed different behavior in pH 11
= 0.5. In this study, the ki, Ki, and Ei are optimized for the unbuffered electrolyte. A two-step oxidative events were
obtaining the Tafel plots. Fittings are shown in Figures S1− observed; the current density first increased until reaching a
S12. plateau around 0.2 mA cm−2 at approximately 1.6 V, which
started increasing further at a potential of 1.95 V with the
■ RESULTS AND DISCUSSION
Electrochemical Behavior of Ni Nanohole-Array
switching of the hydroxide ions to the water moelcules.55
These OER behaviors of the Ni nanohole-array electrode are
Electrodes. Electrochemical potential of Ni was controlled similar to one of the Ni plate electrodes, suggesting that
for the observation of Ni nanohole-array electrodes. Figure 2 electrochemical behavior is consistent even in the presence of
shows the linear sweep voltammograms of the OER activity the nanohole-array (Figure S13).
depending on the electrolyte condition. A prepeak was The Tafel analyses were also conducted for the OER
observed at 1.35 V for the Ni nanohole-array electrode in behavior in each electrolyte condition as shown in Figure
pH 13 (Figure 2a). Similarly, a prepeak was observed at 1.5 V 2d,e,f. In case with the lower overpotential region, for example
for pH 11 buffered electrolyte (Figure 2b). A prepeak was also from 1.45 to 1.5 V in pH 13, The Tafel fitting cannot be
observed at 1.45 V for pH 11 unbuffered electrolyte (Figure applied due to the presence of the capacitive current of the
2c). These peaks can be assigned to the oxidation of the electrode. Similarly, it is also difficult for the high overpotential
surface OH species (Ni(OH)2 + OH−→ NiOOH + H2O + region, for example above 1.63 V, probably due to the presence
e−).9,13,50,51 In fact, from the potentiostatic polarization at the of the bubbles. Tafel slope for OER from Ni nanohole-array
given electrochemical potentials, the disappearance of the electrodes in the pH 13, pH 11 buffered electrolyte showed 62
prepeak was observed due to the charging of the surface mV per decade and 63 mV per decade, respectively. On the
oxidation process (closed circle in Figure 2). Even though the other hand, for both lower and higher overpotential region in
pH condition is the same for the pH 11 unbuffered and pH 11 unbuffered conditions, the Tafel slope showed 156 mV
buffered electrolyte, the electrochemical potential for the per decade and 123 mV per decade, respectively.
prepeak is different. We are assuming that the proton acceptor Next, we utilized machine-learning analysis of the electro-
in pH 11 buffered electrolyte condition, PO43−, affects the chemical activity. Machine-learning model based on the
reactivity with the surface of Ni electrode.52 Similar genetic algorithm was previously developed for the determi-
observation have been reported by using borate anion as nation of the thermodynamic and kinetic parameter.48 The
buffer in the electrolyte due to the difference in equilibrium experimental Tafel plots were fitted with the calculated
constant of proton-coupled electron transfer.53 The superior theoretical data set, which was also fitted with the genetic
reactivity can be expected for the PO43− because concentration algorithm (see Supporting Information). Figure 3 shows the
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Figure 4. Raman spectrum of Ni nanohole-array and Ni plate

electrodes at 1.75 V in pH 11 unbuffered electrolyte. The Raman
Figure 3. Volcano plots analyzed from the OER from Ni nanohole- signals from 480 and 550 cm−1 can be assigned to ν(Ni−OH) and
array electrodes in pH 13 electrolyte (red closed circle), pH 11 ν(Ni-OOH). The broad signals from 1000 to 1100 cm−1 can be
buffered electrolyte (green closed triangle), and pH 11 unbuffered assigned to the active oxygen species. Asterisk represents the
electrolyte (blue open circle for electrochemical potential region from vibrational mode from the ClO4− anion in electrolyte.57
1.5 to 1.6 V, blue open triangle for electrochemical potential region
above 2.0 V). White dotted lines indicates the theoretical line fits for
free-energy relationships.56.
Raman signals from the electrolyte solution can be observed.
For example, stretching modes of Cl−O were observed at 934
volcano plots extracted from the theoretical data fit. As cm−1.57 Deformation modes of ClO4− were observed at 462
expected, the ideal thermodynamic overpotential is decreased and 628 cm−1.57 In addition to that, intense Raman signals
when the reaction intermediates are barrierless. Therefore, the were observed at 480 cm−1, 550 cm−1, and 1000−1100 cm−1.
top of the volcano was observed at the reaction intermediate These peaks are assigned to the specific OER intermediates.
energy GOH = 1.23 eV, GO = 2.46 eV and GOOH = 3.69 eV. As The Raman signals around 480 cm−1 can be assigned to the
pointed out in our previous paper,48 we can find the Ni−OH stretching modes,58 bending modes of Ni−OH,13,18
distribution of the various reaction intermediates in the OER A1g(T) mode,59−62 Eg(T) mode,63 or mixed assignment of A1g(T)
analysis, which is different from the free energy relationship mode and Eg(T) mode.64 Similarly, the Raman signals around
between the reaction intermediates (GOOH = GOH + 3.2).56 In 550 cm−1 can be assigned to the Ni-OOH vibrational modes,58
the case with the pH 13 condition, the distribution of the stretching mode of Ni−OH,13,18 Eg(R) mode,59−62 or mixed
reaction intermediates lies around 1.65 eV for GOH and 4.45 assignment of A1g(T) mode and Eg(T) mode.64 In this paper, we
eV for GOOH. On the case of pH 11 buffered conditions, the discuss the potential dependence of the Raman spectra
distribution of the reaction intermediates lies around 1.23 eV assuming the Ni−OH stretching modes (480 cm−1) and the
for GOH and 3.47 eV for GOOH. In case with the pH 11 Ni-OOH vibrational modes (550 cm−1).58 More precise
unbuffered electrolyte, due to the reactant switching of the assignment of these wavenumber regions for the OER metal
OER process, two energy regions can be found even in the oxide could need further study in details. We observed
energy distribution. In case with the electrochemical potential potential dependence on the relative intensity modulation
region from 1.5 to 1.6 V, where OH− is involve in the OER under the oxygen evolution reaction conditions as described
process, the energy distribution has similar trends as pH 13 later. In addition, the broad band at 1000−1100 cm−1 can be
condition; the distribution of the reaction intermediates lies assigned to NiO-O− as the “active oxygen”
around the 1.51 eV for GOH and 4.52 eV for GOOH. On the modes.13,14,18,21−26,59−63,65
other hand, in case with the electrochemical potential region The “active oxygen” species shows extremely broad features
from 2 V, where H2O is involved in the OER process, the due to the variety in the oxygen species at the Ni oxide surface.
energy distribution has similar trends as the pH 11 buffered Even from the theoretical calculations, the oxygen shows
condition; the distribution of the reaction intermediates lies several Raman signals.21 For example Zhang et al. reported that
around the 1.37 eV for GOH and 3.55 eV for GOOH. Indeed, the the broad oxygen feature is O2n− species at the surface, which
theoretical calculations gives the free energy relationships in can be assigned to the peroxide or superoxide species.66 These
the OER intermediates.56 Even from machine-learning types of oxygen species can be broadly observed for various
analyses, we can find the hidden reaction pathway of the types of the catalysts. For example, Co, Ni, Cu, and Ag foils
OER, which cannot be explained with the linear free energy shows the superoxide groups where Au shows the peroxyl
relationship of the OER intermediates. groups during OER.23 Koper et al., also reported that the
Raman Spectrum of Ni Nanohole-Array Electrodes. deprotonation reaction is important from the Raman spec-
In-situ Raman spectroscopy of the OER intermediates was troscopy,22 and cation effect on OER from the Raman
conducted under electrochemical potential control. Figure 4 spectroscopy.14 The broad feature can also be understood
shows a representative Raman spectra of Ni nanohole-array from the molecular models. For example end-on superoxol Ni
electrode and Ni plate in pH 11 unbuffered electrolyte at 1.75 complex shows 1131 cm−1.67 The bond length of the O−O
V. Interestingly, intense Raman signals were observed for the bond can be variable upon the interaction with the metal
Ni nanohole-array electrode rather than the Ni plate electrode. center. To exemplify the correlation of the Raman shift with
By considering the electrochemical behavior of Ni nanohole- the O−O bond distance, approximately 1200 cm−1 in Raman
array electrode is similar to the Ni plate electrode, we can shift corresponds to the 1.3 Å, whereas 1000 cm−1 in Raman
utilize the Ni nanohole-array electrode for the evaluation of the shift corresponds to the 1.2 Å.68 In addition, the different
Raman behavior under OER conditions. In both case, the charge of oxygen species and orientation exists at the
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Figure 5. Raman spectrum of Ni nanohole-array electrodes in (a) pH 13 electrolyte, (b) pH 11 buffered electrolyte, and (c) pH 11 unbuffered
electrolytes. Electrochemical potential was notated.

Figure 6. Raman peak positions of Ni nanohole-array electrodes in (a) pH 13 electrolyte, (b) pH 11 buffered electrolyte, and (c) pH 11 unbuffered
electrolytes.

surface.25,26 This is the reason why the broad feature of the active oxygen species. Figure 5b shows the Raman spectra of
Raman shift was observed in general. the OER intermediates of the Ni nanohole-array electrode in a
The intense sharp signals were observed in the Ni nanohole- pH 11 buffered electrolyte. Similarly, the intense Raman
array electrodes. For example, Bell et al. reported the broad signals from Ni−OH and Ni-OOH were observed around
signal on the Raman observation. Thickness-dependent from the 1.5 V. The intensities of signals were growing upon
experiments revealed that the Raman signals were broadened the increase of the electrochemical potential. Compared with
within the 5-layer thickness of NiOx layer. Over 12 layer the pH 13 electrolyte condition, active oxygen species can be
thickness of NiOx layer, the Raman signals are sharpened.12 more intensively observed. Even with the same pH conditions
The peak position of the Raman spectra is not dependent on for the pH 11 unbuffered electrolyte, the observed Raman
the electrochemical potential within the same phase of the behavior is distinct (Figure 5c). The intense peaks from Ni−
material. Our group also have reported the use of the OH and Ni-OOH were observed again. The intense signal
plasmonic Au electrode to enhance the Ni OER intermedi- around the active oxygen was also observed. Upon the
ates.15,16 In case with the thin layer of the Ni catalysts, the increasing the electrochemical potential, the intensities of
signals were weak and broad.16 The use of the Ni nanohole- Raman signals were once increased up to 1.75 V. However,
array electrode can be used for the enhanced signal in the Raman intensity start to decrease over 1.95 V. From the
evaluation of the kinetics of the OER intermediates. observation by microscope, the bubbles are formed due to the
Electrolyte-Dependent Raman Behavior of Ni Nano- intensive OER process. The light scattering, due to the
hole-Array Electrodes. OER intermediates are dependent on formation of an O2 bubble, can induce a decrease in overall
the electrolyte environments. Figure 5a shows the Raman Raman signals. We expect that the presence of the bubbles did
spectra of the OER intermediate of the Ni nanohole-array not influence on the Raman shift. Furthermore, the relative
electrode in the pH 13 electrolyte. Weak signal was observed intensity between Ni−OH and Ni-OOH was distinct upon the
with the broad single-like spectrum at 1.25 V. This is due to increase of the electrochemical potential. In addition, active
the rock-salt type crystal structure.12 Upon the increase of the oxygen species can be barely observed over 1.95 V. This is
electrochemical potential, the intense Raman peak was probably due to reactant switching in the OER intermediates.55
observed around 480 and 550 cm−1, which can be assigned Interestingly, active oxygen species are dependent on the
to the Ni−OH stretching and Ni-OOH stretching modes as electrolyte condition. Active oxygen species are strongly
described above. Relatively weak and broad signal was observed in pH 11 buffered electrolyte from 1.6 to 1.85 V.
observed around 1000 cm−1, which can be assigned as the On the other hand, the Raman intensities of the active oxygen
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species are barely observed in case with the lower overpotential oxidation reaction. The peak intensity showed higher values.
region or pH 11 unbuffered electrolyte, for example, at 2.05 V. However, due to the bubble formation or reactant switching,
Koper et al. reported the use of the alkali cations are important Figure 7b shows the different intensity ratio between the
for the observation of the intense Raman signals assigned to NiOH and NiOOH signals. In case with both pH 13 and pH
the active oxygen species.14 We are assuming that the active 11 buffered conditions, the relative intensity of I(NiOH)/
oxygen species might be enhanced by the electrolyte I(NiOOH) remains the values between 1.0 and 1.2. However,
conditions. in case with the pH 11 unbuffered condition, the intensity ratio
Interestingly, the Raman peak positions of the OER change from the 1.2 to 1.8. Even with the same pH condition,
intermediates are dependent on the electrolyte condition. the intensity ratio varies due to the difference in electrode−
Upon the increase of the electrochemical potential, the peak electrolyte interface.
positions of the Ni-OOH stretching modes are not sensitive to The intensity ratio of the OER intermediates probably
the potential or electrolyte conditions. The vibrational reflects the relative amounts of the reaction intermediates. It
frequencies of the Ni-OOH were constantly observed around should be noted that reaction intermediates can be assigned
555 cm−1. On the other hand, Ni−OH peak positions are based on the previous literatures.8,12−14,16,21−24,58,66,70 How-
sensitive to the electrolyte conditions. The peak positions can ever, if the Raman signal have a similar vibrational frequency
be classified to two positions: one is around 483 cm−1 and the with a similar line width, we cannot distinguish the difference
other is 476 cm−1. In the case of the pH 13 electrolyte, the in chemical species. Therefore, we discuss the OER
peak positions are initially around peak positions 483 cm−1 and intermediates based on the spectroscopic results under
switched to the peak positions around 476 cm−1 (Figure 6a). electrochemical potential control. In the case of Raman
In the case with the pH 11 buffered electrolyte, the peak spectroscopy, the cross sections of the Raman signals were
position remained around 483 cm−1 (Figure 6b). In the case important for the determination of the signal intensity. In case
with the pH 11 unbuffered electrolyte, the peak position is with the surface-enhanced Raman scattering, local electric field
initially from the 483 cm−1, and switched to 476 cm−1 and or resonant conditions are quite important for the observation
again reversibly switched to the 483 cm−1 (Figure 6c). In of the Raman signal.11 It is known that Ni nanoparticle with
general, the lower shift of the vibrational frequency the size of the particle of 100−200 nm shows the plasmonic
corresponds to the mode softening of the corresponding resonance at 633 nm.71 Therefore, we assume that the
vibrational modes. We are assuming that slight shift in the Ni− resonance effect for Raman scattering is not clear in the
OH can be induced by local environment upon OER present observation. Since these processes require proton-
intermediate changes by the control of the electrochemical coupled electron transfer at the electrode−electrolyte interface,
potential. the relative ratio is probably determined by the relative
These behaviors are consistent with electrochemical amounts of the OER intermediates in the same phase.
behavior. In the case with the pH 13 electrolyte, the prepeak Therefore, the intensity ratio described in the Figure 7b
due to the OH oxidation was observed around 1.35 V. This indicates the resting state in a turnover rate-limiting step in the
electrochemical potential is consistent with the peak shifts. catalytic cycle.
Similarly, in the case with the pH 11 unbuffered electrolyte, the We are assuming the structural model as following. Ni
peak position shift corresponds to the prepeak of the OH catalyst layer was in situ produced upon the increase of the
oxidation and reactant switching in the electrolyte. Interest- electrochemical potential. Ni catalyst layer is between the
ingly, we observed a consistent peak position in the pH 11 metallic Ni electrode and electrolyte solutions. Because the
buffered electrolyte. This is probably due to the interfacial catalyst layer is composed from the Ni(OH)2, the Raman
interaction between the electrolyte-electrode interface. The signals from Ni−OH are derived from both the catalyst-metal
strong binding of the phosphate in the electrolyte consist the interface and the catalyst-electrolyte interface. Upon the
consistent hydrogen bonding environments, which can be increase of the electrochemical potential NiOOH species
resulting in the differentiating of the Raman observation.69 should be increased. Resting state can be assigned as a rate-
Figure 7 shows the Raman intensity of the Ni nanohole- determining step in the OER catalytic cycle from the Raman
array electrode under different electrolyte conditions. Figure 7a spectra. In case with the pH 13 or pH 11 buffered electrolyte,
shows the Raman intensity of the NiOH signal, which was the rate-determining step can be assumed as the same reaction
extracted from the peak tops around 480 cm−1. Intense Raman step. However, in case with the pH 11 unbuffered condition,
signals were observed after the prepeak due to the OH the intense signals in the NiOH species are strongly observed
probably due to the rate-determining step as the NiOH
species. Considering the electrochemical behavior and volcano
plot in the pH 11 unbuffered condition (Figure 3), the energy
distribution was broadened.
Water electrolysis has been studied in the alkaline conditions
because of the higher overpotential of OER and stability of the
electrode.72−74 The OER process is inherently a multiple
proton-coupled electron transfer process. Therefore, it is still
challenging for the neutral electrolyte condition, which inhibits
the proton transfer in the hydrogen bonding network in
water.70 Even though our work is based on the alkaline
conditions, the reaction mechanism seems complicated toward
Figure 7. (a) Raman intensities of NiOH stretching and (b) Raman the neutral pH. In particular, local pH should be acidic during
intensity ratios in the pH 13 electrolyte (black), pH 11 buffered the OER process in the pH 11 unbuffered condition.44,45 The
electrolyte (red), and pH 11 unbuffered electrolytes (blue). electrocatalytic cycle depending on the electrolyte conditions
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induces the modification in the rate-determining step in the Author Contributions

OER. Exhaustive search of the reaction pathway and The manuscript was written through contributions of all
observation of the OER intermediates can be plausible by authors. All authors have given approval to the final version of
this Raman spectroscopy. Spatial distribution of active states the manuscript.
on the electrode surface could also affect the macroscopic Funding
response of the OER catalysis. The newly found reaction
Any funds used to support the research of the manuscript
pathway can be the key for the opening the OER catalytic
should be placed here (per journal style).
pathway by controlling the electrolyte properties.75,76
Notes
■ CONCLUSIONS The authors declare no competing financial interest.
Here, we studied the OER behavior of the Ni nanohole-array
electrode in various electrolyte conditions. Electrochemical
behavior and machine-learning analysis showed that the
■ ACKNOWLEDGMENTS
The authors acknowledge Prof. Junji Nishii for the interference
behavior of the OER is quite unique to the electrolyte exposure techniques. This work was supported by JSPS
conditions. In addition, in situ Raman observation revealed KAKENHI (JP21K14596, JP 22H02023, and JP22K18315).
unique intermediate behaviors in pH 11 unbuffered conditions. Supports by the JST-PRESTO program: Exploring Quantum
The demonstrated study can be, in principle, applicable to any Frontiers Through Quantum-Classical Interdisciplinary Fusion
electrode to unveil the OER behavior from the energetic and (JPMJPR23FB), the Photoexcitonix Project at Hokkaido
intermediates analysis. The neutral-pH water electrolysis is still University, the MEXT Program: Data Creation and
challenging and unexplored. The study herein provides the Utilization-Type Material Research and Development Project
multiple reaction pathway in the OER for enabling more active (JPMXP1122712807), the JST-Mirai Program (JPMJMI21EB)
OER catalysis for green hydrogen production. and GteX Program (JPMJGX23H2) are also acknowledged.

■
*
ASSOCIATED CONTENT
sı Supporting Information
■ ABBREVIATIONS
OER, oxygen evolution reaction; LSV, linear sweep voltammo-
The Supporting Information is available free of charge at gram
https://pubs.acs.org/doi/10.1021/acs.jpcc.4c06732.
Estimation of the geometric surface area of Ni nanohole-
array electrode, estimation of the concentration of the
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